JPS63179952A - Impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent flame-retardancy and weather resistance as well as good impact strength and moldability, by compounding an impact resistant resin, a crystalline chlorinated polyethylene, a specific flame retardant, a dehydrochlorination-preventing agent and a phenolic antioxidant. CONSTITUTION:The objective composition can be produced by compounding (A) an impact-resistant resin produced by the graft copolymerization of styrene, acrylonitrile and methyl methacrylate to a butadiene-containing rubber, etc., (B) a crystalline chlorinated PE containing 3-50wt.% residual PE crystal, having a chlorine content of 15-50wt.% and exhibiting an amorphous peak at a Bragg angle (2theta) of 12-13 deg. and crystalline peaks assignable to crystalline peaks assignable to crystalline PE at 21 deg. and 24 deg. by wide-angle X-ray diffraction, (C) antimony oxide and a chlorine-containing organic compound, (D) an agent for preventing dehydrochlorination and (E) a phenolic antioxidant. The amounts of the components C, D and E are 5.0-40pts.wt., 0.1-10pts.wt. and 0.1-7.0pts. wt. per 100pts.wt. of the sum of the components A and B, respectively. The ratio of the component A to A+B is 75-99wt.%.

Description

[Detailed description of the invention]

! 2-1 5 The present invention relates to an impact-resistant resin composition that has excellent impact resistance and flame retardancy, and has not only excellent cutting impact resistance but also good flame retardancy. The object of the present invention is to provide an impact-resistant resin composition. At present, impact-resistant resins such as acrylonitrile-butadiene-styrene ternary copolymer resins are used as the body of electrical and electronic equipment such as television receivers, word processors, various computers, and facsimile-1 audio equipment. is widely used. In order to impart flame retardancy to these impact-resistant resins, compositions obtained by blending various flame retardants are generally used. If the amount of flame retardant added is relatively small, the flame retardant property will not be sufficient, and if the amount of flame retardant added is relatively large, the cost will increase and the impact resistance of the composition will decrease. The flame retardant may bleed onto the surface of the molded product, and there are also problems with flame retardancy, such as the occurrence of fire glare. For this purpose, it is considered to incorporate amorphous chlorinated polyethylene rubber, which is often used as a flame retardant. However, although this amorphous chlorinated polyethylene is a rubber, there is a problem in that the impact strength of the resulting composition is not satisfactory. I will do it. From the above, the present invention does not have these drawbacks (problems), that is, it not only has good impact strength and processability, but also has good flame retardancy, and is suitable for use in electrical and electronic equipment. The objective is to obtain an optimal composition during manufacturing. According to the wording and according to the present invention, these problems are solved by (A) impact-resistant resin, (B) crystalline chlorinated polyethylene, (C) antimony oxide and chlorine-containing non-polymeric organic compound ( (hereinafter referred to as "chlorine-containing organic compound"); (D) a dehydrochlorination inhibitor; and (E) a phenolic antioxidant; the total of the impact-resistant resin and crystalline chlorinated polyethylene; The composition ratio of impact resistant resin in the amount is 75
~99% by weight, and the composition ratio of antimony oxide and chlorine-containing organic compound is 5.0 to 40 parts by weight based on 100 parts by weight of the total amount of impact-resistant resin and crystalline chlorinated polyethylene. In addition, the composition ratio of the dehydrochlorination 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 composition ratio of antimony oxide and chlorine-containing organic compound is 0.1 to 10 parts by weight. The composition ratio of antimony oxide in the total amount of is 5 to 95% by weight.
