JPH11100513A - Dropping type flame resistant molding material containing fluororesin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material contg. a fluororesin and having dropping type flame resistance. SOLUTION: This molding material comprises 100 pts.wt. thermoplastic resin (A), 1-100 pts.wt. fire retardant (B), and a fluororesin (C) and the content of (C) is a possible quantity of titration in the combustion test at 0.5 mm thick of VB(vertical Burning) method in accordance to the UL-94 specification (pref. 0.001-10 wt.%). Mostly, (A) is a styrene resin and/or a polyphenylene ether resin, (B) is an arom. phosphoric acid ester, and the total content of an arom. vinyl monomer and the dimer and trimer of the arom. vinyl monomer remained in the molding material is not greater than 1 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant molding material containing a fluorine resin. More specifically, the present invention relates to a drop-type flame-retardant molding material containing a fluororesin.

[0002]

2. Description of the Related Art Thermoplastic resins are used in various fields including automobile parts, home electric parts, OA equipment parts and the like because of their excellent moldability and excellent impact resistance. In addition, the flammability of thermoplastic resins limits their use.

As a method for making a thermoplastic resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to the thermoplastic resin. I have. However, in recent years, the demand for fire safety has been intensely highlighted, and home appliances, O
The regulations of the UL (Underwriters Laboratory) vertical combustion test for A equipment etc. have become more stringent over the years, and the thickness of products and parts has been reduced in order to reduce weight and improve economical efficiency. So, when burning, the fire drops,
For this reason, other products and parts may be damaged, and there is a strong demand for the development of a technique for preventing the spread of fire due to the fall of the fire. As a technique for preventing the spread of fire from dropping fire, a method of increasing the amount of flame retardant is known.However, using a large amount of expensive flame retardant is not only economical but also causes environmental problems and lowers mechanical properties. Is not preferred to promote

[0004] As a conventional technique for preventing a fire from dropping from a fire of a thermoplastic resin, a technique of blending polytetrafluoroethylene (PTFE) with a flame retardant in a styrene resin and / or polyphenylene ether is disclosed (US Pat. No. 4,107,232; 4332714, 435512
6). Since the above-mentioned publication is a flame-retardant composition having no dripping of fire, PTFE is usually added in an amount of 0.1 part by weight or more based on 100 parts by weight of the resin component. For this reason, there is a problem that fibrillation proceeds excessively during the production of the resin composition, so that melt extrusion becomes unstable, and appearance and fluidity are reduced. Japanese Patent Application Laid-Open No. 8-22539 discloses a PTF.
About E, "Using a commercially available processing device, PP
It is difficult to mix as a pure additive in the E resin composition and to melt and mix it. For example, the operability is poor such as adhesion to a flight of a screw of an extruder. Further, PTFE may remain as an unmelted white point in the resin composition. And other problems.

The inventor of the present invention has overcome the above-mentioned problems by suppressing the spread of fire due to a falling fire by delaying the dropping of the fire of a molding material having a specific thickness using PTFE. This fact is not disclosed in the above four publications,
Not even implied.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not have the above-mentioned problems, that is, it prevents the spread of fire due to the dripping of molten metal during combustion, and provides flame retardancy, appearance and impact resistance. It is an object of the present invention to provide a molding material having excellent heat resistance and fluidity.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the prevention of fire spread due to melting and dripping during the burning of a thermoplastic resin molding material. As a result, a flame retardant and a specific amount of a fluorine-based material were added to the thermoplastic resin. By adding the resin, surprisingly flame retardant, especially while preventing the spread of fire due to melt dripping,
The inventors have found that the fluidity and appearance are dramatically improved, and have completed the present invention.

That is, the present invention relates to (A) a thermoplastic resin 100
(B) 1 to 100 parts by weight of a flame retardant,
(C) In a molding material comprising a fluororesin, UL-
A dripping-type flame-retardant molding material containing a fluororesin, characterized by containing a droppable amount of (C) in a combustion test at a thickness of 0.5 mm by the VB (Vertical Burning) method conforming to the 94 standard. (A) is a styrene-based resin and / or polyphenylene ether, (B) is an aromatic phosphate, and an aromatic vinyl monomer remaining in the molding material and a dimer of the aromatic vinyl monomer; An object of the present invention is to provide a fluorine-containing resin-containing drop-type flame-retardant molding material having a total content of trimers of 1% by weight or less.

Hereinafter, the present invention will be described in detail.

The present invention is a drip-type flame-retardant molding material comprising (A) a thermoplastic resin, (B) a flame retardant, and (C) a fluororesin.

The above (A) is a main component of the molding resin composition and plays a role in maintaining the strength of the molded article, and (B) is a component for imparting flame retardancy to the resin component, and (C) ) Is a component for suppressing the spread of fire due to the dropped fire by delaying the dropping of the fire.

