KR810001052B1 - Flame retarding resin composition - Google Patents

Abstract

A flame-retarding resin composion consists of (A) a graft copolymer obtained by bulk and suspension polymerizing an aromatic monoalkenyl monomer and a vinyl-cyano monomer and/or a monomeric alkyl ester of acrylic acid or methacrylic acid in the presence of a diene type rubber component as an optional in gredient (B) a graft copolymer obtioned by emulsion polymerizing a monomeric mixture of the above mentioned monomers in the presence of a diene type rubber latex (C) a chlorinated polyethylene having a degree of chlorination of 25 to 45 wt % (D) tetrabromo-bis-phenol A or a derivative there of and (E) entimony trioxide.

Description

Flame Retardant Resin Composition

The present invention relates to a highly flame retardant and impact resistant resin composition having excellent mechanical strength and good formability.

In more detail, the present invention relates to a highly flame-retardant, impact-resistant resin composition excellent in impact resistance, thermal stability, moldability and gloss, the composition is mainly in the presence of (A) diene rubber component, aromatic monoal A monomer mixture of the above-mentioned graft copolymer obtained by bulk polymerization and suspension polymerization of a kenyl monomer and a vinyl cyan monomer or a monomer of acrylic acid or methacrylic acid and (B) an optional component in the presence of a diene rubber latex as an optional component It consists of the graft copolymer obtained by emulsion polymerization, (C) chlorinated polyethylene of 25 to 45 weight%, (D) tetrabromo bisphenol A or its derivative (s), and (E) antimony trioxide.

Recently, the field of application of plastic materials has been expanded, and ABS resins have been used in various fields such as automobile parts, electric equipments, construction materials, and other molded articles because of their excellent impact resistance and formability. However, as the field of application of these resins has expanded as described above, a number of strict legal regulations have been imposed on these plastic materials, and flame retardants are not only self-extinguishing today, but also flzming dripping during combustion. ) Properties are not required to occur.

As a means of imparting flame retardancy to flammable ABS resins, at least one component selected from a relatively low molecular weight organic flame retardant containing a large amount of halogens, a halogen-containing polymer such as polyvinyl chloride, and an inorganic compound such as antimony trioxide is used. The method of mixing in is generally adopted.

In order to give ABS resins highly flame-retardant property that "flame fall" does not occur during combustion, a combination of halogen-containing organic compounds, especially halogen-containing polymers such as polyvinyl chloride, chlorine and polyethylene, and antimony trioxide is used. It is known that this is effective.

As representative production methods of ABS resins, bulk-suspension polymerization and emulsion polymerization methods are known. For example, when ABS resin is prepared according to the emulsion polymerization method, the rubber content in the resin can be arbitrarily changed because the mixture of vinyl monomers is grafted to the rubber latex. Moreover, since the particle size of the rubber latex is sufficiently small, the molded article of the ABS resin produced by the emulsion polymerization method exhibits excellent gloss. However, emulsifiers or coagulants used in the production method remain in the resins obtained, thus adversely affecting the mechanical properties and thermal stability of the resins. Especially when halogen-containing organic flame retardants and antimony trioxide are mixed in such ABS resins to give them flame retardancy, if impurities such as emulsifiers and coagulants remain in the ABS resins, this increases the flammability of the ABS resins, And an excessive amount of antimony component must be mixed. Moreover, such impurities promote the decomposition of halogen-containing flame retardants. As a result, various troublesome problems arise such as discoloration of the resin and corrosion of the injection molding machine or mold in the molding step.

The ABS resin produced by the bulk-suspension polymerization method is free of such impurities as an emulsifier. Therefore, this ABS resin has good thermal stability, and when the flame retardant is mixed in this ABS resin, the amount of halogen or antimony component required to provide flame retardance to the ABS resin will be much reduced than in the case of ABS resin obtained by emulsion polymerization method. There is a number. In addition, discoloration in the molding step can be significantly reduced.

Other rubber modified impact resistant resins include high impact polyethylene. It is known that in order to achieve the same level in terms of flame retardancy, a larger amount of flame retardant must be mixed in the ABS resin than in this high impact polyethylene.

Therefore, a high level of technology is required to provide flame retardance to body ABS resins without impairing the properties of ABS resins, that is, having higher impact resistance, rigidity and chemical resistance than high impact polystyrene.

