JPH0711148A - Thermoplastic resin composition with excellent flame retardance - Google Patents

Abstract

PURPOSE:To obtain the subject resin compsn. CONSTITUTION:This resin compsn. comprises a thermoplastic resin, a flame retardant comprising an organohalogen compd. and a hydroxylated arom. phosphoric ester, and at leasat one auxiliary flame retardant selected from the group consisting of a compd. having a triazine backbone, a metal oxide, a fluororesin, a polyorganosiloxane, and silica. Thus, the flame-retardant properties can be greatly improved even when the amt. of a conventional flame retardant compounded is reduced. The compsn. is suitable for various applications for which a high flame retardancy is required, such as for electric home appliance parts and office automation apparatus parts.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent flame retardancy. More specifically, flame resistance, heat resistance,
The present invention relates to a thermoplastic resin composition having excellent impact resistance and fluidity.

[0002]

2. Description of the Related Art Thermoplastic resins are superior in moldability as compared with inorganic materials such as glass, and are also excellent in impact resistance, so that they can be used in a wide variety of fields including automobile parts, home electric appliance parts, and OA equipment parts. However, the flammability of thermoplastic resins limits their use.

As a method of making a thermoplastic resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic flame-retardant agent to the thermoplastic resin. There is. However, in recent years, the demand for safety against fire has suddenly been highlighted, and home appliances and O
The regulations of the US UL (Underwriters Laboratory) vertical method combustion test for equipment A and the like have become stricter with the years, and higher flame retardancy is required. As a more advanced flame retardant technology, a method of increasing the amount of the flame retardant is known, but it is not economical to use a large amount of the flame retardant originally, and the generation of toxic gas and mechanical properties It is not preferable because it promotes the decrease. For this reason, it has been desired to develop a method of making a resin flame-retardant by using a flame-retardant in the smallest amount possible.

Conventionally, as a method of improving the flame retardancy of a thermoplastic resin, it has been known to combine a halogen flame retardant and a phosphorus flame retardant.

For example, a retarder polymer composition comprising polyphenylene ether, styrene resin, aromatic phosphate and aromatic halogen compound (Japanese Patent Publication No. 48-3876).
No. 8) or a flame-retardant resin composition comprising a polycarbonate, an ABS resin, an organic phosphorus compound, an inorganic boron compound and a halogen compound (Japanese Patent Laid-Open No. 5-98144). However, although the resin composition of the above publication has excellent flame retardancy, it has a markedly low molding process fluidity, which limits its industrial use.

Further, in the above publication, by combining with a hydroxyl group-containing aromatic phosphoric acid ester, not only flame retardancy is improved, but also molding process fluidity is remarkably improved while maintaining heat resistance and impact strength. It is not disclosed or even implied.

[0007]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is free from the above-mentioned problems, namely, flame retardancy,
It is intended to provide a thermoplastic resin composition having excellent heat resistance, impact resistance, and fluidity.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to a technique for improving the flame retardancy of a thermoplastic resin, and as a result, have identified (A) the thermoplastic resin as a specific (B) flame retardant. It was found that by combining (C) the flame retardant aid, it is possible to dramatically improve flame retardancy and fluidity while maintaining heat resistance and impact resistance. Has reached the present invention.

That is, the present invention provides (A) a thermoplastic resin,
(B) a flame retardant comprising an organic halogen compound and a hydroxyl group-containing aromatic phosphate ester, and (C) one or more selected from triazine skeleton-containing compounds, metal oxides, fluororesins, polydiorganosiloxanes, and silica. The present invention provides a thermoplastic resin composition having the flame retardant aid and excellent in flame retardant properties.

The present invention will be described in detail below. The resin composition of the present invention comprises (A) a thermoplastic resin, a specific (B) flame retardant, and a specific (C) flame retardant aid.

The above-mentioned component (A) is a main component of the molding resin composition and plays a role of maintaining the strength of the molded product, and the component (B) together with the component (C) is the component (A). It is a component for imparting flame retardancy to the component.

Here, it is essential that the flame retardant (B) contains an organic halogen compound and a hydroxyl group-containing aromatic phosphate ester. POX, PXn, HX (X represents halogen) due to the synergistic action of phosphorus and halogen
A compound such as the above is generated, and this covers the surface of the resin as a heavy vapor, thereby exerting an oxygen blocking effect and promoting a flame retarding effect.

