JPH06345935A - Flame-retardant, heat-resistant and impact-resistant aromatic vinyl resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in flame retardancy, heat resistance, impact resistance and flow by mixing an aromatic vinyl resin with a polyphenylene ether and an organohalogen compound. CONSTITUTION:This resin composition is obtained by mixing 100 pts. wt., in total, aromatic vinyl resin having a glass transition temperature of -30 deg.C or below and a particle diameter of 0.1-5.0mum and selected from among a rubber- modified aromatic vinyl resin, an aromatic thermoplastic elastomer and a rubber-modified aromatic vinyl resin and a polyphenylene ether having a reduced viscosity of 0.20-0.70dl/g as measured in a chloroform solution} in a concentration of 0.5g/dl at 30 deg.C with 3-15 pts. wt. (in terms of halogen) organohalogen compound and optionally 0-30 pts. wt. flow improver.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Aromatic vinyl resins are superior in moldability as compared with inorganic substances such as glass, and are also excellent in impact resistance. Therefore, they are used for automobile parts, home electric appliances parts, OA equipment parts and the like. However, its use is limited due to the flammability of aromatic vinyl resins.

As a method for making an aromatic vinyl resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic flame-retardant agent to the aromatic vinyl-based resin, thereby making it flame-retarded to some extent. Has been achieved. However, in recent years, the demand for safety against fires has rapidly increased,
The regulations of the US UL (Underwriters Laboratory) vertical method combustion test for home electric appliances, OA equipment and the like have become stricter with the years, and higher flame retardancy is required. As a more advanced flame retardant technology, a method of increasing the amount of flame retardant is known, but it is not economical to use a large amount of originally expensive flame retardant, and also generation of toxic gas and mechanical properties, It is not preferable because it promotes a decrease in heat resistance. For this reason, it has been desired to develop a method of making a resin flame-retardant by using a flame-retardant in the smallest amount possible.

Conventionally, the mechanical properties of aromatic vinyl resins,
It is known to add polyphenylene ether as a method for suppressing the decrease in heat resistance and improving flame retardancy. For example, a flame-retardant resin composition of a thermoplastic resin such as polyphenylene ether and an aromatic vinyl resin and a bromine flame retardant (JP-A-63-66261), polyphenylene ether, a styrene resin, A retarder polymer composition with an aromatic phosphate and an aromatic halogen compound (JP-B-48-38768) is disclosed. However, the resin composition of the publication is polyphenylene ether.
Although tellurium is the main component, it has excellent impact strength and rigidity, but its molding process fluidity is extremely low, limiting its industrial use. The publication also discloses that a specific amount of polyphenylene ether
It has not been disclosed or even implied that the flame retardancy is significantly improved and the balance properties of fluidity, impact strength and heat resistance are improved by the addition of tellurium and a specific amount of halogen.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is free from the above-mentioned problems, namely, flame retardancy,
An object of the present invention is to provide an aromatic vinyl resin composition having excellent heat resistance, impact resistance and fluidity.

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors on a technique for improving the flame retardancy of aromatic vinyl resins,
By combining (A) an aromatic vinyl-based resin with a flame retardant containing a specific amount of (B) polyphenylene ether and a specific amount of (C) organohalogen compound, surprisingly, heat resistance, While maintaining impact resistance and fluidity,
The inventors have found that it is possible to dramatically improve flame retardancy, and have reached the present invention.

That is, the present invention is a resin composition comprising a flame retardant containing (A) an aromatic vinyl resin, (B) polyphenylene ether, and (C) an organic halogen compound. The resin component [(A), (B)] contains (B) polyphenylene ether in an amount of 15% by weight or less, and the halogen content is 3 to 15 parts by weight based on 100 parts by weight of the resin component. The present invention provides an aromatic vinyl-based flame-retardant, heat-resistant and impact-resistant resin composition.