Here, VB conforming to the UL-94 standard is used.
It is important to contain a droppable amount of (C) in a 0.5 mm thick burning test by the (Vertical Burning) method.
For example, (C) may be added in an amount of 0.1 to 100 parts by weight of (A).
When the amount is in the range of 001 to 10 parts by weight, dropping of the fire is delayed, so that the falling fire has a self-extinguishing property, and it is possible to suppress the spread of fire by the fire. (C) is 0.00
If it is less than 1, the effect of delaying the drop of the fire is small, and the fire tends to drip and spread in the early stage of combustion, while (C) is 1
When the amount exceeds 0 parts by weight, the dripping of the fire is suppressed, so that the energy given from the outside is stored in the molded body and the combustion is continued, and the appearance is deteriorated due to excessive (C) fibrils. In addition, the melt viscosity of the resin tends to increase. The present inventor, by the fire drop control technology of the present application,
The inventors have found that flame retardancy is achieved by releasing energy given from the outside, and the present invention has been completed.

In the present invention, (A) the thermoplastic resin comprises:
There is no particular limitation as long as it is compatible with or homogeneously dispersed with (B). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. . Here, a polyphenylene ether-based, polystyrene-based, or polycarbonate-based thermoplastic resin is particularly preferable as the thermoplastic resin.

The styrenic resin (A-
1) is a rubber-modified styrenic resin and / or a non-rubber-modified styrenic resin, and particularly preferably comprises a rubber-modified styrenic resin alone or a rubber-modified styrenic resin and a non-rubber-modified styrenic resin; There is no particular limitation as long as it is compatible with or homogeneously dispersed with (C).
The rubber-modified styrenic resin refers to a polymer in which a rubbery polymer is dispersed in a matrix in a matrix composed of a vinyl aromatic polymer, and an aromatic vinyl monomer is present in the presence of the rubbery polymer. The monomer and, if necessary, a vinyl monomer copolymerizable therewith, are added, and the monomer mixture is obtained by known polymerization methods such as bulk polymerization, emulsion polymerization, and suspension polymerization.

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

Here, the rubbery polymer preferably has a glass transition temperature (Tg) of -30 ° C. or less.
If it exceeds 30 ° C., the impact resistance tends to decrease.

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

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or the like. Yes, styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

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 in (A-1). When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

If it is necessary to lower the melt viscosity during blending, an acrylate comprising 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, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as 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 from 0 to 40.
% By weight.

The rubbery polymer in the rubber-modified styrenic resin is preferably 5 to 80% by weight, particularly preferably 1 to 80% by weight.
0 to 50% by weight, a graft-polymerizable monomer mixture,
Preferably 95 to 20% by weight, more preferably 90 to 5% by weight.
It is in the range of 0% by weight. Within this range, the balance between impact resistance and rigidity of the target resin composition is improved. Further, the rubber particle diameter of the styrene-based polymer is 0.1 to 5.0.
μm is preferred, and 0.2 to 3.0 μm is particularly preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c of the resin portion, which is a measure of the molecular weight of the rubber-modified styrenic resin (0.5 g / dl,
30 ° C. measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer)
It is preferably in the range of 0.30 to 0.80 dl / g, and more preferably in the range of 0.40 to 0.60 dl / g. Reduced viscosity ηsp of rubber-modified styrenic resin
Means for satisfying the above requirement regarding / c include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent. In the present invention, another polyphenylene ether (A-2) of (A) is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (1).

[0023]

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(However, R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbon and substituted hydrocarbon groups, and may be the same or different. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Preferred, especially poly (2,6-dimethyl-1,4-phenylene ether)
Is preferred. The method for producing the polyphenylene ether is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol Can be easily produced by oxidative polymerization, and in addition, U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357, U.S. Patent No. 3,257,358, and 52-1
It can be easily produced by the methods described in JP-A-7880 and JP-A-50-51197. The reduced viscosity ηsp / c of the polyphenylene ether used in the present invention (0.5
g / dl, chloroform solution, measured at 30 ° C) is 0.2
It is preferably in the range of 0 to 0.70 dl / g,
More preferably, it is in the range of 0.30 to 0.60 dl / g. Reduced viscosity ηsp / c of polyphenylene ether
Means for satisfying the above requirements include adjustment of the amount of catalyst in the production of the polyphenylene ether.

In the present invention, the amount occupied by (A-1) in 100 parts by weight of the resin component consisting of (A-1) and (A-2) is one of the preferable combinations of thermoplastic resins.
1 to 99% by weight, preferably 1 to 50% by weight, more preferably 3 to 40% by weight, most preferably 5 to 5% by weight.
25% by weight.

The aromatic polycarbonate as one of the thermoplastic resins (A) in the present invention can be selected from aromatic homopolycarbonates and aromatic copolycarbonates. The production method includes a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of a caustic alkali and a solvent, or a transesterification method in which a bifunctional phenolic compound is transesterified with diethyl carbonate in the presence of a catalyst. Can be mentioned. The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000. Here, the bifunctional phenolic compound is
2,2′-bis (4-hydroxyphenyl) propane,
2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis ( 4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3,5-diphenyl) butane, 2,2′-bis (4-hydroxy-3,
5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4-hydroxyphenyl) ethane, and especially 2,2′-bis (4-Hydroxyphenyl) propane [bisphenol A] is preferred. In the present invention, the bifunctional phenolic compounds may be used alone or in combination.

The flame retardant used as (B) in the present invention is a halogen-based, phosphorus-based or inorganic flame retardant.