Further, it is important that the aromatic phosphate ester contains a hydroxyl group. By containing a hydroxyl group, when an aromatic vinyl resin is used as the thermoplastic resin (A), a partial compatibility is developed between the two. As an index of the partial compatibility, the solubility parameter (Solubility Pa) between the component (A) and the hydroxyl group-containing phosphate ester in the component (B) is used.
It is preferable that the difference in the ratio (SP value) is in the range of 1.0 to 2.0 (unit: [cal / cm ³ ] 1/2). As a result, during molding processing, the phosphate ester promotes plasticization and acts as a fluidity improver, while when used as a molded body, the phosphate ester is slightly phase-separated due to the partial compatibility between the two. By doing so, the heat resistance is improved. The present inventors have found that this partial compatibility is
It has been found that this is a principle of greatly improving fluidity while maintaining heat resistance.

When a triazine skeleton-containing compound is used as the (C) flame retardant aid, since the phosphoric acid ester contains a hydroxyl group, the phosphoric acid ester has a hydroxyl group between the amino group and the amino group of the triazine skeleton-containing compound. Interactions such as hydrogen bonding develop. As a result, they have found that the compatibility and dispersibility of the triazine skeleton-containing compound are improved and the impact strength is improved, and the present invention has been completed.

The thermoplastic resin of component (A) of the present invention is not particularly limited as long as it is compatible or evenly dispersed with components (B) and (C). For example, polystyrene-based, polyolefin-based, polyvinyl chloride-based, polyphenylene ether-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, etc. may be used alone or as a mixture of two or more thereof. Here, as the thermoplastic resin, polystyrene-based, polyphenylene-based, or polycarbonate-based thermoplastic resins are particularly preferable. The polystyrene-based resin is a rubber-modified styrene-based resin or a rubber-unmodified styrene-based resin.

The most preferable combination as the thermoplastic resin of the present invention is a polymer blend of a rubber-modified styrene resin and a polyphenylene ether, which is a thermoplastic resin containing 50% by weight or more of the rubber-modified styrene resin.

The rubber-modified styrenic resin used as the component (A) in the present invention is a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a vinyl aromatic polymer. Known monomer bulk polymerization, bulk suspension polymerization, solution polymerization, or a mixture of aromatic vinyl monomer and vinyl monomer copolymerizable with aromatic vinyl monomer in the presence of a polymer. It is obtained by emulsion polymerization.

Examples of such resins include high impact polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer) and the like.

Here, the rubber-like polymer is required to have a glass transition temperature (Tg) of -30 ° C. or lower,
If the temperature exceeds 30 ° C, the impact resistance will decrease.

Examples of such a rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like, and a diene rubber is particularly preferable.

The aromatic vinyl monomer which is an essential component in the graft-polymerizable monomer mixture which is polymerized in the presence of the above rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or p-styrene. Chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like are preferable, and styrene is the most preferable, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized.

If desired, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester composed of an alkyl group having 1 to 8 carbon atoms can be used. When it is necessary to further increase the heat resistance of the resin composition,
Monomers such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0 to 40% by weight.

The rubber-like polymer in the rubber-modified styrene resin of the present invention is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20% by weight. %, More preferably 90 to 50% by weight. Outside this range, the impact resistance and rigidity of the intended polymer composition cannot be balanced. Further, the rubber particle diameter of the styrene polymer is 0.
1 to 5.0 μm is preferable, and 0.2 to 3.0 μm is particularly preferable. Within the above range, impact resistance is particularly improved.

The reduced viscosity η _{SP / C} (0.5 g / dl, toluene solution, measured at 30 ° C.), which is a measure of the molecular weight of the rubber-modified styrenic resin of the present invention, is 0.30 to 0.80 dl / g.
Is preferably in the range of 0.40 to 0.60 dl
It is more preferably in the range of / g. Examples of means for satisfying the above requirements regarding the reduced viscosity η _{SP / C} of the rubber-modified styrene-based resin include adjustment of the polymerization initiator amount, the polymerization temperature, and the chain transfer agent amount.

The polyphenylene ether (hereinafter abbreviated as PPE) used as the component (A) in the present invention is
It is a homopolymer and / or a copolymer composed of a bonding unit represented by the following formula.

