JPS6213377B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a highly flame-retardant, impact-resistant resin composition that has excellent mechanical strength and good moldability. More specifically, in the presence of a diene rubber latex and a graft copolymer obtained by bulk-suspension polymerization of an aromatic monoalkenyl monomer and a vinyl cyan monomer in the presence of a diene rubber component. A graft copolymer obtained by emulsion polymerization of a mixed monomer of the above monomer and/or an alkyl ester monomer of (meth)acrylic acid and a degree of chlorination of 25 to 25.
A highly flame-retardant impact-resistant resin composition with excellent impact resistance, thermal stability, moldability, and gloss, consisting of 45% by weight of chlorinated polyethylene, tetrabromobisphenol A or its derivatives, and antimony trioxide. It is about things. In recent years, the fields in which plastic materials are used have become increasingly diverse, and ABS resin, due to its excellent impact resistance and moldability, is used in many fields such as automobile parts, electrical appliances, construction materials, and various other molded products. There is. On the other hand, with the expansion of such uses, various legal regulations have arisen, and when used as a flame-retardant material, it is not only required to have self-extinguishing properties, but also to prevent the occurrence of "sparkling" during combustion. Regulations are becoming increasingly strict, including measures to prevent accidents. Methods for making flammable ABS resin flame retardant include relatively low molecular weight organic flame retardants containing a large amount of halogen, halogen-containing polymer compounds such as polyvinyl chloride, or inorganic compounds such as antimony trioxide. It is common to mix one or more types. In particular, in order to give ABS resin a high degree of flame retardancy that does not cause "sparkling" when burned, halogen-containing organic compounds, especially halogen-containing polymers such as polyvinyl chloride and chlorinated polyethylene, are used. It is known that it is effective to use this compound together with antimony trioxide. Next, bulk suspension polymerization and emulsion polymerization are well known as typical methods for producing ABS resins. For example, when ABS resin is produced by emulsion polymerization, the rubber content in the resin can be varied as desired because it involves graft copolymerization of a vinyl monomer mixture onto rubber latex. In addition, since the particle size of rubber latex is generally small enough, emulsion polymerization ABS
Molded articles made from resin have excellent gloss. However, emulsifiers, salting-out agents, and the like used in the manufacturing process persistently remain in the resin, which adversely affects the mechanical properties and thermal stability of the resin. In particular, when halogen-containing organic flame retardants and antimony trioxide are blended to make ABS resin flame retardant using these emulsion polymerization methods, impurities such as emulsifiers and salting-out agents remaining in the ABS resin promote the combustion of the resin. However, excessive amounts of halogen and antimony are required for flame retardancy, and furthermore, these impurities accelerate the decomposition of halogen-containing flame retardants and increase the coloring of the resin during molding. There are many problems such as corrosion. Next, ABS resin obtained by the bulk suspension method has good thermal stability because it does not contain impurities such as the emulsifiers mentioned above. In comparison, the amount of halogen and antimony required for flame retardancy is small, and the colorability during molding is also extremely good. However, in bulk suspension polymerization, the diene rubber component is dissolved in a vinyl monomer mixture and polymerized, making it difficult to produce ABS resin with a high rubber concentration, and the rubber particles in the resulting ABS resin are relatively large. Therefore, products obtained by molding tend to have poor gloss. On the other hand, high-impact polystyrene is a rubber-modified impact-resistant resin similar to ABS resin, but the amount of flame retardant imparting component required to achieve the same level of flame retardancy as mentioned above is higher than that of high-impact polystyrene.
It is well known that ABS resin is required in larger quantities and is characterized by a higher degree of impact resistance, stiffness, and even chemical resistance than high-impact polystyrene.
More advanced technology is required to make ABS resin flame retardant without sacrificing its properties. Chlorinated polyethylene, which is often used as a flame retardant imparting component, has poor compatibility with high-impact polystyrene, and even if chlorinated polyethylene is blended with high-impact polystyrene, no improvement in impact resistance can be expected; A decrease in rigidity and a delamination phenomenon occur, so that the practical limit for the amount of chlorinated polyethylene to be added is about 10% at most. However, ABS resin and chlorinated polyethylene have good compatibility, and impact resistance is improved in proportion to the amount of chlorinated polyethylene blended. For this reason, a relatively large amount of chlorinated polyethylene is used.
