JPH06100785A - Drip-resistant, flame-retardant, heat-resistant, and impact-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide the thermoplastic resin composition preventing its melt- dropping on combustion and excellent in flame retardancy, impact resistance, heat resistance and flowability. CONSTITUTION:The flame-retardant, heat-resistant, and impact-resistant resin composition comprises (A) a thermoplastic resin, (B) a phosphorus-containing flame retardant comprising an organo-phosphorus compound and/or red phosphorus, and (C) a drip preventing resin comprising a specific structure silicone resin and/or a polyphosphazene.

Description

Detailed Description of the Invention

[0001]

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

[0002]

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

As a method of making a thermoplastic resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic flame-retardant agent to the thermoplastic resin. There is. However, in recent years, the demand for safety against fire has suddenly been highlighted, and home appliances and O
The regulations of the US UL (Underwriters Laboratory) vertical method combustion test for equipment A etc. have become stricter with the years, and the weight of products and parts has become thinner to reduce weight and improve economy. Then, the fire species drop during combustion, which may damage other products and parts, and the development of a technology for preventing the fall of the fire species, so-called drip prevention technology, has been strongly desired. Although a method of increasing the amount of flame retardant is known as a drip prevention technology, it is not economical to use a large amount of flame retardant originally, but it also promotes the generation of toxic gas and deterioration of mechanical properties. Not preferred because of

Further, Japanese Patent Laid-Open No. 64-4656, British Patent No. 2146033, and US Pat. No. 4,3871.
Japanese Patent No. 76 discloses a technique of flame-retarding a thermoplastic resin with a silicone resin. However, not only the flame retardancy and impact resistance of the resin compositions of the above publications and specifications are low, but also the non-softening property and the vinyl group-containing silicone resin dramatically improve the flame retardancy. Is not disclosed.

Further, JP-A-4-154851,
JP-A-4-154852 discloses a resin composition of polyolefin, metal hydroxide and polyphosphazene, but since the composition of the publication uses a large amount of metal hydroxide, There was a problem of poor impact resistance.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has the above-mentioned problems, that is, prevents molten dripping at the time of combustion, and has flame retardancy, heat resistance and impact resistance. The purpose of the present invention is to provide a thermoplastic resin having excellent fluidity and fluidity.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies as to a technique for preventing drip during combustion of a thermoplastic resin, and as a result, compared with the conventional (A) thermoplastic resin, (B) an organophosphorus compound and / or Or, by combining a phosphorus-containing flame retardant that is red phosphorus and (C) a special drip suppressing resin, surprisingly, while maintaining flame retardancy, fluidity and impact resistance, drip resistance during combustion The present invention has been achieved by finding that it is possible to dramatically improve the above.

That is, the present invention relates to (A) a thermoplastic resin,
A resin composition comprising (B) an organic phosphorus compound and / or a phosphorus-containing flame retardant which is red phosphorus, and (C) a silicone resin and / or a drip suppressing resin which is polyphosphazene, wherein A silicone resin, which is non-softening and contains a vinyl group, is a drip-resistant flame-retardant heat-resistant impact-resistant resin composition.

The present invention will be described in detail below. The resin composition of the present invention contains (A) a thermoplastic resin, (B) a phosphorus-containing flame retardant, and (C) a drip suppressing resin, and the object of the invention cannot be achieved even if any of them is lacking. The component (A) constitutes the main component of the molding resin composition, plays a role of maintaining the strength of the molded product, the component (B) imparts flame retardancy to the component (A), and the component (C). Is a component for preventing the molten dripping at the time of combustion with respect to the component (A).

Here, one silicone resin of the (C) drip suppressing resin is required to be non-softening and contain a vinyl group. By having a sufficiently high crosslink density so as not to soften in the temperature range of 0 ° C to 350 ° C, it promotes the formation of SiO ₂ or SiC during combustion,
Suppresses the drip of the molded body. Further, the radicals generated in the initial stage of combustion react with the vinyl group to form a crosslinked structure. On the other hand, the other drip suppressing resin, polyphosphazene, is essential to be a polymer and is not effective with monomer phosphanase. By using such a special resin, it was found that the drip resistance at the time of combustion is significantly improved, and the present invention has been completed.