and impact-resistant resins include butadiene-containing rubber (hereinafter referred to as "butadiene-based rubber") and ethylene-propylene-diene-based multicomponent copolymer rubber containing ethylene and propylene as main components (hereinafter referred to as "ethylene-propylene-based rubber"). A graft obtained by graft copolymerizing styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methyl methacrylate to at least one rubber selected from the group consisting of acrylic ester rubbers) and acrylic ester rubbers. Crystalline chlorinated polyethylene, which is a copolymer, exhibits an amorphous peak at a Black angle of 2θ of 12 to 13 degrees by X-ray wide-angle diffraction, and crystalline peaks at a Black angle of 2θ of 21 or 24 degrees, respectively. This problem can be solved by an impact-resistant resin composition that exhibits a crystallinity peak depending on the polyethylene, has 3 to 50% by weight of polyethylene crystals remaining, and has a chlorine content of 15 to 50% by weight. The present invention will be explained in detail below. (A) Impact-resistant resin The impact-resistant resin used in the present invention consists of at least one rubber selected from the group consisting of butadiene rubber, ethylene-propylene rubber, and acrylic ester rubber, acrylonitrile, and methyl methacrylate. It is obtained by graft copolymerization with at least one vinyl compound selected from the group. (1) Butadiene rubber The butadiene rubber is a rubber containing butadiene as a main component (60% by weight or more), including butadiene homopolymer rubber,
It is 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 Also, ethylene-propylene rubber has ethylene and propylene as main components, 1.4-pentadiene, 1.
Linear or branched diolefins containing two double bonds at the ends, such as 5-hexadiene and 3,3-dimethyl-1,5-hexadiene, 1,4-hexadiene and 6-methyl-1 , 5-hebutadiene, or cyclic diene hydrocarbons such as bicyclo[2,2,1]-hebutene-2 and its derivatives. It is a multicomponent copolymer rubber obtained by copolymerizing a small amount (generally 10% by weight or less) of monomers. The weight ratio of one unit of ethylene monomer to one unit of propylene monomer in these copolymer rubbers and multicomponent copolymer rubbers is 30/70.
Preferably, the ratio is between 70/30 and 70/30. (3) Acrylic ester rubber Also, acrylic ester rubber refers to an acrylic ester (for example, acrylic butyl butyl) and a small amount (generally 10% by weight or less) of other monomers (for example, acrylonitrile). It is obtained by emulsion polymerization of and in the presence of a catalyst such as a persulfate, and is commonly referred to as acrylic rubber. In producing the impact-resistant resin of the present invention, among these rubber-like substances, those having a Mooney viscosity of 20 to 140 are preferable, although it varies depending on the type of the rubber-like substance, and those having a Mooney viscosity of 30 to 120 are particularly preferable. It is. Further, these rubber-like materials are widely produced industrially and are used in a wide variety of fields. Their manufacturing methods, properties and uses are widely known.

[
For example, "Synthetic Rubber Handbook" written by Shu Kanbara (published by Asakura Shoten in 1962). Vinyl compounds (acrylonitrile,
Methyl methacrylate). Graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, aqueous suspension polymerization, and methods that combine these graft polymerization methods (for example, bulk polymerization followed by aqueous suspension polymerization). Generally, the amount of rubber material used to produce 100 parts by weight of impact-resistant resin is 3 to 40 parts by weight, preferably 5 to 35 parts by weight, and particularly preferably 5 to 30 parts by weight. (a relatively large amount of rubber-like material is used to produce a graft polymer containing a large amount of rubber-like material, and the above-mentioned styrene,
A homopolymer resin or copolymer resin of acrylonitrile and methyl methacrylate may be mixed, but in this case, the amount of rubber-like material used is calculated based on the mixture). Also,
The molecular weight of the monomer (styrene, acrylonitrile, methyl methacrylate) bonded to the rubber-like material as a graft chain is usually 1000 to 300,000, preferably 2000 to 200,000. In general, complete bonding of monomers to the rubbery material is rare, and there are graft products and homopolymers or copolymers of monomers that do not bond to the rubbery material. These homopolymers and copolymers are used as they are without separation. (5) Typical examples of impact-resistant resins Typical 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 rubber (SBR). Polymerized rubber (NBR),
Acrylonitrile-butadiene obtained by graft copolymerization of styrene and acrylonitrile
Styrene terpolymer resin (ABS resin), methyl methacrylate-butadiene-styrene terpolymer resin (MBS resin) obtained by graft copolymerizing styrene and methyl methacrylate to butadiene homopolymer rubber or SBR, acrylic acid Acrylonitrile - acrylic acid ester - obtained by graft copolymerizing acrylonitrile and styrene to ester rubber
Examples include styrene terpolymer resin (AAS resin) and graft copolymer resin (AES resin) obtained by graft copolymerizing acrylonitrile and styrene to ethylene-propylene rubber. These impact-resistant resins are manufactured industrially and are used in a wide variety of fields, and the manufacturing method is well known. (B) Crystalline chlorinated polyethylene The crystalline chlorinated polyethylene used in the present invention can be prepared by chlorinating polyethylene powder or particles in an aqueous suspension, or by chlorinating polyethylene dissolved in an organic solvent. (preferably by chlorination in an aqueous suspension). Crystalline chlorinated polyethylene whose chlorine content is 15 to 50% by weight, especially chlorine content of 20 to 45% by weight.