[0027]

[Chemical 1]

However, R ₁ , R ₂ , R ₃ , and R ₄ are each selected from the group consisting of hydrogen, hydrocarbons, and substituted hydrocarbon groups, and may be the same or different from each other. As a specific example of this PPE, poly (2,6-
Dimethyl-1,4-phenine ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like are preferable, and among them, poly (2,6-dimethyl-1,4-phenylene ether). Is preferred. Such P
The method for producing PE is not particularly limited, and for example, a cuprous salt-amine complex obtained by the method described in US Pat. No. 3,306,874 is used as a catalyst, and, for example, 2,6-xylenol is used. It can be easily produced by oxidative polymerization. In addition, US Pat.
06,875, U.S. Pat. No. 3,257,357.
, U.S. Pat. No. 3,257,358, JP-B-52-17880, and JP-A-50-5119.
It can be easily manufactured by the method described in Japanese Patent Publication No. The reduced viscosity η _{SP / C} (0.5 g / d of the PPE used in the present invention
1, chloroform solution, measured at 30 ° C.) is 0.20
It is preferably in the range of 0.70 dl / g, 0.3
It is more preferably in the range of 0 to 0.60 dl / g. Examples of means for satisfying the above requirements regarding the reduced viscosity of PPE include adjustment of the amount of catalyst during production of the PPE.

The flame retardant as the component (B) of the present invention comprises an organic halogen compound and a hydroxyl group-containing aromatic phosphoric acid ester, and the former is 20 to 80 in terms of the amount ratio of both.
%, And the latter is preferably 80 to 20% by weight.

As the organic halogen compound, an aromatic halogen compound, a halogenated epoxy resin, a halogenated polycarbonate, a halogenated aromatic vinyl polymer,
Examples thereof include halogenated cyanurate resins and halogenated polyphenylene ethers, and preferably decabromodiphenyl oxide, tetrabromobisphenol A, an oligomer of tetrabromobisphenol A, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol. Examples thereof include polycarbonates, brominated polystyrenes, brominated crosslinked polystyrenes, brominated polyphenylene oxides, polydibromophenylene oxides, decabrom diphenyl oxide bisphenol condensates and halogen-containing phosphates.

The above-mentioned hydroxyl group-containing aromatic phosphate ester is phosphorus containing one or more phenolic hydroxyl groups in tricresyl phosphate, triphenyl phosphate and condensed phosphate esters thereof. An acid ester, for example, the following compounds.

[0032]

[Chemical 2]

(However, Ar1, Ar2, Ar3, Ar
4, Ar5 and Ar6 are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group and a butylphenyl group, and at least one hydroxyl group is substituted with the above aromatic group in a phosphoric acid ester. Has been done. Further, n represents an integer of 0 to 3, and m represents 1
Represents the above integers. ) Among the hydroxyl group-containing aromatic phosphates of the present invention, diphenylresorcinyl phosphate of the following formula (3) or diphenylhydroquinonyl phosphate of the formula (4) is preferable, and its production method is, for example, It is disclosed in JP-A-1-223158, and can be obtained by the reaction of phenol, hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0034]

[Chemical 3]

The flame retardant of the component (B) of the present invention comprises an organic halogen compound and a hydroxyl group-containing aromatic phosphoric acid ester as essential components, and if necessary, does not contain a hydroxyl group, an organic phosphorus compound, red phosphorus, and an inorganic system. A flame retardant containing a phosphate and an inorganic flame retardant.

Examples of the above-mentioned organic phosphorus compound containing no hydroxyl group include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate salt,
Phosphoric acid ester, phosphorous acid ester and the like, and specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol. Examples thereof include diphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, dipyrocatechol hypophosphite, and the like.

In addition to general red phosphorus, the surface of the red phosphorus is previously coated with a film of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. , Aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide coated with a film composed of a metal hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, zinc hydroxide , A double coating of a thermosetting resin film on a metal hydroxide film selected from titanium hydroxide.

The above-mentioned inorganic phosphate is typified by ammonium polyphosphate.

The above-mentioned inorganic flame retardant is an inorganic material such as aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide or tin oxide hydrate. It is a hydrate of a metal compound, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu-calcium, calcium carbonate, barium carbonate or the like. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have a good flame retarding effect and are economically advantageous.

The flame retardant aid of component (C) of the present invention is one or more flame retardant aids selected from triazine skeleton-containing compounds, metal oxides, fluororesins, polydiorganosiloxanes and silica. .

The triazine skeleton-containing compound is (B)
It is a component for further improving flame retardancy as a flame retardant aid for the hydroxyl group-containing phosphate ester in the component. Specific examples thereof include melamine, melam, melem, melon, melamine cyanurate, succinoguanamine, adipoguanamine, methylglutaloganamin, melamine phosphate, melamine resin, and BT resin. Melamine cyanurate is preferred.

The above metal oxides include antimony trioxide, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide,
Iron oxide, manganese oxide, aluminum oxide, tin oxide,
Titanium oxide and the like.

The above-mentioned fluororesin is a component for further improving the drip resistance, and is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination as long as the drip resistance is not impaired.