The thermoplastic resin as the component (A) of the present invention includes polystyrene type, polyolefin type, polyvinyl chloride type, polyphenylene ether type, polyamide type, polyester type, polyphenylene sulfide type, polycarbonate type, polymethacrylate type. And other thermoplastic resins. Here, a polystyrene-based thermoplastic resin is particularly preferable as the thermoplastic resin, and a polymer blend of a rubber-modified styrene-based resin and a polyphenylene ether-based resin is more preferable.

The rubber-modified styrenic resin as the component (A) of the present invention means a polymer in which a rubber-like polymer is dispersed in particles in a matrix composed of a vinyl aromatic polymer. In the presence of a polymer, an aromatic vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith are added to form a monomer mixture by known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsification. Obtained by polymerizing.

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., 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, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like, and a diene rubber is particularly preferable.

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

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity 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 in the monomer mixture is 0 to 40% by weight.

The rubber-like polymer in the rubber-modified styrene resin of the present invention is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20%. %, 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. Outside the above range, the impact resistance tends to decrease.

The polyphenylene ether (PPE) as the component (A) of the present invention is a homopolymer and / or a copolymer having a bonding unit represented by the following formula.

[0019]

[Chemical 1]

However, R ₁ , R ₂ , R ₃ and R ₄ are each selected from the group consisting of hydrogen, hydrocarbons and substituted hydrocarbon groups and may be the same or different from each other. As a specific example of this PPE, poly (2,
6-dimethyl-1,4-phenylene ether, 2,6-
A copolymer of dimethylphenol and 2,3,6-trimethylphenol is preferable, and among them, poly (2,6-
Dimethyl-1,4-phenylene ether) is preferred.
The method for producing such PPE is not particularly limited. For example, a complex of cuprous salt and amine obtained by the method described in US Pat. No. 3,306,874 is used as a catalyst, and, for example, 2,6 xylenol is used. Can be easily produced by oxidative polymerization, and other than that, US Pat. No. 3,306,875 and US Pat.
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) is 0.2
It is preferably in the range of 0 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 component (B) of the present invention is a phosphorus-containing flame retardant which is an organic phosphorus compound and / or red phosphorus. The organic phosphorus compound, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate,
Examples thereof include phosphoric acid ester and phosphorous acid ester. More specifically, triphenyl phosphate,
Methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite, phenylpyrocatecholphosphite Examples thereof include phyto, ethylpyrocatechol phosphate, dipyrocatechol hyposiphosphate and the like.

Here, a hydroxyl group-containing aromatic phosphoric acid ester is particularly preferable in terms of the balance of fluidity, heat resistance and impact resistance, and it may be used in combination with the above-mentioned organic phosphorus compound not containing a hydroxyl group. The above-mentioned hydroxyl group-containing aromatic phosphoric acid ester is a phosphoric acid ester containing one or more phenolic hydroxyl groups in tricresyl phosphate, triphenyl phosphate, condensed phosphoric acid ester thereof or the like. There are, for example, the following compounds.

[0023]

[Chemical 2]

[0024]

[Chemical 3]

(However, Ar ₁ , Ar ₂ , Ar ₃ and A
r ₄ , Ar ₅ , and Ar ₆ are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group, and a butylphenyl group, and at least one hydroxyl group in the phosphate ester is the above aromatic group. Is substituted with a group. Further, n represents an integer of 0 to 3, and m represents an integer of 1 or more. Among the (B) hydroxyl group-containing aromatic phosphoric acid ester of the present invention, the following formula [Chemical formula 4] diphenylresorcinyl phosphate or [Chemical formula 5] diphenylhydroquinonyl phosphate is preferable, and its production method is ,
For example, it is disclosed in JP-A-1-223158 and can be obtained by the reaction of phenol, hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0026]

[Chemical 4]

[0027]

[Chemical 5]

The red phosphorus in the component (B) of the present invention is selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide on the surface thereof in addition to general red phosphorus. Those coated with a metal hydroxide coating, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, those coated with a metal hydroxide selected from titanium hydroxide and a thermosetting resin, It is also possible to suitably use, for example, a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, which is double-coated with a coating of a thermosetting resin. .

