JP3453184B2 - Flame retardant styrenic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant styrene resin composition having improved light resistance.

[0002]

2. Description of the Related Art Styrene-based resins, especially impact-resistant styrene-based resins, are excellent in physical properties such as processability and mechanical strength, so that they are used in various applications such as home electric appliances and office automation (OA) equipment. It is used as a molding material for housings. Flame retardancy is usually imparted to such a styrene resin by adding a flame retardant such as a halogen compound or antimony oxide.

However, when an ordinary halogen compound is added, a dehydrohalogenation reaction occurs due to the action of light or the like in the presence of oxygen, and due to the generated carbonyl group or conjugated double bond, a styrene resin is produced. Is colored. Therefore, in the field where light resistance is required, a brominated bisphenol type epoxy polymer, which is relatively less colored by light, is used as a halogen-based compound.

As the brominated bisphenol type epoxy polymer, a terminal blocked type polymer in which a terminal epoxy group is blocked with a halogenated phenol compound to impart non-reactivity,
A polymer in which a terminal epoxy group is left to capture a hydrogen halide is known.

For example, JP-A-61-211354 discloses a flame-retardant styrene containing a styrene resin, a brominated bisphenol A type epoxy resin having a terminal epoxy group blocked with a halogen-containing phenol, and a halogen-containing compound. A resin composition is disclosed. In this document, a reaction product of tetrabromobisphenol A and a diglycidyl ether of tetrabromobisphenol A is described as a preferable epoxy resin, and tetrabromobisphenol A is described as a preferable halogen-containing compound. It is also described that antimony trioxide may be added. The polymer in which the terminal epoxy group is blocked as described above has an advantage that it does not gel due to heat during extrusion molding or injection molding and has high moldability. However, the light resistance of the styrene resin is not improved even if the polymer having the terminal epoxy group blocked is added. Therefore, it is necessary to improve the light resistance by adding an ultraviolet absorber or a hindered amine light stabilizer. However, in the field where more excellent light resistance is required, even if the light stabilizer is added, the light resistance is still insufficient.

Further, JP-A-63-72749 discloses a styrene resin, a brominated bisphenol A type epoxy resin in which a part or all of terminal epoxy groups are blocked with a halogen-containing phenol, and antimony trioxide. A flame-retardant styrene resin composition containing the same is disclosed. In this document, the number of repeating units including a bisphenol A skeleton n =
1 brominated bisphenol A type epoxy resin, n = 3
The mixture with the brominated bisphenol A type epoxy resin is used as a flame retardant. Among such epoxy resins, a polymer having a terminal epoxy group remaining can capture hydrogen halide by the terminal epoxy group, and thus can have improved light resistance. However, heat generated during extrusion molding or injection molding causes gelation due to the epoxy groups remaining in the epoxy polymer, causing burn dust during molding, and impairing uniform fluidity of the molten resin composition.
Therefore, black-brown spots or streak-like burnt dust adheres to the molded product, and the surface of the molded product becomes non-uniform, which makes it difficult to efficiently manufacture a high-quality molded product continuously for a long time. Further, since it is necessary to manufacture a plurality of epoxy resins having different degrees of polymerization and add them at a predetermined ratio, workability is lowered.

[0007]

Accordingly, an object of the present invention is to provide a flame-retardant styrenic resin having improved weather resistance despite containing an end-capped epoxy polymer in which terminal epoxy groups are capped. To provide a composition.

Another object of the present invention is to provide a styrene resin composition which has high weather resistance and flame retardancy and is excellent in moldability.

Still another object of the present invention is to provide a flame-retardant styrene resin composition capable of suppressing the production of burnt dust even when molded for a long time and efficiently producing a high quality molded product. To do.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a specific styrene resin is a brominated bisphenol obtained by blocking a terminal epoxy group with a phenol containing no halogen atom. The present invention has been completed by finding that when a combination of an A- type epoxy polymer and antimony trioxide is added, a molded article having excellent light resistance can be obtained and the generation of burnt dust can be significantly suppressed, and the present invention has been completed.

