JPH1036603A - Nonhalogen flame-retardant material for electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material for electronic apparatuses which is excellent in flame retardancy, flowability, and heat resistance by using a specific nonhalogen flame-retardant styrene resin. SOLUTION: This material is prepd. by using a nonhalogen flame-retardant styrene resin having a Vicat softening point according to ASTM D 1525 of 90-150 deg.C. The shear melt viscosity of the resin at the melt temp. 200 deg.C, under a shear rate of 1000sec<-1> is 1-300Pa.s. Pref. the resin comprises 100 pts.wt. rubber-modified styrene resin having a reduced viscosity (ηsp /C) of the resin part of 0.4-0.6, 1-100 pts.wt. flame retardant represented by the formula (a, b, and c are each 1-3; and R<1> , R<2> and R<3> each H or 1-30C alkyl provided the total number of carbon atoms of R<1> , R<2> , and R<3> as the whole compd. is on average 12-30), and 1-100 pts.wt. polyphenylene ether having a reduced viscosity (ηsp /C) of 0.3-0.6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to electronic equipment materials. More specifically, the present invention relates to an electronic device material using a flame-retardant styrene resin composition containing no halogen-based flame retardant and having excellent fluidity and heat resistance.

[0002]

2. Description of the Related Art Electronic equipment parts made of styrene resin have excellent heat resistance, impact resistance and rigidity, and are used in a wide variety of fields including automobile parts, home electric appliance parts, and OA equipment parts. However, the flammability of styrene resins limits their use.

[0003] As a method of making a styrene resin flame-retardant,
It is known to add halogen-based, phosphorus-based, and inorganic-based flame retardants to styrene-based resins, thereby achieving some degree of flame retardancy. However, halogen-based flame retardants have environmental problems, and inorganic flame retardants need to be added in large amounts in order to exhibit flame retardancy, and the impact strength is significantly reduced. And although phosphorus-based flame retardants do not have the above problems, the excellent properties of the original styrene-based resin because engineering plastics are used for flame retardancy,
In particular, liquidity is impaired. For example, polyphenylene ether / polystyrene / red phosphorus (U.S. Pat.
4), polyphenylene ether / phosphate ester / thermoplastic elastomer (US Pat. No. 4,684,682), and polyphenylene ether / polystyrene / organophosphorus compound (JP-A-57-153035) are disclosed. The resin composition of the above publication has excellent flame retardancy and heat resistance when polyphenylene ether is the main component, but has extremely low fluidity, and when polystyrene is the main component, the fluidity is low. Excellent in heat resistance and flame retardancy. As described above, the conventional electronic device materials using the flame-retardant styrene resin were insufficient.

[0004] In addition, when using a phosphorus-based flame retardant, particularly an organic phosphorus compound, the organic phosphorus compound generally has high volatility. The industrial use of electronic device materials using organophosphorus compounds has been narrowed due to the reduction in productivity due to the generation of deposits or the transfer of mold contaminants to molded articles and the occurrence of stress cracks.

As a technique for improving volatility, a resin composition for a laminate comprising a phenol resin and a specific alkyl group-substituted phosphate ester monomer (JP-A-1-95149, JP-A-1-242633, JP-A-1-242633). No. 193328)
Is disclosed. The object of the flame retardant in this publication is a thermosetting resin, which is different from the flame retardant electronic device material of the present invention.

As a technique for making styrene resin flame-retardant, a flame-retardant resin composition comprising a polyphenylene ether, a styrene resin, a metal salt of phosphoric acid, and a phosphate such as tris (nonylphenyl) phosphate (Japanese Patent Laid-Open No. 63
JP-A-305161), a polyphenylene ether resin composition (EP5) comprising polyphenylene ether and high molecular weight polyethylene as essential components and, if necessary, a phosphate such as tris (nonylphenyl) phosphate.
50204), aromatic polycarbonate, ABS resin,
Flame retardant resin composition comprising an AS resin, a phosphate such as tris (nonylphenyl) phosphate, an aromatic sulfonate, and a fibrous reinforcing material (JP-A-6-29906)
No. 0) is disclosed. The above three publications do not disclose that specific resin compositions exhibit excellent resin properties such as fluidity, flame retardancy, and volatility, and that they are used as electronic device materials.