The halogen-based flame retardant (B) is as follows:
Halogenated bisphenols, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, and the like, preferably decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromo Oligomer of bisphenol A, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene,
Brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphoric acid ester, fluorine resin and the like.

As the phosphorus-based flame retardant in the above (B),
Organic phosphorus compounds, red phosphorus, inorganic phosphates and the like can be mentioned.

Examples of the above-mentioned organic phosphorus compounds include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate, phosphite and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate.

Here, as the organic phosphorus compound, an aromatic phosphate ester monomer represented by the following formula (2) and an aromatic phosphate ester condensate represented by the following formula (3) are particularly preferred.

[0032]

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[0033]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r _5, Ar _7, Ar ₈ is an aromatic group selected from at least one phenyl group substituted with an unsubstituted or a hydrocarbon group having 1 to 10 carbon atoms independently. Ar ₆ is a divalent aromatic group having 6 to 20 carbon atoms. m represents an integer of 1 or more. Among the above aromatic phosphate ester monomers, one or two or more phenols may be used, particularly, in a hydroxyl group-containing aromatic phosphate ester monomer, for example, tricresyl phosphate or triphenyl phosphate. Phosphoric acid ester monomer containing a hydroxyl group, or the following formula (4)
Are preferred.

[0035]

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(Where a, b, and c are 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or an alkyl group 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 30 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. In the present invention, among the aromatic phosphate ester monomers, the number average of the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 1
5-30 are preferable, and 20-30 are more preferable,
25 to 30 are most preferred.

Specific substituents include butyl such as nonyl and t-butyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, decyl, undecyl, dodecyl and tridecyl. Pentadecyl group, pentadecyl group, hexadecyl group, heptadecyl group, otadecyl group, nonadecyl group, octadodecyl group and the like.
It can be produced by a known method disclosed in, for example, JP-A-294284. For example, there is a method of reacting an alkylphenol, phosphorus oxychloride, and anhydrous aluminum chloride as a catalyst under heating, or a method of oxidizing a phosphite triester with oxygen to convert it to a corresponding aromatic phosphate.

Among the above aromatic phosphate ester condensates, bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate) and the like are particularly preferable.

Another preferred aromatic phosphate condensate used as (B) in the present invention is represented by the following formula (5).

[0040]

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(Where a, b, c, d, and e are 0 to 3, R ¹ to R ⁵ are hydrocarbons having 1 to 10 carbon atoms, and n represents an integer of 1 to 3) The flame retardant is particularly preferably a condensate of an aromatic phosphate ester substituted at the 2,6-position, and can be produced by a known method disclosed in JP-A-5-1079. For example, a monofunctional phenol substituted at the 2,6-position is reacted with phosphorus oxyhalide in the presence of a Lewis acid catalyst to obtain a diaryl phosphorohalide, which is then reacted with a bifunctional phenol in the presence of a Lewis acid catalyst. There is a way to react.

In the above (B), red phosphorus, which is one of the phosphorus-based flame retardants, is not limited to ordinary red phosphorus, but its surface is previously selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. Coated with a metal hydroxide coating, coated with a coating composed of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, and a thermosetting resin , Aluminum hydroxide, magnesium hydroxide,
Examples thereof include those obtained by double-coating a thermosetting resin film on a metal hydroxide film selected from zinc hydroxide and titanium hydroxide.

In the above (B), one of the inorganic phosphates of the phosphorus-based flame retardant is typically ammonium polyphosphate.

The inorganic flame retardant (B) includes aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide. And hydrates of inorganic metal compounds such as hydrates of, for example, 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 particularly good flame retardant effects and are economically advantageous.

In the present invention, the amount of (B) added is
(A) 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 100 parts by weight with respect to 100 parts by weight.
20 parts by weight, most preferably 5 to 15 parts by weight.

In the present invention, the fluorine resin used as (C) is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene,
Polydifluoroethylene, polytrifluoroethylene,
Examples thereof include polytetrafluoroethylene and a tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The method for producing these fluororesins is described in US Pat. No. 2,393,697 and US Pat.
No. 534,058, for example, using tetrafluoroethylene in an aqueous medium with a radical initiator such as ammonium persulfate and potassium persulfate in an amount of 7 to 70 kg.
The polymerization is carried out at a temperature of from 0 to 200 ° C. under a pressure of / cm ² and then a polytetrafluoroethylene powder is obtained by coagulation from a suspension, dispersion or emulsion or by precipitation.

The method of compounding the fluorine-based resin is to melt-knead the fluorine-based resin, the thermoplastic resin and, if necessary, the dispersant to prepare a master batch, and then melt-knead the thermoplastic resin and the flame retardant. Using a two-stage extruder, or a two-stage extruder capable of side-feeding, melt-kneading the thermoplastic resin and fluorine-based resin and, if necessary, the first stage, and lowering the melting temperature in the second stage to reduce the flame retardant Or a single-stage process of feeding and melt-kneading, or a single-stage process of feeding all components including the fluororesin to the main feeder and melting and kneading. Here, a two-stage process for producing a master batch is preferable from the viewpoint of flame retardancy.