Polyethylene chloride used as a flame retardant imparting component has poor compatibility with high-impact polystyrene, and therefore, even if polyethylene chloride is mixed in high-impact polystyrene, an improvement in impact resistance cannot be expected, and a decrease in rigidity and layering Poor phenomena such as peeling occur.

Therefore, in practical terms, the amount of chlorinated polyethylene mixed into high impact polystyrene should be limited to about 10% or less. In contrast, it can be seen that chlorinated polyethylene has good compatibility with ABS resins, so that when chlorinated polyethylene is mixed into the ABS resin, the impact resistance is improved in proportion to the amount of chlorinated polyethylene mixed. It is known that by mixing a relatively large amount of chlorinated polyethylene into the ABS resin, it is possible to provide flame retardancy to the ABS resin and compensate for the reduction in the impact resistance caused by the mixing of antimony trioxide and the like. However, even if the impact resistance is improved by mixing chlorinated polyethylene, the rigidity and formability of the final resin composition are reduced, and the inherent properties of the ABS resin are considerably lost. As much as possible, it is preferable to mix a minimum amount of chlorinated polyethylene, antimony trioxide, and halogen-containing organic flame retardant in ABS resin in order to provide high flame retardancy to ABS resin while maintaining the inherent properties of ABS resin.

By using ABS resin produced by the bulk-suspension polymerization method, and also using a combination of chlorinated polystyrene, halogen-containing organic flame retardant and antimony trioxide, and optionally using emulsion-polymerized ABS resin, mechanical sweetness and moldability The present inventors have now completed the present invention as a result of repeatedly studying for the purpose of obtaining this excellent, highly flame-retardant and highly impact-resistant resin composition.

In more detail, the present invention, in the presence of a diene rubber component in a bulk polymerization state, polymerizes an alkyl ester of an aromatic monoalkenyl monomer and a vinyl cyan monomer or a monomer of acrylic acid or methacrylic acid, substantially in a suspension polymerization state. At least 20% by weight of the graft copolymer (A) obtained by continuing the polymerization to complete the polymerization, and an aromatic monoalkenyl monomer and a vinyl cyan monomer or a short amount of alkyl ester of acrylic acid or methacrylic acid as a diene rubber latex under emulsion polymerization. 1-12 parts by weight of chlorinated polyethylene (C) having a chlorination degree of 25-45% by weight relative to 80 parts by weight of the graft copolymer (B) obtained by polymerization of 100 parts by weight of the total of these copolymers A and B and tetra Flame retardant resin composition consisting of 5-25 parts by weight of bromobis phenol A (D) or a derivative thereof and 2-10 parts by weight of (E) antimony trioxide Relate to. In other words, the present invention provides a preferred composition comprising 100 parts by weight of a graft copolymer prepared by a bulk-suspension polymer without using any emulsion polymerized graft copolymer. The present invention also provides another preferred composition containing the bulk-suspension graft copolymer and the emulsion graft copolymer, in which the mixing ratio of the bulk-suspension graft copolymer and the emulsion graft copolymer is 20/80 by weight. -90/10.

According to the present invention, the composition including the graft copolymer (A) has greatly improved flame retardant properties. In addition, the composition including both of the graft copolymers (A) and (B) further improves the glossiness as well as the flame retardant properties.

In general, the ABS resin produced by the bulk-suspension polymerization method does not contain impurities contained in the ABS resin produced by the emulsion polymerization method such as an emulsifier, a coagulant, or the like.

For this reason, the amount of flame retardant required to achieve the same level in flame retardant effect is usually smaller in ABS resin produced by the bulk-suspension method than in ABS resin produced by emulsion polymerization method. However, due to process constraints, in the case of ABS resins produced according to the bulk-suspension polymerization process, the rubber content of these resins is relatively low, and thus a defect is observed that the impact strength, which is one of the important characteristics of ABS resins, is lowered. And defects are more pronounced by the addition of flame retardants. When ABS resins having a higher rubber content, prepared according to the emulsion polymerization method, are mixed into ABS resins prepared according to the mass-suspension polymerization method, impact resistance is improved in the resulting resin composition, and a flame retardant is mixed in the resin composition. In the case of ABS resin produced according to the block-bullet polymerization method, the effect observed, that is, the effect of reducing the amount of flame retardant required to achieve a certain level of flame retardancy can be achieved. Moreover, this resin composition has good thermal stability. In particular, when the chlorinated polyethylene, tetrabromo-bisphenol A or derivatives thereof and antimony trioxide are used as the flame retardant of the present invention, the resin composition is expected to have the advantages expected in the case of an ABS resin prepared according to the bulk-suspension method. In this case substantially and completely can be achieved. Therefore, by mixing the ABS resin produced according to the bulk-suspension polymerization method and the ABS resin produced according to the emulsion polymerization method, and the flame retardant system as a mixture, a flame retardant resin composition excellent in mechanical properties, moldability and thermal safety You can get

Plastic burning and various flame retardants have been attempted to solve the plastic flame by complicated mechanisms including various chemical and physical phenomena, but such mechanisms are not yet fully understood.

