JPH0575015B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a flame-retardant resin composition that has excellent flame retardancy and does not cause resin dripping when a molded article is burned. More specifically, UL94 flame retardants are made of styrene polymers copolymerized with polyphenylene ether resins and silane compounds and/or rubber-reinforced styrene polymers and flame retardants.
The present invention relates to a flame retardant resin composition that is easily compatible with -5V. [Prior art and its problems] Resin compositions made of polyphenylene ether resins and styrene resins have excellent mechanical properties, thermal properties, electrical properties, etc., and are used in home appliance parts, power distribution parts,
It is widely used in automobile parts, etc., and its demand has increased significantly in recent years, making it a useful material. On the other hand, flame retardancy is one of the performance demands of the industry for resins. As seen in the UL standards in the United States, flame retardant regulations for resins are becoming increasingly strict and compliance is required, and polymer compositions of polyphenylene ether resins and styrene resins are no exception. In recent years, there has been an increase in demand for materials that comply with the UL94-5V standard, especially in fields such as office machinery and data processing equipment. Molded articles whose resin melts and drips when burned do not comply with this standard. In order to improve the flame retardancy of a composition of polyphenylene ether resin and styrene resin, a technique of blending an aromatic phosphate ester into the composition is
It is disclosed in Japanese Patent Publication No. 53-418 and Japanese Patent Application Laid-open No. 51-73248. However, as the content of polyphenylene ether resin decreases, a larger amount of aromatic phosphate ester needs to be blended. Since the aromatic phosphoric acid ester has a large effect of plasticizing the polyphenylene ale resin composition, the melt viscosity decreases and the dripping of the resin during combustion is promoted. Japanese Patent Application Publication 1973-
Publication No. 7945, Japanese Patent Application Laid-Open No. 1987-74038, Japanese Patent Application Publication No. 1983
Japanese Patent No. 128946 discloses a technique for making flame retardant by blending an organic halide and antimony trioxide together. However, this technique has drawbacks such as lowering the impact resistance of the resin and corroding the mold due to the generation of hydrogen halide. If the blending amount is reduced in order to avoid this drawback, dripping of the resin during combustion will be accelerated, which is undesirable. Therefore, it is not possible to obtain a resin composition with excellent processability and impact resistance that meets the UL94-5V standard using the prior art. Particularly when blending an aromatic phosphate ester, the content of the polyphenylene ether resin must be increased in order to avoid dripping of the resin during combustion. This is undesirable because it impairs economic efficiency. [Means and effects for solving the problems] The present invention comprises a polyphenylene ether resin,
In order to improve the flame retardancy of resin compositions with styrene resins, by blending styrene resins copolymerized with silane compounds, even in areas where the content of polyphenylene ether resins is small, there is relatively little difficulty. The present invention was completed based on the discovery that a resin composition that does not drip during combustion can be obtained by adding a fuel agent. That is, the present invention provides: [] 10 to 70 parts by weight of a polyphenylene ether resin; Styrenic resin copolymerized with one or more silane compounds
A flame-retardant resin composition comprising 29 to 89 parts by weight of a flame retardant and 1 to 20 parts by weight of a flame retardant, and containing a copolymer component of a silane compound in an amount of 0.005 to 0.1% by weight. It is. According to the present invention, the original physical properties of the resin composition of polyphenylene ether resin and styrene resin are hardly impaired, and moreover, the resin composition can be produced at low cost.
Can conform to UL94-5V standard. The polyphenylene ether resin used in the present invention has the general formula

【formula】

[Formula] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, and hydrogen. , R ₅ and R ₆ are not hydrogen at the same time) as the repeating unit, and the constituent unit is [C]
Or a homopolymer consisting of [C] and [D],
Alternatively, copolymers can be used. A typical example of a homopolymer of polyphenylene ether resin is poly(2,6-dimethyl-1,4
-phenylene)ether, poly(2-methyl-6)
-ethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n propyl-1,
4-phenylene)ether, poly(2,6-di-
n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly( 2-methyl-6-chloro-1,4-phenylene)
Ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene)ether,
Examples include homopolymers such as -methyl-6-chloroethyl-1,4-phenylene) ether. Polyphenylene ether copolymer has the general formula

[Chemical formula] (where R ₃ , R ₄ , R ₅ , R ₆ have the same meanings as above) and an alkyl-substituted phenol such as 2,3,6-trimethylphenol, such as O-cresol, etc. It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerizing with. Examples of the styrene resin used in the present invention include styrene compounds, compounds copolymerizable with styrene compounds, and rubbery polymers. Styrenic compounds have the general formula