Methods for producing these fluororesins are described in US Pat. No. 2,393,697 and US Pat.
534,058, for example, tetrafluoroethylene in an aqueous medium using a radical initiator such as ammonium persulfate, potassium persulfate, 7-70 kg
Polymerization at a temperature of 0 to 200 ° C. under a pressure of / cm ² and then polytetrafluoroethylene powder is obtained from suspensions, dispersions or emulsions by coagulation or by precipitation.

Here, it is preferable to melt-knead at a temperature not lower than the melting point of the fluororesin. For example, in the case of polytetrafluoroethylene, it is preferable to melt in the temperature range of 300 to 350 ° C. It melts above the melting point under shearing force, resulting in highly fibrillation and oriented crystallization. And
It is possible to obtain a fluorine-based resin having a special branched higher-order structure with respect to the trunk fiber. As a result, the thermoplastic resin is three-dimensionally entangled with the thermoplastic resin, and melt dripping of the molded body is suppressed. Further, in order to give a high shearing force, it is preferable to melt in a hard resin having a high melt viscosity such as polyphenylene ether rather than a rubber modified resin (for example, rubber modified polystyrene).

In the method for producing a fluorine-based resin having the above-mentioned special higher-order structure, a masterbatch is prepared by melt-kneading a fluorine-based resin, a thermoplastic resin and, if necessary, a dispersant at a melting point of the fluorine-based resin or higher. Then, a thermoplastic resin, a two-step process method of melt-kneading with a flame retardant, or an extruder consisting of two zones capable of side-feeding is used, and the thermoplastic resin and the fluorine-based resin and a dispersant are optionally added in the preceding stage. There is a one-step process method in which the above is melt-kneaded at a temperature equal to or higher than the melting point of the fluororesin, the melting temperature is lowered in the latter stage, and the flame retardant is fed and melt-kneaded.

The above polydiorganosiloxane is a linear silicone oil such as polydimethylsiloxane, or a three-dimensional network formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . It is a silicone resin having a structure. Here, R is an alkyl group such as a methyl group, an ethyl group, a propyl group, or a phenyl group,
An aromatic group such as a benzyl group is shown.

Such polydimethylsiloxane can be obtained by co-hydrolyzing and polymerizing the organohalosilane corresponding to the above structural unit.

The above-mentioned silica is amorphous silicon dioxide, and in particular, a hydrocarbon compound-coated silica whose surface is treated with a hydrocarbon compound-based silane coupling agent is preferable.

Examples of the silane coupling agent include vinyl such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. Group-containing silanes, epoxy silanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-
It is an aminosilane such as phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit having a structure similar to that of the thermoplastic resin is particularly preferable, and for example, p-styryltrimethoxysilane is suitable for the styrene resin.

The treatment of the silane coupling agent on the silica surface is roughly classified into a wet method and a dry method. The wet method is a method in which silica is treated in a silane coupling agent solution and then dried, and the dry method is a method in which silica is charged into a device capable of high-speed stirring such as a Henschel mixer and then stirred. Meanwhile, the silane coupling agent solution is slowly dropped, followed by heat treatment.

When it is necessary to further impart fluidity to the resin composition of the present invention, (D) fluidity improver can be added.

The component (D) is selected from copolymer resins composed of aromatic vinyl units and acrylic acid ester units, aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher aliphatic alcohols, and metallic soaps. One or more fluidity improvers.

The aromatic vinyl unit of the above copolymer resin is
The aromatic vinyl unit shown in the description of the component (A), and the acrylic acid ester unit is an acrylic acid ester composed of an alkyl group having 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate. Here, the content of acrylic acid ester units in the copolymer resin is preferably 3 to 40% by weight, and more preferably 5 to 20% by weight. Also,
Solution viscosity, which is an index of the molecular weight of the copolymer resin (resin 1
0 wt% MEK solution, measurement temperature 25 ° C) is 2-10
It is preferably cP (centipoise). When the solution viscosity is less than 2 cP, the impact strength is significantly reduced, while 1
If it exceeds 0 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aid in the component (D) is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, fluorides, chlorides and the like. .

The higher fatty acids in the component (D) include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid, and ferric acid, and ricinoleic acid, lysine veridic acid, and 9-oxy-12 octadecene. And unsaturated fatty acids such as acids.