That is, the flame-retardant styrene resin composition of the present invention comprises (A1) styrene monomer in an amount of 50 to 95% by weight.
And a non-styrene-based monomer mixture of 50 to 5% by weight
5 to 90 parts by weight of rubber and 95 to 10 parts by weight of rubber component
Raft polymer and (A2) styrene monomer 50-95
Polymerization of 50% to 5% by weight and non-styrenic monomer
The polymer (A1) and the polymer (A
The ratio with 2) is the former / latter = 95-25 / 5-75 (weight
(Amount ratio) to 100 parts by weight of styrene resin (A)
Te, (B) the following formula (III)

[0012]

[Chemical 2]

(In the formula, n represents the number of repeating units)

The weight average molecular weight represented by
00 brominated bisphenol A type epoxy polymer 10
50 parts by weight, and (C) antimony trioxide 5 having an average particle size of 0.5 to 2 μm
10 to 10 parts by weight.

The styrenic resin (A) is (A1)
60 to 85% by weight of a ethylene monomer and a non-styrene monomer
40 to 80 parts by weight of monomer mixture of 40 to 15% by weight
And a graft polymer of 60 to 20 parts by weight of a rubber component,
(A2) 60-85% by weight of styrenic monomer and non-sulfur
40 to 15% by weight of a ethylene-based monomer and a polymer
May be. In addition, in the styrene resin (A),
The ratio of the soft polymer (A1) to the polymer (A2) is the former / the latter.
Person = 70-40 / 30-60 (weight ratio)
Good.

In the present specification, the "weight average molecular weight" is the polystyrene equivalent average molecular weight in gel permeation chromatography.

[0017] The scan styrene-based resin, a homo- or copolymer of a styrene monomer, a copolymer of a styrene monomer and non-styrenic vinyl monomer, the impact resistance styrene containing a rubber component Resin etc. are included. The impact-resistant styrene-based resin includes an impact-resistant styrene-based resin composition containing a rubber component and a styrene-based resin, a styrene-based monomer in the presence of a rubber component, or a styrene-based monomer and a non-styrene-based vinyl. A graft polymer obtained by polymerizing a vinyl monomer mixture containing a monomer is included. The styrene-based resin containing no rubber component may be simply referred to as “rubber-unmodified styrene-based resin”, and the impact-resistant styrene-based resin may be simply referred to as “rubber-modified styrene-based resin”.

Examples of the styrene-based monomer include styrene, alkyl-substituted styrene (for example, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,
4-dimethylstyrene, p-ethylstyrene, pt-
Butyl styrene, etc.), α-alkyl substituted styrene (eg, α-methyl styrene, α-methyl-p-methyl styrene, etc.), halogenated styrene (eg, o-chlorostyrene, p-chlorostyrene, etc.) and the like. . Preferred styrenic monomers include, for example, styrene, p-methylstyrene, α-methylstyrene, especially styrene. These styrene-based monomers may be used alone or in combination of two or more.

The styrenic monomer may be used in combination with the non-styrenic vinyl monomer. Examples of the non-styrene vinyl monomer include (meth) acrylic acid esters such as (meth) acrylonitrile, methyl methacrylate, ethyl acrylate, and butyl acrylate, (meth) acrylic acid, maleic anhydride, N-substituted. Included are copolymerizable vinyl monomers such as maleimide. Preferred non-styrene-based monomers include (meth) acrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide and the like. These non-styrene-based monomers can also be used alone or in combination of two or more. included.

As the rubber component in the graft polymer, for example, polybutadiene rubber, butadiene-isoprene rubber, butadiene-acrylonitrile copolymer, ethylene-bromopyrene rubber, EPDM rubber (ethylene-propylene-non-conjugated diene rubber), polyisoprene rubber,
Non-styrene-based rubber-like polymer containing no styrene unit such as polychloroprene rubber, acrylic rubber, ethylene-vinyl acetate copolymer; styrene containing styrene unit such as styrene-butadiene copolymer, styrene-butadiene block copolymer Examples thereof include rubbery polymers. These rubber-like polymers may be used either individually or in combination of two or more.