In the present invention, in particular, when further improvement in flame retardancy and heat resistance is required, (D) a novolak resin can be blended. When (D) is used in combination with an aromatic phosphate, it is also an agent for improving fluidity and heat resistance, and slightly reduces the compatibility between the resin component and the aromatic phosphate. 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. Polyaddition ”p.437-
455 (Kyoritsu Shuppan Co., Ltd.) ".

An example of the production of a novolak resin is shown in the following formulas (6) and (7).

[0051]

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The above phenols include phenol, o-cresol, m-cresol, p-cresol, 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-hydroxybenzene Sulfonic 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 include formaldehyde,
Acetaldehyde, n-propanal, n-butanal, isopropanal, isobutyraldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylacetaldehyde and the like.

In the present invention, if necessary, one or more compounds selected from saturated higher aliphatic carboxylic acids or metal salts thereof, carboxylic acid ester waxes, organosiloxane waxes, polyolefin waxes and polycaprolactone And (E) a release agent.

Among the above (E), one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof are preferred.

The carboxylic acid of the saturated higher fatty acid is preferably a straight-chain saturated monocarboxylic acid having 12 to 42 carbon atoms. For example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like can be mentioned. Examples of the metal of these metal salts include lithium, sodium, potassium, magnesium, calcium, aluminum, zinc and the like, and particularly preferred are zinc stearate, magnesium stearate, calcium stearate, and aluminum stearate.

The amount of (E) is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight of (A).
0.1 to 5 parts by weight, most preferably 0.3 to 1 part by weight.

In the present invention, if necessary, one or more flame retardant aids (F) selected from triazine skeleton-containing compounds, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, and polyacrylonitrile fibers are blended. can do.

The amount of (F) is preferably from 0.001 to 40 parts by weight, more preferably from 1 to 20 parts by weight, most preferably from 5 to 10 parts by weight, per 100 parts by weight of (A). is there.

The triazine skeleton-containing compound (F) is a component for further improving the flame retardancy as a flame retardant aid of the phosphorus-based flame retardant. Specific examples thereof include melamine, melam represented by the following formula (8), melem represented by the following formula (9), melon (a product obtained by deammonating three to three molecules of melem at 600 ° C. or higher), and the following formula: (1
0) Melamine cyanurate represented by the following formula (11)
Melamine phosphate represented by the following formula (12), succinoguanamine represented by the following formula (12), adipoguanamine, methylglutalogamine, a melamine resin represented by the following formula (13), a BT resin represented by the following formula (14), etc. Although melamine cyanurate is particularly preferable from the viewpoint of low volatility.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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The metal-containing compound as (F) is a metal oxide and / or 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,
It is a simple substance such as tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, or a composite (alloy) thereof, and the metal powder is aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, It is a simple substance of chromium, nickel, copper, tungsten, tin, antimony or the like, or a composite thereof.

The silicone resin (F) is made of SiO
₂ , a silicone resin having a three-dimensional network structure formed by combining structural units of 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 substituent. Here, a silicone resin containing a vinyl group is particularly preferable.

Such a silicone resin can be obtained by co-hydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.

The silicone oil (F) is a polydiorganosiloxane, particularly preferably a vinyl-containing silicone oil, and comprises a chemical bond unit represented by the following formula (15).

[0072]

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R in the above formula is a C1-8 alkyl group, C
It is one or more substituents selected from aryl groups of 6 to 13 and vinyl-containing groups represented by the following formulas (16) and (17), and particularly contains a vinyl group in the molecule.

[0074]

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[0075]

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The vinyl-containing silicone oil has a viscosity of 600 to 1,000,000 centistokes (25
C.), more preferably 90000 to 150 ° C.
000 centistokes (25 ° C.).

The silica as (F) is an amorphous silicon dioxide, particularly preferably a silica coated with a hydrocarbon compound, the surface of which is treated with a hydrocarbon compound silane coupling agent. The hydrocarbon compound-coated silica contained is preferred.

The silane coupling agent may be a vinyl such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Group-containing silane, epoxy silane 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
Aminosilane such as -phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit similar in structure to the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is preferable for a styrene-based resin.

The treatment of the silica surface with the silane coupling agent 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.The dry method is a method in which silica is charged into a high-speed stirring device such as a Henschel mixer and stirred. This is a method in which a silane coupling agent solution is slowly dropped while performing a heat treatment.

The aramid fiber as (F) preferably has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. Isophthalamide or polyparaphenylene terephthalamide is converted to an amide polar solvent or sulfuric acid. And solution spinning by a wet or dry method.

The polyacrylonitrile fiber (F) has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 500 μm.
It is preferably 10 mm, and 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 wet spinning is performed by dissolving the polymer in a solvent such as nitric acid and wet spinning in water. It is manufactured by the method.

In the present invention, if necessary, a copolymer resin comprising an aromatic vinyl unit and an acrylic 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) selected from soaps can be blended.

The amount of (G) is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of (A).
0.5 to 10 parts by weight, most preferably 1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin (G) is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene And the like, and styrene is most preferred, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. The acrylate unit is an acrylate ester having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate.

