JPH0931295A - Low-volatile drippable flame-retardant resin composition excellent in thermal resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition that does not develop mold deposits even when subjected to long continuous molding and excels in rigidity, impact strength and fluidity. SOLUTION: This resin composition comprises (A) 65-98 pts.wt. of a rubber- modified styrene-based resin, (B) 1-15 pts.wt. of a polyphenylene ether, and (C) 1-20 pts.wt. of an aromatic phosphoric ester of the formula ((a) to (c) are each 1 to 3; R<1> to R<3> are each H or a 1-30C hydrocarbon, and total no. of C in substituent groups R<1> -R<3> is 12-25 in average as in the whole compound; preferable examples of the component (C): bisnonylphenyl phenylphosphate, nonylphenyl t-butylphenyl phenylphosphate, etc.). The component A is the main component which retains strength of moldings, the component B improves thermal resistance and flame retardancy, and component C is a flame retardant that acts as dripping accelerator in burning.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a drip-proof flame-retardant resin composition. More specifically, it relates to a flame-retardant resin composition of low volatile property, which does not cause mold deposit even after continuous molding for a long period of time, and which is excellent in heat resistance, rigidity and impact strength, and which can be dropped. is there.

[0002]

2. Description of the Related Art Styrene-based resins are excellent in impact resistance in addition to excellent moldability.
Although it is used in various fields such as home electric appliance parts and OA equipment parts, its use is limited due to the flammability of styrene resins. As a method of making a styrene-based resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to a styrene-based resin, thereby achieving some degree of flame retardancy. However, when using a halogen-based flame retardant, suffocation death due to toxic gas generated from the halogen-based flame retardant at the time of a fire, or blindfold the evacuees with black smoke, leading to loss of escape and burning death, Further, there is a problem of corrosiveness of electric system due to acid gas of smoke. In addition, there are problems such as damage to the furnace by acid gas and environmental pollution such as acid rain during incineration.

From such a background, it is desired to develop a method for making a styrene resin flame-retardant without using a halogen-based flame retardant. On the other hand, an inorganic flame retardant or a phosphorus flame retardant is used as a flame retardant technique. It has been known. However, although the resin composition obtained by the above technique is excellent in flame retardancy, it is not always satisfactory in impact strength, molding process fluidity, and heat resistance. There is a problem that productivity is lowered due to contamination, so-called mold deposit, or mold contamination is transferred to a molded product to cause stress cracks, which narrows industrial use. As a technique for improving volatility, a resin composition for laminates comprising a phenol resin and a specific alkyl group-substituted phosphate monomer (JP-A-1-95149, JP-A-1-242633, JP-A-1-193328). ) Is disclosed. The target of the flame retardant of this publication is a thermosetting resin, which is different from the drip-proof flame retardant resin composition for the styrene resin of the present invention. In addition, an antistatic agent comprising a phosphoric acid ester such as a sulfonate and dinonylphenylphenyl phosphate (Japanese Patent Laid-Open No. 3-64368) is disclosed.
The agents in that publication are not flame retardants and are essentially different from the present invention.

A flame retardant comprising a phenyl group, an isopropylphenyl group, and a phosphate having a carbon number of 4 to 12 and an alkyl group-substituted phenyl group (Japanese Patent Laid-Open No. 2-7).
No. 92) is disclosed. According to the definition of the present invention, the number-average carbon number of the substituent of the phosphate in the publication is less than 12, and thus the volatility is not sufficient. Further, phosphorus having a hydrocarbon group selected from an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 12 to 22 carbon atoms, a phenyl group and an alkylphenyl group having 7 to 15 carbon atoms (alkyl group having 1 to 9 carbon atoms). A method for producing an acid triester (Japanese Patent Laid-Open No. 3-294284) is disclosed. Not only is this publication different in that it is a production method, but by using a specific substituent-containing aromatic phosphate ester monomer in this publication, continuous moldability (while maintaining dropping flame retardancy) No significant improvement in low volatility) is disclosed or even implied.

[0005]

In view of the above situation, the present invention does not have the above-mentioned problems, that is, it does not cause mold deposit even when continuous molding for a long time (low volatility) heat resistance, It is an object of the present invention to provide a drip-proof flame-retardant resin composition having excellent rigidity.