The drip suppressing resin as the component (C) of the present invention is a silicone resin and / or polyphosphazene. It is essential that the silicone resin does not soften in the temperature range of 0 ° C. to 350 ° C. and contains a vinyl group. Silicone resin that satisfies this condition is S
iO ₂ , RSiO _3/2 , (R) ₂ SiO, (R) ₃ Si
It is a copolymer having a three-dimensional network structure formed by combining structural units of O _1/2 , RViSiO, and (R) ₂ ViSiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group and a propyl group, or an aromatic group such as a phenyl group and a benzyl group, and Vi represents a vinyl-containing group such as the following formulas [Chemical Formula 6] [Chemical Formula 7]. Show.

[0030]

[Chemical 6]

[0031]

[Chemical 7]

The silicone resin of the present invention is 0 ° C to 350 ° C.
In order to exhibit non-softening property in the temperature range of 1, the average number of organic groups directly bonded to silicon atoms is 2.0 or less, preferably 1.
It must be 5 or less. Such a silicone resin is obtained by cohydrolyzing and polymerizing the organohalosilane corresponding to the above structural unit.

Another polyphosphazene of the (C) drip suppressing resin of the present invention is a polymer having a bond of a phosphorus atom and a nitrogen atom in the main chain and is represented by the following general formula [Chem. 8].

[0034]

[Chemical 8]

Here, in the formula, R ₁ and R ₂ each represent an alkoxy group, an aryloxy group or an amino group. The alkoxy group and allyloxy group may be substituted with a halogen atom, an allyl group, an amino group, a hydroxyl group or the like. Also,
The amino group may be substituted with an alkyl group, an allyl group or the like. n is an integer. Specific examples of the polyphosphazene used in the present invention are polypropoxyphosphazene, polyphenoxyphosphazene, polyaminophosphazene, polyfluoroalkylphosphazene and the like.

Next, (D) triazine skeleton-containing compound, (E) fluororesin, and (F) higher fatty acid amide compound can be blended in the resin composition of the present invention, if necessary. The (D) triazine skeleton-containing compound is
(B) A component for further improving flame retardancy as a flame retardant aid for a phosphorus-containing flame retardant. Specific examples thereof include melamine, melam, melem, melon, melamine cyanurate, succinoguanamine, adipoguanamine, methylglutaloganamin, melamine phosphate, melamine resin, and B.
Examples thereof include T-resin, and among them, melamine cyanurate is particularly preferable.

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

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

The (F) higher fatty acid amide compound is a component for improving fluidity,
It is a reaction product with (a) diamines or (b) amino alcohols. Here, the higher fatty acid has 11 to 2 carbon atoms
It is a fatty acid having one alkyl group or alkenyl group, and stearic acid is particularly preferable.

The diamines have 2 to 10 carbon atoms.
Of the above hydrocarbon diamines, and ethylenediamine is particularly preferable. Further, the amino alcohols are hydrocarbon amino alcohols having 2 to 10 carbon atoms, and examples thereof include monoethanolamine, 3-amino-1-propanol and 4-amino-1-butanol.

As the higher fatty acid amide compound as the component (F) of the present invention, ethylene bis stearylamide is particularly preferable, and the fluidity is improved while maintaining flame retardancy, heat resistance and impact resistance. Let The resin composition of the present invention contains 1 part of the (B) phosphorus-containing flame retardant per 100 parts by weight of the (A) thermoplastic resin.
˜40 parts by weight, (C) drip suppressor 0.1 to 20 parts by weight, (D) triazine skeleton-containing compound 0 to 30 parts by weight, (E) fluororesin 0 to 10 parts by weight, (F). The higher fatty acid amide compound is preferably in the range of 0 to 10 parts by weight. If it deviates from the above range, the drip resistance, flame resistance, impact resistance, heat resistance and fluidity tend to be unbalanced.

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

By subjecting the composition of the present invention thus obtained to, for example, injection molding or extrusion molding, a molded article excellent in drip resistance, flame retardancy, fluidity, heat resistance and impact resistance can be obtained. can get.

[0044]

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 styrene-based resin is obtained by calculating the particle diameter of the butadiene-based polymer in the transmission electron micrograph taken by the ultrathin section method of the injection composition, and using the following formula. calculate.

Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene polymer particles whose particles are Di.) (2) Reduced viscosity ηSP / C rubber-modified styrene Methyl ethyl ketone 18 to 1 g of resin
Add a mixed solvent of 2 ml of methanol and 2 ml of methanol at 2
Shake for hours and centrifuge for 30 minutes at 18000 rpm 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 dissolved in toluene to give a solution having a concentration of 0.5 g / dl, and 10 ml of this solution was placed in a Canon-Fenske viscometer.
At 30 ° C., the number of seconds t _{1 during} which the solution flowed was measured. On the other hand, the flowing down time t ₀ of pure toluene was separately measured with the same viscometer and calculated by the following mathematical formula. ηSP / C = {(t ₁ / t ₀ -1)] / C (C: polymer concentration g / dl) On the other hand, for the reduced viscosity ηSP / C of the component (A) PPE, 0.1 g is dissolved in chloroform. And concentration 0.5g
/ Dl solution and measured in the same manner as above. (3) Softening temperature of silicone resin It was measured by a differential scanning calorimetry (DSC). Specifically, a Shimadzu thermal analyzer DT-40 was used to raise the temperature of a 5 mg sample at 10 ° C./min under a nitrogen stream, and the endothermic peak was taken as the softening temperature. (4) Structure of Silicone Resin (Measurement of Vinyl Group) Infrared absorption spectroscopy was used. In particular,
Characteristic absorption of vinyl group (1595, 1000, 960 Kaiser 1 using Shimadzu IR spectrophotometer IR-470)
/ Cm ^-1 ). (5) Izod impact strength It was measured at 23 ° C. by a method according to ASTM-D256 (V notch, 1/8 inch test piece). (6) Vicat softening temperature Measured by a method according to ASTM-D1525, and used as a measure of heat resistance. (7) Melt Flow Rate (MFR) The melt flow rate was measured by a method based on ASTM-D1238, an index of fluidity. 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). (8) Flame retardance and drip resistance VB (Vertical Bur) compliant with UL-94
(1/8 inch test piece).

[0047]

Examples 1 to 3, Comparative Examples 1 to 5 (a) Production of thermoplastic resin Production of rubber-modified styrene resin (HIPS) Polybutadiene [(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 Binding = 95/2/3 (weight ratio)) (Nippon Zeon Co., Ltd., trade name Nipol 1220S)
L)] was dissolved in the following mixed solution to form a uniform solution.

Polybutadiene 10.5% by weight Styrene 72.2% by weight Ethylbenzene 15.0% by weight Mineral oil 2.0% by weight α-Methylstyrene dimer 0.27% by weight 1,1-bis (t-butylper) Oxy) -3,3,5-trimethylcyclohexane 0.03% by weight Then, the above mixed solution was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage was stirred at 190 rpm, 126 rpm.
℃, the second stage is 50 rpm, 133 ℃, the third stage is 20 rp
m, 140 ° C, and the fourth stage was polymerized at 20 rpm and 155 ° C. Subsequently, this polymerization liquid having a solid content of 73% was introduced into a degassing apparatus to remove unreacted monomers and solvent to obtain a rubber-modified styrene resin (referred to as HIPS). As a result of analyzing the obtained rubber-modified styrenic resin, the rubber content was 1
4% by weight, the weight average particle diameter of rubber was 2.4 μm, and the reduced viscosity ηSP / C was 0.53 dl / g.

Manufacture of polyphenylene ether (PPE) After thoroughly replacing the inside of a stainless reactor having an oxygen blowing port at the bottom of the reactor with a cooling coil and stirring blades with nitrogen, the bromide second Copper 54.8 g, di-n-
Butylamine 1110 g, and toluene 20 liters,
8.75 kg of 2,6-oxylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into a reactor. While stirring, oxygen was continuously blown into the interior of the reactor to an internal temperature of 30 ° C. Polymerization was carried out for 180 minutes while controlling. 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). The reduced viscosity ηSP / C was 0.55 dl / g.

Next, the above PPE and polystyrene (Styron 685, trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) were mixed at a weight ratio of 70/30, and melt-extruded at 350 ° C. with a twin-screw extruder. The obtained pellet is called PPE-MB. (B) Phosphorus-containing flame retardant Production of organic phosphorus compound containing hydroxyl group-containing aromatic phosphoric acid ester Phenol 122.7 parts by weight (molar ratio 2.0), aluminum chloride 0.87 parts by weight (molar ratio 0.1. 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. 71.7 parts by weight (molar ratio 1.0) of resorcin was added to the produced 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. Then, the reaction product was cooled and washed with water to remove the catalyst and the chlorine content to obtain a phosphoric acid ester mixture (hereinafter referred to as FR). When this mixture was analyzed by GPC (gel permeation chromatography), it was found that diphenyl resorcinyl phosphate represented by the following formula:
TPP-OH), triphenyl phosphate (hereinafter referred to as TPP), and an aromatic condensed phosphoric acid ester represented by the following formula (Formula 10) (hereinafter referred to as TPP dimer).
And the weight ratio is 54.2 / 18.3 / 2, respectively.
It was 7.5.