The higher fatty acid ester in the component (D) is a monohydric alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, and a monohydric alcohol of a polybasic acid such as a phthalic acid diester of diphenylstearyl phthalate. Esters, and further sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate. , Sorbitan esters such as polyoxyethylene sorbitan monooleate, stearic acid monoglyceride,
Oleic acid monoglyceride, capric acid monoglyceride, fatty acid ester of glycerin monomer such as behenic acid monoglyceride, polyglycerin stearic acid ester, polyglycerin oleic acid ester, polyglycerin fatty acid ester such as polyglycerin lauric acid ester, polyoxyethylene monoester Examples thereof include fatty acid esters having a polyalkylene ether unit such as laurate, polyoxyethylene monostearate and polyoxyethylene monooleate, and neopentyl polyol fatty acid esters such as neopentyl polyol distearate ester.

The higher fatty acid amides in the component (D) are monoamides of saturated fatty acids such as phenylstearic acid amide, methylolstearic acid amide, and methylolbehenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, and coconut oil fatty acid. N, N'-2-substituted monoamides such as diethanolamide and oleic acid diethanolamide, and methylenebis (12-
Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide, ethylenebisstearic acid amide, ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-xylinbis (12-
Aromatic bisamides such as (hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol in the component (D) is
Examples include monohydric alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols such as sorbitol and mannitol, and polyoxyethylene dodecylamine and polyoxyethylene boctadecylamine, and polyoxyethylene allylated ethers and the like. Allylated ether having alkylene ether unit, and polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxy Polyoxyethylene alkyl phenyl ether such as ethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether,
Polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A
It is a dihydric alcohol having a polyalkylene ether unit such as ether or polyoxyethylene polyoxypropylene glycol ether.

The metal soap in the component (D) is a metal salt of the higher fatty acid such as stearic acid such as barium, calcium, zinc, aluminum or magnesium.

The resin composition of the present invention contains 5 to 40 parts by weight of the flame retardant (B) and 5 to 30 parts by weight of the flame retardant aid (C) per 100 parts by weight of the thermoplastic resin (A). It is preferable to add 0 to 30 parts by weight of the fluidity improver (D), if necessary. Within the above range, the balance characteristics of flame retardancy, molding processability (fluidity), impact resistance and heat resistance are excellent.

The resin composition of the present invention can be obtained by, for example, melt-kneading each of the above components with a commercially available single-screw extruder, a twin-screw extruder, or the like. At that time, an antioxidant such as hindered phenol is used. , UV absorbers such as benzotriazole and hindered amine, tin-based heat stabilizers, other inorganic and halogen-based flame retardants, lubricants such as stearic acid and zinc stearate, fillers, reinforcing agents such as glass fibers, dyes and pigments Colorants and the like can be added as necessary.

The composition of the present invention thus obtained is molded by, for example, an injection molding machine or extrusion molding, and is excellent in molding processability (flowability), flame retardancy, heat resistance and impact resistance. Goods are obtained.

[0064]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were performed using the following methods or measuring instruments.

(1) Rubber weight-average particle diameter: The weight-average particle diameter of the rubber-modified styrene-based resin is determined by the particle diameter of the butadiene-based polymer in the transmission electron micrograph taken by the ultrathin section method of the resin composition. , Calculated by the following formula. Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles having a particle diameter of Di). (2) Reduced clay ηsp / c rubber-modified styrene-based resin 18 g of methyl ethyl ketone in 1 g
Add a mixed solvent of 2 ml of methanol and 2 ml of methanol, and add 2 ml at 25 ° C.
Shake for hours and centrifuge for 30 minutes at 18000 rpm at 5 ° C. The supernatant was taken out, the resin component was precipitated with methanol, and then dried. Resin 0.1 thus obtained
g was dissolved in toluene to give a solution having a concentration of 0.5 g / dl, 10 ml of this solution was placed in a Canon-Fenske viscometer, and the number of seconds t _{1 at} which the solution flowed was measured at 30 ° C. On the other hand, the fractionalization time t ₀ of pure toluene was separately measured with the same viscometer and calculated by the following mathematical formula.

[0066]

[Equation 1]

On the other hand, the reduced viscosity ηs of PPE as the component (A)
For p / c, dissolve 0.1 g in chloroform,
A solution having a concentration of 0.5 g / dl was prepared and measured in the same manner as above.

(3) Izod impact strength: ASTM-D
It measured at 23 degreeC by the method based on 256 (V notch,
1/8 inch test piece).

(4) Vicat softening temperature: ASTM-D1
It was measured by a method according to 525 and used as a scale of heat resistance.

(5) Melt flow rate (MFR): An index of fluidity, which was measured by a method according to ASTM-D-1238. It was determined from the extrusion amount per minute (g / 10 minutes) under the conditions of a load of 5 kg and a melting temperature of 200 ° C.

(6) Flame retardance VB (Vertical Bur) compliant with UL-94
Ning) method (1/8 inch test piece).