Here, the content of the acrylate unit in the copolymer resin is preferably 3 to 40% by weight.
5-20% by weight is preferred. Also, the solution viscosity (MEK of 10% by weight of resin) which is an index of the molecular weight of the copolymer resin is used.
(Solution, measurement temperature 25 ° C.) is preferably 2 to 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength decreases, while if it exceeds 10 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aid as (G) includes liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

The higher fatty acids as (G) include saturated fatty acids other than those described in the section of (E) mold release agent, and unsaturated fatty acids such as ricinoleic acid, ricinberidic acid and 9-oxy-12-octadecenoic acid. It is.

The higher fatty acid ester as (G) is a monohydric alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, or a monohydric alcohol ester of a polybasic acid such as diester stearate of diphenylstearyl phthalate. And sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, sorbitan triolate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate , Sorbitan esters such as polyoxyethylene sorbitan monooleate, monoglyceride stearate,
Fatty acid esters of glycerin monomers such as oleic acid monoglyceride, capric acid monoglyceride, behenic acid monoglyceride, polyglycerin fatty acid esters such as polyglycerin stearate, polyglycerin oleate, polyglycerin laurate, and polyoxyethylene mono 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.

The higher fatty acid amide as (G) includes monoamides of saturated fatty acids such as phenylstearic acid amide, methylolstearic acid amide, methylolbehenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, and coconut oil fatty acid diethanolamide. And N, N′-substituted monoamides such as oleic acid diethanolamide and the like.
Saturated fatty acid bisamides such as (hydroxyphenyl) stearamide, ethylenebis (stearic acid amide), ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-xylylenebis (12
-Hydroxyphenyl) stearic acid amide and the like.

The higher aliphatic alcohol as (G) is
Monohydric alcohols such as stearyl alcohol and cetyl alcohol; polyhydric alcohols such as sorbitol and mannitol; and polyoxyethylene dodecylamine and polyoxyethylene bactadecylamine. Allylated ethers having an alkylene ether unit, polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl phenyl ether such as ethylene octyl phenyl ether and 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 as (G) is a metal salt of a higher fatty acid such as stearic acid described above, such as barium, calcium, zinc, aluminum or magnesium.

In the present invention, if necessary, a thermoplastic elastomer (H) can be blended. Examples thereof include polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene, and polyvinyl chloride. And the like, and a polystyrene-based thermoplastic elastomer is particularly preferable.

The amount of (H) is preferably 0.5 to 20 parts by weight, more preferably 100 parts by weight of (A).
It is 1 to 10 parts by weight, most preferably 2 to 5 parts by weight.

The above-mentioned polystyrene-based thermoplastic elastomer is a block copolymer composed of an aromatic vinyl unit and a conjugated diene unit, or a block copolymer in which the conjugated diene unit is partially hydrogenated.

The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromobenzene. Styrene is the most preferable, and styrene is most preferable. However, other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

The conjugated diene monomer constituting the block copolymer includes 1,3-butadiene, isoprene and the like.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or a partially hydrogenated unit thereof is represented by B. When displaying with,
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
A block copolymer or (SB) nX (where n is 3 to 6)
Integer. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound. It is preferable to use a star-shaped (star) block copolymer having a B-part as a bonding center. Above all, SB type 2 and SBS 3
And SBSB type 4 linear block copolymers are preferred.

In the present invention, when light resistance is required, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, a halogen scavenger, a light shielding agent, a metal deactivator, or a quencher may be used, if necessary. One or more lightfastness improvers (I) selected from agents can be blended.

The amount of (I) is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 1 to 5 parts by weight, per 100 parts by weight of (A). Department.

The method for producing the resin composition of the present invention includes:
(A-1) First, a styrene resin and (A-2) are melted,
Then, (B) and (C) are added and melt-kneaded in the same extruder, or (A-1) a styrene resin, (A-1)
-2) or a method of manufacturing a master batch containing (C) as necessary, and kneading the master batch with the remaining styrene resin or the remaining (B).

Regarding the twin-screw extruder used in the production of the flame-retardant resin composition of the present invention, especially when polyphenylene ether is contained, the ratio L / D of the screw length L to the cylinder inner diameter D is 20 to 20. 50, and has two or more supply openings of a main feed opening and a side feed opening which are different in the distance from the tip of the twin-screw extruder. It is preferable that a kneading portion is provided between the portions and between the distal end portion and the supply opening located at a short distance from the distal end portion, and the length of the kneading portion is D to 10D, respectively.

Examples of preferred compositions of the flame-retardant resin composition of the present invention include the following. Consisting of a rubber-modified styrene resin and a rubber-unmodified styrene resin,
10 to 90% by weight of the styrene resin (A-1);
2) With respect to 100 parts by weight of a resin component comprising 90 to 10% by weight of polyphenylene ether, (B) 5 to 15 parts by weight of an aromatic phosphate ester, and (C) 0.03 to 0.3 parts by weight of polytetrafluoroethylene. .

In the case of the above composition, excellent balance of flame retardancy, especially drop-type flame retardancy, appearance, continuous moldability, moldability (fluidity), impact resistance and heat resistance.

The composition thus obtained is, for example,
It can be continuously molded for a long time using an injection molding machine or an extrusion molding machine, and the obtained molded product has excellent flame retardancy (drop-type flame retardancy), fluidity, heat resistance and impact resistance ing.

[0105]

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 the examples and comparative examples were performed using the following methods or measuring instruments.