In general, however, the combustion of plastics is the oxidation of combustible gases formed by pyrolysis of plastics.

The "flame drop" generated during the combustion of the plastic is due to the flow of the plastic due to the heat of combustion, and if a halogen-containing organic flame retardant is present, it blocks the air from the combustion surface and the gas of the combustible gas undergoing oxidation reaction. ) By generating the non-combustible gas of the halogen compound that can prevent combustion. Antimony trioxide itself does not have the effect of a flame retardant, but in the presence of halogen, it forms an antimony halide to enhance the transition of halogen, and at the same time improves the effect of trapping groups.

Chlorinated polyethylene exhibits the effect of the flame retardant by halogen, while at the same time it prevents the flow of plastic by the heat of combustion due to the gelation of double bonds (GEL) formed in the main chain of the polymer by dehydrogen chloride. Moreover, the formation of charcoal is enhanced and the effect of preventing "fall of flame" during combustion is evident. By mixing chlorinated polyethylene, halogen-containing organic flame retardants and antimony trioxide in ABS resins, the results of the study aimed at developing highly flame-retardant resin compositions that do not cause "falling flames". Although it must be mixed in excess of the amount, if the amount of chlorinated polystyrene alone is composed of ABS resin prepared according to the mass-suspension method and ABS resin prepared according to the emulsion polymerization method, polyethylene chloride, tetrabro It has been found that if a mixture of parent bisphenol A or its derivatives and antimony trioxide is increased beyond a certain level in a flame retardant resin composition, a surprising phenomenon occurs that the resin composition becomes combustible again. In order to provide flame retardancy again That is, it is necessary to increase the amount of tetrabromo-bisphenol A or a derivative thereof and antimony trioxide. In more detail, when 1 to 12 parts by weight of chlorinated polyethylene is used with respect to 100 parts by weight of a resin composition composed of ABS resin prepared according to the bulk-suspension polymerization method, and optionally an ABS resin prepared according to the emulsion polymerization method. However, the total amount of tetrabromo-bisphenol A and antimony trioxide required to achieve flame retardancy that does not cause "falling flame" falls within a certain range, but when the amount of chlorinated polyethylene increases beyond the above range, The total amount of halogens and antimony trioxide needed to provide significantly increases.

In this case, the physical properties of the resin composition are naturally lowered by the increased amount of the flame retardant component, and the obtained resin composition has no advantage from an economic point of view because the flame retardants are more expensive than resins. When chlorinated polyethylene is used in an amount not exceeding 12 parts by weight with respect to 100 parts by weight of resins, the flame retardant action of bromine and antimony in tetrabromo-bisphenol A is well balanced with the gelation phenomenon, and with a relatively small amount of flame retardant components Flame retardancy can be provided to an ABS resin composition.

According to the prior art, polyethylene chloride, a relatively inexpensive flame retardant, has been used in large amounts to enhance impact resistance as well as the flame retardant effect, and therefore, other flame retardant components, namely antimony trioxide and halogen-containing organic flame retardants, are mixed in large amounts. I had to let it. When the amount of chlorinated polyethylene exceeds 12 parts by weight with respect to 100 parts by weight of ABS resin, it was not clear why the amount of flame retardant components must be increased to achieve the intended flame retardant effect.

I could only say that the combustion mechanism was probably changed. For example, the gelling effect by chlorinated polyethylene surpasses the air blocking effect by halogen and antimony in gas phase and the action of capturing the oxidation reactor, and the softened surface is revitalized by reducing the flow of resin due to combustion heat or the thermal conductivity of the resin composition. It is increased by the change of sex, which translates into an increase in the amount of flame retardant components.