(7) Solubility parameter of each component (So
Lubricity Parameter: SP value (δ) Polymer Engineering and S
Science, 14, (2), 147 (1974).

[0073]

[Equation 2]

(Δel: cohesive energy per unit functional group, Δvl: molecular volume per unit functional group, δ [unit: (cal / cm ³ ) 1/2] The SP value of the polymer or the blend was calculated by proportional distribution of the weight ratio of the SP value of each component of the monomer unit or the blend on the assumption that the addition rule was established.

(8) Smoke emission It was measured by the method according to JIS-D1201. That is,
Suga Test Machine Co., Ltd. Smoke concentration measuring instrument with oxygen index method combustion tester ON-1D type, oxygen concentration 26% by volume
Smoke under the combustion conditions of (L0I), the optical path length (L) 0.5m
Introduced into the smoke detector. Then, irradiate with a halogen lamp and obtain the minimum transmittance (T) (%) from the light amount of the light receiving part,
The extinction coefficient Cs is calculated by the following formula.

Cs = (2.3 / L) log ₁₀ (100 / T) However, the sample size is 3.1 mm (thickness) * 6.0.
mm (width) * 127.0 mm (length).

The following components were used as the components used in Examples and Comparative Examples.

(A) Thermoplastic resin (component A) Rubber-modified styrene resin (HIPS) Polybutadiene {(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2/3) (Nippon Zeon Co., Ltd., trade name Nipol 122 OSL)}
Was dissolved in the following mixed solution to form a uniform solution.

Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-methylstyrene dimer 0.27% by weight 1,1-bis (t-butylperoxy) -3,3,3 5-Trimethylcyclohexane 0.03% by weight Then, the above mixed solution was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage had a stirring rate of 190 rpm, 126
℃, the second stage is 50 rpm, 133 ℃, the third stage is 20 rp
m, 140 ° C., and the fourth stage was 20 rpm and 155 ° C. for polymerization. Subsequently, the polymerization liquid having a solid content of 73% was introduced into a devolatilization device to remove unreacted monomers and a solvent to obtain a rubber-modified styrene resin (referred to as HIPS-1). As a result of analyzing the obtained rubber-modified styrene resin, the rubber content was 12.
3% by weight, the weight average particle diameter of rubber was 2.2 μm, and the reduced viscosity ηsp / c was 0.52 dl / g.

The SP value of HIPS is 10.3, and 10.52 and 8.64 are used as the SP values of polystyrene and polybutadiene, respectively, and the weight ratio of the above components is 87.7 / 12.3. It was calculated by proportional distribution.

Rubber-unmodified aromatic vinyl resin (polystyrene (GPPS)) Commercially available polystyrene (weight average molecular weight 270,000, number average molecular weight 120,000) {(Asahi Kasei Co., Ltd.) (hereinafter GPP
S)) was used. The SP value is 10.52.

Manufacture of polyphenylene ether (PPE) A) Manufacture of high molecular weight PPE The inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor, a cooling coil inside and a stirring blade was sufficiently replaced with nitrogen. After that, cupric bromide 54.8 g, di-n-
Butylamine 1110 g, and toluene 20 liters,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into a reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 180 minutes while controlling the internal temperature to 30 ° C. After the polymerization was completed, the precipitated polymer was filtered off. A methanol / hydrochloric acid mixture was added to this to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and dried to obtain powdery polyphenylene ether (referred to as PPE-1). Reduced viscosity η _SP is 0.55
It was dl / g. The SP value is 8.67.

B) Production of low molecular weight PPE In the production of the above high molecular weight PPE-1, the polymerization time was 9
The same experiment as PPE-1 was repeated except that it was shortened to 0 minutes. The obtained polyphenylene ether was treated with PPE-
2. The reduced viscosity ηsp / C was 0.41 dl / g. The SP value is 8.67.

(B) Flame retardant Organic halogen compound (tetrabromobisphenol A
Epoxy oligomer (FR-X)) Commercially available brominated flame retardant (Molecular weight 16 manufactured by Tohto Kasei Co., Ltd.)
00 Trade name YDB-408 (bromine content 51% by weight)
(Referred to as FR-X) was used.