It is already well known that it is added to ABS resin to impart flame retardancy and at the same time compensate for the decrease in impact resistance caused by antimony trioxide. However, contrary to the improvement in impact resistance, the rigidity, moldability, and thermal stability of the final resin composition are reduced, and the original characteristics of ABS resin are considerably impaired. In order to maintain the original properties of this ABS resin as much as possible and to make it highly flame retardant, a halogen-containing organic flame retardant is further added to chlorinated polyethylene and antimony trioxide. It is desirable to achieve flame retardancy with the minimum amount of compounding. The present inventors utilized two types of ABS resin produced by bulk-suspension polymerization method and emulsion polymerization method, and by combining chlorinated polyethylene, halogen-containing organic flame retardant, and antimony trioxide, improved mechanical strength and moldability. The present invention was achieved as a result of extensive research aimed at providing an impact-resistant resin composition with excellent flame retardancy. That is, in the presence of a diene rubber component, an aromatic monoalkenyl monomer and a vinyl cyan monomer are first polymerized under bulk polymerization conditions, and then the polymerization is continued under suspension polymerization conditions. 20-90% by weight of graft copolymer obtained by completing polymerization
and a graft copolymer 10 obtained by polymerizing a diene rubber latex with an aromatic monoalkenyl monomer, a vinyl cyanide monomer, and/or an alkyl ester monomer of acrylic acid or methacrylic acid under emulsion polymerization conditions. 1 to 12% of chlorinated polyethylene with a degree of chlorination of 25 to 45% by weight per 100 parts by weight of ~80% by weight and these graft copolymers.
The present invention relates to a flame-retardant resin composition comprising 5 to 25 parts by weight of tetrabromobisphenol A or a derivative thereof and 2 to 10 parts by weight of antimony trioxide. Generally, ABS resins obtained by bulk-suspension polymerization do not contain impurities such as emulsifiers and salting-out agents that are present in ABS resins obtained by emulsion polymerization. Perhaps due to this reason, the amount of flame retardant required to achieve the same level of flame retardancy tends to be smaller in bulk-suspension ABS resins than in emulsion polymerization ABS resins. Due to process constraints, bulk-suspension ABS resin has the disadvantage that the rubber content in the resin is relatively low, and the impact strength, which is a major feature of ABS resin, is low. This drawback is further exacerbated. However, this lump-suspension method
A resin composition made by blending an emulsion polymerized ABS resin with a high rubber content with an ABS resin has improved impact resistance, and as an even more excellent effect, when a flame retardant is blended into a mixed resin composition of these two types, it becomes lumpy. Suspension method
It is recognized that a relatively small amount of flame retardant may be required to impart a certain level of flame retardancy, a feature seen in the case of ABS resins. In addition, the obtained flame retardant resin composition was found to have good thermal stability, especially in the flame retardant system of the present invention, chlorinated polyethylene, tetrabromobisphenol A or its derivatives, and antimony trioxide. The lump-suspension method has almost the same advantages expected for ABS resin, but the lump-suspension method
A mixed resin composition of ABS resin and emulsion polymerization ABS resin is obtained, and as a result, a flame-retardant resin composition with excellent mechanical properties, moldability, and thermal stability is obtained. In general, the combustion of plastics and the flame retardation using various flame retardants are a complex process of chemical and physical phenomena.
It is a complex mechanism that is still not fully understood. However, the combustion of plastics is usually an oxidation reaction of flammable gas generated by the decomposition of plastics due to heat, and the "flame" during this process is thought to be caused by the flow of plastics due to the heat of combustion. When a halogen-containing organic flame retardant is present in this system, nonflammable halogen compound gas is generated, which blocks air at the combustion surface and at the same time traps radicals during the oxidation reaction of combustible gases, preventing combustion. It will be done. Antimony trioxide itself does not have a flame retardant effect, but when it coexists with a halogen system, it generates antimony halides, which promotes the movement of halogens and at the same time enhances the radical trapping effect. On the other hand, chlorinated polyethylene has the above-mentioned flame retardant effect due to the halogen, and at the same time, double bonds are generated in the polymer main chain due to dehydrochlorination. This gelation caused by double bonds prevents the fluidization of the plastic due to the heat of combustion, and at the same time promotes the formation of carbides, resulting in "flame" during combustion.
