JPS62232449A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent mechanical properties and hardly causes the dropping of sparks combustion, by blending an arom. monovinyl resin contg. an org. functional silane compd., with a specified resin and a flame retarder. CONSTITUTION:An org. functional silane compd. (a) (e.g., gamma- methacryloxypropyltrimethoxysilane) is copolymerized with an arom. vinyl monomer (b) (e.g., styrene) and optionally a monomer (c) copolymerizable therewith (e.g., acrylonitrile) to obtain an arom. monovinyl resin (A) contg. the org. functional silane compd. as a comonomer. 1-100pts.wt. component A is blended with 1-100pts.wt. thermoplastic polyester resin (e.g., a polycarbonate) and/or polyamide resin (B) (e.g., nylon 6 or 66), a flame retarder (C) (e.g., decabromodiphenyl oxide) and optionally an antioxidant, a lubricant, a flame- retardant aid, etc., to obtain the compsn. contg. 0.005-0.1wt% org. functional silane compd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermoplastic resin composition with excellent flame retardancy.
More specifically, the object is to provide a thermoplastic resin composition in which dripping of sparks during combustion is significantly reduced.

(Prior art and its problems) Conventionally, aromatic monovinyl resins have been used in large quantities in various fields such as home appliances, interior decoration, and miscellaneous goods industries due to their excellent properties. Recently, blends of so-called engineering plastics such as polyester resins (e.g. polyethylene terephthalate, polycarbonate) and polyamide resins (e.g. 6-nylon) have been developed to improve the performance of aromatic monovinyl resins such as impact resistance, heat resistance and abrasion resistance. On the other hand, the above-mentioned engineering plastics, which are widely used in mechanical parts, electrical and electronic parts, automobile parts, etc., are being combined with aromatic monovinyl resins to improve their moldability and economic efficiency. Many blends have been tried and put into practical use.Blends of these aromatic monovinyl resins and the engineering plastics mentioned above have the disadvantage that they are easily flammable and continue to burn on their own once they start burning. It has the disadvantage that its uses are naturally limited.

In particular, flame retardant treatment is necessary when used as home appliances or electrical and electronic components, and many so-called flame retardants are used, including halogen compounds such as chlorine and bromine, and compounds containing phosphorus. There is a known method of blending them to make them flame retardant.

However, in recent years, the requirements for fire safety have come into sharp focus, and regulations for U.S. UL (Underwriters Laboratories) Vertical Flame Testing for home appliances, office automation equipment, etc. have become more and more strict as the years go by. As the wall thickness of products and parts has become thinner in order to improve economic efficiency and improve economic efficiency, sparks can drip during combustion and cause damage to other products and parts. There is a strong demand for the development of a technology to prevent fire from falling, a so-called anti-drip technology.Dip prevention technologies include methods such as increasing the amount of latent retardants, adding inorganic substances that do not burn, and using olefin polymers. A method is known in which a combination of

The method of increasing the amount of flame retardant shortens the combustion time, thereby reducing the drip properties, but it is not a desirable method because it requires the use of large amounts of flame retardant, which is originally expensive. . Methods of blending non-combustible inorganic substances include a method using potassium titanate, mica, sericite, and asbestos as disclosed in JP-A-52-127958, and a method of adding nickel titanate and calcium as described in JP-A-57-85838. method is known. However, these substances lack affinity for diene compounds of aromatic monovinyl resins and engineering resins, resulting in poor mechanical properties. Japanese Patent Publication No. 53-4634
Publication No. 3 describes a method of adding polyolefin! Kaisho 53
Publication No. 149244 discloses a method of adding 7) -r-toolefin polymer, but it is not satisfactory as it uses expensive resin and reduces rigidity and heat resistance. .

The present invention has improved the above-mentioned drawbacks, and as a result of intensive studies on blends of aromatic monovinyl resins and engineering resins that have low dripping properties during combustion, we have developed aromatic monovinyl resins copolymerized with specific organofunctional silane compounds. By using resin, the amount of flame retardant used can be reduced.
The present invention was achieved by discovering that a flame-retardant thermoplastic resin with extremely low dripping properties during combustion and excellent mechanical properties can be obtained.

(Means for Solving the Problems) That is, the present invention uses an aromatic monovinyl resin (I) containing an organic functional 7-run compound as a copolymerization component, a thermoplastic polyester resin, and a polyamide resin. 1m
Or two or more types of resin CI
This is a flame-retardant thermoplastic resin composition characterized by containing ~0.1% by weight.