[0006]

Means for Solving the Problems As a result of diligent studies on a technique for preventing mold deposit, which is one index showing the moldability of a styrene resin composition, the present inventors have found that polyphenylene ether can be added to styrene resin. And, by blending the aromatic phosphate ester containing the above-mentioned specific substituent, surprisingly, while suppressing the mold deposit, it becomes possible to dramatically improve the dropping flame retardancy. Heading, arrived at the present invention. That is,
The present invention is a rubber-modified styrene resin (component A) 65-9.
8 parts by weight, polyphenylene ether (B component) 1 to 15
The present invention provides a flame-retardant low-volatile flame-retardant resin composition having excellent heat resistance, which comprises 1 part by weight and 1 to 20 parts by weight of an aromatic phosphate ester (component C) represented by the following general formula (1). .

[0007]

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(Where a, b, c are 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or a hydrocarbon having 1 to 30 carbon atoms, and the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 to 25 on average in the whole compound. When a plurality of aromatic phosphates having different substituents are used, the total number of carbon atoms of the substituents R ¹ , R ² and R ³ of the B component is represented by a number average, and each aromatic component of the B component is represented. It is the sum of the products of the weight fraction of the group phosphoric acid ester component and the total number of carbon atoms of the substituents of each component. Hereinafter, the present invention will be described in detail. The resin composition of the present invention contains a specific amount of a rubber-modified styrene resin (component A), polyphenylene ether (component B) and an aromatic phosphate ester having a specific substituent (component C).

The component A constitutes the main component of the molding resin composition and plays a role of maintaining the strength of the molded product. The component B is a component that improves the heat resistance and flame retardancy of the component A, and the component C is a flame retardant that acts as a drip accelerator during combustion. Here, the C component is an aromatic phosphate ester monomer, and the substituents R ¹ , R ² , and R ³ are hydrogen or have 1 to 30 carbon atoms.
Of hydrocarbons, and the substituents R ¹ , R ² , and
It is important that the total carbon number of R ³ is on average 12 to 25. It has been found that when the total number of carbon atoms is less than 12 on average, the flame retardancy is excellent, but the volatility is high, while when it exceeds 25, the flame retardancy decreases, and the present invention has been completed.

The rubber-modified styrenic resin used as the component A in the present invention includes a rubber-modified product alone or a resin containing a rubber-modified styrene-based resin mainly containing the rubber-modified product. The rubber-modified styrenic resin is a polymer in which a rubber-like polymer is dispersed in particles in a matrix of a vinyl-aromatic polymer, and the aromatic vinyl monomer is present in the presence of the rubber-like polymer. And, if necessary, a vinyl monomer copolymerizable therewith is added, and the monomer mixture is obtained by known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization. Examples of such resins include high impact polystyrene, ABS resin (acrylonitrile-
Butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AE
S resin (acrylonitrile-ethylene propylene rubber-
Styrene copolymer). Here, the rubber-like polymer needs to have a glass transition temperature (Tg) of -30 ° C or lower, and if it exceeds -30 ° C, the impact resistance decreases. Examples of such a rubber-like polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubber obtained by hydrogenating the above diene rubber, isoprene rubber, chloroprene rubber, polyacrylic acid. An acrylic rubber such as butyl and an ethylene-propylene-diene monomer terpolymer (EPDM) can be mentioned, and a diene rubber is particularly preferable.

The aromatic vinyl monomer which is an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the above rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or p-methylstyrene. 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 α-methylstyrene is used mainly in styrene, the dropping property is further improved. If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as a component of the rubber-modified styrene resin. When it is necessary to increase 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. Further, when it is necessary to further increase the heat resistance of the resin composition, a monomer such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, or N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is from 0 to 40% by weight.

The rubber-like polymer in the rubber-modified styrenic resin contained in the resin composition of the present invention is preferably 5 to
80% by weight, particularly preferably 10 to 50% by weight, the graft-polymerizable monomer mixture preferably being in the range of 95 to 20% by weight, more preferably 90 to 50% by weight.
Within this range, the balance between impact resistance and rigidity of the desired resin composition is improved. Further, the rubber particle diameter of the styrene polymer is preferably 0.1 to 5.0 μm, and particularly 0.2
~ 3.0 μm is preferable. Within the above range, impact resistance is particularly improved. Reduced viscosity ηsp / which is a measure of the molecular weight of the rubber-modified styrene resin contained in the resin composition of the present invention
c (0.5 g / dl, toluene solution, measured at 30 ° C.) is
It is preferably in the range of 0.40 to 0.60 dl / g, and more preferably in the range of 0.50 to 0.60 dl / g. As means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrene-based resin, adjustment of the amount of polymerization initiator, polymerization temperature, amount of chain transfer agent and the like can be mentioned. The polyphenylene ether used as the component B in the present invention is a homopolymer and / or a copolymer having a bonding unit represented by the following formula.