[0007]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has been repeatedly studied on materials for electronic devices, particularly materials for housings and internal parts of televisions and OA devices (office devices, electronic information processing devices). . In order to reduce the weight, increase the size, integrate molding, and shorten the molding cycle, these electronic equipment materials can be molded at a high shear rate that can be molded at lower temperatures even if a complicated thin-walled mold is used. Liquidity is required. On the other hand, heat resistance that can withstand internal heat generation and high temperature use due to long use of electronic devices is required,
Generally, in the case of improving the fluidity, it is necessary to overcome the trade-off technical restrictions that necessarily lower the heat resistance. If a fire is encountered, consideration must be given to its inherent flammability and the effects on the environment such as generated gas. That is, the electronic device material must be not only excellent in heat resistance and flame retardancy, but also environmentally friendly.

[0008] An object of the present invention is to provide a resin material satisfying all of these requirements. That is, an object of the present invention is to provide an electronic device material using a flame-retardant styrene-based resin composition containing no halogen-based flame retardant and having excellent fluidity and heat resistance.

[0009]

Means for Solving the Problems The present inventors have made intensive studies on the technical development of materials for electronic equipment, and as a result, it has been surprising that the novel non-halogen flame-retardant styrene resin satisfies specific characteristics. Furthermore, they have found that the flame retardancy, fluidity, and heat resistance are dramatically improved, and have reached the present invention.

That is, the present invention relates to an electronic device material using a non-halogen flame-retardant styrene resin having a Vicat softening temperature of 90 to 150 ° C. specified in ASTM-D1525. 1000
a non-halogen flame-retardant electronic device material having a shear melt viscosity of ¹ to 300 (Pa · s) in sec- ¹ .
In particular, the non-halogen flame-retardant styrene resin is (A) 100 parts by weight of a rubber-modified styrene resin having a reduced viscosity ηsp / C of the resin portion of 0.4 to 0.6, and (B) the following formula (1). The non-halogen flame-retardant electronic equipment material described above, comprising 1 to 100 parts by weight of the indicated flame retardant and (C) 1 to 100 parts by weight of polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6. Is what you do.

[0011]

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(Where a, b, and c are from 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. Hereinafter, the present invention will be described in detail.

The electronic device material of the present invention has a specific Vicat softening temperature as defined above and a specific shear melt viscosity under high shear rate melting conditions.

The Vicat softening temperature is an index of heat resistance, and it is essential that the temperature be 90 to 150 ° C. 90 ° C
If the temperature is lower than 150 ° C., the fluidity may be reduced if the temperature is lower than 150 ° C.

A melting temperature of 200 ° C. and a shear rate of 10
00sec ~ ¹ shear melt viscosity is ¹ ~ 300 (Pa ・
s) is essential. In particular, in order to easily form a thin molded product of 2 mm or less, or to shorten the molding cycle by setting a molding temperature of 200 ° C., the shear viscosity is 300 Pa · s or less under the above melting conditions. is important. On the other hand, the shear viscosity is 1 Pa · s
If it is less than this, it is found that it is not preferable because of excessive filling at the time of molding or heat resistance is lowered, and the present invention has been completed.

The non-halogen flame-retardant styrenic resin of the present invention is not particularly limited as long as it satisfies the above characteristics. For example, (A) a rubber-modified styrenic resin, (B) an aromatic phosphate ester monomer And a flame-retardant resin composition comprising (C) polyphenylene ether.

The above (A) is a main component of the molding resin composition and plays a role of maintaining the strength of the molded article, and (B) is a component for imparting flame retardancy to the styrene resin. C)
Is a component for imparting impact strength, heat resistance and flame retardancy to (A).

In the present invention, in particular, UL-94 regulated V
(A) The reduced viscosity ηsp / C of the resin portion is 0.4 to 0.4.
0.6 parts by weight of a rubber-modified styrenic resin,
This is achieved by combining (B) 1 to 100 parts by weight of the flame retardant represented by the above formula (1) and (C) 1 to 100 parts by weight of a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6. be able to. By satisfying the requirements of the reduced viscosity of the present invention, dripping and fluidity of fire,
The impact strength balance characteristics are improved.

In the present invention, the styrene resin (A) is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, particularly a rubber-modified styrene resin alone or a rubber-modified styrene resin and a rubber-unmodified styrene resin. It is preferable that the resin is made of a resin and is not particularly limited as long as it is compatible with or homogeneously dispersed with (B) to (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 a resin include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer).