It has the effect of preventing The present inventors have conducted research to obtain a highly flame-retardant resin composition without "sparkling" by blending chlorinated polyethylene, a halogen-containing organic flame retardant, and antimony trioxide with ABS resin. ABS
Naturally, a certain amount or more of the above three types of flame retardant components are necessary to make resin flame retardant, but surprisingly, bulk suspension ABS resin and emulsion polymerization method
When a resin composition containing ABS resin is blended with chlorinated polyethylene, tetrabromobisphenol A or its derivative, and antimony trioxide, only the content of chlorinated polyethylene is increased in the blend once it has achieved a high degree of flame retardancy. A phenomenon was observed in which the resin composition became flammable again, and in order to make it flame retardant, it was necessary to increase the amount of other flame retardant components, such as tetrabromobisphenol A or its derivative, and antimony trioxide. In other words, if 1 to 12 parts by weight of chlorinated polyethylene is used for 100 parts by weight of a resin composition using bulk-suspension ABS resin, it is difficult to achieve a high degree of flame retardancy without "sparkling". A certain range is recognized for the total amount of tetrabromobisphenol A and antimony trioxide required in the resin composition, but if chlorinated polyethylene is used in excess of this amount, the amount necessary for flame retardation will be reduced. The total amount of halogen and antimony trioxide increases rapidly. Naturally, an increase in the flame retardant component required to make the resin flame retardant deteriorates the physical properties of the resulting resin composition, and since the flame retardant is more expensive than the resin, it is not economically advisable. When this chlorinated polyethylene is used in an amount of 12 parts by weight or less, the flame-retardant effect of bromine and antimony in tetrabromobisphenol A and the gelation phenomenon work in an exquisite balance, allowing ABS resin to be made with a relatively small amount of flame-retardant components. However, in the past, a large amount of relatively inexpensive chlorinated polyethylene was used as a flame retardant, and at the same time the impact resistance of the resin was improved, so other flame retardant ingredients such as trioxide were used. Large amounts of antimony and halogen-containing organic flame retardants were required. When more than 12 parts by weight of this chlorinated polyethylene is used, the reason for the significant increase in the amount of flame retardant components required is not fully understood other than that the flame retardant mechanism may change, but examples include halogen, antimony, etc. The gelling effect of chlorinated polyethylene increases compared to the air blocking effect and oxidation reaction radical scavenging effect in the gas phase, reducing the fluidity of the resin due to combustion heat, renewing the combustion surface, and improving heat conduction of the resin composition. It is presumed that the required amount of flame retardant components will change significantly due to changes in the degree of combustion and an increase in the combustible surface. The diene rubber component used in the graft copolymer produced by the bulk suspension method in the present invention is as follows:
Among butadiene and isoprene-based rubbers, polybutadiene and butadiene-styrene copolymer rubbers with relatively high stereoregularity using lithium or organometallic compound catalysts are particularly good. There is no particular limitation on the amount of diene rubber component used, but generally speaking, 2 to 40 parts by weight of the rubber component is used per 100 parts by weight of the vinyl monomer mixture, but 2 to 20 parts by weight part is preferred. The average diameter of the dispersed rubber particles is 0.2 to 2.0 μ, preferably 0.3
~1.2μ. Next, as the aromatic monoalkenyl monomer used in the graft copolymer, styrene is most suitable, but various substituted styrenes such as α-methylstyrene and p-methylstyrene can also be used, and these and styrene can be used. Mixtures can be used as well. Next, as the vinyl cyan monomer, acrylonitrile is most suitable, but methacrylonitrile and the like can also be used. There is no particular limitation on the mixing ratio of the aromatic monoalkenyl monomer and vinyl cyan monomer, but generally the aromatic monoalkenyl monomer is 80 to 55 parts by weight, and the vinyl cyan monomer is 80 to 55 parts by weight. is used in an amount of about 20 to 45% by weight. The type of polymerization initiator and molecular weight regulator used to produce the graft copolymer of the present invention,
There is no particular limitation on the amount, and not only commonly known amounts are widely used, but in some cases it may be added cumulatively to each step of bulk polymerization and suspension polymerization. There are no limitations on the suspending and dispersing agent, and for example, so-called organic protective colloids such as polyvinyl alcohol and hydroxyethyl cellulose, or fine powders of inorganic salts such as calcium phosphate and magnesium hydroxide can be used. There are no particular restrictions on the polymerization temperature conditions, but it is usually 60 to 100℃ for bulk polymerization and 60℃ for suspension polymerization.