% by weight of crystalline chlorinated polyethylene is preferred. The polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10% by weight of α-olefin (generally having at most 12 carbon atoms). Its density is generally between 0.900 and 0.900.
980 g/cm'. Moreover, its molecular weight is 50,000 to 800,000. The crystalline chlorinated polyethylene of the present invention has a remaining polyethylene crystal content of 3 to 50% by weight, and its representative characteristics are as follows:
Specific gravity is 1.00-1.30, JISK-8301
Tensile breaking strength is 50-1 in tensile test measurement according to
50 g/crn', and the tensile elongation at break is 500 to 8
It is 00%. Also, the hardness (Shore A) is 70-9
8, and the volume resistivity (measured according to ASTM D-254) is 1.0 x 10 ~ 1.0 x 1015 Ωscm
It shows characteristics such as. The X-ray wide-angle diffraction pattern was analyzed using an X-ray wide-angle diffractometer (manufactured by Rigaku Denki Co., Ltd., trade name: Geigerflex 202B).
Figure 1 shows the X-ray wide-angle diffraction diagram of the crystalline chlorinated polyethylene used in the Examples, which was measured with α-rays on Cu- using The line wide-angle diffraction diagram is shown as the dotted line (a) in Figure 2, and the X-ray wide-angle diffraction diagram of the ethylene-butene-1 copolymer used as the raw material for these chlorinated polyethylenes is shown in Figure 2 (Real line 11 (b)). Shown as From the X-ray wide-angle diffraction diagram, the ethylene-butene-1 copolymer (crystalline polyethylene) has crystallinity of (110) plane at Bragg angle 2θ = 21 degrees and (200) plane at Bragg angle 2θ = 24 degrees. It can be seen that it shows a peak. In addition, amorphous chlorinated polyethylene has a Bragg angle of 2θ = 12 degrees to 1
Although an amorphous peak clearly appears in three cases, the crystalline peak of the crystalline polyethylene completely disappears. Furthermore, for crystalline chlorinated polyethylene, the Bragg angle 2θ=12
It is clear that it shows a peak equivalent to that of amorphous chlorinated polyethylene at a Bragg angle of 2θ to 13 degrees, and crystallinity peaks that depend on crystalline polyethylene at Bragg angles 2θ=21 and 24 degrees, respectively. 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 manufacturing conditions of chlorinated polyethylene. (C) Antimony Oxide Further, the antimony oxide used in the present invention is generally used as a flame retardant aid for chlorine-containing organic compounds described below. Representative examples include antimony trioxide and antimony pentoxide. These chlorine-containing organic compounds and antimony oxide are well known from "Handbook, Rubber/Plastic Compounded Chemicals" mentioned later. The average particle size of the antimony oxide is usually 1 to 150 microns. (D) Chlorine-containing organic compound The chlorine-containing organic compound used in the present invention is widely known as a flame retardant. The molecular weight of the chlorine-containing organic compound is usually 30,000 or less, and the boiling point is 300°C or more. In addition, the chlorine content of the chlorine-containing organic compound is 5 to 80
Weight%. Representative examples of this chlorine-containing organic compound include tetrakis(hydroxymethyl)phosphonium autochloride, chlorinated paraffin, chlorinated polyolefin,
Dimethyl chlorendate, perchloropentacyclodecane, bisphenol A tetrachloride, phthalic anhydride tetrachloride,
bistarolopropyl φ dichloropropyl phosphate,
Mention may be made of trischloroethyl phosphate and tris(dichloropropyl) phosphate. (E) Dehydrochlorination inhibitor Furthermore, the dehydrochlorination inhibitor used in the present invention is generally a polymer containing halogen atoms (mainly chlorine atoms), such as a vinyl chloride polymer, which undergoes dehydrochlorination caused by heat or the like. It is widely used to prevent hydrogen chloride. The dehydrochlorination inhibitors are broadly classified into metal soaps, inorganic acid salts, metal oxides, organic tin compounds, and pure organic compounds. A typical example of these is the patent application filed in 1983.