(1) Reduced viscosity of rubber-modified styrene resin and polyphenylene ether ηsp / C A mixed solvent of 18 ml of methyl ethyl ketone and 2 ml of methanol was added to 1 g of the rubber-modified styrene resin and shaken at 25 ° C. for 2 hours.
Centrifuge at 18000 rpm for 30 minutes. The supernatant was taken out and the resin component was precipitated with methanol and then dried.

0.1 g of the resin thus obtained was
In the case of rubber-modified polystyrene, it is dissolved in toluene, and in the case of rubber-modified acrylonitrile-styrene copolymer resin, it is dissolved in methyl ethyl ketone to obtain a solution having a concentration of 0.5 g / dl. The solution falling time T ₁ (second) was measured at 30 ° C. On the other hand, the falling time T ₀ (second) of pure toluene or pure methyl ethyl ketone 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) On the other hand, regarding the reduced viscosity ηsp / C of polyphenylene ether, 0.1 g was dissolved in chloroform and the concentration was reduced. 0.
A solution of 5 g / dl was prepared and measured in the same manner as above.

(2) Analysis of Flame Retardant 5 g of the resin composition is dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge. (20,000r
pm, 1 hour) Then, 2 ml was added to the supernatant obtained by separation.
A double amount of methanol was added to precipitate a resin component, and the solution portion and the resin portion were separated using an ultracentrifuge. For the solution part, use GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan;
HLC-8020; column, manufactured by Tosoh Corporation, two G1000HXL; mobile phase, tetrahydrofuran; flow rate, 0.8 ml / min; pressure, 60 kg
f / cm ² ; temperature INLET 35 ° C, OVEN 4
0 ° C., RI 35 ° C .; sample loop 100 ml; injected sample amount 0.08 g / 20 ml], and the area ratio of each component on the chromatogram is assumed to be the weight fraction of each component, and the phosphate ratio is determined from the area ratio. And residual aromatic vinyl monomer and dimer and 3 of aromatic vinyl monomer
The composition and amount of the monomer were determined. On the other hand, regarding the above resin portion, a Fourier transform nuclear magnetic resonance apparatus (proton-FT-
NMR), the ratio of the integral value of the aromatic proton or the aliphatic proton was determined, and the amounts of the rubber-modified styrene resin and the thermoplastic resin such as polyphenylene ether were determined.

(3) Volatility evaluation (thermogravimetric balance test: TG
Method A) Using a Shimadzu thermal analyzer DT-40 manufactured by Shimadzu Corporation of Japan, the temperature was raised at 40 ° C./min under a nitrogen stream, and the 1% by weight temperature was used as a measure of volatility.

(4) Izod Impact Strength Measured at 23 ° C. by a method according to ASTM-D256.

(V-Notch, 1/4 inch Test Specimen) (5) Vicat Softening Temperature Measured by a method in accordance with ASTM-D1525, and used as a measure of heat resistance.

(6) Melt flow rate (MFR) The melt flow rate was measured by a method in accordance with ASTM-D1238 as an index of melt fluidity. It was determined from the extruded amount per 10 minutes (g / 10 minutes) under the conditions of a load of 5 kg and a melting temperature of 200 ° C.

(7) Flame retardancy and fire-dropping fire spreadability VB (Vertical Bur) conforming to UL-94
ning) method. (0.5 mm Thickness Specimen) In addition, in order to evaluate the dropping fire spread of the fire, a metal plate was placed at a distance of 12 ″ from the lower part of the test specimen, and the extinction time of the dropped fire was measured.

The following components were used in Examples and Comparative Examples.

(A) Styrene resin Rubber-modified styrene resin (HIPS) polybutadiene (weight ratio of cis 1,4 bond / trans 1,4 bond / 1 vinyl 1,2 bond = 95/2/3) (Nippon Zeon ( Co., Ltd., brand name Nipol 122 OSL)｝
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 0.27% by weight t-butylperoxyisopropyl carbonate 0.03% by weight Is continuously supplied to a series four-stage reactor equipped with a stirrer, and the first stage has a stirring speed of 190 rpm and 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 led to a devolatilizer to remove unreacted monomers and a solvent to obtain a rubber-modified aromatic vinyl resin (referred to as HIPS-1). As a result of analyzing the obtained rubber-modified aromatic vinyl resin, the rubber content was 12.1% by weight, and the weight average particle diameter of the rubber was 1.5 μm.
m, and the reduced viscosity ηsp / c was 0.53 dl / g.

Further, rubber-modified styrene resins having different reduced viscosities ηsp / c were produced by adjusting the amount of the polymerization initiator, the polymerization temperature and the amount of the chain transfer agent. The results are shown in Table 2.