Here, the rubbery polymer needs to have a glass transition temperature (Tg) of -30 ° C. or less,
If the temperature exceeds -30 ° C, the impact resistance decreases.

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 and 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 components of the rubber-modified styrenic resin in (A). When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to lower the melt viscosity during blending, an acrylate ester having 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.

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

Examples of the phosphorus-based flame retardant (B) include organic phosphorus compounds, red phosphorus, and inorganic phosphates.

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 phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate.

Here, particularly, as the organic phosphorus compound, an aromatic phosphate monomer represented by the following formula (2):
An aromatic phosphate condensate represented by the following formula (3) is preferred.

[0032]

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[0033]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r ₅ and Ar ₆ represent a phenyl group, a xyenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group,
An aromatic group selected from 4,4'-dioxydiarylalkane groups. N represents an integer of 0 to 3;
Represents an integer of 1 or more. Among the above aromatic phosphate ester monomers, particularly, hydroxyl group-containing aromatic phosphate ester monomers such as tricresyl phosphate and triphenyl phosphate shown in the above formula (2) are exemplified. Phosphate ester monomers containing one or more phenolic hydroxyl groups or aromatic phosphate ester monomers represented by the following formula (1) 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. , A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an otadecyl group, a nonadecyl group, an octadodecyl group, and the like. Can be substituted, but a para-substituted product is preferable. The total number of carbon atoms of the alkyl group substituted by one phosphate ester monomer is 12 to
Most preferably, the number of aromatic rings substituted by only one alkyl group is more than that of the phosphate ester monomer having only one aromatic ring substituted by only one long-chain alkyl group. The phosphoric acid ester monomer has better heat resistance and water resistance. For example, even when the total number of carbon atoms of the alkyl group to be substituted is 18, bis (nonylphenyl) is more preferable than octadecylphenyldiphenylphosphate.
Phenyl phosphate is preferable because of its high heat resistance.

In the present invention, among the organic phosphorus compounds, a phosphate ester monomer in which at least one of R ¹ , R ² , and R ³ is a nonyl group is preferable, and R ¹ , R ² , and R ³ are preferred.
Is most preferred from the viewpoints of fluidity and volatility in the aromatic phosphate ester monomer [tris (nonylphenyl) phenylphosphate] having a nonyl group. When the phosphoric acid ester monomer is contained in the flame retardant at 50% by weight or more, a particularly large flame retardant effect is exhibited. The phosphoric acid ester monomer is excellent in fire dropping properties, and is extremely excellent as a flame retardant of rank V-2 according to UL-94 flame retardancy standards. This fact was not previously known.

From the viewpoint of resistance to volatilization, the total number of carbon atoms of the substituents must satisfy the requirements of the present invention, but the ratio of those having a total number of carbon atoms of the substituent of less than 12 is 1% by weight or less. In some cases, even better volatility is developed.

From the viewpoint of the thermal stability of the flame retardant, particularly from the viewpoint of heat discoloration resistance, JIS-K6
751 or less, more preferably 0.5 mgKOH / g, and / or the alkylphenol is preferably 1% by weight or less, more preferably 0.5% by weight or less. Is more preferably 1000 ppm or less. When the hindered phenolic antioxidant is contained in the flame retardant in an amount of 1 to 1000 ppm by weight, the thermal stability is remarkably improved.

Next, from the viewpoint of light resistance, the substituents R ¹ , R ² , and R ³ are not aryl groups, and even when they are alkyl groups, it is preferable that the alkyl groups have few branches. One alkyl group is particularly preferred.

Further, the number of substituents to be substituted on one aromatic ring of the aromatic phosphate ester is preferably one. The viscosity of an aromatic phosphate ester monomer in which one aromatic ring is substituted with a plurality of substituents is high, and the viscosity increases with the number of substituents. When the viscosity of the aromatic phosphate ester monomer becomes high, not only the handling problem but also the high viscosity makes purification difficult, and the above-mentioned impurities remain, thereby deteriorating the light resistance and heat discoloration resistance.