As the diene rubber component used for the graft copolymer (A) by the bulk-suspension method of the present invention, butadiene rubbers, isoprene rubbers, and copolymers of such diene monomers and styrene or acrylonitrile can be used. have. Among them, polybutadiene or butadiene-styrene copolymer rubbers having a relatively high spatial order of regularity and synthesized using lithium or organometallic compound catalysts are particularly preferred. The amount used for the diene rubber component is not very important. Generally, the diene rubber component is used 2-40 parts by weight, preferably 2-20 parts by weight, based on 100 parts by weight of the mixture of vinyl monomers. The uniform flat size of the dispersed rubber particles is 0.2-2.0 μ, preferably 0.3-1.2 μ.

-메틸스티렌 및 P-메틸스티렌과 같은 대용스티렌류를 사용할 수 있으며, 또한 이러한 대용스티렌과 스티렌의 혼합물도 사용할 수가 있다. 아크릴로니트릴은 비닐시안 단량체로서 가장 바람직하지만, 메타크릴로니트릴 등을 사용해도 된다.Styrene is most preferred as the aromatic monoalkenyl monomer used in the graft copolymer (A). not only,

Substituted styrenes such as -methyl styrene and P-methyl styrene can be used, and a mixture of such substitute styrene and styrene can also be used. Although acrylonitrile is most preferable as a vinyl cyan monomer, methacrylonitrile etc. may be used.

Regarding alkyl ester monomers of acrylic acid or methacrylic acid, esters having 1 to 18 carbon atoms of alkyl, in particular methyl methacrylate are preferred. The mixing ratio of the aromatic monoalkenyl monomer and the vinyl cyan monomer or the alkyl ester of acrylic acid or methacrylic acid is not particularly important, but in general, 80-55% by weight aromatic monoalkenyl monomer, 0-45% by weight vinyl cyan monomer, 0-45% by weight of the alkyl ester is used.

The total weight of the vinyl cyan monomer and alkyl ester is 25-45% by weight.

In the present invention, the type and amount of the polymerization initiator and the molecular weight regulator used in the production of the graft copolymer (A) are not particularly important, and therefore, a known regulator may be used in a known amount. In some cases, the bulk polymerization and the suspension polymerization may be performed separately, and the products obtained in both processes may be mixed at the same time. Furthermore, suspension dispersants are not very important, and for example, so-called organic protective colloids such as polyvinyl alcohol and hydroxyethyl cellulose and inorganic salts such as calcium phosphate and magnesium hydroxide can be used. In addition, temperature conditions are not particularly important. In general, the bulk polymerization is preferably carried out at 60-100 ° C. and the suspension polymerization at 60-140 ° C. The graft copolymer (A) comprises a copolymer obtained from a mixture of homo-monomers by a suspension polymerization method, a bulk polymerization method or a bulk-suspension polymerization method and a graft copolymer obtained according to the block-suspension polymerization method. do. Customary emulsion polymerization conditions are applied to the production of the graft copolymer (B) in powder invention. Examples of the diene rubber latex include a latex of a copolymer of polybutadiene latex and butadiene of vinyl monomers such as styrene, acrylonitrile or methyl methacrylate. Substantially comparable rubber latex as well as crosslinked gel containing rubber latex can be used in the present invention. The amount of diene rubber latex is not particularly important, but in general, the amount of the latex is 10-100 parts by weight based on 100 parts by weight of the mixture of vinyl monomers. The average size of the dispersed rubber particles of the diene rubber latex is 0.05-0.5μ, and preferably 0.1-0.3μ. The very aromatic monoalkenyl monomers and vinyl cyan monomers described above in relation to the graft copolymer (A) can be used for the production of the graft copolymer (B). Although the mixing ratio of the vinyl monomers is not very important, generally a mixture consisting of 55-80% by weight of an aromatic monoalkenyl monomer, 0-45% by weight of vinyl cyanide monomer and 0-45% by weight of an alkyl ester of acrylic acid or methacrylic acid is used. do. Such vinyl monomers may be added completely at one time at the start of the polymerization, but in some cases may be added continuously or separately depending on the stage.

As surfactants used to prepare the graft copolymer (B) according to the emulsion polymerization method, for example, sodium salts of alkylbenzene sulfonic acid, sulfate esters of higher alcohols, sodium and potassium salts of disproportionated rosin acid, and higher fatty acids And anionic surfactants such as sodium and potassium salts.