-139528. These dehydrochlorination inhibitors are described on pages 266 to 3113 of Rubber Digest Co., Ltd., ed., Handbook, Rubber/Plastic Compounded Chemicals (published in 1972 by Rubber Digest Co., Ltd.). Among these dehydrochlorination inhibitors, inorganic acid salts, metal oxides and organic tin compounds are preferred, and inorganic acid salts and metal oxides are particularly preferred. Particularly suitable are dibasic lead phthalate, dibasic lead stearate, tribasic lead sulfate, basic lead silicate, magnesium oxide and lead oxide. (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 these phenolic antioxidants, the general formula of typical ones is the following formula [Formula (■) to Formula IV)]
It is expressed as H [hereinafter referred to as "phenolic compound (1)"] R6R6 R5R5 (m) [hereinafter referred to as "phenolic compound (3)"] and R7R7 R8R8 (IV) [hereinafter referred to as "phenolic compound (4)"] 〕however,
R1, R2 and R3 may be the same or different, and may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, or a hydrogen atom or an alkyl group having 4 carbon atoms.
~20 cycloalkyl groups, alkyl groups having 1 to 20 carbon atoms! -A hydrocarbon group selected from the group consisting of an alkylcycloalkyl group and a l-alkylbenzyl group having an alkyl group having 1 to 20 carbon atoms, and at least two of R1, R2 and R3 are It is a hydrocarbon group, R4 is an alkyl group having 1 to 6 carbon atoms, R and R8 may be the same or different, and 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 and R6 is the hydrocarbon group or the above aralkyl group, and R7 and R
8 may be the same or different, and is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
having a group or an alkyl group having 1-12 carbon atoms l
-alkylcycloalkyl group or 1-alkylbenzyl group, R8 is a fullkylidene group or alkylene group having 1 to 12 carbon atoms, X is an integer of 1 to 8, and y is 1.2 or 3. A representative example of the phenolic compound (1) is disclosed in Japanese Patent Application Laid-open No. 49-49
No. 5051 and is described in each specification. Of this phenolic compound (1), in the above formula (I), R1
, R2 and R3 each preferably have at most 8 carbon atoms. In addition, a representative example of the phenolic compound (2) is JP-A-41
It is described in each specification of No. 1-78488 and No. 411-137892. Among the phenolic compounds,
In the above formula (II), it is preferable that R4 has 3 or 4 carbon atoms. Furthermore, a representative example of phenolic compound (3) is
This is clearly stated in the specifications of No. 9-130502 and No. 49-137Ei92. Among these phenolic compounds, in the above formula (m), those in which R and R6 have 18 or less carbon atoms are preferred, and those with 4 or more carbon atoms are particularly preferred. Moreover, a representative example of phenolic compound (4) is
It is described in each specification of No. 9-131159 and No. 411-1378112. Among the phenolic compounds, in the above formula (IV), R and R8 preferably have at most 18 carbon atoms, particularly preferably 4 or less. Further, R9 preferably has at most 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Furthermore, by incorporating a thiopropionate antioxidant and/or an organic phosphorus antioxidant, the heat resistance (processability at high temperatures) of the resulting composition can be improved, preventing deterioration and discoloration. It is possible to produce molded products without any problems. (G) Thiopropionate-based antioxidant side chain Thiopropionate-based antioxidants are used as antioxidants for organic substances such as synthetic resins, similar to the above-mentioned phenolic antioxidants. It is often used in combination with the above-mentioned phenolic antioxidants. Among the thiopropionate antioxidants, the general formulas of typical ones are shown as the following formulas [formulas (V) to VI)]. Rlo-0-C-C:nH2n-S-CnH2n-C-