The most preferred combination of the aromatic phosphate ester monomers in the present invention contains mainly tris (nonylphenyl) phosphate (TNPP) and a small amount of bis (nonylphenyl) phenylphosphate (BNPP). And the number average of the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 20 to 27, preferably 25 to 27, more preferably 26 to 27, and most preferably 26.5 to 27. . In order to satisfy the above number average of the total number of carbon atoms, for example, BNPP is 78 to 0% by weight, preferably 2% by weight.
2 to 0% by weight, more preferably 11 to 0% by weight, most preferably 5 to 0% by weight, and TNPP of 22 to 10% by weight.
0% by weight, preferably 78-100% by weight, more preferably 89-100% by weight, most preferably 95-10% by weight.
It is in the range of 0% by weight. The flame retardant of such a combination is particularly excellent in balance characteristics of flame retardancy, fluidity, heat resistance, impact strength, water gloss retention, and surface hardness of the obtained molded article. TNPP not only has a high volatility resistance and a high effect of imparting heat resistance, but also has excellent water gloss retention because it is structurally symmetric. As described above, TNPP exerts a specific effect and cannot be predicted by conventional knowledge.

The aromatic phosphate monomer used in the present invention is described in JP-A-1-95149 and JP-A-3-95149.
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.

Of the aromatic phosphate ester condensates, bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate) and the like are particularly preferred.

In the above (B), red phosphorus, which is one of the phosphorus-based flame retardants, is obtained by preliminarily selecting the surface of aluminum hydroxide, magnesium hydroxide, zinc hydroxide or titanium hydroxide in addition to general red phosphorus. 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 inorganic phosphate 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, (B) is added in an amount of 1 to 10 with respect to 100 parts by weight of the rubber-modified styrene resin.
0 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 20 parts by weight, and most preferably 5 to 15 parts by weight.

In the present invention, the polyphenylene ether (C) is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (4).

[0051]

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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), 2,6-dimethylphenol and 2,3,3-dimethylphenol.
A copolymer with 6-trimethylphenol is preferred,
Among them, 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, US Pat. No. 3,306,87
No. 5, U.S. Pat. No. 3,257,357,
U.S. Pat. No. 3,257,358 and JP-B-52
It can be easily produced by the methods described in JP-A-17880 and JP-A-50-51197. Reduced viscosity ηsp / c of the polyphenylene ether used in the present invention
(0.5 g / dl, chloroform solution, measured at 30 ° C.)
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. Reduced viscosity η of polyphenylene ether
Means for satisfying the above requirements regarding sp / c include adjustment of the amount of a catalyst in the production of the polyphenylene ether.

The amount of (C) added in the present invention is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the styrene resin.
It is 3 to 20 parts by weight, most preferably 5 to 15 parts by weight.

In the present invention, if necessary, a saturated higher aliphatic carboxylic acid or a metal salt thereof, a carboxylic ester wax, an organosiloxane wax,
One or more release agents (D) selected from polyolefin wax and polycaprolactone can be blended.

Among the above (D), 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 (D) is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, and most preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the styrene resin.
1 part by weight.

In the present invention, if necessary, one or more flame retardants selected from triazine skeleton-containing compounds, novolak resins, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, fluororesins, and polyacrylonitrile fibers. Auxiliaries (E) can be included.

The amount of (E) is determined based on the amount of the rubber-modified styrenic resin 1
The amount is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 10 parts by weight with respect to 00 parts by weight.

The triazine skeleton-containing compound as (E) 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 (5), melem represented by the following formula (6), and melon (melem 3 at 600 ° C. or higher).
A product of deammonification of three molecules from a molecule), melamine cyanurate represented by the following formula (7), melamine phosphate represented by the following formula (8), succinoguanamine represented by the following formula (9), adipate Examples thereof include guanamine, methylglutaloganamine, a melamine resin represented by the following formula (10), and a BT resin represented by the following formula (11). Melamine cyanurate is particularly preferable from the viewpoint of volatility resistance.

[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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[0068]

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The novolak resin (E) is a flame retardant aid and, when used in combination with a hydroxyl group-containing aromatic phosphate, 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. Polyaddition "p.437-455 (Kyoritsu Shuppan Co., Ltd.)".

An example of the production of a novolak resin is represented by the following formula (1)
2) and (13).

[0071]

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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.

The metal-containing compound as (E) 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 (E) 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 is obtained by co-hydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.

The silicone oil (E) is a polydiorganosiloxane, particularly preferably a vinyl-containing silicone oil, and comprises a chemical bond unit represented by the following formula (14).

[0078]

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R in the above formula is a C1-8 alkyl group,
It is one or more substituents selected from aryl groups of 6 to 13 and vinyl-containing groups represented by the following formulas (15) and (16), and particularly contains a vinyl group in the molecule.