As the polymerization initiator, for example, peroxides such as potassium peroxide, hydroperoxides such as P-methane hydroperoxide, and combination initiators such as Kummen hydroperoxide-Fe ⁺⁺ -glucose may be used. As a molecular weight regulator, well-known regulators can also be used. Incidentally, the graft copolymer (B) comprises a mixture of a graft copolymer obtained according to the emulsion polymerization method and another copolymer prepared from a mixture of the same vinyl monomers according to the emulsion polymerization method.

If the graft copolymer (B) is mixed in the composition of the present invention, the mixing ratio of the graft copolymer (A) and (B) in the present invention is 20-90% by weight of the graft copolymer (A) % Is preferred, more preferred than this is 30-85% by weight, the amount of graft copolymer (B) is 10-80% by weight, more preferably 15-70% by weight.

The highly flame retardant resin composition of the present invention prepared by mixing the flame retardant component in a resin composition composed of the above mixing ratios of the graft copolymers (A) and (B) has well-balanced physical properties. In more detail, discoloration and corrosion of the injection molding machine or mold during the molding step inevitably occurring in the resins produced by emulsion polymerization do not occur in the resin composition of the present invention, and do not contain impurities. The excellent thermal stability of resins formed by bulk-suspension polymerization can be retained in the resin composition of the present invention. Moreover, the mechanical strength of the resin composition of the present invention is very high. The content of the rubber component of the present invention is 3-40% by weight, preferably 5-30% by weight based on the total amount of the graft copolymers (A) and (B).

The composition of the present invention may also consist of a copolymer of vinyl monomers. In more detail, as one embodiment, the present invention relates to a graft copolymer (A) or a polymer (A) with the graft copolymer (A) by a suspension, bulk or block-suspension polymerization method. Air obtained from a mixture with a copolymer obtained from a mixture of the same monomers and a mixture of the same monomers as in the graft copolymer (B) or the copolymer (B) by the emulsion polymerization method with the graft copolymer (B). 1-12 parts by weight of chlorinated polyethylene (C) having a degree of chlorination of 25-45% by weight relative to 100 parts by weight of the mixture with the mixture, (D) 5-25 parts by weight of tetrabromo-bisphenol A or its derivatives, And a flame retardant resin composition composed of 2-10 parts by weight of antimony trioxide. In this composition, component (B) or a mixture thereof is optional.

Chlorinated polyethylene (C) having a degree of chlorination of 25-45% by weight for use in the present invention is formed by chlorinating polyethylene, ethylene-propylene copolymers or ethylene-butene copolymers by customary methods. The bound chlorine atoms are distributed as uniformly as possible in the polymer, and it is preferable that no residue crystals exist that degrade the function as rubber. Chlorinated polyethylene is mixed in an amount of 1-12 parts by weight based on 100 parts by weight in total of the graft copolymers (A) and (B). If the amount of chlorinated polyethylene is less than 1 part by weight, it is not possible to achieve the effect of preventing the falling of flame, and if the amount of chlorinated polyethylene is more than 12 parts by weight, as indicated above, the amount of other flame retardant components is In order to achieve flame retardancy, it must be increased, and therefore, the physical properties of the resin composition are lowered, which brings economic disadvantages.

As another flame retardant (D), derivatives such as tetrabromo-bisphenol A or hydroxyalkylesters having 2-3 carbon atoms, hydroxyhalogenated alkyl ether compounds or oligomers of tetrabromo bisphenol A are used.

The aimed effect of the present invention is that this flame retardant (D) can only be achieved when other flame retardants are used in combination with (C) and (E).

Antimony triacid (E) is an indispensable component for obtaining a highly efficient flame retardant resin composition. If you do not use antimony and want to achieve the purpose of flame retardant using only halogen, halogen must be used in very large amount. When the total amount of graft copolymers (A) and (B) is 100 parts by weight and the amount of chlorinated polyethylene (C) is 1-12 parts by weight, tetrabromo-bisphenol A (D) and antimony trioxide (E) The amounts are 5-20 parts by weight and 2-10 parts by weight, respectively. If these components (D) and (E) are used in small amounts, the desired flame retardancy cannot be achieved.

If these components are used in large amounts, the flame retardancy becomes excessive, the physical properties of the final resin composition are reduced and economically disadvantageous.

In addition to the above indispensable components, the resin compositions of the present invention also include additives such as heat stabilizers, antioxidants, lubricant pigments, and the like customarily used in the art.