[0085]

[Chemical 4]

Organic Phosphorus Compound A) Hydroxyl Group-Containing Aromatic Phosphate Ester (FR
-1) Preparation of phenol 122.7 parts by weight (molar ratio 2.0) and aluminum chloride 0.87 parts by weight (molar ratio 0.01) in a flask at 90 ° C. 100 parts by weight of phosphorus oxychloride (molar ratio 1). 0.0) was added dropwise over 1 hour. 71.7 parts by weight (molar ratio 1.0) of resorcin was added to the produced intermediate (I), and further reacted. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Then, the reaction product was cooled and washed with water to remove the catalyst and the chlorine content to obtain a phosphoric acid ester mixture (hereinafter referred to as FR-1). When this mixture was analyzed by GPC (gel permeation chromatography), the following formula (3) diphenylresorcinyl phosphate (hereinafter referred to as TPP-OH), triphenyl phosphate (hereinafter referred to as TPP) and the following formula (3) 5) aromatic condensed phosphoric acid ester (hereinafter referred to as TPP dimer), and the weight ratio is 54.2 / 18.3 /.
It was 27.5.

[0087]

[Chemical 5]

B) Hydroxyl Group-Free Aromatic Phosphate Ester [Triphenyl Phosphate (TPP)] Commercially available aromatic phosphate ester [manufactured by Daihachi Chemical Industry Co., Ltd.,
Trade name TPP (referred to as TPP)] was used.

C) Hydroxyl group-free aromatic phosphate ester (FR-2) Commercially available aromatic condensed phosphate ester [Dahachi Chemical Industry Co., Ltd.
Made by the trade name CR733S (referred to as FR-2)] was used.

The above-mentioned aromatic condensed phosphoric acid ester is
According to the GPC analysis, the TPP represented by the following formula (6)
It was composed of dimer and TPP oligomer, and the weight ratio of each was 65/35.

[0091]

[Chemical 6]

(However, n = 1: TPP dimer n ≧ 2: referred to as TPP oligomer) D) Hydroxyl group-free aromatic phosphate ester (F
R-3) Commercially available aromatic condensed phosphoric acid ester derived from bisphenol A [manufactured by Daihachi Chemical Industry Co., Ltd., trade name CR741C]
(Referred to as FR-3)] was used.

The aromatic condensed phosphoric acid ester is
According to GPC analysis, TCP represented by the following equation (7)
It was composed of -A-dimer, TCP-A-oligomer and tricresyl phosphate (TCP), and the weight ratio was 80.4 / 14.1 / 5.5, respectively.

[0094]

[Chemical 7]

(However, n = 1: TCP-A-dimer n ≧ 2: TCP-A-oligomer.) (C) Flame retardant aid Triazine skeleton-containing compound Commercially available melamine cyanurate [Nissan Chemical Co., Ltd.] Manufactured by MC 610 (hereinafter referred to as MC)] was used.

Fluorine-based resin (PTFE) Commercially available polytetrafluoroethylene (trade name: Teflon 6J (referred to as PTFE), manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was used as an inhibitor for the dropping of fire species. P
Regarding the method of adding TFE, PPE-1 / GPPS /
A masterbatch of PTFE / EBS (68.6 / 29.4 / 1/1 (weight ratio)) was added to the above-mentioned melting point of PTFE at 330 or higher.
It was carried out by a method in which it was prepared at a temperature of 0 ° C. and was blended with the thermoplastic resin composition so as to have a specified amount. Kneading with high shearing force above the melting point of PTFE promotes fibrillation,
The effect of suppressing dripping of fire is improved.

(D) Fluidity improver (EBS) Commercially available ethylenebisstearic acid amide {the following formula (8)} {trade name Kaowax EB manufactured by Kao Corporation
-FF (referred to as EBS)} was used.

[C ₁₇ H ₃₅ CONH] ₂ (CH ₂ ) ₂ (8) Examples 1 and 2 Comparative Examples 1 to 3 Component A [HIPS / GPPS / PPE-1 / PPE-2]
= 63/11/22/4 (weight ratio)] 100 parts by weight, the flame retardant (component B) / MC / PTFE / in Table 1
The EBSs were mechanically mixed in a weight ratio of X / 14 / 0.04 / 4, respectively, using a Toyo Seiki Seisakusho Labo Plastomill at a melting temperature of 250 ° C. and a rotation speed of 50 rpm for 7 times.
Melted for a minute. However, since the melting temperature of PPE is high, first, GPPS / PPE was melted at 300 ° C., and then the remaining components were melted under the above conditions.

From the resin composition thus obtained, a 1/8 inch thick test piece was prepared by hot pressing, and the Vicat softening temperature, Izod impact strength, MFR, smoke emission and flame retardancy were evaluated. It was The results are shown in Table 1 and FIG.

From Table 1 and FIG. 1, it is understood that when an organic halogen compound and a hydroxyl group-containing aromatic phosphoric acid ester are used together as a flame retardant, a synergistic effect is exhibited and the flame retardancy is dramatically improved. .