The preferred rubber component is polybutadiene,
Included are butadiene-acrylonitrile copolymer, ethylene-propylene rubber, EPDM rubber, acrylic rubber, styrene-butadiene copolymer, and styrene-butadiene block copolymer. These rubber components may be copolymerized with a polymerizable vinyl monomer, for example, (meth) acrylic acid lower alkyl ester such as methyl methacrylate, ethyl acrylate and ethyl methacrylate.

The acrylic rubber is mainly composed of an alkyl acrylate, particularly an acrylate having an alkyl group having about 1 to 8 carbon atoms (eg, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate). Includes rubber. Acrylic rubber is vinyl acetate,
It may be a copolymer with a copolymerizable monomer such as acrylonitrile, styrene, methyl methacrylate and vinyl ether.

Acrylic rubber is used in a relatively small amount, preferably within a range of 5% by weight or less based on the whole rubber component,
Crosslinkable monomer having an ethylenically unsaturated bond, for example,
It may be a copolymer with alkylene glycol di (meth) acrylate, polyoxyalkylene glycol di (meth) acrylate, polyester (meth) acrylate, butadiene or isoprene. The acrylic rubber is a crosslinked diene rubber (for example, polybutadiene) using a conjugated diene as a raw material, or a copolymer of a conjugated diene and an ethylenically unsaturated monomer (for example, styrene or acrylonitrile), and (meth) acrylic acid. It may be a rubber having a multilayer structure composed of a polymer such as a (meth) acrylic monomer such as an ester. In the rubber having a multilayer structure, the polymer containing the rubber component may form the core or the shell.

A polymer containing a butadiene unit (eg, polybutadiene) is often used as the rubber component. The rubbery polymer containing a butadiene unit may be a polymer containing a high-cis butadiene unit having a high cis-1,4 structure content, and may contain a low cis butadiene unit having a low cis-1,4 structure content. It may be a polymer.

The glass transition temperature Tg of the rubber component is 10 ° C. or less, preferably −150 ° C. to 0 ° C., and more preferably −.
It is about 100 ° C to -10 ° C. If the glass transition temperature of the rubber component exceeds 10 ° C., the impact strength of the molded product tends to be lowered.

The preferred styrenic resin contains at least a rubber-modified resin. That is, the preferable styrene-based resin includes (1) a rubber-modified styrene-based resin and (2) a mixed resin composition of the rubber-modified styrene-based resin (1) and a rubber-unmodified styrene-based resin.

The rubber-modified styrenic resin (1) is preferably an impact-resistant styrenic resin in which at least a styrenic monomer is graft-polymerized with a rubber component. Examples of the rubber-modified styrene resin include impact-resistant polystyrene (HIPS) obtained by polymerizing styrene in polybutadiene, ABS resin obtained by polymerizing acrylonitrile and styrene in polybutadiene, AAS resin obtained by polymerizing acrylonitrile and styrene in acrylic rubber, and chlorine. ACS resin in which acrylonitrile and styrene are polymerized in modified polyethylene, AES resin in which acrylonitrile and styrene are polymerized in ethylene-propylene rubber (EPDM rubber), terpolymer in which acrylonitrile and styrene are polymerized in an ethylene-vinyl acetate copolymer, An example is an MBS resin obtained by copolymerizing polybutadiene with methyl methacrylate and styrene. These rubber-modified styrene resins can be used alone or in combination of two or more.

The content of the rubber component of the rubber-modified styrene resin (1) can be selected within a wide range according to the characteristics of the rubber-modified styrene resin, and is, for example, 1 to 95% by weight, preferably 2 to 75% by weight. And more preferably about 3 to 60% by weight.

The rubber-modified styrene resin (1), particularly the rubber component dispersed in the graft polymer, has an average particle diameter of, for example, 0.09 to 5 μm, preferably 0.1 to 3 μm, and more preferably 0.1. It is about 1 μm. If the average particle size of the rubber component is less than 0.09 μm, the impact strength of the molded product is reduced, and if it exceeds 5 μm, the gloss and surface appearance of the molded product are likely to be deteriorated. The rubber component has a particle size distribution
It may be dispersed as rubber-dispersed particles having a plurality of peaks (for example, two peaks).