In the present invention, the mixing of the graft copolymers (A) and (B), chlorinated polyethylene (C), tetrabromo-bisphenol A flame retardant (D) and antimony trioxide (E) may be carried out by any special means or order of addition. This can be achieved by using a heatroll Banbuy mixer or an extruder. As described above, the present invention provides another composition having very improved flame retardant properties, which composition mainly contains aromatic monoalkenyl monomers and vinyl cyan monomers or acrylic esters in the presence of diene rubber components under bulk polymerization conditions. Or 100 parts by weight of a graft copolymer (A) obtained by polymerizing a monomer alkyl ester of methacrylic acid and continuing the polymerization under suspension polymerization conditions in order to substantially terminate the polymerization, and a chlorinated polyethylene having a chlorination degree of 25 to 45% by weight. (C) 1-12 weight part, 5-25 weight part of tetrabromo bisphenol A or its derivative (D), and 2-10 weight part of antimony trioxide (E).

This composition has the same effects and advantages as the composition comprising the graft copolymers (A) and (B).

Moreover, the preferred amount of chlorinated polyethylene is 3-12 parts by weight, more preferably 3-10 parts by weight based on 100 parts by weight of the graft copolymers.

The invention is described in detail in accordance with the following examples, all of which are referred to parts by weight.

Standard Example

Preparation of Graft Copolymers

Graft Copolymer (A) -1:

The composition consisting of the following components was charged into a closed reactor equipped with a powerful stirrer. After the rubber component was completely decomposed, the temperature was raised to 70 ° C., and the bulk polymerization was performed over 4 hours.

Composition X:

Styrene-butadiene rubber

(15 parts of Tafcen 2000A manufactured by Asagohi Kasei Kogoo

Styrene 72.

Acrylonitrile 28.

Benzoyl peroxide 0.15.

Dicumyl Peroxide 0.0 8.

t-dodecyl mercaptan 0.35.

The resulting reaction mixture was transferred to another closed reactor filled with an aqueous product consisting of 100 parts by weight of water, 4 parts by weight of magnesium hydroxide and 0.05 parts by weight of sodium laurate, and the mixture was suspended in the aqueous acid by stirring. The temperature was then raised to 120 ° C. and suspension polymerization was carried out for 5 hours.

The resulting polymer particles were cooled, the dispersant was decomposed by hydrochloric acid, washed with product and dried.

The graft copolymer thus obtained is designated as "copolymer" (A) -1 ". The average rubber particle size of this graft copolymer (A) -1 was 0.8 micrometer.

Graft Copolymer (A) -2:

Sterene-Butadiene Rubber Composition Y Composition Z

(Manufactured by Asahi Kasei Kogyo

Tafden 2000 A) Part 8

Styrene Part 62 10.

28 parts acrylonitrile

0.15 parts benzoyl peroxide

Dicumyl peroxide 0.08part

0.25 parts of t-dodecyl mercaptan 0.20.

The composition Y was charged into a closed reactor equipped with a strong stirrer, and after the rubber component was completely decomposed, the temperature rose to 70 ° C., and the bulk polymerization was carried out for 4 hours.

At this point, the composition Z was added and the mixture was stirred for 10 minutes.

The reaction mixture thus obtained was transferred into another closed reactor filled with aquatic acid water consisting of 100 parts by weight of water and 4 parts by weight of magnesium hydroxide and 0.05 parts by weight of sodium laurate, and the reaction mixture was stirred and suspended in the aqueous acid. . Then, the temperature rose to 120 ° C. and suspension polymerization was carried out for 5 hours.

The obtained polymer particles were cooled, and the dispersant was decomposed by hydrochloric acid, and the resulting product was washed with water and dried.

The graft copolymer thus obtained is

It was designated as 'graft copolymer (A) -2'.

The average rubber particle of the graft copolymer (A) -2 was 0.37 mu.

Graft Copolymer (A) -3:

Ingredients

Styrene-butadiene rubber

(Asahi Kasei Kogyo Co., Ltd. Tafden 2000A) 35 copies

Styrene Part 75

25 parts acrylonitrile

0.15 parts benzoyl peroxide

Dicumyl peroxide 0.08part

0.35 part of t-dodecyl mercaptan

Graft copolymer (A) -3 was prepared using the above components and was carried out as in the graft copolymer (A) -1. The average rubber particle of the obtained copolymer was 0.7 micrometers.

Graft Copolymer (B) -1:

Graft copolymer (B) -1 was prepared using polybutadiene rubber latex (having a rubber concentration of 50%) synthesized by a known method and the following components.