[0013]

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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. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like, Above all, poly (2,6-dimethyl-1,4-phenylene ether)
Is preferred. The method for producing such polyphenylene ether is not particularly limited, and for example, US Pat.
Using a complex of a cuprous salt and an amine according to the method described in 306,874 as a catalyst, for example, 2,
It can be easily produced by oxidatively polymerizing 6-xylenol. In addition to that, US Pat. No. 3,306,875, US Pat. No. 3,257,357, and US Pat. No. 3,257,358 Calligraphy and Japanese Patent Publication Sho 52-178
It can be easily produced by the methods described in JP-A No. 80 and JP-A-50-51197. The PP used in the present invention
Reduced viscosity of E (0.5 g / dl, chloroform solution, 3
(0 ° C. measurement) is preferably in the range of 0.20 to 0.70 dl / g, and more preferably in the range of 0.30 to 0.60 dl / g. Means for satisfying the above-mentioned requirement regarding the reduced viscosity of PPE include adjustment of the amount of catalyst in the production of PPE. The C component aromatic phosphoric acid ester contained in the resin composition of the present invention is represented by the following general formula (1).

[0015]

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(Where a, b, c are 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or a hydrocarbon having 1 to 30 carbon atoms, and the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 to 25 on average in the whole compound. Here, when it is composed of a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² and R ³ of the B component is represented by a number average. Is the sum of the products of the weight ratio of each aromatic phosphate ester component and the total number of carbon atoms of the substituents of each component. ) The average of the total number of carbon atoms of the above substituents is preferably 12 to 20, and more preferably 15 to 18. As examples of the substituents, those containing a nonylphenyl group and a t-butyl group are preferable, and among the aromatic phosphoric acid esters, bisnonylphenylphenyl phosphate, nonylphenyl t-butylphenyl phenylphosphate and the like are listed. It can be preferably used. The resin composition of the present invention can be compatible or evenly dispersed with the components A and B, if necessary.
A thermoplastic resin (D component) other than the B component can be blended. For example, a polyolefin type, a polyvinyl chloride type, a polyphenyl ether type, a polyamide type, a polyester type, a polyphenylene sulfide type, a polycarbonate type, a polymethacrylate type, etc., or a mixture of two or more thereof may be used. In the resin composition of the present invention, an organic phosphorus compound other than the C component, red phosphorus, an inorganic phosphate, an inorganic flame retardant, etc. may be added as a flame retardant (E component) other than the C component, if necessary. be able to.

The above-mentioned organic phosphorus compound is, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphoric acid ester, phosphorous acid ester and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, diphenyl phosphate. Neopentyl hypophosphite, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, and dipyrocatechol hypophosphite.
The red phosphorus used as the flame retardant in the present invention is a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide, in addition to general red phosphorus. Those that have been covered,
Aluminum hydroxide, magnesium hydroxide, zinc hydroxide, water coated with a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, water For example, a film of a metal hydroxide selected from titanium oxide is doubly coated with a film of a thermosetting resin.

The inorganic phosphate used as the flame retardant is typically ammonium polyphosphate. Further, as the inorganic flame retardant that can be contained if necessary, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, Examples thereof include hydrates of inorganic metal compounds such as hydrates of tin oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate and barium carbonate. 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 resin composition of the present invention may optionally contain one or more compounds selected from triazine skeleton-containing compounds, novolac resins, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, fluororesins and polyacrylonitrile fibers. The flame retardant auxiliary agent (F component) can be blended. The triazine skeleton-containing compound is a component for further improving the flame retardancy as a flame retardant aid for phosphorus-based flame retardants. Specific examples thereof include melamine, melam represented by the following formula (2), melem represented by the following formula (3), melon (a product obtained by deammonification of three molecules of melem at 600 ° C. or higher), the following formula: Melamine cyanurate represented by (4), melamine phosphate represented by the following formula (5), succinoguanamine, adipguanamine, methylglutaloganamin represented by the following formula (6), represented by the following formula (7) Examples thereof include melamine resin and BT resin represented by the following formula (8), and melamine cyanurate is particularly preferable from the viewpoint of volatility resistance.