In the mixed resin composition (2) of the rubber-modified styrene-based resin and the rubber-unmodified styrene-based resin, the rubber-unmodified styrene-based resin may be, for example, a styrene-based monomer homopolymer or copolymer ( For example, polystyrene), at least one selected from styrene-based monomers and non-styrene-based monomers (for example, (meth) acrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide).
Copolymers with one or more kinds of monomers) (for example, styrene-methyl methacrylate copolymer, acrylonitrile-styrene copolymer (AS resin), styrene-maleic anhydride copolymer, styrene-N-substituted maleimide) (Copolymer etc.)
Are exemplified. The rubber-unmodified styrenic resin may be used alone or in combination of two or more. The rubber-unmodified styrene-based resin often contains components common to the rubber-modified styrene-based resin except the rubber component.

In the mixed resin composition (2), the ratio of each monomer, the ratio of the rubber-modified styrene resin and the rubber-unmodified styrene resin, the content of the rubber component in the total amount of the mixed resin composition, etc. Can be appropriately selected within a range that does not impair the moldability, the mechanical strength and the appearance of the molded product. For example, the ratio of each monomer in the rubber-modified styrene resin and the rubber-unmodified styrene resin is styrene monomer / non-styrene monomer = 10 to 95/90 to 5 (wt%), preferably It can be selected in a wide range of about 25 to 90/75 to 10 (% by weight). Further, the ratio of the rubber-modified styrene resin and the rubber-unmodified styrene resin is the former / the latter = 95 to 5.
/ 5 to 95 (weight ratio), preferably 90 to 15/10
It can be selected within the range of about 85 (weight ratio). Further, the content of the rubber component in the total amount of the mixed resin composition is, for example, 1
It is about 50 to 50% by weight, preferably about 1.5 to 40% by weight.

Preferred styrene-based mixed resin composition (2)
Is a graft polymer of (A1) a monomer mixture of a styrene-based monomer and a non-styrene-based monomer, a rubber component having a glass transition temperature Tg of 10 ° C. or lower, and (A2) a styrene-based monomer. And a polymer formed of a monomer mixture of a non-styrenic monomer.

In the monomer mixture in the above (A1) and (A2), the ratio of the styrene type monomer and the non-styrene type monomer is, for example, the former / the latter = 50 to 95/50.
~ 5 (wt%), preferably 55-90 / 45-10
(Wt%), more preferably 60-85 / 40-15
(% By weight). 50% by weight of styrene monomer
If it is less than, flowability and injection moldability tend to decrease,
If it exceeds 95% by weight, the impact strength of the molded product tends to decrease.

In such a mixed resin composition, (A
1) The ratio of the monomer mixture and the rubber component is the former / the latter =
5 to 90/95 to 10 (parts by weight), preferably 25 to 8
5/75 to 15 (parts by weight), more preferably 40 to 8
It is about 0/60 to 20 (parts by weight). If the proportion of the rubber component exceeds 95% by weight, the appearance and gloss of the molded product are likely to be deteriorated, and if it is less than 10% by weight, the impact strength of the molded product is likely to be deteriorated.

The ratio of the graft polymer (A1) to the polymer (A2) is the former / the latter = 95 to 25/5 to 75 (wt%), preferably 85 to 35/15 to 65 (wt%),
More preferably, it is 70-40 / 30-60 (% by weight). If the proportion of the polymer (A2) is less than 5% by weight, the fluidity tends to decrease, and if it exceeds 75% by weight, the impact strength of the molded article tends to decrease.

The copolymer (A2) is often produced as a by-product in the graft polymerization process for producing the graft polymer (A1).
The copolymer formed in the graft polymerization process is not included.

The styrene resin can be produced by a conventional method, for example, emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like. The rubber-modified styrene resin (graft polymer) is often produced by bulk polymerization or suspension polymerization. In the polymerization, if necessary, benzene,
Solvents such as ethylbenzene, toluene, xylene, solvents inert to the reaction such as mineral oil, molecular weight regulators,
Antioxidants, lubricants, plasticizers and the like may be added.