0-R11(Vl) CN (-CH2-0-C-CnH2n -S-R12
)4(Vl) (However, R, R and R12 may be the same or different, and may be an alkyl group having 1 to 20 carbon atoms, allyl
l) is a hydrocarbon group selected from the group consisting of groups and aralkyl groups, and n is an integer from 1 to 20. ) Typical examples of the thiopropionate antioxidants are listed in Rubber Digest Co., Ltd.'s Handbook of Rubber-Plastic Compound Chemicals.
゛ (Rubber Digest, published in 1972) No. 10
Pages 5 to 111 and edited by Yamada et al. "Plastic Compounds (Basics and Applications)". (Taiseisha, published in 1960), pages 111 to 13
It is described in detail on page 0. Among the thiopropionate antioxidants, in the formulas (V) and (VI) above, those in which R, R and R12 each have at most 20 carbon atoms are preferable, especially those with 12 or more carbon atoms. is suitable. Representative examples of suitable thiopropionate antioxidants include dilaurylthiopropinate and pentaerythritol tetrakis (β-laurylthiopropionate). (H) Organophosphorus antioxidants Also, organophosphorus antioxidants are used as antioxidants for organic substances such as synthetic resins, similar to the aforementioned phenolic antioxidants and thiopropinate antioxidants. It is often used in combination with the above-mentioned phenolic antioxidants and thiopropinate antioxidants. The general formula of a typical organic phosphorus antioxidant is shown as the following formula (■). (Margins below) R130\ R140-P (■) R150/ (However, R, R, and R15 may be the same or different, and include a hydrogen group and an alkyl group having 1 to 20 carbon atoms,
The hydrocarbon group is selected from the group consisting of an aryl group, an aralkyl group, an alkaryl group, and an alkenyl group, in which at least one is a hydrocarbon group. Typical examples of the organic phosphorus antioxidants are listed on pages 287 to 289 of Rubber Digest Co., Ltd., “Handbook of Rubber and Plastic Compounded Chemicals” (Rubber Digest Co., published in 1971) and “For Plastics and Rubber”. It is described in detail on pages 183 to 195 of Additive Practical Handbook (published by Kagaku Kogyo Co., Ltd. in 1972).
, R and R15 each preferably have 8 to 20 carbon atoms. Representative examples of suitable organophosphorus antioxidants include triphenyl phosphite, triotadecyl phosphite, and trinolylphenyl 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 crystalline chlorinated polyethylene is 75 to 99% by weight;
5 to 98% by weight is preferred, particularly 80 to 98% by weight. If the composition ratio of the impact resistant resin to the total amount of the impact resistant resin and crystalline chlorinated polyethylene is less than 75% by weight, the flame retardance of the resulting composition is good, but the rigidity and impact resistance are poor. unfavorable because it reduces On the other hand, if it exceeds 98% by weight, the rigidity and impact resistance are excellent, but dripping and blowing occur in flame retardation, resulting in insufficient flame retardancy. The composition ratios of the other composition components based on 100 parts by weight of the total amount of the impact resistant resin and crystalline chlorinated polyethylene are as follows. For antimony oxide and chlorine-containing organic compounds, their total amount is 5.0 to 40 parts by weight, and 5.0 to 40 parts by weight.