[Formula, R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is 0 to 5
is an integer. ) means a compound represented by Specific examples of these include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Compounds that can be copolymerized with styrene compounds include methacrylic esters such as methyl methacrylate and ethyl methacrylate; acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile. Compounds include acid anhydrides such as maleic anhydride, which are used together with styrene compounds. In addition, as a rubbery polymer,
Although not particularly limited, specific examples include polybutadiene rubber, polybutene rubber, polyisoprene rubber, ethylene-propylene copolymer rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and natural rubber. These can be used alone, in combination with a styrene compound, or in combination with a styrene compound and a compound copolymerizable with the styrene compound. The silane compounds used in the invention contain on the one hand a copolymerizable double bond and on the other hand preferably substituted silane units. Specific examples of particularly useful silane compounds include γ
- methacryloxypropyltrimethoxysilane,
Examples include γ-methacryloxypropylmethyldimethoxysilane and γ-methacryloxypropyltriethoxysilane. The flame retardant used in the present invention is not particularly limited, and may be any flame retardant used to make thermoplastic resins and thermosetting resins flame retardant. Among these flame retardants, aromatic phosphate esters are particularly preferred. Preventing resin dripping during combustion using the technology of the present invention is preferable because it easily complies with the UL94-5V standard and also provides a resin composition that does not reduce impact resistance or corrode molding molds. . In the present invention, the content of the polyphenylene ether resin in the resin composition is preferably in the range of 10 to 70% by weight. If the content of the resin is less than 10% by weight, the improvement effect of the polyphenylene ether resin will not be sufficiently exhibited, which is not preferable. In particular, when an aromatic phosphate ester is blended, the flame retardant effect is not sufficiently exhibited. If it exceeds 70% by weight, without using the technology of the present invention,
Materials that meet the UL94-5V standard can be obtained. In the present invention, the amount of the silane compound in the styrene resin copolymerized with the silane compound is preferably 2% by weight or less. If the amount of the compound exceeds 2% by weight, it is not preferable because when it is melt-kneaded with the polyphenylene ether resin and the flame retardant, it will not mix sufficiently and cause unevenness in the surface gloss of the molded product. Further, the amount of the compound copolymerizable with the styrene compound is preferably 50 parts by weight or less based on the styrene compound. If the amount of the compound exceeds 50 parts by weight, the compatibility with the polyphenylene ether resin will be extremely impaired and the molded article will easily peel off, which is not preferred. Furthermore, the amount of rubbery polymer in the styrene resin is not particularly limited, but is preferably 3 to 3.
60 parts by weight is desirable. If the amount of the polymer is less than 3 parts by weight, the effect of improving impact resistance will not be sufficiently exhibited, which is undesirable, and if it exceeds 60 parts by weight, it is undesirable, since the rigidity of the resin composition will be impaired and it will be difficult to make it flame retardant. . In the present invention, the blending amount of the flame retardant is preferably in the range of 1 to 20% by weight. If the amount of the flame retardant is less than 1% by weight, the flame retardant effect will not be sufficiently exhibited, which is not preferable, and if it exceeds 20% by weight, the physical properties and economic efficiency of the resin composition will be greatly impaired, which is not preferable. In the present invention, the content of the styrene resin copolymerized with a silane compound is selected from the range of 29 to 89% by weight. The content of the silane compound in the resin composition of the present invention needs to be in the range of 0.005 to 0.1% by weight. The content of the compound is
If it is less than 0.005% by weight, it will hardly be effective in suppressing resin dripping during combustion. Also,
If it exceeds 0.1% by weight, the appearance of the molded product will be impaired, which is not preferable. In the present invention, all polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used to produce the styrenic resin copolymerized with a silane compound. The method for producing the resin composition of the present invention is not particularly limited, and a kneading machine such as an extruder, heating roll, kneader, or Banbury mixer can be used. When kneading the resin composition of the present invention using a kneader, it is desirable to knead it in a dry nitrogen atmosphere at as low a temperature as possible. When kneaded under such conditions, the condensation reaction between the silane compounds during the kneading process can be suppressed, making it possible to obtain a material that does not impair the surface gloss of the molded product. The resin composition of the present invention may contain other additives, such as stabilizers such as plasticizers, antioxidants or ultraviolet absorbers, or dyes and pigments. In addition, fillers such as glass fiber, carbon fiber, calcium carbonate, and talc can be added. Furthermore, thermoplastic resins such as polyolefin, polystyrene, hydrogenated styrene-butadiene copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, polyamide, polyester, etc. can be added. (Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Parts and percentages in the examples indicate parts by weight and percentages by weight, respectively. The UL94-5V test shown in the example was conducted using an injection molding machine at 127