[0020]

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[0021]

[Chemical 6]

The novolac resin is a flame retardant aid,
When used in combination with a hydroxyl group-containing aromatic phosphoric acid ester, it is also a fluidity and heat resistance improver. The resin is a thermoplastic resin obtained by condensing phenols and aldehydes in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid, and the production method is "Polymer Experimental Science 5 Polycondensation and Polyaddition". (Kyoritsu Shuppan Sho 55-8-15) p. 43
7-455. An example of production of novolac resin is shown in the following formulas (9) and (10).

[0023]

[Chemical 7]

The above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol and 2,5-
Dimethyl-, 3,5-dimethyl-, 2,3,5-trimethyl-, 3,4,5-trimethyl-, pt-butyl-, pn-octyl-, p-stearyl-, p-phenyl -, P- (2-phenylethyl)-, o-isopropyl-, p-isopropyl-, m-isopropyl-, p
-Methoxy- and p-phenoxyphenol, pyrocatechol, resorcinol, hydroquinone, salicylaldehyde, salicylic acid, p-hydroxybenzoic acid, methyl p-hydroxybenzoate, p-cyano- and o.
-Cyanophenol, p-hydroxybenzenesulfonic acid, p-hydroxybenzenesulfonamide, cyclohexyl p-hydroxybenzenesulfonate, 4-hydroxyphenylphenylphosphinic acid, methyl 4-
Hydroxyphenylphenylphosphinate, 4-hydroxyphenylphosphonic acid, ethyl 4-hydroxyphenylphosphonate, diphenyl 4-hydroxyphenylphosphonate and the like. The aldehydes are formaldehyde, acetaldehyde, n-propanal, n
-Butanal, isopropanal, isobutyraldehyde, 3-methyl-n-butanal, benzaldehyde,
Examples include p-tolylaldehyde and 2-phenylacetaldehyde.

The metal-containing compound is a metal oxide and / or a metal powder. The metal oxide is aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide,
Cobalt oxide, bismuth oxide, chromium oxide, tin oxide,
It is a simple substance such as antimony oxide, nickel oxide, copper oxide, or tungsten oxide or a composite (alloy) thereof, and the metal powder is aluminum, iron, titanium, manganese, zinc,
Molybdenum, cobalt, bismuth, chromium, nickel,
It is a simple substance of copper, tungsten, tin, antimony, etc. or a composite thereof. The silicone resin is Si
It is a silicone resin having a three-dimensional network structure formed by combining structural units of O ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituents. Here, a silicone resin containing a vinyl group is particularly preferable.

Such silicone resin can be obtained by cohydrolyzing and polymerizing the organohalosilane corresponding to the above structural unit. The silicone oil is
It is a polydiorganosiloxane having a chemical bond unit represented by the following formula (11).

[0027]

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R in the above is a C1-8 alkyl group, C6
To 13 aryl groups, and one or more substituents selected from vinyl-containing groups represented by the following formulas (12) and (13), and it is particularly preferable that the molecule contains a vinyl group.

[0029]

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The viscosity of the silicone oil is 10 to 1
It is preferably 000000 centipoise (25 ° C), more preferably 30 to 150 centipoise (25 ° C). Said silica is amorphous silicon dioxide, particularly preferably a hydrocarbon compound-coated silica treated with a hydrocarbon compound-based silane coupling agent on the silica surface,
Furthermore, a hydrocarbon group-containing silica containing a vinyl group is preferable. The silane coupling agent is a vinyl group-containing silane such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, Epoxysilanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (aminoethyl)
It is an aminosilane such as γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit having a structure similar to that of the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is suitable for a 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 to charge silica into a high-speed stirring device such as a Henschel mixer, and stir it while stirring. Is slowly dropped and then heat treated. The aramid fibers have an average diameter of 1 to
It is preferable that the average fiber length is 500 μm and the average fiber length is 0.1 to 10 mm. It is produced by dissolving isophthalamide or polyparaphenylene terephthalamide in an amide-based polar solvent or sulfuric acid and performing solution spinning by a wet or dry method. You can The fluororesin is a flame retardant aid and is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and the like. If necessary, the fluorine-containing monomer may be used in combination with a copolymerizable monomer so long as the drip resistance is not impaired.