Preferably it is carried out at ~140°C. The graft copolymer may be a suspension polymerization method, a bulk polymerization method, or a bulk-suspension polymerization method in which the same vinyl monomer mixture is added to the graft copolymer obtained by the above-mentioned bulk-suspension polymerization method. Also included are blends of copolymers obtained. Conventional emulsion polymerization conditions are applied to the production of the graft copolymer in the present invention. Diene-based rubber latexes include polybutadiene latexes and copolymer rubber latexes of butadiene and vinyl monomers such as styrene, acrylonitrile, or methyl methacrylate. Further, rubber latex with substantially no crosslinking or rubber latex containing crosslinked gel may be used. The amount of diene rubber latex used is not particularly limited, but the rubber component is generally 10 to 100 parts by weight per 100 parts by weight of the vinyl monomer mixture. The average diameter of dispersed rubber particles in diene rubber latex is
It is 0.05-0.5μ, preferably 0.1-0.3μ. Next, the types of aromatic monoalkenyl monomer and vinyl cyan monomer used in this graft copolymer are the same as in the case of the graft copolymer. Furthermore, as the alkyl ester monomer of acrylic acid or methacrylic acid, methyl methacrylate is most suitable, but esters of alkyl alcohols having up to about 18 carbon atoms can also be used.
There are no particular limitations on the mixing ratio of vinyl monomers, but generally the aromatic monoalkenyl monomer is 50 to 80% by weight, and the vinyl cyan monomer is 0 to 45% by weight.
The amount of the alkyl ester monomer of acrylic acid or methacrylic acid used is about 0 to 50% by weight. The vinyl monomer may be used in its entirety from the start of polymerization, but may be added continuously or in portions depending on the case. Next, the surfactants used when producing a graft copolymer by emulsion polymerization method include sodium alkylbenzene sulfonate, sodium salt of higher alcohol sulfate, sodium salt of disproportionated rosin acid, potassium salt, and salt of higher fatty acid. Anionic surfactants such as sodium salts and potassium salts. The initiator for the polymerization may be a persulfate such as potassium persulfate, a hydroperoxide such as p-menthane hydroperoxide, or a combination such as cumene hydroperoxide-Fe ⁺⁺ -glucose. Also, common known molecular weight regulators can be used. Incidentally, the graft copolymer also includes a blend of a graft copolymer obtained by an emulsion polymerization method as described above with a copolymer obtained by an emulsion polymerization method made of the same vinyl monomer mixture. . The blending ratio of the graft copolymer in the present invention is 20 to 90% by weight of the graft copolymer and 10 to 80% by weight of the graft copolymer, particularly preferably 30 to 85% by weight and 15 to 70% by weight of the graft copolymer. %, and a highly flame-retardant resin composition in which the flame retardant component according to the present invention is blended with a blended resin composition within this range is less susceptible to coloring during molding due to the emulsion polymerization method, and less likely to be easily colored during injection. There is almost no corrosion in the molding machine or mold, and when using bulk suspension ABS resin that contains almost no impurities, it enjoys the excellent thermal stability and excellent mechanical strength. It can exhibit performance with well-balanced physical properties. The content of the rubber component in the composition of the present invention is usually 3 to 40% by weight, preferably 5 to 30% by weight, based on the total weight of the graft copolymer.