Comparative Examples 4 to 6 The relationship between the type of organic phosphorus compound and flame retardancy and physical properties was examined. That is, in Example 1, the same experiment as in Example 1 was repeated except that the organophosphorus compound shown in Table 2 was used instead of FR-1. The results are shown in Table 2 and FIG.

From Table 2, it can be seen that the presence of the hydroxyl group provides a very good balance of flame retardancy, smoke generation, fluidity, impact strength and heat resistance.

When a triazine skeleton-containing compound such as MC is used as the flame retardant aid, the triazine skeleton-containing compound is reacted with the hydroxyl group and the amino group of the triazine skeleton-containing compound by an interaction such as a hydrogen bond. It is assumed that the compatibility and dispersibility are improved and the impact strength is improved.

By containing a hydroxyl group, when an aromatic vinyl resin is used as the thermoplastic resin (A), a partial compatibility is exhibited between the two. As an index of the partial compatibility, the solubility parameter (Solubility Para) between the component (A) and the component (B) is used.
The difference ΔSP value was used. That is,
Component (A) (HIPS / GPPS / PPE-1 / PPE
-2) has an SP value of 9.9, while the hydroxyl group-containing phosphate ester (TPP-OH) in the component (B),
TPP, TPP dimer, TPP oligomer, TCP,
TCP-A-dimer, TCP-A-oligomer SP
The values are 11.8, 10.7, 10.8, 10.
8, 8.8, 9.3, and 9.4, and the ΔSP values are 1.9, 0.8, 0.9, 0.9, 1.1, and 0.
6 and 0.5. (See FIG. 2) Here, when the ΔSP value is about 1 or less, complete compatibility is exhibited and the fluidity is improved, but the heat resistance is reduced. However, when the ΔSP value is 1.5 to 2.0 like TPP-OH, it exhibits partial compatibility. As a result, at the time of molding process, it promotes plasticization and acts as a fluidity improver, while at the time of use as a molded product, the phosphate ester is slightly phase-separated due to the partial compatibility of the two, and thus the heat resistance is improved. Is expected to improve.

FIG. 3 shows the mechanism of flame retardancy of the resin composition of the present invention.

First, the combustion reaction in the solid phase will be described. In the presence of the oxygen-containing polymer, the phosphorus-containing flame retardant acts as a dehydrating agent to form a carbonized film (char), and the flame retardancy is improved due to the improved heat insulating property and the oxygen blocking effect. Here, when the triazine skeleton-containing compound is present, phosphoric acid amide is produced as an intermediate, promoting phosphorylation and promoting the formation of a carbonized film. Further, the special high-order structure fluororesin suppresses dripping during combustion due to the thickening effect or entanglement effect during combustion.

Next, in the gas phase, the OH produced by the phosphorus radicals and halogen radicals in the phosphate ester during combustion.
Radical scavengers such as radicals
venger). In addition, the synergistic action of phosphorus and halogen produces compounds such as POX, PXn, and HX (X represents halogen), which exerts an oxygen blocking effect by covering the resin surface as heavy vapor. , Promote flame retardant effect.

It is considered that the flame retardancy is dramatically improved by the above two effects of the solid phase and the gas phase.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

EFFECTS OF THE INVENTION The composition of the present invention has a high degree of flame retardance, fluidity, heat resistance,
And a resin composition having excellent impact resistance.

This composition is suitable for home electric appliance parts, OA equipment parts and the like, and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 is a diagram illustrating the synergistic effect of aromatic phosphate ester and an organic halogen compound to withstand flame retardancy, based on Table 1. The vertical axis represents the flame-out time of the combustion test according to the UL-94VB method, and the horizontal axis represents the weight ratio of each component in the total 100% by weight of the aromatic phosphate ester and the organic halogen compound. Here, the dotted line shows the case where there is no synergistic effect, and the solid line shows the synergistic effect of the two components of the present invention.

FIG. 2 is a diagram showing SP values (solubility parameters) calculated by the Fedors equation of the thermoplastic resins and organic phosphorus compounds shown in Table 2.

FIG. 3 is a diagram showing a flame retardant mechanism of a flame retardant in a gas phase and a solid phase.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08K 5/521 KCB // (C08L 101/00 27:12 83:04)

Claims (1)

[Claims] 1. A flame retardant comprising (A) a thermoplastic resin, (B) an organic halogen compound and a hydroxyl group-containing aromatic phosphate ester, and (C) a triazine skeleton-containing compound, a metal oxide, a fluororesin, and a polydiene. A thermoplastic resin composition having one or more flame retardant aids selected from organosiloxane and silica and having excellent flame retardant properties.