JPH0762100B2 - Flame-retardant thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent flame retardancy, and more specifically, a thermoplastic resin composition in which dropping of fire species during combustion is significantly reduced. A resin composition is provided.

(Conventional Technology and Its Problems) Conventionally, aromatic monovinyl resins have been widely used in various fields such as home electric appliances, interior decoration, and sundries industries due to their excellent properties. Recently, blends with polyester resins (for example, polyethylene terephthalate, polycarbonate) and polyamide resins (for example, 6 nylon), which are so-called engineering plastics, have been used for the purpose of improving performance such as impact resistance, heat resistance, and abrasion resistance of aromatic monovinyl resins. It is being actively conducted. On the other hand, the engineering plastics, which are widely used for mechanical parts, electric / electronic parts, automobile parts, etc., are often tried to be blended with an aromatic monovinyl resin in order to improve their moldability and economic efficiency. It has been put to practical use. Blends of these aromatic monovinyl resins and the above engineering plastics have the drawback that they are flammable and continue to burn naturally once they start to burn, and therefore their use must be limited. ing. Especially when it is used as a home electric appliance or electric / electronic product, it is necessary to carry out a flame retardant treatment. In fact, many so-called flame retardants are blended, including halogen compounds such as chlorine and bromine, and compounds containing phosphorus. There is known a method of making flame retardant.

However, in recent years, the demand for fire safety has been rapidly closed, and the demand for home appliances, office automation equipment, etc.
UL (Underwriters Laboratory) Vertical combustion test rules have become stricter over the years, and the weight of products and parts has become thinner to reduce weight and improve economic efficiency. When the product drips and damages other products and parts, it will happen, and development of a technique for preventing the fall of this kind of fire, so-called drip prevention technique, has been strongly desired. As a dripper prevention technology,
Known methods include increasing the amount of flame retardant, adding an inorganic substance that does not burn, and adding an olefin polymer or elastomer. The method of increasing the amount of flame retardant decreases the drip property due to the shortening of the combustion time, but originally it is not preferable because it requires a large amount of expensive flame retardant and the cost is high. . As a method of compounding an inorganic substance that does not burn, JP-A-52-127958 discloses a method of using potassium titanate, mica, sericite, asbestos, JP-A-57-85838 discloses nickel titanate,
A method of adding calcium is known. However, these substances lack the affinity for a blend of an aromatic monovinyl-based resin and an engineering resin, so that they have a drawback that mechanical properties are lowered. JP-A-53-46343
JP-A-53-14 discloses a method of adding polyolefin.
The 9244 publication discloses a method of adding an elastomer and an olefin polymer, but is expensive resin,
Rigidity and heat resistance are reduced, which is not satisfactory.

The present invention has improved the above-mentioned drawbacks, and as a result of diligent study on a blend of an aromatic monovinyl resin having a low drip property during combustion and an engineering resin, an aromatic monovinyl resin obtained by copolymerizing a specific organic functional silane compound. By using resin, the amount of flame retardant used is small,
The present invention has been achieved by finding that a flame-retardant thermoplastic resin having extremely low drip property during combustion and excellent mechanical properties can be obtained.

(Means for Solving Problems) That is, the present invention relates to one or more silane compounds selected from γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane or γ-methacryloxypropyltriethoxysilane. Aromatic monovinyl resin (I) containing 1 to 10 as a copolymerization component
0 part by weight and one or more resins (II) 1 selected from thermoplastic polyester resins and polyamide resins
-100 parts by weight and 5 to 25 parts by weight of the flame retardant (III) per 100 parts by weight of (I) and (II) in total, (I)
The flame-retardant thermoplastic resin composition is characterized in that the silane compound therein is contained in the composition (I), (II) or (III) in an amount of 0.005 to 0.1% by weight.

The silane compound used in the present invention is one or more silane compounds selected from γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethylmethoxysilane or γ-methacryloxypropyltriethoxysilane.