As the organofunctional silane compound used in the present invention,
A compound having a vinyl group that can be copolymerized with an aromatic monovinyl compound or having an sl (-OR) group (where 几 is a methoxy group, an ethoxy group, etc.), such as r-methacryloxypropyltrimethoxysilane, γ- Examples include methacryloxypropyltriethoxysilane and γ-methacryloxypropylmethyldimethoxysilane.

One type or 2's or more of these may be used.

In addition to styrene, monomers used in aromatic monovinyl resins include α-methylstyrene, α-substituted stenone, 0-methylstyrene, p-tetrarostyrene, 2
y4y6)! One or more mixtures of nuclear substituted styrenes such as J-bromstyrene, and substances containing these as main components and copolymerizable with them, such as acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, maleic anhydride, Examples include monomer mixtures containing small amounts of N-phenylmaleimide and the like.

The method for producing the aromatic monovinyl resin (I) copolymerized with an organic functional silane compound is to add the above-mentioned aromatic monovinyl monomer to which an organic functional silane compound is added, by a generally well-known method. , for example, by a suspension-bulk polymerization method or a bulk polymerization method. Further, the aromatic monovinyl resin may be a rubber-modified aromatic monovinyl resin, which is produced by a suspension-bulk polymerization method or a bulk polymerization method from a solution in which a rubbery polymer is dissolved in the above-mentioned aromatic monovinyl monomer. can do. As a rubbery polymer,
Conjugated 1,3-dienes having 4 to 6 carbon atoms, such as homopolymers of 1,3-butadiene, copolymers of 1,3-butadiene and isoprene, 1,3-butadiene/and other copolymerizable compounds For example, copolymers of styrene, nuclear alkyl-substituted styrene with methylstyrene, dimethylstyrene, acrylonitrile, methacrylonitrile, alkyl esters of acrylic acid and methacrylic acid, or copolymers of 1,3-butadiene and isoprene with other of the above. It is a copolymer with a compound. These may be used alone or as a mixture of two or more. Particularly preferred are polybutadiene rubber and butadiene-styrene copolymer rubber. Alternatively, a resin obtained by blending an aromatic monovinyl resin (I) containing an organic functional silane compound as a copolymerization component and an aromatic monovinyl resin containing no silane compound may also be used.

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

The blending ratio of the aromatic monovinyl resin (1) containing an organic functional silane compound as a copolymerization component and one or more resins (n) selected from thermoplastic polyester resins and polyamide resins is Although free, the above resin (
1) It is preferable that the ratio is 1 to 100 parts by weight and 1 to 100 parts by weight of the resin (1).

The flame retardant used in the present invention (l may be a known flame retardant that can be used for aromatic monovinyl resins.Also, a known flame retardant that can be used for thermoplastic polyester resins and polyamide resins) For example, halogenated flame retardants include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonate resins,
Examples include halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenyl ethers, halogenated polyphenylthio-ethers, and preferably decabromodiphenyl oxide, brominated bisphenol epoxy resins, brominated Bisphenol phenoxy resin, brominated bisphenol polycarbonate resin, brominated polystyrene resin, brominated crosslinked polystyrene resin, brominated bisphenol cyanuride-HU
II, brominated polyphenylene oxide, polydibromophenylene oxide, decabromo diphenyl oxide bisphenol condensate (tetrabromo bispheno,
- Le A1 (oligomers, etc.). Examples of phosphorus-based flame release agents include non-halogen phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triptoxy-tyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and octyldiphenyl phosphate. , tris(I) tetraloethyl) phosphate, tris(cycloprovir)
phosphate, tris(chloropropyl) phosphate, bis(2,8 diglomoprovir) 2.3 dichloropropyl phosphate, tris(2,3 dibromopropyl)
Examples include halogen-containing phosphoric acid esters such as phosphate and bis(chloropropyl) monooctyl phosphate.

The content of the organofunctional silane compound used in the present invention must be 0.005 to 0.1% by weight in the composition. If the amount is less than this range, the effect of suppressing the dripping of sparks during combustion will be small and sufficient flame retardancy will not be obtained. On the other hand, if it exceeds 0.1% by weight, the melt fluidity will be significantly reduced during kneading of the aromatic monovinyl resin, thermoplastic polyester resin, polyamide resin, polyether resin, and flame retardant, making it impractical. It's dim. In order to obtain a composition that has the effect of preventing and suppressing dripping during combustion and has practical moldability, it is necessary that the content is 0.005 to 0.01% by weight.