The present invention will be described in detail below. The resin composition of the present invention comprises (A) an aromatic vinyl resin, a specific amount of (B) polyphenylene ether, and a specific amount of (C) an organohalogen compound as a flame retardant. The resin component consisting of the above components (A) and (B) is a component that forms the main component of the molding resin composition and plays a role of maintaining the strength of the molded product, and the component (C) is relative to the resin component. It is a component for imparting flame retardancy.

Here, the polyphenylene ether as the component (B)
Tell is not only used as a heat resistance and impact resistance improver,
It suppresses thermal decomposition of the aromatic vinyl resin as the component (A) and acts as a flame retardant aid for the flame retardant (C). Also, (B)
The component is polar (C) because it contains oxygen.
It also acts as a dispersant or a compatibilizer for the component (C) by interacting with the organic halogen compound in the component, such as hydrogen bonding. It is important that the component (B) is contained in the resin component in an amount of 15% by weight or less. 15% by weight of component (B)
If it exceeds, the fluidity will decrease.

Further, it is important that the halogen content is 3 to 15 parts by weight with respect to 100 parts by weight of the resin component.
If it is less than 3 parts by weight, the flame retardancy is lowered, while if it exceeds 15 parts by weight, the impact strength is lowered. Thus, it was found that the flame retardancy was significantly improved only by using the specific amount of polyphenylene ether and the specific amount of halogen, and the present invention was completed.

The component (A) of the present invention is a rubber-modified aromatic vinyl resin, an aromatic vinyl-based thermoplastic elastomer, or a rubber-unmodified aromatic vinyl resin. The rubber-modified aromatic vinyl resin in the component (A) of the present invention is a polymer in which a rubber-like polymer is dispersed in particles in a matrix composed of a vinyl aromatic polymer. The rubber-like polymer In the presence of an aromatic vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith to form a monomer mixture by a known bulk polymerization method, bulk suspension polymerization method, solution polymerization method, or Obtained by graft polymerization by an emulsion polymerization method.

Examples of such resins include high impact polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer) and the like. Here, the rubbery polymer needs to have a glass transition temperature (Tg) of -30 ° C or lower, and if it exceeds -30 ° C, the impact resistance is lowered.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate and an ethylene-propylene-diene monomer-terpolymer (EPDM), and the like. Particularly, a diene rubber is preferable, and a butadiene unit is preferable from the viewpoint of impact strength and thermal stability. It is more preferable that the butadiene-based polymer has a ratio of cis 1,4 bonds in the chain of 70% by weight or more.

The aromatic vinyl monomer which is an essential component of the graft-polymerizable monomer mixture to be polymerized in the presence of the rubber-like polymer is, for example, styrene, paramethylstyrene or 2,4- Dimethyl styrene, ethyl styrene,
p-tert-butylstyrene, p-chlorostyrene,
Nuclear alkyl-substituted styrenes such as p-bromostyrene and 2,4,5-tribromostyrene, or α-alkyl substituted styrenes such as α-methylstyrene and α-methyl-p-methylstyrene, most preferably styrene. However, it is also possible to copolymerize styrene as a main component with the other aromatic vinyl monomer.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified aromatic vinyl resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity during blending, an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Furthermore, when it is necessary to further increase the heat resistance of the resin composition, a monomer such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, or N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer is 0 to 40% by weight in the monomer mixture.

The rubber-like polymer in the rubber-modified aromatic vinyl resin of the present invention is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 50% by weight. 20% by weight, more preferably 90 to 50% by weight. Outside this range, the impact resistance and rigidity of the desired resin composition cannot be balanced. Furthermore, the rubber particle size of the styrene-based polymer is
0.1 to 5.0 μm is preferable, especially 0.2 to 3.0 μm
m is preferred. Within the above range, the impact strength is improved.

The above-mentioned aromatic vinyl-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 portion is hydrogenated. The aromatic vinyl monomer constituting the block copolymer is the aromatic vinyl monomer described in the description of the component (A), and styrene is the most preferable, but styrene is the main component and the other aromatic vinyl monomers are the same. The monomers may be copolymerized.