As the monomer used for the aromatic monovinyl-based resin, besides styrene, α-substituted styrene such as α-methylstyrene, o-methylstyrene, p-chlorostyrene, 2,
One or a mixture of two or more nuclear-substituted styrenes such as 4,6 tribromostyrene and substances containing these as the main components and copolymerizable with them, such as acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, anhydrous Examples thereof include a monomer mixture containing a small amount of maleic acid, N-phenylmaleimide and the like. The method for producing an aromatic monovinyl-based resin (I) obtained by copolymerizing a specific silane compound is a known method well known in the art, for example, a suspension-method of adding the silane compound-added aromatic monovinyl-based monomer to the aromatic monovinyl-based monomer. It can be produced by a bulk polymerization method or a bulk polymerization method. The aromatic monovinyl-based resin may be a rubber-modified aromatic monovinyl-based resin, and a solution obtained by dissolving the rubber-like polymer in the aromatic monovinyl-based monomer or the like is subjected to a suspension-bulk polymerization method or a bulk polymerization method. Can be manufactured. As a rubber-like polymer, conjugated C3-C6 1,3-
Homopolymers of dienes, such as 1,3-butadiene, copolymers of 1,3-butadiene and isoprene, other copolymerizable compounds with 1,3-butadiene, such as styrene, methyl styrene of nuclear alkyl-substituted styrene, dimethyl Styrene, acrylonitrile, methacrylonitrile, copolymers of acrylic acid and methacrylic acid with alkyl esters, or 1,3
-A copolymer of ptadiene, isoprene and the other copolymerizable compound. These are used alone or as a mixture of two or more kinds. Particularly preferred are polybutadiene rubber and butadiene-styrene copolymer rubber. A resin obtained by blending an aromatic monovinyl-based resin (I) containing a silane compound as a copolymer component and an aromatic monovinyl-based resin containing no silane compound may be used.

The thermoplastic polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid and a fatty acid glycol as main components. Examples of the thermoplastic polyester resin include polyethylene terephthalate, polybutylene terephthalate, polycarbonate and the like. Examples of the polyamide resin include 6 nylon and 6-6 nylon.

Aromatic monovinyl resin (I) containing a silane compound as a copolymerization component, and one or more resins selected from thermoplastic polyester resins and polyamide resins (I
The mixing ratio with I) is arbitrary, but the above resins (I) 1 to 1
The proportion of 00 parts by weight and 1 to 100 parts by weight of the above resin (II) is preferable.

The flame retardant (III) used in the present invention may be a known flame retardant which can be used for an aromatic monovinyl resin. Further, a known flame retardant which can be used as a thermoplastic polyester resin or polyamide resin may be used. For example, halogen-based flame retardants include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonate resins, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenyl ethers, halogenated polyphenylthiols. Examples thereof include ethers, preferably decabromodiphenyl oxide, brominated bisphenol epoxy resin, brominated bisphenol phenolic resin, brominated bisphenol polycarbonate resin, brominated polystyrene resin, brominated crosslinked polystyrene resin, bromide. Bisphenol cyanurate resin, brominated polyphenylene oxide,
Polydibromophenylene oxide and decabromodiphenyl oxide bisphenol condensates (tetrabromobisphenol A, oligomers thereof, etc.). The phosphorus-based flame retardant, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxycotyl phosphate, triphenyl phosphate, tricresyl phosphate,
Non-halogen phosphates such as cresyl diphenyl phosphate, octyl diphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3 dibromopropyl) 2, Examples thereof include halogen-containing phosphates such as 3 dichloropropyl phosphate, tris (2,3 dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate.

The above flame retardants are added according to the desired flame retardancy rank.
The specific amount of the flame retardant added depends on the type of flame retardant and the flame retardancy rank to be finally obtained, but in general it is 100 parts by weight in total of (I) and (II) according to the standard method. Against 5 to 2
5 parts by weight.

The content of the silane compound used in the present invention is required to be 0.005 to 0.1% by weight in the compositions (I), (II) and (III). If the amount is less than this range, the effect of suppressing the dropping of fire species during combustion is small and sufficient flame retardancy cannot be obtained. On the other hand, if the amount exceeds 0.1% by weight, the melt fluidity during kneading of the aromatic monovinyl resin, the thermoplastic polyester resin, the polyamide resin, the polyether resin and the flame retardant is remarkably reduced, which is impractical. In order to obtain a composition which has an effect of suppressing dripping during combustion and has practical moldability, it is necessary to be 0.005 to 0.1% by weight.

Further, the composition of the present invention comprises one or more resins (I) selected from aromatic monovinyl resins (I) containing a specific silane compound, polyester resins and polyamide resins.
It can be produced by melt-kneading I) and the flame retardant (III) with an extruder, a kneader, a Banbury mixer or the like.