[0080]

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[0081]

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

The silica as (E) is amorphous silicon dioxide, particularly preferably 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, or 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 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.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 (E) 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 fluorine-based resin (E) is a flame-retardant aid, and is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and a tetrafluoroethylene / hexafluoropropylene copolymer.
If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The polyacrylonitrile fiber (E) 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 acrylate unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty alcohol, or a metal One or two or more fluidity improvers (F) selected from soaps can be blended.

The amount of (F) is determined based on the rubber-modified styrenic resin 1
0.1 to 20 parts by weight with respect to 00 parts by weight,
More preferably, it is 0.5 to 10 parts by weight, most preferably 1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin as (F) 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 aids as (F) include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

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

The higher fatty acid ester as (F) 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 phthalic diester 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.

Higher fatty acid amides as (F) include 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 (F) 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 (F) 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 (G) 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 (G) is the same as that of the rubber-modified styrenic resin 1
For 0.5 parts by weight, preferably 0.5 to 20 parts by weight,
More preferably, 1 to 10 parts by weight, most preferably, 2 to 10 parts by weight.
-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 light resistance improvers (H) selected from the above agents can be blended.

[0106] The amount of (H) is determined based on the rubber-modified styrenic resin 1
The amount 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 with respect to 00 parts by weight.

(C) A method for producing a resin composition using polyphenylene ether is to first melt a styrene resin and (C), then add (B), and melt-knead the same extruder. , Or styrenic resin,
There is a method in which (C) or, if necessary, a masterbatch blended with (B) is produced, and then the masterbatch is kneaded with the remaining styrene resin or the remaining (B).

In the case of the twin-screw extruder used in the production of the above flame-retardant resin composition, especially when polyphenylene ether is contained, the ratio L / D of the screw length L to the cylinder inner diameter D is 20 to 50. It is preferable that the main feed opening and the side feed opening have different distances from the tip of the twin-screw extruder.
A plurality of supply openings, and a kneading portion between the plurality of supply openings and between the distal end and the supply opening close to the distal end; It is preferable that the length of each part is 3D to 10D, respectively.

Examples of preferred compositions of the flame-retardant resin composition constituting the electronic device material of the present invention include the following. With respect to 100 parts by weight of styrene resin (A), which is composed of 10 to 90 parts by weight of rubber-modified styrene resin and 90 to 10 parts by weight of non-rubber-modified styrene resin, TN
5 to 15 parts by weight of an aromatic phosphate ester monomer (B) containing PP alone or TNPP and mainly BNPP,
(C) 3 to 10 parts by weight of polyphenylene ether.

In the case of the above composition, excellent balance characteristics of flame retardancy, in particular, drop-type flame retardancy, continuous moldability, moldability (flowability), impact resistance and heat resistance are obtained.

Since the composition thus obtained has excellent fluidity, it can be easily and continuously molded for a long period of time by an injection molding machine for electronic equipment materials. The product is flame retardant (drop type flame retardant), fluidity,
Excellent heat resistance and impact resistance.

[0112]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present 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
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 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. 10 ml of this solution is placed in a Canon-Fenske viscometer, The solution falling time T1 (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, 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. Was determined in terms of composition and amount. On the other hand, for the above resin portion, the ratio of integral values of aromatic protons or aliphatic protons was determined by using a Fourier transform nuclear magnetic resonance apparatus (proton-FT-NMR), and a rubber-modified styrene resin and polyphenylene ether, etc. The amount of the thermoplastic resin was determined.

(3) Evaluation of Volatility of Phosphorus-Based Flame Retardant (Thermogravimetric Balance Test: TGA Method) 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. Warm and the weight loss at 300 ° C. or 400 ° C. was taken as a measure of volatility.

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

(V notch, 1/8 inch test piece) (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 VB (Vertical Bur) conforming to UL-94
ning) method. (1/8 inch test piece) (8) Measurement of shear melt viscosity Using a capillary rheometer manufactured by ROSAND, the shear melt viscosity (Pa · s) was determined under the conditions of a melt temperature of 200 ° C. and a shear rate of 1000 sec to ¹ , and the flow was measured. It was a measure of gender.