The polyacrylonitrile fiber has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm.
It is preferable that the polymer is dissolved in a solvent such as dimethylformamide and the like, and dry spinning is performed by dry spinning in an air stream at 400 ° C., or a wet spinning method in which the polymer is dissolved in a solvent such as nitric acid and wet spinned in water. It is manufactured by The resin composition of the present invention may optionally contain a copolymer resin comprising an aromatic vinyl unit and an acrylic acid ester unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, or a metal. One or more fluidity improvers (G component) selected from soap can be contained. The aromatic vinyl unit of the copolymer resin is the aromatic vinyl unit shown in the description of the component A, and the acrylate ester unit is composed of an alkyl group having 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate. It is an acrylic acid ester. Here, the content of acrylic acid ester unit in the copolymer resin is 3 to 40.
Weight% is preferable, and 5 to 20 weight% is more preferable. Further, the solution viscosity (methyl ethyl ketone solution containing 10% by weight of resin, measurement temperature: 25 ° C.), which is an index of the molecular weight of the copolymer resin, is preferably 2 to 10 cp (centipoise). When the solution viscosity is less than 2 cp, the impact strength decreases, while when it exceeds 10 cp, the fluidity improving effect decreases.

The aliphatic hydrocarbon processing aid is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin and partial oxides thereof, or fluorides, chlorides and the like. The higher fatty acids include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid and ferric acid, and unsaturated fatty acids such as ricinoleic acid, lysine elaidic acid and 9-oxy12 octadecenoic acid.

The higher fatty acid esters are monohydric alcohol esters of fatty acids such as methyl phenylstearate and butyl phenylstearate, and monobasic alcohol esters of polybasic acids such as phthalic acid diester of diphenylstearyl phthalate, and sorbitan mono Laurate, 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, behenic acid monoglyceride and other glycerin monomer fatty acids Fatty acid ester of polyglycerin such as ester, polyglycerin stearate, polyglycerin oleate, polyglycerin laurate, polyalkylene such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate Fatty acid ester having ether unit and neopentyl polyol such as neopentyl polyol distearic acid ester An all fatty acid esters and the like.

The higher fatty acid amides are saturated fatty acid monoamides such as phenylstearic acid amide, methylol stearic acid amide, and methylol behenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide and coconut oil fatty acid diethanolamide, oleic acid diethanolamide. And N, N′-2 substituted monoamides and the like, and methylene bis (12-hydroxyphenyl) stearic acid amide, ethylene bis (12-hydroxyphenyl) stearic acid amide, hexamethylene bis (12- Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide and aromatic bisamides such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol is a monohydric alcohol such as stearyl alcohol or cetyl alcohol,
Polyhydric alcohols such as sorbitol and mannitol, and polyoxyethylene dodecylamine, polyoxyethylene octadecylamine and the like, further allyl ether and polyoxyethylene lauryl ether having a polyalkylene ether unit such as polyoxyethylene allyl ether, Polyoxyethylene alkyl ether such as polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Alkyl phenyl ether, poly epichlorohydrin ether, polyoxyethylene bisphenol A ether, poly Carboxymethyl ethylene glycol,
It is a dihydric alcohol having a polyalkylene ether unit such as polyoxypropylene bisphenol A ether and polyoxyethylene polyoxypropylene glycol ether. The metal soap is a metal salt of higher fatty acid such as stearic acid such as barium, calcium, zinc, aluminum or magnesium.

The resin composition of the present invention may contain a thermoplastic elastomer (component H), if desired,
For example, polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, polyvinyl chloride-based, and the like, and polystyrene-based thermoplastic elastomer is particularly preferable. The polystyrene-based thermoplastic elastomer is a block copolymer composed of an aromatic vinyl monomer and a conjugated diene monomer, or a block copolymer in which the conjugated diene monomer portion is partially hydrogenated. The aromatic vinyl monomer constituting the block copolymer is the aromatic vinyl monomer described in the explanation of the component A, and styrene is the most preferable, but styrene is the main component and the other aromatic vinyl monomers are the same. The monomers may be copolymerized. Examples of the conjugated diene monomer forming the block copolymer include 1,3-butadiene and isoprene.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl monomer is represented by S, and a polymer block composed of a conjugated diene and / or its partially hydrogenated unit is represented. When displayed in B, SB, S (BS) _n (where n is an integer of 1 to 3), S
(BSB) _n (where n is an integer of 1 to 2) linear block copolymer and (SB) _n X (where n is an integer of 3 to 6; X is silicon tetrachloride, tin tetrachloride, poly) It is preferably a star block copolymer having a B portion represented by a coupling agent residue such as an epoxy compound) as a bond center. Above all, type 2 of SB, type 3 of SBS, S
BSB type 4 linear block copolymers are preferred.
The resin composition of the present invention comprises a styrene-based resin containing a rubber-modified styrene-based resin as a main component as a component, and a rubber-unmodified styrene-based resin if necessary, and poly (2,6-dimethyl-1) as a B-component. , 4-phenylene ether),
The C component is preferably a combination with an alkyl group-substituted aromatic phosphate monomer such as bisnonylphenyl phenyl phosphate, and the F component is preferably combined with polydimethylsiloxane.