Weight%. Incidentally, the composition of the present invention includes cases where a copolymer of a vinyl monomer is mixed and added, and therefore also includes the following embodiments. An aromatic monoalkenyl monomer and a vinyl cyanide monomer are first polymerized under bulk polymerization conditions in the presence of a diene rubber component, and then polymerization is continued under suspension polymerization conditions to substantially complete the polymerization. The graft copolymer obtained by completion or this graft copolymer,
20 to 90% by weight of a polymer obtained by blending a copolymer obtained by a suspension polymerization method, a bulk polymerization method, or a bulk suspension polymerization method consisting of the above monomer mixture, and an aromatic compound in a diene rubber latex. A graft copolymer obtained by polymerizing a monoalkenyl monomer and a vinyl cyan monomer and/or an alkyl ester monomer of acrylic acid or methacrylic acid under emulsion polymerization conditions, or to this graft copolymer, The degree of chlorination is 25 to 80% by weight of a polymer obtained by blending a copolymer obtained by emulsion polymerization method consisting of the above monomer mixture, and a total of 100 parts by weight of these graft copolymers. A flame-retardant resin composition comprising 1 to 12 parts by weight of 45% by weight chlorinated polyethylene, 5 to 25 parts by weight of tetrabromobisphenol A or its derivative, and 2 to 10 parts by weight of antimony trioxide. . In the present invention, chlorinated polyethylene with a degree of chlorination of 25 to 45% by weight is one obtained by chlorinating polyethylene, ethylene-propylene copolymer, or ethylene-butene copolymer using a normal method as a raw material,
It is desirable that the bound chlorine be distributed as uniformly as possible in the polymer, with few residual crystals present that would impair its rubber performance. Also, chlorosulfonated polyethylene, such as "Hyperon"
(trade name manufactured by DuPont, USA) is also included in this category. The amount of chlorinated polyethylene to be used is 1 to 12 parts by weight, preferably 3 to 12 parts by weight, more preferably 3 to 10 parts by weight, and 1 part by weight based on 100 parts by weight in total with the graft copolymer. If the amount is less, the effect of preventing "flame drip" during combustion cannot be expected, while if the amount is more than 12 parts by weight, as mentioned above, the amount of other flame retardant components required to achieve a high degree of flame retardancy will increase. This adversely affects the physical properties of the resin composition and is not economically advisable. Other flame retardants in the present invention include tetrabromobisphenol A or derivatives thereof, ie carbon atoms of 2 to
These flame retardants include hydroxyalkyl ethers or hydroxyhalogenated alkyl ether compounds of No. 3, and oligomers of tetrabromobisphenol A, and the effects of the present invention are exhibited only in the case of these flame retardants. Antimony trioxide in the present invention is an essential component in order to efficiently obtain a resin composition having a high degree of flame retardancy. If the objective were to be achieved using only halogen without using antimony, a significantly large amount of halogen would be required. The total amount of tetrabromobisphenol A and antimony trioxide used together with the graft copolymer is 100%.
Parts by weight and 1 to 12 parts by weight of chlorinated polyethylene (B) are 5 to 20 parts by weight and 2 to 10 parts by weight, respectively, and if the amount used is less than this range, the desired flame retardation will not be achieved; If the amount used exceeds this range, it will result in excessive flame retardation, resulting in a decrease in the physical properties of the final resin composition, and will also be economically disadvantageous. In addition to the above-mentioned four components, commonly used additives such as heat stabilizers, antioxidants, lubricants, colorants, etc. can also be blended as needed. In the present invention, the graft copolymer, chlorinated polyethylene, tetrabromobisphenol A system, and antimony trioxide can be mixed using a conventional mixing device, such as a hot roll or a Banbury mixer, without requiring any special means or order. It can be easily produced using a mixer or an extruder. The present invention will be described in detail with reference to Examples below, where all parts in the examples are by weight. Reference example <Manufacture of graft copolymer> Graft copolymer 1 Composition A Styrene-butadiene rubber (“Tufden 2000A”)
(Manufactured by Asahi Kasei Industries, Ltd.) 15 parts Styrene 72 parts Acrylonitrile 28 parts Benzoyl peroxide 0.15 parts Dicumyl peroxide 0.08 parts Tertiary dodecyl mercaptan 0.35 parts Composition A was charged into a closed reactor equipped with a powerful stirring device until the rubber component was completely dissolved. After melting, raise the temperature to 70℃,
Time bulk polymerization was carried out. Next, add 100 parts of water and 4 parts of magnesium hydroxide in advance.