35 parts by weight is desirable, and 10 to 35 parts by weight is particularly preferred. If the total composition ratio of antimony oxide and chlorine-containing organic compound is less than 5.0 parts by weight, a composition having sufficient flame retardancy cannot be obtained. On the other hand, 4
If the amount exceeds 0 parts by weight, not only the molding processability of the composition will decrease, but also the thermal stability during molding will deteriorate. In addition, the composition ratio of chlorine-containing organic compounds in the total amount of antimony oxide and chlorine-containing organic compounds is 5 to 95% by weight (
That is, the composition ratio of antimony oxide is 95 to 5% by weight.
), preferably 10 to 80% by weight, particularly 20 to 80% by weight.
% by weight is preferred. Furthermore, for the dehydrochlorination inhibitor, the amount is 0.1 to 10 parts by weight, preferably 0.1 to 7.0 parts by weight, and 0.1 to 10 parts by weight.
6.0 parts by weight is preferred. For phenolic antioxidants, it is 0.1 to 7.0 parts by weight, and 0.1 to 6.0 parts by weight.
Parts by weight are preferred, particularly 0.1 to 5.0 parts by weight. In addition, when using a thiopropionate antioxidant and/or an organophosphorus antioxidant in addition to the phenolic antioxidant, the composition ratio of these should be the total amount of impact-resistant resin and crystalline chlorinated antioxidant. It is generally at most 7.0 parts by weight, preferably 6.0 parts by weight, based on 100 parts by weight of the total amount of polyethylene. In addition, the composition ratio of thiopropionate antioxidants and organophosphorus antioxidants in the total amount of phenolic antioxidants, thiopropionate antioxidants, and organophosphorus antioxidants is The total amount is at most 80% by weight, preferably 75% by weight or less. If the composition ratio of dehydrochlorination inhibitor and 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 amount exceeds the upper limit, not only will it not be possible to achieve the effect of the addition, but also contamination of the mold during molding or bleeding may occur on the surface of the resulting molded product. (K) Manufacture of composition, molding method, etc. To manufacture the composition of the present invention, the above-mentioned impact-resistant resin, crystalline chlorinated polyethylene, flame retardant consisting of antimony oxide and chlorine-containing organic compound, dechlorination Although the objective can be achieved by uniformly blending hydrogen inhibitors, phenolic antioxidants, and these with thiopropionate antioxidants and/or organophosphorus antioxidants, thermoplastic resins ( 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 intended use of the composition. It may be added to the extent that it does not impair the properties of the composition of the present invention. Mixing methods include a tri-blending method using a mixer such as a Henschel mixer, which is commonly used in the field of synthetic resins, and a method of tri-blending using a mixer such as an open roll, extrusion mixer, kneader, and Banbury mixer while melting. One method is to mix them. Among these mixing methods, two or more of these mixing methods may be used in combination to obtain a more uniform composition (for example,
(pre-triblending and then melt-mixing the mixture). In particular, even when tri-blend is used in combination, or when one or more melt-kneading methods are used together, when producing a molded article by the molding method described below, it is possible to use a pelletizer to produce pellets. It is preferable. Of the above mixing methods, regardless of whether it is melt-kneaded or molded using the molding method described below, it must be carried out at a temperature that melts the impact-resistant resin, crystalline chlorinated polyethylene, and chlorine-containing organic compound used. . However, if carried out at high temperatures, these may cause thermal decomposition or dehydrohalogenation reactions.
It is necessary to carry out the following. The composition of the present invention may be molded into a desired shape by applying molding methods commonly practiced in the field of synthetic resins, such as injection molding, extrusion molding, compression molding, and blow molding. Alternatively, after forming the sheet 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. Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, in the Examples and Comparative Examples, the tensile strength (hereinafter referred to as "TB") and elongation (hereinafter referred to as "rE B") was measured in the tensile test.
J) was measured using a Tensilon tester according to JIS K8911. In addition, the melt flow index (hereinafter referred to as rM, 1.J) is JIS KI3.