A reactor equipped with a stirrer was charged with 150 parts of water containing dissolved rubber latex, mercaptan, monomer mixture and sodium salt of heterogeneous rosin acid, and the temperature was raised to 60 ° C.

At this temperature, 20 parts of water containing sodium persulfate dissolved therein were added over 3 hours. Thus, polymerization was carried out at 60 ° C. for 3 hours. Hydrochloric acid was added to the obtained graft polymer, and this temperature was raised to condense the polymer, which was then dehydrated, washed and dried. The graft copolymer thus formed was designated as 'Graft copolymer (B) -1'. The average rubber particle of Copolymer (B) -1 was 0.1-0.2 micrometer.

Graft Copolymer (B) -2:

The graft copolymer and the polybutadiene latex amount was changed to 50 parts by weight, and t-decyl mercaptan was prepared in the same manner as described above for the graft copolymer (B) -1 except that the amount was changed to 0.6 parts by weight. . The obtained polymer was designated as 'Graft Copolymer (B) -2'. The average particle size of the graft copolymer (B) -2 was 0.1-0.2 mu.

[Production of Styrene-Acrylonitrile Copolymer]

A reactor equipped with a stirrer was filled with 100 parts by weight of water in which 0.5 parts of hydroxyapatite and 0.0 parts of sodium lauryl acid were dissolved and dispersed, and the monomer mixture was added to this aqueous acid and stirred and suspended therein. The temperature rose to 72 ° C. and suspension polymerization was carried out for 10 hours. The obtained polymer particles were cooled, and the dispersant was decomposed by hydrochloric acid, and the obtained product was washed with water and dried to obtain a styrene-acrylonitrile copolymer.

Example 1

First, the graft copolymer (A) -185 parts by weight prepared in the standard example and the graft copolymer (B) -115 parts by weight prepared in the standard example had a chlorination degree of 35% in advance (Daisolac G, manufactured by Soda Co., Ltd.). 18 parts by weight of chlorinated polyethylene having 5 parts by weight of tetraboromo-bisphenol A, 5 parts by weight of antimony trioxide, 0.3 parts by weight of triphenyl phosphite as a stabilizer, and 1 part by weight of tin dibutyl maleate. The mixture was tableted by an extruder and molded into test pieces by an injection molding machine (molding temperature 210 ° C.). The physical characteristics of the obtained test piece were calculated | required.

Example 2

Specimens were prepared in the same manner as described in Example 1 except that the amounts of graft copolymer (A) -1 and graft copolymer (B) -1 were changed to 70 parts by weight and 30 parts by weight, respectively. . The physical properties of these test pieces were obtained.

Example 3

The test pieces were prepared in the same manner as described in Example 1 except that the respective amounts of the graft copolymers (A) -1 and (B) -1 were changed to 50 parts by weight. The physical properties of these specimens were determined.

Example 4

It was prepared as described in Example 1 except that the amounts of graft copolymers (A) -1 and (B) -1 were changed to 30 parts by weight and 70 parts by weight, respectively. The physical properties of these specimens were determined.

Comparative Example 1

The test pieces were prepared in the same manner as described in Example 2 except that graft copolymer (A) -1 was not used and the amount of graft copolymer (B) -1 was changed to 100 parts by weight. . The physical properties of these specimens were determined.

The results obtained in Examples 1-4 and Comparative Example 1 are shown in Table 1.

TABLE 1

Tensile strength in Table 1 is determined according to the method of ASTM D-638, impact strength is determined according to the method of ASTM D-256. And flammability is decided by the method of UL specification No.94. Discoloration was evaluated according to visual observation.

In the next ensuing embodiment, the method of determining physical properties is the same as that described above.

In Example 1-4, a resin composition having good mechanical and thermal properties and flame retardancy was obtained. In Comparative Example 1, even though the same flame retardant system was used, the flame retardancy and the gloss of the molded article were insufficient.

Example 5

Test pieces were prepared in the same manner as described in Example 2, except that the amount of chlorinated polyethylene was changed to 8 parts by weight. The physical properties of these test pieces were obtained and the results are shown in Table 2.

Example 6

The test pieces were prepared by the same method as described in Example 2, except that the amount of chlorinated polyethylene was changed to 10 parts by weight. The physical properties of these specimens were determined to obtain the results shown in Table 2.