The composition of the present invention also includes an aromatic monovinyl resin (I) containing an organofunctional silane compound, a polyester resin,
It can be produced by melt-kneading a resin (II) selected from polyamide resins or two or more types of resin (II) and a flame retardant in an extruder, Nigu, Banbury mixer, or the like.

As described above, the purpose of the present invention is to reduce the dripping of sparks during combustion, and the vertical combustion test method specified in UL94 was adopted as the determination method.

A test piece with a wall thickness of 716 inches or 732 inches, a width of 2 inches, and a length of 5 inches is placed with its long axis so that its lower end is 3/8 inch above the tip of the Sunzen burner tube. Fix it vertically with a clamp and apply a test flame to the bottom end in a windless condition. After igniting for 10 seconds, move the test flame away and measure the combustion time (first ignition). Immediately after extinguishing the test flame, ignite the next one for 10 seconds and measure the combustion time in the same way (second ignition). Repeat the same procedure for 5 test pieces, and if the maximum combustion time does not exceed 10 seconds and the average combustion time is 5 seconds or less, and there are no drippings, the flammability rank is called V-o, and the maximum combustion time is 30 seconds. No more than 25 seconds on average,
If there are no drippings, the flammability rank is V-1; similarly, if the maximum combustion time is 30 seconds or less and the average is 25 seconds or less, and there are drips, the flammability rank is eV-2.
It is called.

On the other hand, the length is 5 inches, the width is 2 x 7 inches, the thickness is 8.1/1
A 6-inch test piece was fixed with a clamp with its long axis perpendicular.
Apply a test flame to the bottom end in calm conditions. The burner was ignited away from the specimen and the total flame height was 5 inches.
”/2 inch.Apply the test flame to one corner of the lower end of the test piece for 5 seconds and then release it for 5 seconds until the test flame has been applied 5 times. After removing the test flame for the 5th time, wait for at least 60 seconds. If there is no continued flame or flameless combustion and no dripping of any material, this combustion rank is referred to as s-V.

Since V-O and V-Level materials do not drip during combustion, they are overwhelmingly used in electrical and electronic parts, mechanical parts, thin-walled small connectors, etc., which have been increasing in recent years.
Most of the materials are of V-2 level, and it can be said that there is no use of V-2 level materials.

Furthermore, the flame retardance of materials used in OA1 information equipment and the like is becoming more stringent, and UL-945-V level is increasingly required.

In order to improve the thermal stability, photostability, and moldability of the composition of the present invention, various additives such as epoxies, phenols, antioxidants such as phosphates, and ultraviolet absorbers such as benzophenone and benzotriazole are added. lubricants such as paraffin wax, fatty acid ester, fatty acid amide, metal soap, etc. can be added.

It is also possible to use flame retardant aids that have the effect of further increasing the effectiveness of the flame retardant. Examples thereof include molybdenum compounds and antimony compounds, and particularly preferred are sodium antimonate and antimony trioxide. Furthermore, reinforcing fillers can be used for the purpose of improving mechanical properties and heat resistance. Examples include fibrous reinforcing agents such as glass fiber and carbon fiber,
mica, talc, clay, calcium silicate, glass foil,
Examples include granular or flaky fillers such as glass peas. Particularly preferred are glass fiber and mica.

(Effects of the Invention) The flame retardant thermoplastic resin composition of the present invention requires only a small amount of flame retardant, and has a flame retardant rank of V-0, V-1, which is required for electrical appliances, office equipment, etc. It has a non-dripping property that clears the s-V rank, and can be applied to various industrial products.

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

Example 1 γ-methacryloxypropyltrimethoxysilane 0°1
10.0 parts by weight of a copolymer consisting of 25.0 parts by weight of acrylonitrile and 74.9 parts by weight of styrene monomer, and polybutadiene 1 obtained by dissolving polybutadiene in the styrene monomer and acrylonitrile and polymerizing the mixture with stirring.
Copolymer (ABC) 60.5.0% by weight, 25.0% by weight of acrylonitrile, and 60.0% by weight of styrene.
0 parts by weight, 30.0 parts by weight of polycarbonate, 7.0 parts by weight of the flame retardant tetrabromobisphenol A monomer, and 5.0 parts by weight of the flame retardant aid antimony trioxide were melt-mixed in a 40φ extruder and formed into pellets. . After drying the resulting pellets, injection molding was performed to obtain 5 inches long and 1/2 width.
A molded article for combustion testing with a wall thickness of 8 inches was obtained. This test piece was subjected to a combustion test according to the UL94 method, and it was confirmed that no sparks were dripped during the test. The flammability ranks are shown in the table.