In the examples and comparative examples, the following HIPS
Was used. (Tables 1 and 2) HIPS-1: polybutadiene rubber, rubber content is 12.
HIPS-2: polybutadiene rubber, rubber content: 1% by weight, rubber weight average particle size: 1.5 μm, reduced viscosity ηsp / c: 0.53 dl / g
HIPS-3: polybutadiene rubber, rubber content: 1% by weight, rubber weight average particle diameter: 1.5 μm, reduced viscosity ηsp / c: 0.79 dl / g
HIPS-4: polybutadiene rubber, rubber content: 1% by weight, rubber weight average particle diameter: 1.5 μm, reduced viscosity ηsp / c: 0.60 dl / g
HIPS-5: polybutadiene rubber, rubber content: 1% by weight, rubber weight average particle size: 1.5 μm, reduced viscosity ηsp / c: 0.58 dl / g
1 wt%, rubber weight average particle size is 1.5 μm, reduced viscosity ηsp / c is 0.40 dl / g HIPS-6: rubber content is 12.1 wt%, rubber weight average particle size is 1.5 μm, The reduced viscosity ηsp / c is 0.3
5 dl / g Non-rubber-modified styrene resin (GPPS) Polystyrene having a weight average molecular weight of 200,000 (produced by Asahi Kasei Kogyo Co., Ltd.) was used (referred to as GPPS).

(B) Polyphenylene ether (PPE)
After the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor and having a cooling coil and stirring blades inside was sufficiently replaced with nitrogen, 54.8 g of cupric bromide, di-n-
1110 g of butylamine and 20 liters of toluene,
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 the 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 powdery polyphenylene ether (referred to as PPE-1). The reduced viscosity ηsp / C was 0.41 dl / g.

Further, polyphenylene ethers having different reduced viscosities ηsp / c were produced by adjusting the amount of catalyst or controlling the polymerization time in the production of polyphenylene ether. Table 3 shows the results.

(C) Phosphorus-based flame retardant (1) 1,3-phenylene bis (diphenyl phosphate) (FR-1) Commercially available resorcinol-derived aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.) Trade name CR733S (hereinafter referred to as FR-1) was used. In addition, according to GPC analysis, the aromatic condensed phosphoric acid ester is composed of a TPP dimer (n = 1) represented by the following formula (18) and TP
P oligomer (n ≧ 2), and the weight ratio was 65/35, respectively.

[0124]

Embedded image

(2) 1,3-phenylene bis (di 2,6
Preparation of -dimethylphenyl phosphate) (FR-2) 244 parts by weight of 2,6-xylenol, 20 parts by weight of xylene, and 1.5 parts by weight of magnesium chloride were added to a reactor,
Heat and mix. When the temperature of the reaction solution reached 120 ° C., 153 parts by weight of phosphorus oxychloride was added dropwise over 2 hours. The hydrochloric acid gas generated at this time was led to a water scrubber. After the addition of phosphorus oxychloride was completed, the temperature of the reaction solution was gradually raised to 180 ° C. over 2 hours to complete the reaction. The yield of the obtained intermediate di (2,6-xylyl) phosphorochloride was 99.7%. Then, the obtained intermediate 45
Parts by weight, 55 parts by weight of resorcinol, aluminum chloride
5 parts by weight were added to the reactor, mixed by heating, and the temperature of the reaction solution was gradually raised to 180 ° C. over 2 hours to perform a dehydrochlorination reaction. After aging for 2 hours at the same temperature, 20
The reaction was further aged for 2 hours under reduced pressure of 0 mmHg to complete the reaction. Xylene 50 was added to the reaction solution thus obtained.
0 parts by weight and 200 parts by weight of a 10% hydrochloric acid aqueous solution were added to remove remaining catalyst and the like, and washing with water was repeated. The purified reaction solution was cooled to room temperature with stirring to crystallize, washed with methanol, and dried at 100 ° C. under reduced pressure to obtain the following formula (1)
1,3-phenylenebis (di2,6-dimethylphenyl phosphate) (hereinafter referred to as FR-2) represented by 9) was obtained.

[0126]

Embedded image

(3) Production of tris (nonylphenyl) phosphate (FR-3) 431.0 parts by weight of nonylphenol (3.0 by mole),
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. 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 was cooled and washed with water to remove the catalyst and chlorine, thereby obtaining tris (nonylphenyl) phosphate (hereinafter, referred to as FR-3).

The average of the total number of carbon atoms of the substituent is 2
7.0.

(4) Bisphenol A Bis (diphenyl phosphate) (FR-4) Commercially available aromatic condensed phosphoric acid ester derived from bisphenol A (trade name: CR741 manufactured by Daihachi Chemical Industry Co., Ltd.) ｝) Was used. In addition, according to GPC analysis, the aromatic condensed phosphate ester is a TPP-A-dimer represented by the following formula (20) (n = 1)
And TPP-A-oligomer (n ≧ 2) and triphenyl phosphate (TPP).
4.7 / 13.0 / 2.3.

[0130]

Embedded image

(5) Triphenyl phosphate (FR-
5) A commercially available aromatic phosphate ester monomer [trade name TPP (hereinafter referred to as FR-5) manufactured by Daihachi Chemical Industry Co., Ltd.] was used.

(D) Fluorinated resin Commercially available polytetrafluoroethylene (trade name: Teflon 6J (PTF
E) was used.

(E) Novolak resin Commercially available phenol novolak resin (Asahi Organic Materials Co., Ltd.)
Made and trade name SP1006N (referred to as NK) was used.