The ratio of each component of the resin composition of the present invention is A
The component is 65 to 98 parts by weight, preferably 80 to 94
Parts by weight, more preferably 84 to 90 parts by weight, component B is 1 to 15 parts by weight, preferably 3 to 10 parts by weight, more preferably 5 to 8 parts by weight, and component C is 1 to 1 parts by weight.
It is 20 parts by weight, preferably 3 to 10 parts by weight, more preferably 5 to 8 parts by weight. Here, within the above range,
It has excellent balance characteristics of continuous moldability, flame retardancy against drops, moldability (fluidity), impact resistance and heat resistance. The melt extrusion method of the resin composition of the present invention may be carried out by melt-extruding all the components at the same time, or by first melting the resin components and then again by melt-extruding the polymer additive, or from a plurality of zones. There is a one-step extrusion method in which the resin component is melted in the former stage and the polymer additive is melt-extruded in the latter stage in the extruder.

The resin composition of the present invention can be obtained by, for example, melt-kneading each of the above components in a commercially available single extruder or a twin-screw extruder, and at that time, an antioxidant such as hindered phenol or benzo UV absorbers such as triazole 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, etc. A colorant or the like can be added if necessary.
The composition of the present invention thus obtained can be continuously molded for a long period of time using, for example, an injection molding machine or an extrusion molding machine, and the obtained molded article has a dropping flame retardance,
Excellent heat resistance, rigidity and impact resistance.

[0041]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention. The measurements in Examples and Comparative Examples were performed using the following methods or measuring machines. (1) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified aromatic vinyl resin is calculated by calculating the particle diameter of the butadiene-based polymer in the transmission electron microscope photograph taken by the ultrathin section method of the resin composition, and using the following formula. Calculate by Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles whose particles are Di) (2) Reduced viscosity ηsp / c 1 g of rubber-modified styrene-based resin and methyl ethyl ketone 18
and a mixed solvent of methanol and 2 ml of methanol.
Shake for 5 hours and centrifuge at 18000 rpm for 30 minutes at 5 ° C. The supernatant was taken out and a resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to give a solution having a concentration of 0.5 g / dl, and 10 ml of this solution was placed in a Canon-Fenske viscometer.
At 30 ° C., the number of seconds t _{1 during} which the solution was flowing was measured. On the other hand, the flowing down time t ₀ of pure toluene was measured separately using the same viscometer, and calculated by the following formula. ηsp / c = (t ₁ / t ₀ −1) / C (C: polymer concentration g / dl) (3) Izod impact strength Measured at 23 ° C. by a method according to ASTM-D256 (V notch, 1 / 4-inch test piece) (4) Surface impact strength The surface impact strength was measured at 23 ° C by a method similar to ASTM-D1709. Specifically, using a DuPont impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.), a dart (weight 200 g) having a hammer tip diameter of 6.4 mmR and a length of 5.2 mm, a pedestal diameter of 9.5 mm, and a hole depth. Molded body (70
mm square, 2 mm thick molded body) Fixed in contact with the surface and dropped from the height of 50 cm to the molded body, and 50% of the molded body is destroyed by 50% load And the drop load was multiplied to calculate the 50% breaking energy. This 50% breaking energy was defined as surface impact strength. The unit is kgcm.

(5) Rigidity The flexural modulus was measured by the method according to ASTM-D790 and used as a measure of rigidity. (6) Heat distortion temperature It was measured by a method based on ASTM-D648 and used as a scale of heat resistance. (Test load 18.5 kg / cm ² , 1/4
Inch thickness test piece) (7) Vicat softening temperature Measured by a method according to ASTM-D1525 and used as a scale of heat resistance. (8) Molding process fluidity The melt flow rate (MFR) was measured by the method based on ISO-R1133 and used as a measure of the molding process fluidity. It was determined from the extrusion rate (g / 10 minutes) per 10 minutes under the conditions of a load of 5 kg and a melting temperature of 200 ° C. (9) Flame-retardant property (dripping self-extinguishing property) VB (Vertical Bur) compliant with UL-94
(1/8 inch test piece) (10) Volatility (thermogravimetric balance test) Shimadzu thermal analyzer DT-40 was used under a nitrogen stream for 10
The temperature at which the temperature was raised at ° C / min and the weight was reduced by 1% was used as a measure of volatility.