Examples of the conjugated diene monomer constituting the block copolymer include 1,3-butadiene and isoprene. When the block structure of the block copolymer is represented by S for a polymer block composed of an aromatic vinyl unit and B for a polymer block composed of a conjugated diene and / or its hydrogenated unit, SB , S (BS) n (where n is an integer of 1 to 3), S (BSB) n (where n is an integer of 1 to 2) linear block copolymer, or (SB) nX (However, n
Is an integer of 3 to 6. X is a coupling agent residue such as silicon tetrachloride, tin tetrachloride and polyepoxy compound. It is preferable that it is a star-shaped block copolymer having a B portion as a bond center, which is represented by (4). Among them, SB type 2 and S
BS-type 3 and SBSB-type 4 linear-block copolymers are preferred.

On the other hand, the rubber-unmodified aromatic vinyl resin is an aromatic vinyl resin containing no rubber component in the rubber-modified aromatic vinyl resin. The component (B) of the present invention, polyphenylene ether (hereinafter abbreviated as PPE).
Is a homopolymer and / or a copolymer composed of a bonding unit represented by the following formula.

[0020]

[Chemical 1]

However, R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, hydrocarbons, and substituted hydrocarbon groups, and may be the same or different from each other. As a specific example of this PPE, poly (2,
6-dimethyl-1,4-phenylene ether, 2,6-
Dimethylphenol and 2,3,6-trimethylphenol
Copolymers with poly (2,6-
Dimethyl-1,4-phenylene ether) is preferred.
The method for producing such PPE is not particularly limited, and, for example, using a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 as a catalyst, for example, 2,6 xyleno It can be easily produced by oxidative polymerization of silane, and it is also possible to obtain it in addition to US Pat. No. 3,306,875 and US Pat. No. 3,25.
No. 7,357, U.S. Pat. No. 3,257,358, and Japanese Examined Patent Publication No. 52-17880.
It can be easily manufactured by the method described in 0-51197. The reduced viscosity of the PPE used in the present invention (0.5
g / dl, chloroform solution, measured at 30 ° C) was 0.
It is preferably in the range of 20 to 0.70 dl / g,
It is more preferably in the range of 0.30 to 0.60 dl / g. Examples of means for satisfying the above requirements regarding the reduced viscosity of PPE include adjustment of the amount of catalyst during production of the PPE.

The flame retardant containing the organohalogen compound as the component (C) of the present invention contains a halogen-based flame retardant as an essential component, and optionally a phosphorus-based or inorganic flame retardant or a flame retardant auxiliary agent. . The halogen-based flame retardant is an aromatic halogen compound, a halogenated epoxy resin, a halogenated polycarbonate, a halogenated aromatic vinyl polymer, a halogenated cyanurate resin, a halogenated polyphenylene ether, a fluorine-based resin, etc. Is decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A oligomer, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated Polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, ethylenebistetrabromophthalimide and halogen-containing Phosphoric acid esters and the like.

From the viewpoint of the effect of improving fluidity and the effect of dispersibility in the presence of the component (B) polyphenylene ether, a brominated bisphenol epoxy resin is particularly preferable. The phosphorus-based flame retardant in the component (C) is an organic phosphorus compound, red phosphorus, an inorganic phosphate or the like.

The above-mentioned organic phosphorus compound is, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinic acid salt, phosphoric acid ester, phosphorous acid ester and the like. More specifically, triphenyl phosphate, methyl neobenthyl phosphite, hentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite. , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, dipyrocatechol hypophosphite.

Here, in particular, a hydroxyl group-containing aromatic phosphoric acid ester is preferable from the viewpoint of the balance of fluidity, heat resistance and impact resistance, and it may be used in combination with the above organic phosphorus compound not containing a hydroxyl group. Further, the red phosphorus used in the present invention is a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide, in addition to general red phosphorus. Coated, coated with a coating composed of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide , A double layer of a thermosetting resin coating on a liquid film of a metal hydroxide selected from zinc hydroxide and titanium hydroxide.