Comparative Example 1 Copolymer 10 consisting of 0.1% by weight of γ-methacryloxypropyltrimethoxysilane of Example 1, 25.0% by weight of acrylonitrile, and 74.9% by weight of styrene monomer
．． 0 parts by weight, 25.0% by weight of acrylonitrile
A copolymer consisting of 75.0% by weight of styrene monomer (
AS) A test piece was prepared in the same manner as in Example 1, except that 10.0 parts by weight was used, and a flammability test was conducted. Since no organofunctional silane compounds were present, dripping was observed during the combustion test.

Example 2 Polybutadiene was dissolved in γ-methacryloxypropyltrimethoxysila/, styrene monomer, and acrylonitrile and polymerized with stirring. Polybutadiene content: 15.0% by weight, γ-methacryloxypropyltrimethoxysilane: 0 .1-fold fZ%, acrylonitrile 25.0
% by weight, copolymer consisting of 59.9% by weight of styrene 50
．． A combustion test was conducted in the same manner as in Example 1 on a test piece consisting of 0 parts by weight, 50.0 parts by weight of polycarbonate, 7.0 parts by weight of flame retardant tetrabromobisphenol A monomer, and 5.0 parts by weight of antimony trioxide. I did it. The flammability ranks are shown in the table.

Comparative example 2 r-methacryloxypropyltrimethoxysilane 2.5
10.0 parts by weight of a copolymer consisting of 25.0% by weight of crylonitrile and 72.5% by weight of styrene monomer, and polybutadiene obtained by dissolving polybutadiene in styrene monomer acrylonitrile and polymerizing it with stirring. Content 15.0% by weight, acrylonitrile 25.0% by weight
, a copolymer consisting of 60.0% by weight of styrene (ABC)
A composition was prepared in the same manner as in Example 1 using 60.0 parts by weight of polycarbonate, 30.0 parts by weight of polycarbonate, 7.0 parts by weight of the flame retardant tetrabromobisphenol A, and 5.0 parts by weight of the flame retardant aid antimony trioxide. In order to obtain this, melt kneading was carried out using a 40φ extruder, but the fluidity was significantly reduced and melt kneading was impossible. It turned out to be of little practical use.

Example 3 γ-methacryloxypropyltrimethoxysilane 0.1
30.0 parts by weight of a copolymer consisting of 25.0 parts by weight of acrylonitrile and 74.9 parts by weight of a styrene monomer, and 7 parts by weight of polybutadiene and 7 parts by weight of a styrene monomer. Polybutadiene obtained by dissolving the mixture in acrylonitrile and polymerizing it with stirring. A copolymer (AB
S) tO, 0 parts by weight, 60.0 parts by weight of polycarbonate, and flame retardant tetrabromobisphenol A monomer 7
．． A combustion test was conducted in the same manner as in Example 1 on a test piece consisting of 1 part of 0 weight J and 5.0 parts by weight of antimony trioxide as a flame retardant aid. The flammability ranks are shown in the table.

Example 4 γ-methacryloxyprobyltrimethoxysilane 0.7
5.0 parts by weight of a copolymer consisting of 99.3% by weight of styrene monomer and polyethylene terephthalate) (
100.0 parts by weight of PET), 15.0 parts by weight of brominated polystyrene as a flame retardant, 3.0 parts by weight of sodium antimonate as a flame retardant aid, and 35.0 parts by weight of glass fiber as a reinforcing filler in a 40φ extruder. The mixture was melt-kneaded and made into pellets. After drying the obtained pellet, a molded article for combustion testing with a length of 5 inches, a width of 72 inches, and a wall thickness of 32 inches was obtained by injection molding. This test piece was subjected to a flammability test using the UL94 method, and it was confirmed that no sparks were dripped during the test. The flammability rank was V-o.

Comparative Example 3 γ-methacryloxypropyltrimethoxysilane of Example 4 0.7 ti%,! :Styrene monomer 99.
In Comparative Example 3, instead of a copolymer consisting of 3% by weight,
γ-methacryloxypropyl trimethoxysila 10.0
A flammability test was conducted in the same manner as in Example 4 using a copolymer consisting of 5% by weight and 99.95% by weight of styrene/monomer.