On the other hand, as an evaluation of the mold deposit, continuous operation was carried out under the following molding conditions, and the adhesion state of the mold was observed. A. Molding machine: manufactured by Toyo Kikai Kinzoku Co., Ltd. Injection molding machine "pl"
astar ”mold clamping force 50 ton injection amount 80 cm ³ machine number 1133 B.A. Mold: Terminal block separator 50.5mm × 74mm
× 5 mm C.I. Molding conditions Temperature: Nozzle Front heater Central heater Rear heater 200 ° C Mold 60 ° C Injection pressure: 65-55kg / cm ² Back pressure: 6kg / cm ²
Injection speed: 100% Mold filling amount: 11.5g
Molding cycle: 27 seconds (injection time: 5 seconds, cooling time: 15 seconds, mold opening / clamping time: 7 seconds) The following components were used in each of the examples and comparative examples.

(A) Styrene 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 1220SL)}
Was dissolved in the following mixture to give a uniform solution. Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-Methylstyrene dimer (chain transfer agent) 0.27% by weight 1,1-bis (t-butylperoxy) -3, 3,5-Trimethylcyclohexane (polymerization initiator) 0.03% by weight Then, the above mixture was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage was stirred at 190 rpm, 126 rpm.
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
m, 140 ° C., and polymerization was performed at 20 rpm and 155 ° C. in the fourth stage. 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 aromatic vinyl resin (referred to as HIPS). As a result of analyzing the obtained rubber-modified aromatic vinyl resin, the rubber content was 1
The weight average particle diameter of the rubber was 2.1 μm, the reduced viscosity ηsp / c was 0.53 dl / g.

Rubber-unmodified styrenic resin [polystyrene (GPPS)] Commercially available polystyrene (weight average molecular weight 270,000, number average molecular weight 120,000) [(Asahi Kasei Co., Ltd. (hereinafter GPPS
)] Was used. (B) Manufacture of polyphenylene ether (PPE) After the inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor and having a cooling coil and stirring blades inside was sufficiently replaced with nitrogen, cupric bromide was used. 54.8 g, di-n-
Butylamine 1110 g and toluene 20 liters, n
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of 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 90 minutes while controlling the internal temperature to 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A mixed solution of methanol / hydrochloric acid was added thereto to decompose the remaining catalyst in the polymer, further sufficiently washed with methanol, and dried to obtain a powdered polyphenylene ether (referred to as PPE). Reduced viscosity η _sp is 0.41 dl
/ G.

(C) Aromatic Phosphate Ester (Component C) Triphenyl Phosphate (TPP) Commercially available aromatic phosphate ester [manufactured by Daihachi Chemical Industry Co., Ltd.,
Trade name TPP (referred to as TPP)] was used. Alkyl group-substituted aromatic phosphate ester (FR-1)
287.3 parts by weight of nonylphenol (molar ratio 2.0),
0.87 parts by weight of aluminum chloride (molar ratio 0.01) was placed in a flask, and 100 parts by weight of phosphorus oxychloride (molar ratio 1.0) was added dropwise at 90 ° C. over 1 hour. 61.4 parts by weight of phenol (molar ratio 1.0) was added to the resulting intermediate, and further reacted. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Next, the reaction product is cooled, washed with water to remove the catalyst and chlorine, and mixed with a phosphate mixture (hereinafter referred to as F).
R-1). This mixture was mixed with GPC (gel permeation chromatography Tosoh Corp., H
LC-8020) mobile phase tetrahydrofuran analysis revealed that bisnonylphenyl phenyl phosphate (hereinafter referred to as DNP), trisnonylphenyl phosphate (hereinafter referred to as TNPP) and nonylphenyl diphenyl phosphate (hereinafter referred to as NDP).
) And nonylphenol, and the weight ratio was 77.8 / 11.3. / 8.4 / 2.5, respectively.

The average total carbon number of the substituents is 1
7.9 (18 × 0.778 + 27 × 0.113 +
9 × 0.084 = 17.9) Production of Alkyl Group Substituted Aromatic Phosphate Ester (FR-2) In the production of FR-1, 1 mol of phosphorus oxychloride was substituted with 3 mol of phenol or nonylphenol instead of phenol. The same experiment was performed, except that nonylphenol was used and that the reaction was a one-step reaction by simultaneous addition. When the reaction product thus obtained was analyzed by GPC,
It was 100% of trisnonylphenyl phosphate (referred to as TNPP). The average of the total number of carbon atoms of the substituent is 27.0.