The above-mentioned inorganic phosphate used in the present invention is typically ammonium polyphosphate.
The inorganic flame retardant in the component (C) is aluminum hydroxide,
Magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, hydrates of inorganic metal compounds such as hydrates of tin oxide, zinc borate, zinc metaborate , Barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate,
Examples thereof include magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide and red phosphorus. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have a good flame retarding effect and are economically advantageous.

The flame retardant aid in the component (C) is a triazine skeleton-containing compound, antimony trioxide, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, iron oxide, manganese oxide, aluminum oxide, tin oxide, titanium oxide. And the like, and silicone resins such as polydiorganosiloxane. Here, the above-mentioned triazine skeleton-containing compound is particularly preferable as the flame retardant aid for the phosphorus-based flame retardant. Specific examples thereof include melamine, melam, melon, melamine silanurate, succinoguanamine, adivoguanamine, methylglutaloganamin, melamine phosphate, melamine resin, and BT resin, but particularly volatility-resistant. From the viewpoint of, melamine cyanurate is preferable.

When it is necessary to further impart fluidity to the resin composition of the present invention, (D) fluidity improver can be added. The component (D) is a copolymer resin comprising an aromatic vinyl unit and an acrylic acid ester unit, a phosphoric acid ester, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, a metal. One or more fluidity improvers selected from soaps.

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

The phosphoric acid ester in the component (D) is triphenyl phosphate, tricresyl phosphate,
Phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, ethyl pyrocatechol phosphate, dipyrocatechol hypophosphate,
Resorcinyl diphenyl phosphate, resorcin bis diphenyl phosphate and the like.

The aliphatic hydrocarbon-based processing aid in the component (D) is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, fluorides, chlorides and the like. . The higher fatty acids in the component (D) include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid, and ferric acid, and ricino-acid, lysine veridic acid, and 9-oxy-12 octadecenoic acid. And unsaturated fatty acids.

The higher fatty acid ester in the component (D) is a monovalent alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, and a monovalent acid of a polybasic acid such as a phthalic acid diester of diphenylstearyl phthalate. Alcohol ester, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, poly Oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, sorbitan ester such as polyoxyethylene sorbitan monooleate, stearic acid monoglyceride,
Oleic acid monoglyceride, capric acid monoglyceride, fatty acid ester of glycerin monomer such as behenic acid monoglyceride, polyglycerin stearic acid ester, polyglycerin oleic acid ester, polyglycerin fatty acid ester such as polyglycerin lauric acid ester, polyoxyethylene monoester Fatty acid esters having polyalkylene ether units such as laurate, polyoxyethylene monostearate, polyoxyethylene monooleate, and neopentylpolyols such as neopentylpolyol distearate Fatty acid esters and the like.

The higher fatty acid amide in the component (D) is a monoamide of a saturated fatty acid such as phenylstearic acid amide, methylol stearic acid amide, methylol behenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanololamide. , And N, N′-2 substituted monoamides such as coconut oil fatty acid dietanol and oleic acid dietanolamide, and methylenebis (12-
Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide, ethylenebisstearic acid amide, ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-xylylenebis (12)
An aromatic bisamide such as -hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol in the component (D) is
Monovalent alcohols such as stearyl alcohol and cetyl alcohol, polyvalent alcohols such as sorbitol and mannitol, and polyoxyethylene dodecylamine and polyoxyethylene voctadecylamine. Furthermore, allyl ether having a polyalkylene ether unit such as polyoxyethylene allyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether
Polyoxyethylene alkyl ethers such as ter, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. Phenyl ether,
Polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A
It is a divalent alcohol having a polyalkylene ether unit such as ether or polyoxyethylene polyoxypropylene glycol ether.