? According to 3G, the temperature is 210℃ and the load is 2.18K.
The impact test was conducted according to ASTM 025B at temperatures of 23°C and -20°C. Furthermore, the flame retardancy test was performed according to the UL-94 method, and the presence or absence of drips was observed with the naked eye. In addition, the impact-resistant resin used in the examples and comparative examples,
Manufacture of crystalline chlorinated polyethylene, amorphous chlorinated polyethylene, antimony oxide, chlorine-containing organic compounds, dehydrochlorination inhibitors, phenolic antioxidants, thiopropionate antioxidants, and organophosphorus antioxidants The method, type, physical properties, etc. are shown below. ((A) m-impact resin) As the impact-resistant resin, acrylonitrile-butadiene-
Styrene ternary copolymer resin (hereinafter referred to as rABsJ), methyl methacrylate-butadiene-styrene ternary copolymer resin (hereinafter referred to as rMBsJ), acrylonitrile-acrylic acid ester rubber-styrene ternary copolymer resin (hereinafter referred to as rAAS J) 1Es), acrylonitrile-olefin rubber-styrene multi-component copolymer resin (hereinafter referred to as 1Es
J) were manufactured and 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, respectively. Crystalline chlorinated polyethylene] As crystalline chlorinated polyethylene, butene-1 is added to 3.0
Polymerization% containing ethylene-butene-1 copolymer (density
0.840 g/c rrf, average molecular weight approximately 15
) was chlorinated in an aqueous suspension to obtain crystalline chlorinated polyethylene [chlorine content 30.2% by weight, amount of residual polyethylene crystals 7.15% by weight, Mooney viscosity (ML
l+4) 110, hereinafter referred to as rBCPEJ] was manufactured. [(C) Amorphous chlorinated polyethylene] As amorphous chlorinated polyethylene, the density is 0.1150.
Chlorinated polyethylene [chlorine content 40.2% by weight, amorphous, Mooney viscosity (MS, +4 ) 80, hereafter rcP
EJ) was manufactured. [(D) Antimony oxide and chlorine-containing organic compound] Density is 5.25 g/c as antimony oxide
antimony trioxide (hereinafter referred to as "5b203")
Furthermore, as the chlorine-containing organic compound, chlorinated paraffin having a chlorine content of 68% by weight or more (softening point of 95° C. or lower, referred to as rcPJ) was used. [(E) Dehydrochlorination inhibitor] As a dehydrochlorination inhibitor, magnesium oxide having a specific surface area of 150 m'/g (100 mesh pass, hereinafter rM
gOJ) and calcium stearate (hereinafter referred to as rCa-St) were used. [(F) Phenolic antioxidant, etc.] As a phenolic antioxidant, n-year-old tadecyl-3-(4°-hydroxy-3°, 5′-di-tert-butyl-phenyl) propionate (rA0- Dilauryl thiodipropionate (hereinafter referred to as rAO-2J) was used as a thiopropionate antioxidant, and triotadecyl phosphite (hereinafter referred to as rAO-2J) was used as an organophosphorus antioxidant. -34) was used. Examples 1 to 10, Comparative Examples 1 to 14 The impact-resistant resin and crystalline chlorinated polyethylene whose amounts and types are shown in Table 1 in advance (the total amount of these is 100 parts by weight) were mixed in a Henschel mixer. Antimony oxide, chlorine-containing organic compound, dehydrochlorination inhibitor, phenolic antioxidant, etc., whose amounts and types are shown in Table 1, are further added to each mixture obtained. A tri-blend was performed for a minute. The temperature of each mixture thus obtained was 160°C in cylinder 1, 180°C in cylinder 2,
180℃ for cylinder 3, 180℃ for adapter
In Gui, the composition (
pellets) were produced. Each pellet thus obtained was heated to a temperature of 210'
Hot pressing was carried out under the conditions of O and pressure of 200 kg/cm' with a preheating time of 3 minutes and a pressing time of 2 minutes to produce a sheet with a thickness of 2 mm. Comparative Example 15 Instead of BCPE used in Example 6, CPE