Production of Alkyl Group-Substituted Aromatic Phosphate Ester (FR-3) In the production of FR-1, 2 moles of phenol was replaced with 2 moles of phenol instead of 2 moles of nonylphenol. The same experiment was performed except that 1 mol of nonylphenol was used instead of.
The phosphoric acid ester mixture thus obtained was treated with FR-
No. 3. When this mixture was analyzed by GPC, it was found to be nonylphenyl diphenyl phosphate (N
(Referred to as DP), DNP, TPP and nonylphenol in a weight ratio of 77.8 / 11.3. / 8.
It was 4 / 2.5. The average of the total carbon numbers of the substituents is 9.0 (9 × 0.778 + 18 × 0.113).
= 9.0).

Examples 1 to 3 and Comparative Examples 1 to 4 HIPS / GPPS / PPE / aromatic phosphates listed in Table 1 were mixed at a weight ratio of 65/37/7/7,
Side-screw twin screw extruder (Werner Pf
ZSK-40mmφ manufactured by Leiderer,
Melt extrusion was performed. That is, PPE / G is used in front of the extruder.
PPS is melted at 320 ° C., and the remaining resin component and aromatic phosphate are side-fed at a later stage, and the rotation speed is 295.
Melt kneading was carried out at 240 ° C. at an rpm of 80 kg / h. Cylinder temperature of the pellets thus obtained was 2 using an injection molding machine [Toshiba Machinery Co., Ltd. model IS80A].
Test pieces were prepared under the conditions of 30 ° C. and mold temperature of 60 ° C., and the volatility and flame retardancy were evaluated. Table 1 and FIG. 1 show the results. In addition, as described in the section of the above measurement method, 25
Continuous 10,000-shot molding was performed under a temperature condition of 0 ° C. Table 1
Also, according to FIG. 1, when the total number of carbon atoms of the substituents of the aromatic phosphoric acid ester is in the range of 12 to 25 on average, the flame-retardant and continuous moldability (low volatility) balance characteristics are excellent. I know that

[0051]

[Table 1]

Examples 4 to 7 and Comparative Examples 5 and 6 Test pieces were prepared from the compositions shown in Table 2 in the same manner as in Example 1, and MFR, Izod impact strength, surface impact strength, tensile strength, and tensile strength were measured. Elongation, flexural strength, flexural modulus, heat distortion temperature, Vicat softening temperature and flame retardancy were evaluated. The results are shown in Table 2 and FIG.

[0053]

[Table 2]

According to Table 2 and FIG. 2, PPE is 1 to 15.
It can be seen that the balance properties of fluidity, heat resistance, rigidity, impact strength and flame retardancy are remarkably improved when the parts by weight are present.

[0055]

Industrial Applicability The composition of the present invention is a drip-proof flame-retardant resin composition having a remarkably small mold deposit even after continuous molding for a long period of time, and having excellent impact resistance, rigidity, heat resistance and fluidity. . This composition is suitable for home electric appliance parts, office automation equipment parts, etc., and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 is an average value of the total number of carbon atoms of a substituent of an aromatic phosphoric acid ester and the flame retardancy of a molded article of a resin composition (extinction time:
It is a figure showing the relationship with the second).

FIG. 2 is a diagram showing the relationship among the number of parts of PPE added in 100 parts by weight of a resin component composed of components A and B, MFR, Vicat softening temperature, and flame retardancy.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C08L 51/04 71:12)

Claims (1)

[Claims] 1. A rubber-modified styrene resin (component A) 65.
~ 98 parts by weight, polyphenylene ether (component B) 1 ~
A low-volatility dripping flame-retardant resin composition having excellent heat resistance, which contains 15 parts by weight and 1 to 20 parts by weight of an aromatic phosphate ester (component C) represented by the following general formula (1). Embedded image (In the formula, a, b, and c are 1 to 3, R ¹ , R ² , and R ³ are hydrogen or a hydrocarbon having 1 to 30 carbon atoms, and the substituents R ¹ , R ² , and R are the whole compound. The total number of carbon atoms of ³ is 12 to 25. Here, in the case of comprising a plurality of aromatic phosphates having different substituents, the carbon atoms of the substituents R ¹ , R ² and R ³ of the B component are The total number is represented by a number average and is the sum of the products of the weight fraction of each aromatic phosphate ester component in the B component and the total carbon number of the substituents of each component.)