The metal soap in the component (D) is a metal salt of higher fatty acid such as stearic acid such as barium, calcium, zinc, aluminum or magnesium. The resin composition of the present invention contains (C) an organophosphorus compound so that the halogen content is 3 to 15 parts by weight with respect to 100 parts by weight of the resin component consisting of (A) and (B). Further, it is preferable to add 0 to 30 parts by weight of the fluidity improver (D), if necessary. Here, in the above range, the balance characteristics of molding processability (flowability), flame retardancy, impact resistance, and heat resistance are excellent.

The resin composition of the present invention can be obtained by, for example, melt-kneading each of the above components with a commercially available single-screw extruder, a twin-screw extruder or the like. Inhibitor, benzotriazole and hinder
UV absorbers such as doamine, tin-based heat stabilizers, other inorganic and halogen-based flame retardants, lubricants such as stearic acid and zinc stearate, fillers, reinforcing agents such as glass fibers, coloring agents such as dyes and pigments Etc. can be added as needed.

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

[0038]

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

(1) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified styrenic resin is obtained by determining the particle diameter of the butadiene-based polymer in the transmission electron microscope photograph taken by the ultrathin section method of the resin composition. It is calculated by the following formula. Weight average particle diameter = ΣNi · Di4 / ΣNi · Di3 (where Ni is the number of butadiene-based polymer particles whose particles are Di). (2) Reduced viscosity ηSP / C Rubber-modified styrene-based resin 1 g with methyl ethyl ketone 18
Add a mixed solvent of 2 ml of methanol and 2 ml of methanol, and add 2 ml at 25 ° C.
Shake for time and centrifuge at 18000 rpm for 30 minutes at 5 ° C. The supernatant was taken out, the resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to give a solution having a concentration of 0.5 g / dl, and 10 ml of this solution was placed in a Canon-Fenske viscometer.
At 30 ° C., the number of seconds t1 during which the solution flowed was measured. On the other hand, the flowing seconds t0 of pure toluene was measured separately with the same viscometer,
It was calculated by the following mathematical formula. ηSP / C = (t1 / t0-1) / C (C: polymer concentration g / dl) On the other hand, regarding the reduced viscosity ηSP / c of the component (B) PPE, 0.1 g is dissolved in chloroform and the concentration 0.5 g /
A dl solution was prepared and measured in the same manner as above.

(3) Solution viscosity of component (D) [copolymer resin] The copolymer resin of component (D) is replaced with methyl ethyl ketone (ME).
K) to prepare a 10 wt% resin solution. Next, 10 ml of this solution was placed in a viscometer, and the falling time t1 was measured in a constant temperature bath at 25 ° C. On the other hand, using a viscometer calibration standard solution of which viscosity is already known (prepared based on JIS Z8809-1978), the drop time t0
Was calculated, and the viscosity tube coefficient K was calculated by the following equation, and the solution viscosity was obtained from the product of the number of seconds of dropping the polymer solution and the viscosity tube coefficient K. The unit is centipoise (cP).

Viscosity tube coefficient K = (η0 d) / (t0 d0) η0: viscosity of standard solution at 25 ° C. (cP) t0: drop time of standard solution at 25 ° C. (sec) d: polymer of 10% by weight Solution Density (g / cm3) d0: Density of Standard Solution at 25 DEG C. (g / cm3) (4) Izod Impact Strength Measured at 23 DEG C. according to ASTM-D256. (V notch, 1/8 inch test piece) (5) Vicat softening temperature Measured by a method according to ASTM-D1525 and used as a scale of heat resistance.

(6) Melt flow rate (MFR) The melt flow rate was measured by a method according to ASTM-D1238. 10 at a load of 5 kg and a melting temperature of 200 ° C
It was determined from the extrusion rate per minute (g / 10 minutes).
(7) Flame retardance VB (Vertical Bur) compliant with UL-94
Ning) method. (1/8 inch test piece) (8) Pyrolysis behavior (thermogravimetric balance test) Using a Shimadzu thermal analyzer DT-40 under an air stream, 10
The temperature was raised to 550 ° C at a rate of ° C / min, and the thermal decomposition behavior was measured.