Comparative Examples 2, 3, 4 and 5

Test pieces were prepared by the same method as described in Example 2 except that the amount of chlorinated polyethylene was changed as indicated in Table 2. And instead of tetrabromo-bisphenol A, hexabromo benzene was used in the amount shown in Table 2 to obtain the results shown in Table 2.

TABLE 2

Compared with the highly flame retardant resin compositions of Examples 2, 5 and 6 having excellent physical properties, the flame retardancy of the resin compositions obtained in Comparative Examples 2 and 3 was reduced. More specifically, flame retardancy was only 94V-0 at 1/8 inch thick and combustion occurred at 1/16 ＂thickness.

In Comparative Examples 4 and 5, hexa bromobenzene was used in an amount corresponding to the bromine amount of tetrabromo-bisphenol A used in Examples 2,5 and 6, and the effect of the flame retardant was tetrabromo-bisphenol A It was worse than that achieved by.

And hexabromo benzene, unlike tetrabromo-bisphenol A, did not exhibit leading edge specificity for the amount of chlorine and polyethylene used.

Example 7

The test pieces were prepared in the same manner as described in Example 2, except that the graft copolymer (A) -170 parts by weight obtained in the standard example and 30 parts by weight of the graft copolymer (A) -2 obtained in the standard example were used. Prepared. The physical properties of these specimens were determined to obtain the results shown in Table 8.

Example 8

30 parts by weight, 40 parts by weight and 30 parts by weight of the graft copolymer (A) -1, the graft copolymer (B) -2 and the styrene-acrylonitrile copolymer obtained in the standard examples were used, respectively. , Test pieces were prepared by the method as described in Example 2. The physical properties of these specimens were determined to obtain the results shown in Table 3.

Example 9

70 parts by weight of the graft copolymer (A) -2 and 30 parts by weight of the graft copolymer (B) -2 were prepared in the same manner as described in Example 2 except that they were used. The physical properties of these specimens were determined to obtain the results shown in Table 3.

TABLE 3

EXAMPLES 10, 11, and 12

100 parts by weight of the bulk-suspended ABS resin (A) -3 prepared in the standard example, chlorinated polyethylene having 35% by weight of chlorine in an amount shown in Table 4 (Diosolac G-235, manufactured by Soda Co., Ltd.), 3 5 parts by weight of antimony oxide, 16 parts by weight of tetrabromo-bisphenol A (TBA), 0.3 part by weight of triphenyl phosphite and 1 part by weight of tin dibutyl maleate were mixed.

The resulting mixture was extruded into pellets and the test pieces were obtained by injection molding from pellets at 210 ° C. The properties of these test pieces were measured and the results are shown in Table 4.

[Comparative Examples 6 and 7]

Except for the amount of chlorinated polyethylene ie 18 parts and 25 parts shown in Table 4, the test pieces were obtained in the same manner as in Example 10. The measurement results of the physical properties of the test pieces are shown in Table 4.

Comparative Example 8

It obtained in the same manner as in Example 10 except that 10 parts by weight of hexabromo-benzene (HBB) was used instead of tetrabromo-bisphenol A.

The measurement results of the characteristics of these test pieces are shown in Table 4.

Comparative Example 9

The test pieces were obtained in the same manner as in Example 10 except that 100 parts by weight of the ABS resin obtained by emulsion polymerization was used without using the dispersion-polymerized ABS resin.

The results are shown in Table 4.

TABLE 4

Claims (1)

Under bulk polymerization conditions, aromatic monoalkenyl monomers are polymerized with vinylcyanone monomers, alkylester monomers of acrylic esters or methacrylic acid, in the presence of a diene rubber component, under a suspension polymerization state to substantially complete the polymerization. 20% to 90% by weight of the graft copolymer (A) obtained by the polymerization and the aromatic monoalkenyl monomer in the presence of diene rubber latex under emulsion polymerization conditions, an alkyl ester monomer of vinyl cyan monomer, acrylic acid or methacrylic acid, these 100 parts by weight of a graft copolymer component consisting of 10 to 80% by weight of a graft copolymer (B) obtained by polymerization with a monomer selected from the mixture, and 1 to 12 parts by weight of chlorinated polyethylene having a chlorination degree of 25 to 45% by weight. (C), 5 to 25 parts by weight of tetrabromo-bisphenol A or its derivatives (D) and 2 to 10 A flame retardant resin composition comprising an amount of antimony trioxide (E).