As described above, the present invention is to reduce the dropping of fire species at the time of combustion, but the vertical combustion test method defined in UL94 was adopted as the determination method. Wall thickness 1/8 inch, 1/16
Inch, 1/32 inch, 1/2 inch wide, 5 inch long test piece 3 / on the tip of the tube with Bunsen burner at the bottom
Fix the long axis vertically with a clamp so that it comes to 8 inches, and apply a test flame to the lower end without wind. After igniting for 10 seconds, the test flame is moved away and the burning time is measured (first ignition). Immediately after extinguishing, the next ignition is performed for 10 seconds and the burning time is similarly measured (second ignition). The same test was performed on five test pieces, and when the burning time did not exceed 10 seconds at maximum and the average was 5 seconds or less and there were no drops, the flammability rank was V-0.
Similarly, if the burning time does not exceed a maximum of 30 seconds and the average is 25 seconds or less and there is no drip, the flammability rank is called V-1, and similarly, the burning time does not exceed a maximum of 30 seconds and the average is 25 seconds. When it is below and there is a drop, its flammability rank is V-2.
Is called.

On the other hand, a test piece having a length of 5 inches, a width of 1/2 inch, and a thickness of 1/8, 1/16 inch is fixed by clamping the long axis vertically, and a test flame is applied to the lower end without wind. The burner ignites away from the specimen and adjusts the overall flame height to 5 inches and the blue flame height to 1 1/2 inches. Place the test flame on one corner of the bottom edge of the test piece.
Repeat the operation of applying for 5 seconds and releasing for 5 seconds until applying 5 times. When the flaming or non-flaming combustion is not continued for 60 seconds or more and no substance is dropped after removing the test flame for the fifth time, this combustion rank is referred to as 5-V.

Since V-0 and V-1 level materials do not drip at the time of combustion, the materials used are overwhelmingly V- in electrical and electronic parts, mechanical parts, thin small connectors, etc.
Many of them are 0 level, and it is safe to use V-2 level materials.

Further, the flame resistance of materials used for OA, information equipment, etc. is more severe, and UL-945-V level is being required.

For the purpose of improving the thermal stability, light stability and moldability of the composition of the present invention, various additives such as antioxidants such as epoxies, phenols and phosphenols, and ultraviolet rays such as benzophenone and benzotriazole. Absorbents, paraffin wax, fatty acid esters, fatty acid amides, lubricants such as metallic soaps, and the like can be added.

Further, a flame retardant auxiliary agent having an effect of further increasing the effect of the flame retardant can be used. Examples thereof include molybdenum compounds and antimony compounds, with sodium antimonate and antimony trioxide being particularly preferred. Further, a reinforcing filler can be used for the purpose of improving mechanical properties and heat resistance. Examples thereof include fibrous reinforcing agents such as glass fibers and carbon fibers, and granular or flaky fillers such as mica, talc, clay, calcium silicate, glass foil and glass beads. Particularly preferred are glass fiber and mica.

(Effects of the Invention) The flame-retardant thermoplastic resin composition of the present invention requires a small amount of flame-retardant, and has flame-retardant ranks V-0, V-1, which are required for electric appliances, office equipment and the like. It has a non-dripping property that clears the 5-V rank and can be applied to various industrial product applications.

(Example) Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 0.1% by weight of γ-methacryloxypropyltrimethoxysilane, 25.0% by weight of acronitrile and 7 of styrene monomer
A copolymer composed of 10.0 parts by weight of a copolymer composed of 4.9% by weight, 15.0% by weight of polybutadiene obtained by dissolving polybutadiene in a styrene monomer and acrylonitrile and polymerized under stirring, 25.0% by weight of acrylonitrile, and 60.0% by weight of styrene. (ABS) 60.0 parts by weight and polycarbonate 30.0
Parts by weight, 7.0 parts by weight of the flame retardant tetrabromobisphenol A monomer, and 5.0 parts by weight of flame retardant aid antimony trioxide.
The mixture was melted and mixed into a pellet with a 40φ extruder. After drying the pellets obtained, they were injection-molded to have a length of 5 inches and a width.
A molded product for combustion test having a thickness of 1/2 inch and a thickness of 1/8 inch was obtained.
This test piece was subjected to a combustion test according to the method of UL94, and it was confirmed that there was no dripping of fire during the test. The flammability rank is as shown in the table.

Comparative Example 1 Example 1 and 25.0% by weight of acrylonitrile and styrene monomer in place of 10.0 parts by weight of a copolymer composed of 0.1% by weight of γ-methacryloxypropyltrimethoxysilane, 25.0% by weight of acrylonitrile and 74.9% by weight of styrene monomer.
A test piece was prepared and a flammability test was conducted in the same manner as in Example 1 except that 10.0 parts by weight of a copolymer (AS) consisting of 75.0% by weight was used. Since it contains no silane compound,
Dropping was observed during the combustion test.