Here, the thermal decomposition start temperature is defined as an inflection point at which the weight loss suddenly starts. On the other hand, the decomposition rate of the resin component is determined by measuring the temperature of the pure resin component excluding additives such as flame retardant per 1 ° C. in the temperature range between the decomposition initiation temperature and the temperature at which the weight loss thereafter becomes slow. Weight reduction. (9) Glass transition temperature Tg It was measured by a differential scanning calorimetry (DSC). Specifically, a Shimadzu thermal analyzer DT-40 was used to measure the temperature of a 5 mg sample at 10 ° C./min under a nitrogen stream. The compatibility is determined by the difference Δ between the Tg of the resin component and the Tg of the composition.
It was performed by Tg. That is, the larger ΔTg, the greater the interaction between the resin component and the flame retardant component, and the better the compatibility.

The following components were used as the components used in Examples and Comparative Examples. (A) Rubber-modified aromatic vinyl resin (component A) Rubber-modified aromatic vinyl resin (HIPS-1) Polybutadiene (cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 33/49 / 18) / polystyrene = 10/90 (weight ratio), rubber weight average particle diameter 2.0 μm, reduced viscosity ηsp / c 0.75 dl /
g rubber modified aromatic vinyl resin (Asahi Kasei Co., Ltd.)
Manufactured by HIPS-1) was used.

Rubber modified aromatic vinyl resin (HIPS-
2) Polybutadiene (cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2/3) /polystyrene=12.3/87.7 (weight ratio), weight average particle of rubber Diameter 1.3 μm, reduced viscosity ηsp / c 0.79d
A rubber-modified aromatic vinyl resin (referred to as HIPS-2 manufactured by Asahi Chemical Industry Co., Ltd.) having an amount of 1 / g was used.

Aromatic vinyl-based thermoplastic elastomer
(TPE) A commercially available styrene thermoplastic elastomer [styrene / butadiene block copolymer (40/60 weight ratio) manufactured by Asahi Kasei Kogyo Co., Ltd.] was used. (Referred to as TPE) Rubber-unmodified aromatic vinyl resin [polystyrene (GPP
S)] Commercially available polystyrene (weight average molecular weight 270,000, number average molecular weight 120,000) [(Asahi Chemical Industry Co., Ltd.) (hereinafter GPP
S))] was used.

(B) Polyphenylene ether (PPE:
(Component B) After the inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor and having a cooling coil and stirring blades inside was thoroughly replaced with nitrogen, 54.8 g of cupric bromide, diester -N-
Butylamine 1110 g, and toluene 20 liters,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into a reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 180 minutes while controlling the internal temperature to 30 ° C. After the polymerization was completed, the precipitated polymer was filtered off. A methanol / hydrochloric acid mixture was added to this to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and then dried to obtain powdery polyphenylene ether (referred to as PPE). Reduced viscosity ηSP is 0.55dl
/ G.

(C) Flame Retardant (C Component) Ethylene Bistetrabromophthalimide (FR-1) Commercially available brominated flame retardant [Ethyl Chemicals
Brand name Saytex BT-93 (bromine content 67
Wt%) (referred to as FR-1)] was used.

[0050]

[Chemical 2]

Tetrabromobisphenol A epoxy oligomer (FR-2) Commercially available brominated flame retardant [Molecular weight 16 manufactured by Toto Kasei Co., Ltd.]
00 Brand name YDB-408 (bromine content 51% by weight)
(Referred to as FR-2)] was used.

[0052]

[Chemical 3]

Modified Tetrabromobisphenol A Epoxy Oligomer (FR-3) Commercially available brominated flame retardant [manufactured by Dainippon Ink and Chemicals, Inc.
Molecular weight 1400 End-capped type Product name Plum
EC-14 (bromine content 59% by weight) (referred to as FR-3)] was used.

[0054]

[Chemical 4]

Brominated Phosphate (FR-4) As a commercially available brominated flame retardant, tris (tribromoneopentyl) phosphate [trade name CR900 (manufactured by Daihachi Chemical Industry Co., Ltd.) (bromine content 71% by weight)] (Referred to as FR-4)] was used.