As the bisphenol type epoxy polymer (B), a halogenated epoxy polymer having a bisphenol skeleton in which the terminal epoxy group is blocked with phenols, for example, bisphenol A, bisphenol F,
Examples include various halogenated epoxy polymers having a bisphenol skeleton such as bisphenol AD. In the epoxy polymer represented by the general formula (I), examples of the alkylene group Z include, for example, methylene group, methylmethylene group, dimethylmethylene group, 1-methyl-1-ethylmethylene group, 1-methyl-1-. Examples thereof include a butylmethylene group and a hexylmethylene group. Preferred Z is a methylene group corresponding to a bisphenol F type epoxy polymer,
In particular, a dimethylmethylene group corresponding to the bisphenol A type epoxy polymer is included.

The feature of the present invention, under which functions as a flame retardant
The terminal epoxy group of the halogenated bisphenol type epoxy resin represented by the formula (I) is blocked by phenols containing no halogen atom instead of halogenated phenol.

[0040]

[Chemical 3]

(In the formula, X is a bromine atom or a chlorine atom,
Radix a and b are integers of 1 to 4, n is the number of repeating units
However, X may be different depending on a, b and n.
Z is an alkylene group and Ar1 and Ar2 are the same or different.
An ant which may have a substituent excluding a halogen atom.
Group group)

That is, in the above general formula (I), the aryl groups Ar1 and Ar2 may be the same or different and each may have a substituent excluding a halogen atom. Aryl group A
Examples of phenols corresponding to r1 and Ar2 include phenol, o-cresol, m-cresol,
Examples include p-cresol, 3,5-xylenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 3,5-diethylphenol, thymol, carvacrol, α-naphthol, β-naphthol and the like.

The preferred halogenated bisphenol type epoxy polymer (B) includes, for example, the following formula (II)

[0044]

[Chemical 4] (In the formula, X is a bromine atom, a and b are integers of 1 to 3, R is
Is a lower alkyl group, the number of substituents c and d is an integer of 0 to 5, and n is the number of repeating units), and a brominated bisphenol A type epoxy polymer and the like are included.

Examples of the alkyl group R include lower alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl and hexyl groups. The alkyl group R is often a methyl group.

The alkyl group R may be substituted at any position of the aryl groups Ar1 and Ar2, and when Ar1 and Ar2 are phenyl groups, o-, m- or p-
It may be substituted at any of the -positions. In many cases, the number of repeating units n is about 1 to 15.

Among the epoxy polymers (B) represented by the formulas (I) and (II), X is a bromine atom, a and b are integers of 1 to 3 (particularly 2), c and d is 0 to 2 (particularly 0 or 1). The aryl groups Ar1 and Ar2 are often phenyl groups.

The more preferable epoxy polymer (B) includes a polymer represented by the following formula (III).

[0049]

[Chemical 5]

(In the formula, n represents the number of repeating units)

The weight average molecular weight of the epoxy polymer (B) can be selected within a range that does not impair the moldability and the uniform mixing property, and is, for example, 600 to 15,000, preferably 750.
~ 12000, more preferably 1000-10000
It is a degree. When the weight average molecular weight of the epoxy polymer (B) is less than 600, the heat resistance of the molded product tends to be reduced to 1,500.
If it exceeds 0, the mechanical strength of the molded product, for example, the impact strength tends to decrease.

The amount of the halogenated bisphenol type epoxy polymer (B) used can be selected within a range capable of imparting flame retardancy to the styrene resin and not deteriorating the characteristics of the molded article.
For example, 5 to 50 relative to 100 parts by weight of styrene resin
The amount is about 10 to 50 parts by weight, preferably about 15 to 45 parts by weight. Styrene resin 100
If the ratio of the epoxy polymer (B) to the weight part is less than 5 parts by weight, the flame retardancy is not improved so much, and if it exceeds 50 parts by weight, dripping is apt to occur in the combustion test of the molded product and the flame retardancy is lowered. However, there are cases where the UL standard 94 VO in the United States cannot be achieved.

Such an epoxy polymer can be obtained by a conventional method, for example, by reacting a halogenated bisphenol type epoxy resin with the above phenols in the presence of a basic catalyst. Examples of the halogenated bisphenol type epoxy resin include bisphenol type epoxy resins corresponding to the general formula (I), such as tetrachlorobisphenol A type epoxy resin and tetrabromobisphenol A type epoxy resin.