Example 2 Content of polybutadiene obtained by dissolving polybutadiene in γ-methacryloxypropyltrimethoxysilane, styrene monomer and acrylonitrile and polymerizing with stirring.
15.0 wt%, γ-methacryloxypropyltrimethoxysilane 0.1 wt%, acrylonitrile 25.0 wt%, styrene 59.9 wt% copolymer 50.0 parts by weight, polycarbonate 50.0 parts by weight, flame retardant tetrabromobisphenol A monomer 7.0 A test piece consisting of 1 part by weight and 5.0 parts by weight of antimony trioxide was subjected to the combustion test in the same manner as in Example 1. The flammability rank is as shown in the table.

Comparative Example 2 γ-methacryloxypropyltrimethoxysilane 2.5% by weight, acrylonitrile 25.0% by weight and styrene monomer
10.0 parts by weight of a copolymer consisting of 72.5% by weight, polybutadiene content obtained by dissolving polybutadiene in styrene monomer acrylonitrile and polymerizing under stirring 15.0% by weight, acrylonitrile 25.0% by weight, styrene 60.0% by weight
60.0 parts by weight of a copolymer (ABS) consisting of 30.0 parts by weight of a polycarbonate and a flame retardant tetrabromobisphenol A
7.0 parts by weight and 5.0 parts by weight of flame retardant aid antimony trioxide were melt-kneaded with a 40φ extruder to obtain a composition in the same manner as in Example 1, but the fluidity was remarkably reduced, and melt-kneading was impossible. It was. I realized that it was not practical.

Example 3 0.1% by weight of γ-methacryloxypropyltrimethoxysilane, 25.0% by weight of acrylonitrile and styrene monomer
30.0 parts by weight of a copolymer consisting of 74.9% by weight, polybutadiene dissolved in styrene monomer acrylonitrile and polymerized under stirring to obtain a polybutadiene content of 15.0% by weight, acrylonitrile 25.0% by weight, styrene 60.0% by weight
10.0 parts by weight of a copolymer (ABS), 60.0 parts by weight of polycarbonate, 7.0 parts by weight of a flame retardant tetrabromobisphenol A monomer, and 5.0 parts of a flame retardant aid antimony trioxide.
A test piece consisting of parts by weight was subjected to a combustion test in the same manner as in Example 1. The flammability rank is as shown in the table.

Example 4 Copolymer of 0.7% by weight of γ-methacryloxypropyltrimethoxysilane and 99.3% by weight of styrene monomer 5.
0 parts by weight and polyethylene terephthalate (PET) 100.0
Parts by weight, 15.0 parts by weight of flame retardant brominated polystyrene,
3.0 parts by weight of flame retardant auxiliary sodium antimonate and 35.0 parts by weight of reinforcing filler glass fiber were melt-kneaded in a 40φ extruder,
Pelletized. The pellet obtained was dried and then injection-molded to obtain a molded article for combustion test having a length of 5 inches, a width of 1/2 inch and a wall thickness of 1/32 inch. This test piece was subjected to a flammability test by the method of UL94, and it was confirmed that there was no dripping of fire during the test. The flammability rank was V-0.

Comparative Example 3 Instead of the copolymer composed of 0.7% by weight of γ-methacryloxypropyltrimethoxysilane and 99.3% by weight of styrene monomer in Example 4, in Comparative Example 3, 0.05% by weight of γ-methacryloxypropyltrimethoxysilane was used. Example 4 using a copolymer consisting of 99.95% by weight of styrene monomer.
A flammability test was conducted in the same manner as in.

The content of the silane compound was low, and dripping was observed during the combustion test. The flammability rank was V-2.

Example 5 0.1% by weight of γ-methacryloxypropyltrimethoxysilane, 60% by weight of methyl methacrylate, 80 parts by weight of a copolymer composed of 39.9% by weight of styrene monomer, 20.0 parts by weight of polyethylene terephthalate (PET), and a flame retardant. 15.0 parts by weight of brominated polystyrene, 3.0 parts by weight of flame retardant aid sodium antimonate, and 35.0 parts by weight of reinforcing filler glass fiber were melt-kneaded in a 40φ extruder to form pellets. The pellets obtained were dried and then injection-molded to obtain a molded article for combustion test having a length of 5 inches, a width of 1/2 inch and a wall thickness of 1/32 inch. This test piece was subjected to a flammability test by the method of UL94, and it was confirmed that there was no dripping of fire during the test. The flammability rank was V-0.