[0056]

[Chemical 5]

Antimony trioxide (FR-5) Commercially available antimony trioxide (trade name Antimony Bloom 10 manufactured by Dowa Mining Co., Ltd.) is used as a flame retardant aid.
0A (referred to as FR-5)] was used. (D) Fluidity improver (D component) Phosphate ester (triphenyl phosphate: TP
P) Commercially available aromatic phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.,
Trade name TPP (referred to as TPP)] was used.

Liquid paraffin (MO) Commercially available liquid paraffin was used. (Referred to as MO) Copolymer resin (BAS) 13.6 parts by weight of butyl acrylate, styrene 66.
4 parts by weight, 20 parts by weight of ethylbenzene, 0.15 parts by weight of t-dodecyl mercaptan as a chain transfer agent, and 1,1-bis (t-butylperoxy) as an initiator.
A mixture of 0.03 parts by weight of -3,3,5-trimethylcyclohexane at a rate of 1.2 liters / hour and a volume of 2.
Continuously feed to a 1 liter fully mixed reactor 140
Polymerization was carried out at ° C. The polymerization solution was continuously introduced into an extruder with a vent, the unreacted monomer and the solvent were removed under the conditions of 260 ° C. and 40 Torr, and the polymer was continuously cooled and solidified to obtain a particulate copolymer resin (BAS). Called).
This has a solution viscosity of 2.7 cP and a resin composition of 14% by weight of butyl acrylate unit and 86% by weight of styrene unit.
Met. (The resin composition ratio is based on the proton stirring magnetic resonance spectroscopy.)

[0059]

Examples 1 to 4 Comparative Examples 1 to 6 HIPS-1 / G
Table 1 shows PPS / PPE / FR-1 / FR-5 / TPP.
Weight ratio stated (bromine content / FR-5 = 67/33 constant)
Were mechanically mixed with each other and melted for 7 minutes at a melting temperature of 250 ° C. and a rotation speed of 50 rpm using a Labo Plastomill manufactured by Toyo Seiki Seisakusho. However, since the melting temperature of PPE is high, first, GPPS / PPE was melted at 300 ° C., and then the remaining components were melted under the above conditions.

From the resin composition thus obtained, a test piece having a thickness of 1/8 inch was prepared by hot pressing, and the Vicat softening temperature, Izod impact strength, MFR and flame retardancy were evaluated. The results are shown in Table 1 and FIG. FIG. 1 shows the thermal decomposition behavior of a composition (Example 1 or Comparative Example 1) with or without PPE in the resin component. The thermal decomposition temperatures are 336 ° C. and 333 ° C., respectively, while the decomposition rate of the resin component is 0.7, respectively.
3, 0.95% by weight / ° C. Therefore, it can be seen that the presence of PPE suppresses the thermal decomposition of the aromatic vinyl resin and improves the flame retardancy.

[0061]

Examples 1, 2, 5-8 Comparative Examples 2, 4, 7 In a composition in which PPE is present or absent in the resin component, the dependency of the flame retardant (FR-1 / FR-5) on the amount added is shown. investigated. HIPS-1 / GPPS / PPE / FR-1 /
The weight ratio of FR-5 / TPP shown in Table 2 (bromine content / F
The same experiment as in Example 1 was repeated except that (R-5 = 67/33 constant) was changed. The results are shown in Table 2 and FIG.

According to Table 2 and FIG. 2, PP is included in the resin component.
It can be seen that in the composition in which E is present, even if the amount of the flame retardant added is reduced, the flame retardance is slowly reduced.

[0063]

Examples 9 to 11 Comparative Examples 8 to 10 In a composition in which PPE was or was not present in the resin component, the dependency of the flame retardant (FR-2 / FR-5) on the amount added was examined.
HIPS-2 / GPPS / PPE / FR-2 / FR-5
The same experiment as in Example 1 was repeated except that / TPP or BAS was changed to the weight ratio shown in Table 3 (bromine content / FR-5 = 67/33 constant). The results are shown in Table 3, FIG. 3, FIG. 4 and FIG.