The reaction mixture was transferred to another closed reactor in which an aqueous dispersion containing 0.05 parts of sodium laurate was prepared and stirred to suspend it. Thereafter, the temperature was raised to 120°C and suspension polymerization was carried out for 5 hours. After cooling the resulting polymer particle system, the dispersant was decomposed with hydrochloric acid, washed with water, and dried. The obtained graft copolymer is designated as -. The average rubber particle size of -1 was 0.8 microns.

【table】

[Table] Putane Composition A was placed in a closed reactor equipped with a powerful stirring device, and after the rubber component had completely dissolved, the temperature was raised to 70°C.
Bulk polymerization was carried out for a period of time, at which point Composition B was additionally added and stirring was carried out for 10 minutes. Next, add 100 parts of water and 4 parts of magnesium hydroxide in advance.
The reaction mixture was transferred to another closed reactor in which an aqueous dispersion containing 0.05 parts of sodium laurate was prepared and stirred to suspend it. Thereafter, the temperature was raised to 120°C, and suspension polymerization was carried out for 5 hours. After cooling the obtained polymer particle system, the dispersant was decomposed with hydrochloric acid,
Washed with water and dried. The obtained graft copolymer is designated as -2. The average rubber particle size of graft copolymer-2 is
It was 0.37μ. Graft copolymer 1 A graft copolymer is produced using polybutadiene latex (rubber concentration 50%) synthesized by a known method. Polybutadiene latex 30 parts Styrene 72 parts Acrylonitrile 28 parts Potassium persulfate 0.5 parts Tertiary dodecyl mercaptan 0.5 parts Disproportionated sodium rosinate 2 parts Water 170 parts Rubber latex,
Add 150 parts of water in which mercaptan, monomer mixture and disproportionated sodium rosinate were dissolved and heat at 60°C.
and dissolved potassium persulfate at this temperature.
20 parts of water were added over 3 hours. Polymerization was carried out at 60°C for an additional 3 hours. Hydrochloric acid was added to the resulting graft polymer, it was heated to coagulate, and after dehydration and washing, it was dried. The obtained graft copolymer -1
shall be. The average rubber particle size of -1 was 0.1 to 0.2 microns. Graft copolymer 2 The graft copolymer obtained by synthesizing the above graft copolymer-1 under the same conditions as in -1 except that the polybutadiene latex was changed to 50 parts and the tertiarydodecyl mercaptan was changed to 0.6 parts.
shall be. The average rubber particle size of -2 was 0.1 to 0.2 microns. <Production of styrene-acrylonitrile copolymerization> Styrene 72 parts Acrylonitrile 28 parts Lauroyl peroxide 0.34 parts Tertiarydodecyl mercaptan 0.30 parts 100 parts of 0.5 parts of hydroxyapatite and 0.01 part of sodium laurate dissolved and dispersed in a reaction vessel equipped with a stirring device. of water is added thereto, and the above monomer mixture is added thereto and stirred to suspend. Thereafter, the temperature was raised to 72°C and suspension polymerization was carried out for 10 hours. After cooling the resulting polymer particle system, the dispersant was decomposed with hydrochloric acid, washed with water, and dried to obtain a styrene-acrylonitrile copolymer. Example 1 85 parts and 15 parts of graft copolymers -1 and -1 obtained in Reference Example were added to chlorinated polyethylene with a degree of chlorination of 35% ("Daisorak G-235" manufactured by Osaka Soda Co., Ltd.). 5 parts and tetrabromobisphenol
After pre-blending 18 parts of A, 5 parts of antimony trioxide, and 0.3 parts of triphenyl phosphite and 1 part of dibutyltin maleate as stabilizers, pellets were formed using an extruder, and pellets were formed using an injection molding machine (molding temperature
Test pieces were prepared at 210℃) and their physical properties were measured. Example 2 The physical properties were measured under the same conditions as in Example 1 except that 70 parts and 30 parts of graft copolymers -1 and -1 were used, respectively. Example 3 The same procedure as in Example 1 except that 50 parts each of graft copolymers -1 and -1 were used.