Antimony trioxide (C) is used in the form of powder. The average particle size of antimony trioxide (C) is, for example, 0.1 to 5 μm, preferably 0.2 to 3 μm, more preferably about 0.5 to 2 μm, and particularly 1 to 1.5 μm.
It is a degree. If the average particle size is less than 0.1 μm, the light resistance is reduced, and if it exceeds 5 μm, the impact strength of the molded product is likely to be reduced.

The amount of antimony trioxide (C) used can be selected within a range that imparts flame retardancy to the styrene resin and does not deteriorate the properties of the molded product. For example, 1 part is used per 100 parts by weight of the styrene resin. -10 parts by weight, preferably 3
It is about 10 to 10 parts by weight, more preferably about 5 to 10 parts by weight. If the ratio of antimony trioxide to 100 parts by weight of the styrene resin is less than 1 part by weight, the flame retardancy is not improved so much, and if it exceeds 10 parts by weight, the impact strength of the molded product tends to be lowered.

The ratio of the epoxy polymer (B) functioning as a flame retardant to the antimony trioxide (C) is, for example, 1 part antimony trioxide (C) per 100 parts by weight of the epoxy polymer (B). -60 parts by weight, preferably 5-5
The amount is 0 parts by weight, more preferably about 10 to 40 parts by weight.

The composition of the present invention contains a UV absorber (eg, benzotriazole-based, salicylate-based, benzophenone-based, cyanoacrylate-based UV absorber), an inorganic oxide (in order to improve light resistance, if necessary. For example,
Zinc oxide, titanium oxide, cerium oxide, etc.) may be contained. A plasticizer (for example, a phosphoric acid ester or a phthalic acid ester) may be added to improve fluidity during molding. Further, in order to improve the thermal stability, antioxidants such as phenol-based, phosphite-based and thioether-based antioxidants may be added.

The composition of the present invention contains various additives such as reinforcing agents such as glass fibers, carbon fibers and metal fibers, fillers such as calcium carbonate, barium sulfate and glass beads, antistatic agents, lubricants, releasing agents. It may contain a mold agent, a flame retardant, a coloring agent and the like.

The composition of the present invention is prepared by melt-mixing the respective components using a kneader (eg, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a kneader, etc.) simultaneously or stepwise, and if necessary. It is useful for producing various molded articles by a molding method such as injection molding or extrusion molding after preparing pellets and the like from the molten mixture.

The flame-retardant styrene resin composition of the present invention comprises
It can be used for a wide variety of applications such as various molded products, for example, household appliances such as daily necessities, vacuum cleaners, refrigerators, washing machines, fans, radios, televisions, housings of electronic devices, interior and exterior parts for vehicles, and the like.

[0061]

The composition of the present invention can be used with a specific styrenic resin.
Since the end-capped epoxy polymer in which the terminal epoxy group of the epoxy polymer is capped with a fat and a phenol having no halogen atom is combined with antimony trioxide, the weather resistance of the molded product can be remarkably improved. Further, it has high weather resistance and flame retardancy, and is excellent in moldability. Furthermore, even if the styrene-based resin composition is used for molding for a long time, it is possible to suppress the generation of burnt dust and efficiently manufacture a high-quality molded product.

[0062]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

Example 1 (A1) 75% by weight of styrene and 2 of acrylonitrile
Polymer (50 parts by weight) obtained by graft polymerization of 60 parts by weight of a mixture of 5% by weight and 40 parts by weight of polybutadiene by emulsion polymerization method (A2) 70% by weight of styrene and 30% by weight of acrylonitrile copolymerized by suspension polymerization method With respect to 100 parts by weight of the styrene-based resin made from the combined 50 parts by weight, (B) the following formula (III)

[0064]

[Chemical 6]

30 parts by weight of an end-capped brominated bisphenol A type epoxy polymer having a weight average molecular weight of 2,000, (C) 8 parts by weight of antimony trioxide having an average particle diameter of 1.5 μm, and hydrotalcite 0. Mix 5 parts by weight, and use a 40 mmφ extruder (with vent) for 2
It was melt-mixed at 30 ° C. and made into chips. Then, using the obtained chips, injection molding was performed at 230 ° C. to prepare test pieces (50 mm × 90 mm × 3 mm).