Test conditions: Long die length 16 mm Long die diameter 1 mm Short die length 0.25 mm Short die diameter 1 mm Die entry angle 180 deg (9) Formability evaluation A part of the electronic device parts shown in FIG. The moldability was evaluated based on whether the resin having a thickness of 1.2 mm and a height of 100 mm was connected to a 2.5 mm-thick plate and the resin was solidly filled.

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
rpm, 140 ° C, 4th stage is 20rpm, 155 ° C
The polymerization was carried out. 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. As a result of analyzing the obtained rubber-modified aromatic vinyl resin (referred to as HIPS-1), the rubber content was 12.1% by weight, the weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl. / G
Met.

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 Examples and Comparative Examples, the following HIPS
Was used. (Tables 1 and 2) HIPS-1: polybutadiene rubber, rubber content is 12.
The weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl / g.

HIPS-2: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.79 dl / g.

HIPS-3: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, and reduced viscosity ηsp / c is 0.60 dl / g.

HIPS-4: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.58 dl / g.

HIPS-5: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.40 dl / g.

HIPS-6: rubber content: 12.1% by weight, rubber weight average particle size: 1.5 μm, reduced viscosity ηs
p / c is 0.35 dl / g.

Rubber-unmodified 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. The polymer was sufficiently washed with methanol and then 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. The results are shown in Table 1.

(C) Phosphorus flame retardant triphenyl phosphate (TPP) A commercially available aromatic phosphate ester monomer [trade name TPP (trade name: TPP) manufactured by Daihachi Chemical Industry Co., Ltd.] was used.
The phosphorus content is 9.5% by weight.

Preparation of Alkyl-Substituted Aromatic Phosphate Monomer (FR-1) Nonylphenol 287.3 parts by weight (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 was cooled and washed with water to remove the catalyst and chlorine, thereby obtaining a phosphoric ester mixture (hereinafter referred to as FR-1). This mixture was subjected to GPC (gel permeation chromatography, Tosoh Corporation).
Manufactured by HLC-8020 mobile phase tetrahydrofuran. ) And nonylphenol in a weight ratio of 77.8 / 11.3 / 8.4 /
2.5.

The average of the total number of carbon atoms of the substituent is 1
7.9, (18 × 0.778 + 27 × 0.113
+ 9 × 0.084 = 17.9) The phosphorus content is 5.5% by weight.

On the other hand, BNPP or TNPP was obtained by distilling the above aromatic phosphate ester monomer mixture (FR-1) and further fractionating by liquid chromatography.

Production of Various Alkyl-Substituted Aromatic Phosphate Monomers In the production of FR-1, commercially available alkylphenol or "ENCYCLOPEDIA OF CHEMIC" was used.
AL TECHNOLOGY "ThirdEditi
on VOLUME 2 [ALKYLPHENOL
S "p. 72-96 (A WILEY-INTER
SCIENCE PUBLICATION John
Wiley & Sons New York 1978)
Various alkylphenols were synthesized by controlling the molar ratio with phosphorus oxychloride using various alkylphenols obtained by the method described. The purification method was carried out by the above-mentioned water washing, distillation or preparative fractionation by liquid chromatography. Table 3 shows various alkyl group-substituted aromatic phosphate monomers.

Examples 1 to 16 Comparative Examples 1 to 3 HIPS having different reduced viscosities ηsp / C shown in Tables 1 and 2,
Using PPE, mixing at the composition ratios shown in Tables 1 and 2, and a side-feedable twin screw extruder (cylinder inner diameter D = 40 m
mΦ, L / D = 46, length of the kneading part between the main feed / first supply opening: 8.9D, tip part
Length of the kneading portion between the first supply openings: 12.
Using 5D), melt extrusion was performed. That is, when PPE is used in the former stage of the extruder (from the main feed opening to the first supply opening [side feeder]), the HIPS / PPE is fed from the main feeder.
Melting was performed at 0 ° C., and TNPP was fed from a side feeder to melt at 230 ° C. On the other hand, when PPE is not used, HIPS is melted at 230 ° C. in the former stage of the extruder, and TNPP is fed at 230 ° C. from the side feeder to 230 ° C.
Melted at ° C.

The pellets obtained in this manner were injected into an injection molding machine (Model JSW J100 manufactured by Japan Steel Works, Ltd.).
In EP), test pieces were prepared under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the flame retardancy, MFR, Izod impact strength, and Vicat softening temperature were evaluated. Also,
The shear viscosity was measured by the method described in the above section on measuring the pellets. The results are shown in Tables 1 and 2 and FIG.