The physical properties were measured under the same conditions. Example 4 The same conditions as in Example 1 were used except that 30 parts and 70 parts of graft copolymers -1 and -1 were used, respectively, and the physical properties thereof were measured. Comparative Example 1 In Example 2, all operations were carried out under the same conditions as in Example-2 except that graft copolymer-1 was not used and 100 parts of graft copolymer-1 was used.
We measured its physical properties. Comparative Example 2 In Example 2, all operations were performed under the same conditions as in Example 2, except that Graft Copolymer-1 was not used and Graft Copolymer-1 was used, and the physical properties thereof were measured. The results of Examples 1, 2, 3, and 4 and Comparative Examples 1 and 2 are summarized in Table 1.

[Table] The physical property values in the table are tensile strength: ASTM D
-638, impact strength ASTM D256, flammability: UL standard
Measure according to No. 94. In addition, the colorability is determined by the naked eye. Everything below is the same. In Examples 1, 2, 3, and 4, resin compositions with good mechanical and thermal properties and highly flame retardant were obtained, whereas in Comparative Example 2, the same flame retardant system was used. However, the flame retardance is insufficient, and the discoloration due to heat is large. In addition, in Comparative Example 1, although the mechanical and thermal properties were good, the gloss of the molded product was significantly lacking. Example 5 All operations were carried out under the same conditions as in Example 2 except that 8 parts of chlorinated polyethylene was used in Example 2,
We measured its physical properties. The results are shown in Table 2. Example 6 The same conditions as in Example 2 were used except that 10 parts of chlorinated polyethylene was used, and the physical properties thereof were measured. The results are shown in Table-2. Comparative Examples 3, 4, 5, 6 Everything was the same as Example 2 except that the amount of chlorinated polyethylene used and hexabromobenzene was used instead of tetrabromobisphenol A as shown in Table 2. It was operated under the same conditions and its physical properties were measured.

[Table] In contrast to the highly flame-retardant resins of Examples 2, 5, and 6, which have excellent properties, the flame retardance of Comparative Examples 3 and 4 is lower, and the resins with a thickness of 1/8″ barely have 94V-0. However, it burns at 1/16″ thickness. Moreover, the thermal stability is also reduced. On the other hand, in Comparative Examples 5 and 6, in which hexabromobenzene was used with approximately the same bromine content as tetrabromobisphenol A used in Examples 2, 5, and 6, the flame retardance was more effective than tetrabromobisphenol A. Moreover, unlike tetrabromobisphenol A, there is no specificity in the ratio of use with chlorinated polyethylene. Example 7 Example 2 except that 70 parts and 30 parts of graft copolymers -1 and -2 obtained in Reference Example were used.
The physical properties were measured under the same conditions. Example 8 Graft copolymers-1 and -2 obtained in Reference Example and styrene-acrylonitrile copolymer were
The physical properties were measured under the same conditions as in Example 2 except that 30 parts, 40 parts, and 30 parts were used. The results of Examples 7 and 8 are summarized in Table 3. Example 9 -2 and -1 were used in amounts of 70 parts and 30 parts, respectively, and the same procedure and measurement as in Example 2 were carried out. The results are shown in Table-3. Example 10 All operations were carried out under the same conditions as in Example 2 except that 3 parts of chlorinated polyethylene were used in Example 2,
We measured its physical properties. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1. In the presence of a diene rubber component, an aromatic monoalkenyl monomer and a vinyl cyanide monomer are first polymerized under bulk polymerization conditions, and then polymerization is continued under suspension polymerization conditions. Then, 20 to 90% by weight of the graft copolymer obtained by substantially completing the polymerization, and an aromatic monoalkenyl monomer, a vinyl cyan monomer, and/or acrylic acid or methacrylic acid are added to the diene rubber latex. Graft copolymer obtained by polymerizing alkyl ester monomers under emulsion polymerization conditions
10-80% by weight of these graft copolymers,
1 to 12 parts by weight of chlorinated polyethylene with a degree of chlorination of 25 to 45% by weight, 5 to 25 parts by weight of tetrabromobisphenol A or its derivative, and 2 to 10 parts by weight of antimony trioxide based on a total of 100 parts by weight. A flame-retardant resin composition characterized by: 2. The flame-retardant resin composition according to claim 1, which contains 3 to 12 parts by weight of the chlorinated polyethylene.