Example 6 0.1% by weight of γ-methacryloxypropyltrimethoxysilane, 25% by weight of acrylonitrile and 7 of styrene monomer
15.0 parts by weight of a copolymer consisting of 4.9% by weight, polybutadiene dissolved in styrene monomer acrylonitrile and polymerized with stirring to obtain a polybutadiene content of 15.0% by weight, acrylonitrile 25.0% by weight, styrene monomer 60
Example 4 75 parts by weight of a copolymer (ABS) consisting of 1% by weight, 10.0 parts by weight of polyethylene terephthalate (PET) and 13.0 parts by weight of the flame retardant tetrabromobisphenol A monomer.
A flammability test was conducted in the same manner as in. There was no dripping during the test, and the flammability rank was V-0.

Example 7 Copolymer 10 composed of 0.7% by weight of γ-methacryloxypropyltriethoxysilane and 99.3% by weight of styrene monomer
Parts by weight, 92% by weight of styrene monomer and 8 of methacrylic acid
60.0 parts by weight of a copolymer (SMAA) composed of 10% by weight, 30.0 parts by weight of polycaprolactam (2300 manufactured by Asahi Kasei), 18 parts by weight of flame retardant decabrombiphenyl ether, and 4.0 parts by weight of flame retardant aid antimony trioxide. The reinforcing filler glass fiber (5.0 parts by weight) was melt-kneaded with a 40φ extruder to form a pellet. After the obtained pellets were dried, they were injection-molded to obtain molded articles for combustion test having a length of 5 inches, a width of 1/2 inch, a wall thickness of 1/8 inch, and 1/16 inch. This test piece was subjected to a flammability test in accordance with the method of UL94, and it was confirmed that no sparks were dropped during the test. The flammability rank was V-0.

Comparative Example 4 Instead of the copolymer of 0.7% by weight of γ-methacryloxypropyltriethoxysilane of Example 7 and 99.3% by weight of styrene monomer, in Comparative Example 4, styrene monomer was used.
A flammability test was conducted in the same manner as in Example 7 using a polymer of 100% by weight. During the test, dripping was observed and the flammability rank was V-2.

Example 8 Copolymer 1 consisting of 0.7% by weight of γ-methacryloxypropyltrimethoxysilane and 99.3% by weight of styrene monomer
0.0 parts by weight and polycaprolactam (Asahi Kasei 2300) 90.0
Parts by weight, flame retardant decabromphenyl ether 20 parts by weight, flame retardant aid antimony trioxide 5.0 parts by weight, reinforcing filler SB block copolymer 10.0 (Asahi Kasei Tuffprene) parts by weight in the same manner as in Example 7, A molded article for flammability test was obtained.
During the combustion test, it was confirmed that there was no dripping of fire,
1/8 inch has a flammability rank of 5-V and a wall thickness of 1/16
Achieved flammability rank V-0 in inches.

Comparative Example 5 Copolymer 2 composed of 2.0% by weight of γ-methacryloxypropyltrimethoxysilane and 98.0% by weight of styrene monomer
0.05 parts by weight, 35.0 parts by weight of a copolymer (SMAA) consisting of 92% by weight of styrene monomer and 8% by weight of methacrylic acid, 45.0 parts by weight of polycaprolactam (2300 manufactured by Asahi Kasei) and 13.0 of tetrabrombisphenol A flame retardant. % By weight, 4.0 parts by weight of flame retardant aid antimony trioxide, and 5.0 parts by weight of reinforcing filler glass fiber were melt-kneaded with a 40φ extruder to obtain a composition in the same manner as in Example 7. Was significantly reduced, and melt-kneading was impossible. I realized that it was not practical.

Claims (1)

[Claims] 1. An aromatic monovinyl containing as a copolymerization component one or more silane compounds selected from γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and γ-methacryloxypropyltriethoxysilane. Resin (I) 1-100
Parts by weight and one or more resins (II) 1 to 2 selected from thermoplastic polyester resins and polyamide resins.
100 parts by weight and 100 parts by weight of (I) and (II) in total,
5 to 25 parts by weight of the flame retardant (III), and the silane compound in (I) is added to the composition of (I), (II) and (III).
A flame-retardant thermoplastic resin composition comprising 0.005 to 0.1% by weight.