On the other hand, molding was performed at a resin temperature of 200 ° C. using an injection molding machine for electronic equipment parts, and the state of resin filling of the parts shown in FIG. 1 was observed.

[0145]

[Table 1]

[0146]

[Table 2]

[0147] According to Table 1, the melting temperature of 200 ° C., a shear melt viscosity of a shear rate of 1,000 sec ~ ¹ 300
When (Pa · s) is exceeded, it is found that filling of the resin becomes difficult. It is preferable to use HIPS or PPE having a specific molecular weight as a resin satisfying such conditions. In particular, when ηsp / C of HIPS is in the range of 0.4 to 0.6, fluidity, impact strength, and flame retardancy balance characteristics are excellent, and when PPE is present, heat resistance and heat resistance are improved. The balance between the fluidity and the impact strength is improved. In particular, PPE is blended in an amount of 15 parts by weight or less with respect to the rubber-modified styrene resin, and the reduced viscosity ηsp / C is 0.3 to 0.6.
It can be seen that in the case of, the balance characteristics of fluidity, heat resistance, impact strength and flame retardancy are further improved.

Reference Example Various aromatic phosphate ester monomers shown in Table 3 were allowed to stand at 250 ° C. for 5 minutes in a nitrogen stream by a thermogravimetric balance test method, and the residual amount was determined. The results are shown in Table 3. Table 3
According to the formula, the substituents R1, R2, R3
It can be seen that when the total number of carbon atoms is 12 or more, excellent volatility resistance is exhibited.

[0149]

[Table 3]

Examples 17 to 27 In Example 1, the final resin composition was HIPS-1 / G
Except that the composition was changed to PPS / PPE-1 / aromatic phosphate ester described in Table 4 = 70/30/3/7 / (weight ratio), it was manufactured and evaluated in the same manner as in Example 1. Was. Further, the temperature of the aromatic phosphate was raised at a rate of 40 ° C./min under a nitrogen stream by a thermogravimetric balance test method, and the relationship between the temperature and the weight loss was determined. Table 4 shows the results.

[0151]

[Table 4]

[0152]

Industrial Applicability The present invention relates to an electronic device material using a flame-retardant styrene-based resin composition containing no halogen-based flame retardant and having excellent fluidity and heat resistance.

The electronic equipment materials of the present invention include home appliances such as VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, air conditioners, humidifiers, electric hot air machines and the like. Housing, chassis or parts, C
D-ROM main frame (mechanical chassis), printer, fax, PPC, CRT, word processor,
Electronic cash register, office computer system,
Floppy disk drive, keyboard, type, E
OA equipment housing such as CR, 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 There are electronic and electric materials such as motor parts, etc., and the role played by these industries is great.

[Brief description of the drawings]

FIG. 1 has a gate portion with a diameter of 3 mm as described in the section on moldability evaluation, a plate with a thickness of 2.5 mm and a thickness of 1.2 mm,
A part of the electronic device part connected with a rib of 00 mm is shown.

FIG. 2 is a graph showing the relationship between shear rate and shear melt viscosity at 200 ° C. in Examples 3, 6 and Comparative Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 71/12 LQP C08L 71/12 LQP

Claims (2)

[Claims] 1. An electronic device material using a non-halogen flame-retardant styrene resin having a Vicat softening temperature of 90 to 150 ° C. specified in ASTM-D1525, wherein the resin has a melting temperature of 200 ° C. and a shear rate of 1000 sec to ¹ A non-halogen flame-retardant electronic device material having a shear melt viscosity of 1 to 300 (Pa · s). 2. A non-halogen flame-retardant styrene resin,
(A) The reduced viscosity ηsp / C of the resin portion is 0.4 to 0.6.
100 parts by weight of a rubber-modified styrenic resin, (B)
1 to 100 parts by weight of a flame retardant represented by the following formula (1),
The non-halogen flame-retardant electronic device material according to claim 1, comprising (C) 1 to 100 parts by weight of a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6. Embedded image (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 substituents R ¹ , R ² , R The total number of carbon atoms of ³ is an average of 12 to 30. Here, when a plurality of aromatic phosphates having different substituents are used, the substituents R ¹ , R ² , R The total number of carbon atoms of ³ is represented by a number average and 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 substituents of each component.)