Example 2 Instead of the end-capped brominated bisphenol type epoxy polymer of Example 1, an end-blocked brominated bisphenol A type epoxy polymer represented by the above formula (III) and having a weight average molecular weight of 10,000 was used. A test piece was produced in the same manner as in Example 1 except that it was used.

Example 3 In place of the end-capped brominated bisphenol A epoxy polymer of Example 1, an end-capped brominated bisphenol A epoxy polymer represented by the formula (III) and having a weight average molecular weight of 1000 was used. A test piece was produced in the same manner as in Example 1 except that it was used.

Comparative Example 1 Instead of the end-capped brominated bisphenol-type epoxy polymer of Example 1, the following formula was used in which both end epoxy groups were capped with tribromophenol.

[0069]

[Chemical 7]

A test piece was prepared in the same manner as in Example 1 except that the brominated bisphenol type epoxy polymer having a weight average molecular weight of 2000 was used.

Comparative Example 2 Instead of the end-capped brominated bisphenol type epoxy polymer of Example 1, the following formula having glycidyl groups at both ends

[0072]

[Chemical 8]

A brominated bisphenol type epoxy polymer having a weight average molecular weight of 1,600 (epoxy equivalent 82
A test piece was produced in the same manner as in Example 1 except that 0 g / eq) was used.

The performance of the test pieces obtained in the examples and comparative examples was evaluated according to the following method.
The results are shown in Table 1.

Flame resistance: Underwriters Laboratory (USA) UL standard UL94 (September 3, 1985)
Flame retardancy was evaluated according to a combustion test based on the 3rd edition of the date).

Light resistance: A test piece was attached to a Xenon wether-ometer manufactured by Atlas.
Ci 35A) was used to irradiate ultraviolet rays for 300 hours, and the color difference (ΔE) from the test piece before ultraviolet irradiation was measured.

Thermal stability: at a rate of 150 per hour,
1200 test pieces were continuously injection-molded for 8 hours, and the occurrence rate of burnt dust was determined. In addition, when the test piece had one or more black spots exceeding 0.07 mm ² , it was determined that burnt dust had occurred.

[0078]

[Table 1]

As is clear from the table, the use of the styrene resin compositions of the examples can greatly improve the weather resistance and the generation of burnt dust.

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Claims (4)

(57) [Claims] 1. (A1) Styrene-based monomer 50-95 weight
% And non-styrenic monomer 50 to 5 wt% monomer
5 to 90 parts by weight of the mixture and 95 to 10 parts by weight of the rubber component
Graft polymer of (A2) styrene monomer 50-
95% by weight and 50 to 5% by weight of non-styrenic monomer
A polymer, which comprises the graft polymer (A1) and a polymer
The ratio with (A2) is the former / latter = 95-25 / 5-75
(Weight ratio) 100 parts by weight of styrene resin (A)
On the other hand, (B) the following formula (III) : (Wherein n represents the number of repeating units)
Brominated bisphenol A type with molecular weight of 600-15000
10 to 50 parts by weight of epoxy polymer, and (C) antimony trioxide 5 having an average particle size of 0.5 to 2 μm
A flame-retardant styrene resin composition containing 10 to 10 parts by weight . 2. A styrenic resin (A) is made of (A1) styrene.
60-85% by weight of len-based monomer and non-styrene-based monomer
40 to 80 parts by weight of monomer mixture of 40 to 15% by weight
And a graft polymer of 60 to 20 parts by weight of a rubber component,
(A2) 60-85% by weight of styrenic monomer and non-sulfur
The flame-retardant styrene-based resin composition according to claim 1 , which comprises a polymer of 40 to 15% by weight of a ethylene-based monomer . 3. A graph of styrene resin (A)
The ratio of the polymer (A1) and the polymer (A2) is the former / the latter
= 70-40 / 30-60 (weight ratio), The flame-retardant styrene resin composition according to claim 1. 4. Brominated bisphenol A type epoxy polymerization
The flame-retardant styrene resin composition according to claim 1 , wherein the weight average molecular weight of the body (B) is 750 to 12,000 .