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

Example 5 r-methacryloxypropyltrimethoxysilane 0.1
% by weight, 60% by weight of methyl methacrylate, and 80 parts by weight of a copolymer consisting of 39.9% by weight of styrene monomer;
20.0 parts by weight of polyethylene tele 7 tarley) (PET), 15.0 parts by weight of brominated polystyrene as a flame retardant,
3.0 parts by weight of sodium antimonate as a flame retardant aid and 35.0 parts by weight of glass fiber as a reinforcing filler were melt-kneaded in a 40φ extruder and formed into pellets. After drying the obtained pellet, injection molding was performed to obtain a molded article for combustion testing having a length of 5 inches, a width of 2 inches, and a wall thickness of 32 inches. This test piece was subjected to a flammability test using the UL94 method, and it was confirmed that no sparks were dripped during the test. Flammability 2 ink is V-O
Met.

Example 6 γ-methacryloxyprobyl trimethoxy 7 run 0.1
15.0 parts by weight of a copolymer consisting of 25% by weight of acrylonitrile and 74.9% by weight of styrene monomer;
Polybutadiene content 15.0% by weight, obtained by dissolving polybutadiene in styrene monomer/acrylonitrile and polymerizing it while stirring, acrylonitrile z5. oMIk%,
Copolymer (ABS) consisting of 60% by weight of styrene monomer
)753! Volume part, polyethylene tele 7 tally) (P
A flammability test was conducted in the same manner as in Example 4 using 10.0 parts by weight of ET) and 13.0 parts by weight of the flame retardant tetraprom bisphenol A monomer. There was no dripping during the test, and the flammability rank was VO.

Example 7 γ-Methacryloxyprobyltriethoxycin 0.7
10 parts by weight of a copolymer consisting of 99.3% by weight of styrene monomer and 92% by weight of styrene monomer.
and 8% by weight of methacrylic acid (SMAA)
60.0 parts by weight, polycaprolactam (Fushikasei 23
00) 30.0 parts by weight of flame retardant decabrombiphenyl ether 18i parts, flame retardant aid antimony trioxide 4.0 parts by weight, and reinforcing filler glass fiber 5.0 parts by weight were melted in a 40φ extruder. Kneaded and pelletized. After drying, the resulting pellets were injection molded into 5-inch lengths.
A molded article with a width of A inch, a wall thickness of 14 inches, and a thickness of 1/16 inch was obtained for combustion testing.This test piece was subjected to a flammability test according to the UL94 method, and it was confirmed that no sparks were dripped during the test. The flammability rank was V-O.

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

Example 8 r-me, tacryloxyprobil trimethoxy 7 run 0.
10.0 parts by weight of a copolymer consisting of 7% by weight and 99.3% by weight of styrene monomer, 90.0 parts by weight of polycaprolactam (Fushikasei 230G), 20 parts by weight of flame retardant decabrombiphenyl ether, and flame retardant. A molded article for flammability testing was obtained in the same manner as in Example 7 using 5.0 parts by weight of antimony trioxide as an auxiliary agent and 10.0 parts by weight of a reinforcing filler 8B block copolymer (Tufprene manufactured by Seikasei Co., Ltd.). It was confirmed that there was no dripping of sparks during the combustion test, and the 8-inch wall thickness achieved a flammability rank of 5 V't, and the 1716-inch wall thickness achieved a flammability rank of V-O.

Comparative Example 5 r-methacryloxypropyltrimethoxysilane 2.0
fii chi and styrene monomer98. Copolymer (SM
AA) 35.0 parts by weight, 45.0 parts by weight of polycaprolactam (Fushikasei 2300), 13.0% by weight of the flame retardant tetrabromobisphenol A hetamine, and 4.0 parts by weight of the flame retardant aid antimony trioxide. 5.0 parts by weight of reinforcing filler glass fibers were melt-kneaded using a 40φ extruder to obtain a composition in the same manner as in Example 7, but the fluidity decreased significantly and melt-kneading was impossible. there were. It turned out to be of little practical use.

Claims (1)

[Claims] An aromatic monovinyl resin (I) containing an organofunctional silane compound as a copolymerization component, one or more resins (II) selected from thermoplastic polyester resins and polyamide resins, and a flame retardant ( III), characterized in that the composition contains 0.005 to 0.1% by weight of an organofunctional silane compound.