(The blending amount was the same as in Example 16), but tri-blending and melt-kneading were performed under the same conditions as in Example 6 to produce pellets. The obtained pellets were hot pressed in the same manner as in Example 6 to create a sheet. Comparative Example 16 Tri-blending and melt-kneading were performed under the same conditions as in Example 6, except that the amount of BCPE used in Example 6 was changed to 30 parts by weight, and pellets were manufactured. The obtained pellets were hot pressed in the same manner as in Example 6 to create a sheet. Tensile strength (T) of each sheet obtained as above
, measurement of elongation (EB), impact test (23℃ and -2
0'O), a flame retardancy test was conducted. Furthermore, the melt flow index (M,
1. ) were measured. The results are shown in Table 2. (Hereinafter, blank spaces) In Comparative Example 14, deterioration occurred during melt-kneading and sheet creation. From the results of the above Examples and Comparative Examples, it is clear that the impact-resistant resin composition obtained by the present invention has a
It is clear that not only the impact properties are excellent even at low temperatures, but also the flame retardance is good. Furthermore, the composition obtained by the present invention not only has good tensile strength, but also has a well-balanced composition with melt flow index and flame retardancy, so it is promising for use in housings, etc. it is obvious. The impact-resistant resin composition obtained by the present invention not only has good impact resistance, but also exhibits the following effects (characteristics). (1) Excellent weather resistance. (2) Good flame retardancy is 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 above-mentioned excellent effects, but also has good flame retardancy, so that it can be used in the following fields. (1) Television receiver (2) Word processor, various computers (3)
) Facsimiles - Electrical equipment and electronic equipment such as audio equipment (4) Housings for home appliances (5) Automobile instrument panels

[Brief explanation of the drawing]

FIG. 1 is an X-ray wide-angle diffraction diagram of crystalline chlorinated polyethylene (BCPE) used in Examples. In addition, (a) (dotted line) in Figure 2 is an X-ray wide-angle diffraction diagram of amorphous chlorinated polyethylene (CPE) used in the Examples and Comparative Examples, and (b) (solid line) in Figure 2
is an X-ray wide-angle diffraction diagram of the ethylene-butene-1 copolymer used in the production of these chlorinated polyethylenes.

Claims (1)

[Scope of Claims] (A) Impact-resistant resin, (B) Crystalline chlorinated polyethylene, (C) Flame retardant comprising antimony oxide and a chlorine-containing non-polymer organic compound, (D) Dehydrochlorination It consists of an inhibitor and (E) a phenolic antioxidant, and the composition ratio of the impact resistant resin to the total amount of the impact resistant resin and crystalline chlorinated polyethylene is 75%.
~99% by weight, and the composition ratio of antimony oxide and chlorine-containing non-polymer organic compound to 100 parts by weight of the total amount of impact-resistant resin and crystalline chlorinated polyethylene is 5.0 to 40% as a total amount thereof. The composition ratio of the dehydrochlorination 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, the composition ratio of antimony oxide in the total amount of antimony oxide and chlorine-containing non-polymer organic compound is 5 to 95% by weight, and the impact-resistant resin is composed of butadiene-containing rubber, ethylene and At least one rubber selected from the group consisting of ethylene-propylene-diene multi-component copolymer rubber containing propylene as a main component and acrylic ester rubber, and at least one rubber selected from the group consisting of styrene, acrylonitrile, and methyl methacrylate. It is a graft copolymer obtained by graft copolymerization with a vinyl compound, and crystalline chlorinated polyethylene exhibits an amorphous peak at a Black angle 2θ of 12 degrees to 13 degrees by X-ray wide-angle diffraction method.
Furthermore, the black angle 2θ shows crystallinity peaks depending on crystalline polyethylene at 21 degrees and 24 degrees, respectively, 3 to 50% by weight of polyethylene crystals remain, and the chlorine content is 15 to 50% by weight. Impact resin composition.