[0134]

Examples 1-4, Comparative Examples 1-2 HIPS-1 / GPP
S / PPE-1 / FR-1 / PTFE / NK were mixed at the weight ratio shown in Table 1 and a twin-screw extruder capable of side feeding (ZSK manufactured by Werner Pfleiderer Co., Ltd.)
-40 mmΦ) and melt extrusion was performed. That is, GPPS / PPE-1 is melted at 300 ° C. in the first stage of the extruder, and the remaining components are side-fed in the second stage while the rotation speed is 295 rpm, the discharge rate is 80 kg / h and the second stage temperature is 24
It was melt-kneaded at 0 ° C.

A test piece was prepared from the pellet thus obtained using an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 60 ° C., and the MFR and Izod impact strength were measured. The Vicat softening temperature,
The appearance and the flame retardancy were evaluated. Table 1 shows the results.

[0136]

[Table 1]

According to Table 1, only when PTFE is contained, there is no dropping fire spread and good self-extinguishing property is exhibited, but when the PTFE content exceeds 10 parts by weight, the appearance of the molded article is deteriorated. . It was also found that the addition of the novolak resin improved the fluidity and heat resistance.

[0138]

Examples 5 to 19 Reduced viscosities ηsp / C shown in Tables 2 and 3
Were mixed at the composition ratios shown in Tables 2 and 3 using different HIPS and PPE, and the same experiment as in Example 1 was performed to evaluate. The results are shown in Tables 2 and 3.

According to Tables 2 and 3, ηsp / C of HIPS
Is in the range of 0.4 to 0.6, fluidity, impact strength, and excellent flame retardancy balance characteristics, and,
The presence of PPE improves the balance of heat resistance, flame retardancy and impact strength.
0 to 25% by weight, and the reduced viscosity ηsp / C is 0.1%.
It can be seen that when the ratio is 3 to 0.6, the balance characteristics of fluidity, heat resistance, impact strength and flame retardancy are further improved.

[0140]

[Table 2]

[0141]

[Table 3]

[0142]

Examples 20 to 25 Using the aromatic phosphate ester (B) shown in Table 4 and mixing at the composition ratio shown in Table 4, Example 1 was used.
An experiment similar to the above was performed and evaluated. The results are shown in Table 4.

[0143]

[Table 4]

[0144]

Examples 26 to 29 Polystyrene containing a large amount of residual styrene monomer and oligomer (styrene dimer and trimer) was produced by changing the polymerization temperature and the amount of the chain transfer agent, and HIPS-1 was purified. HIPS obtained
To produce rubber-modified polystyrene having different amounts of residual styrene monomer and oligomer. Then, they were blended at the composition ratio shown in Table 5, and the same experiment as in Example 1 was performed to evaluate. The results are shown in Table 5.

According to Table 5, it is found that the flame retardancy is greatly improved by reducing the residual styrene monomer and oligomer in the resin composition to 1% by weight or less.

[0146]

[Table 5]

[0147]

Examples 30 to 35, Comparative Example 3 PC-containing compositions as shown in Table 6 were produced, and the same experiment as in Example 1 was carried out and evaluated. The results are shown in Table 6.

[0148]

[Table 6]

[0149]

According to the present invention, a dropping type flame-retardant molding material containing a fluororesin can be obtained.

The molding material of the present invention can be used for home appliance housings such as VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, air conditioners, humidifiers, electric warm air machines, etc. , Chassis or parts, CD-R
OM mainframe (mechanical chassis), printer,
Fax, PPC, CRT, word processing copier, electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR,
OA equipment housing such as calculator, toner cartridge, telephone, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser,
AC adapter, FBT high pressure bobbin, FBT case,
IFT coil bobbin, jack, volume shaft,
Suitable for electronic and electrical materials such as motor parts, and automotive materials such as instrument panels, radiator grills, clusters, speaker grills, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc. And play a large role in these industries.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 101/00 27:12)

Claims (7)

[Claims] 1. A molding material comprising (B) 1 to 100 parts by weight of a flame retardant and (C) a fluorine-based resin with respect to 100 parts by weight of a thermoplastic resin. A drop-type flame-retardant molding material containing a fluororesin, which contains a dripping amount of (C) in a combustion test with a thickness of 0.5 mm by a Vertical Burning method. 2. The fluorine-containing resin-containing drop-type flame-retardant molding material according to claim 1, wherein (C) is 0.001 to 10% by weight. 3. The thermoplastic resin according to claim 1, wherein (A) the thermoplastic resin is (A-1) 1 to 99% by weight of a styrene resin and / or (A-2) 99 to 1% by weight of polyphenylene ether.
The drop-type flame-retardant molding material containing a fluororesin described in the above. 4. The dripping-type flame-retardant molding material according to claim 1, wherein (B) the flame retardant is an aromatic phosphate ester. 5. The method according to claim 1, wherein the total content of the aromatic vinyl monomer remaining in the molding material and the dimer and trimer of the aromatic vinyl monomer is 1% by weight or less. Item 5. A drop-type flame-retardant molding material containing a fluororesin according to any one of Items 1 to 4. 6. The dripping flame-retardant molding material according to claim 1, wherein (B) the flame retardant is an aromatic phosphate ester. 7. (A) is the reduced viscosity ηsp / C of the resin part.
7. A fluorine-containing resin according to any one of claims 1 to 6, which is a rubber-modified styrene resin having a reduced viscosity of 0.4 to 0.6 and a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6. Drop-type flame-retardant molding material.