According to Table 3 and FIG. 3, PP is included in the resin component.
It can be seen that in the composition in which E is present, even if the amount of the flame retardant added is reduced, the flame retardance is slowly reduced. In addition, according to the optical micrograph of FIG. 4, PP is included in the resin component.
It can be seen that the dispersibility of the flame retardant in the composition with or without E (Example 9, Comparative Example 8) is better in the composition with PPE. In particular, the numbers of flame retardant particles of 5 μm or more are 165 and 518 particles / mm 2, respectively, and it is speculated that PPE acts as a compatibilizer for the flame retardant.

Then, from the measurement result of the glass transition temperature (Tg) by the DSC method of FIG.
-2 of the composition (Comparative Example 8) using H-2 and HIPS-
It can be seen that the difference ΔTg from the Tg of 2 is 7.3 ° C., whereas the ΔTg when HIPS-2 / PPE (Example 9) is used as the resin component is 10.5 ° C. From this fact, the Tg shift due to the addition of the flame retardant (FR-2) was larger in the composition in which PPE was present, suggesting the interaction between the PPE and the flame retardant (FR-2).

From the above results, PPE suppresses the thermal decomposition of styrene resin, and is a compatibilizing agent by the interaction such as hydrogen bond between the hydroxyl group or epoxy group of bromine-substituted epoxy flame retardant and oxygen of PPE. It was found that the flame retardancy-improving effect is exhibited by these two effects.

[0067]

Examples 12 to 14 Comparative Example 11 HIPS-2 /
GPPS / TPE / PPE / FR-3 / FR-4 / FR
Other than changing -5 / MO to the weight ratio shown in Table 4,
The same experiment as in Example 1 was repeated. Table 4 shows the result.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

EFFECTS OF THE INVENTION The composition of the present invention has a high degree of flame retardance, fluidity, heat resistance,
And a resin composition having excellent impact resistance. This composition is suitable for home electric appliance parts, office automation equipment parts, etc., and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 Example 1 (resin component HIPS-1 / PPE = 9)
It is the figure which showed the thermal decomposition behavior of the resin composition of Comparative Example 1 (resin component HIPS-1). The vertical axis and the horizontal axis represent the weight and temperature of the composition, respectively.

FIG. 2 is a diagram showing the additive amount dependency of a flame retardant (FR-1 / FR-3) in a composition in which PPE is or is not present in a resin component. The ordinate and the abscissa respectively represent the extinction time of the flammability test in the UL-94V method and the bromine weight% of FR-1 with respect to 100 parts by weight of the resin component.

FIG. 3 is a diagram showing the additive amount dependency of a flame retardant (FR-2 / FR-3) in a composition in which PPE is or is not present in a resin component. The ordinate and the abscissa respectively indicate the flameout time of the flammability test in the UL-94V method and the bromine weight% of FR-2 with respect to 100 parts by weight of the resin component.

FIG. 4 is an optical micrograph of a composition (Example 9, Comparative Example 8) in which PPE is or is not present in the resin component.

FIG. 5 is a diagram showing the measurement results of Tg (glass transition temperature) of a composition (Example 9 and Comparative Example 8) in which PPE is present or absent in a resin component by a DSC method. For comparison, the Tg of only the flame retardant (FR-2) and the resin component is also shown.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08L 71:12)

Claims (1)

[Claims] 1. A resin composition comprising a flame retardant containing (A) an aromatic vinyl resin, (B) polyphenylene ether, and (C) an organohalogen compound, wherein the resin component in the composition. The polyphenylene ether (B) in [(A), (B)] is contained in an amount of 15% by weight or less, and the halogen content is 3 to 15 parts by weight with respect to 100 parts by weight of the resin component. An aromatic vinyl-based flame-retardant heat- and impact-resistant resin composition.