A vertical combustion test was conducted using a test piece formed into a size of 12.7 x 3.18 mm. Example 1 Copolymer 5 consisting of 99.3% styrene and 0.7% γ-methacryloxypropyltrimethoxysilane
1 part, 50 parts of a graft copolymer consisting of 8% polybutadiene and 92% styrene, 35 parts of poly(2,6-dimethyl-1,4-phenylene) ether, and 10 parts of triphenyl phosphate using an extruder.
A composition was obtained by kneading at 250°C. UL94 of the composition
-5V test was conducted. The results are shown in the table. Example 2 20 parts of polystyrene, 3.0 parts of a graft copolymer consisting of 10% polybutadiene, 89.9% styrene and 0.1% γ-methacryloxypropyltriethoxysilane, poly(2,6-dimethyl-1,4-
(phenylene) ether and 10 parts of tricresyl phosphate using an extruder under a nitrogen atmosphere.
A composition was obtained by kneading at 250°C. UL94 of the composition
-5V test was conducted. The results are shown in the table. Example 3 Styrene 74.8%, acrylonitrile 25% and γ-
methacryloxypropylmethyldimethoxysilane
18 parts of copolymer consisting of 0.2%, 20 parts of polybutadiene
%, 40 parts of a copolymer consisting of 60% styrene and 20% acrylonitrile, poly(2,6-dimethyl-1,
30 parts of 4-phenylene) ether and 12 parts of tetrabromobisphenol A were kneaded using an extruder at 260°C under a nitrogen atmosphere to obtain a composition. The composition was subjected to UL94-5V testing. The results are shown in the table. Example 4 Copolymer consisting of 99.9% styrene and 0.1% γ-methacryloxypropylmethyldimethoxysilane
10 parts, 22 parts of a graft copolymer consisting of 10% polybutadiene and 90% styrene, 65 parts of poly(2,6-dimethyl-1,4-phenylene) ether, and 3 parts of tricylenyl phosphate using an extruder. ,
A composition was obtained by kneading at 280°C. UL94 of the composition
-5V test was conducted. The results are shown in the table. Example 5 Copolymer 5 consisting of 98.3% styrene and 1.7% γ-methacryloxypropyltrimethoxysilane
parts, 57 parts of polystyrene, 10 parts of a block copolymer consisting of 40% butadiene and 60% styrene, 2,6-
15 parts of copolymer consisting of 95% dimethylphenol and 2,3,6-trimethylphenol, 9 parts of decabrom biphenyl ether, 3 parts of antimony trioxide
1 part of 2,6-di-tert-butyl-4-methylphenol using an extruder under a nitrogen atmosphere.
A composition was obtained by kneading at 250°C. UL94- of the composition
A 5V test was conducted. The results are shown in the table. Comparative Example 1 A composition was obtained in the same manner as in Example 1, except that polystyrene was used in place of the copolymer of styrene and γ-methacryloxypropyltrimethoxysilane. The composition was subjected to UL94-5V testing. The results are shown in the table. Comparative Example 2 Styrene, acrylonitrile, and γ- of Example 3
A composition was obtained in the same manner as in Example 3, except that a copolymer consisting of 75% styrene and 25% acrylonitrile was used in place of the copolymer consisting of methacryloxypropylmethyldimethoxysilane. The composition was subjected to UL94-5V testing. The results are shown in the table. Comparative Example 3 A composition was obtained in the same manner as in Example 4, except that tricylenyl phosphate in Example 4 was removed.
The composition was subjected to UL94-5V testing. The results are shown in the table. Comparative Example 4 A copolymer consisting of 97.5% styrene and 2.5% γ-methacryloxypropyltrimethoxysilane was used in place of the copolymer consisting of 98.3% styrene and 1.7% γ-methacryloxypropyltrimethoxysilane in Example 5. A composition was obtained in the same manner as in Example 5 except for using. When this composition was molded at 250°C, a molded product with noticeable unevenness in surface gloss was obtained.
In addition, a UL94-5V test for the composition was conducted. The results are shown in the table.

【table】

Claims (1)

[Claims] 1 [] Polyphenylene ether resin 10~
70 parts by weight, [] Styrenic resin copolymerized with one or more silane compounds selected from γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, or γ-methacryloxypropyltriethoxysilane
A flame-retardant resin composition comprising 29 to 89 parts by weight of a flame retardant and 1 to 20 parts by weight of a flame retardant, and containing a copolymer component of a silane compound in an amount of 0.05 to 0.1% by weight. . 2 The polyphenylene ether resin has the formula [Formula] [Formula] (wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are an alkyl group or an aryl group having 1 to 4 carbon atoms. , halogen, hydrogen, etc., and R ₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and the constitutional unit is
Claim 1, which is a homopolymer or copolymer consisting of [C] or [C] and [D]
Compositions as described in Section. 3. The composition according to claim 2, wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether. 4 The potaphenylene ether resin is 2,6-
Claim 2, which is a copolymer of dimethylphenol and 2,3,6-trimethylphenol
Compositions as described in Section. 5. The composition according to claim 1, wherein the compound copolymerized with the silane compound is styrene, acrylonitrile, or polybutadiene. 6. The composition according to claim 1, wherein the flame retardant is an aromatic phosphate ester.