[0051]

[Chemical 9]

[0052]

[Chemical 10]

Hydroxyl group-free aromatic phosphate ester Commercially available aromatic condensed phosphate ester [Dahachi Chemical Industry Co., Ltd.
Manufactured by the trade name CR733S (called poly-FR)]. According to GPC analysis, the aromatic condensed phosphoric acid ester has a T value represented by the following formula [11].
It was composed of PP dimer and TPP oligomer, and the weight ratio of each was 65/35.

[0054]

[Chemical 11]

However, n = 1 TPP dimer and n ≧ 2 TPP oligomer. (C) Drip suppressing resin Silicone resin A commercially available silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A) Product name Multifunctional silicone resin X-40-21
35 (hereinafter referred to as Si-1), the following [Chemical Formula 12]
It contains the structural unit of [Chemical Formula 13].

In addition, absorption of vinyl group was detected by infrared absorption spectrum. (1595, 1000, 960
1 / cm ⁻¹ ) (see FIG. 1). By DSC measurement, 0 ℃ ~
No softening point was detected at 350 ° C.

[0057]

[Chemical 12]

[0058]

[Chemical 13]

[0059]

[Chemical 14]

B) Product name Multifunctional silicone resin X
-40-2134 (hereinafter referred to as Si-2) and the following structural units of [Chemical Formula 15] and [Chemical Formula 16] are contained. In addition, absorption of vinyl group was not detected by infrared absorption spectrum. (See Figure 1).

By DSC measurement, no softening point was detected between 0 ° C and 350 ° C.

[0062]

[Chemical 15]

[0063]

[Chemical 16]

C) Trade name Silicone resin X-21
-5861 (hereinafter referred to as Si-3) In addition, absorption of vinyl group was not detected by infrared absorption spectrum. According to the DSC measurement, the softening temperature is 49.
It was 7 ° C. D) Trade name Silicone resin X-21-5862
(Hereinafter, referred to as Si-4) Further, absorption of vinyl group was not detected by infrared absorption spectrum.

According to the DSC measurement, the softening temperature is 63.9.
It was ℃. Polyphosphazene Commercially available polyphosphazene was used. A) Poly (fluoroalkylphosphazene) Daikin Industries, Ltd., trade name Ipel-F404N
C [Manufacturer: Ethyl Corporation (USA)] (hereinafter referred to as PN-1) B) Phosphazene monomer [Phosphazene monomer having the structure of [Chemical 17] [Idemitsu Petrochemical Co., Ltd., trade name Idemitsu PPZ- U-1000] (hereinafter,
(Referred to as PN-2)

[0066]

[Chemical 17]

(D) Compound containing triazine skeleton Commercially available melamine cyanurate [manufactured by Nissan Chemical Industries, Ltd.,
The product name MC-610 (hereinafter referred to as MC)] was used. (E) Higher fatty acid amide Commercially available ethylene bisstearyl amide (Kao Corporation)
Manufactured by Kao Wax EB FF). (Hereinafter, referred to as EBS) (F) Preparation and evaluation of composition HIPS (A) / PPE-MB (A) / FR (B) / p
oly-FR (B) / drip suppressing polymer (C) / M
C (D) / EBS (F) is 71/29/12/8 / X /
The mixture was mechanically mixed at a mixing ratio of 16/2 and melted for 5 minutes at a melting temperature of 250 ° C. and a rotation speed of 50 rpm using a Labo Plastomill manufactured by Toyo Seiki Seisakusho. A 1/8 inch thick test piece was prepared from the resin composition thus obtained by hot pressing, and the flame retardancy, Vicat softening temperature, Izod impact strength and MFR were evaluated. The results are shown in Table 1.

According to Table 1, the resin composition containing non-softening property, vinyl-containing silicone resin, or polyphosphazene has drip resistance, flame retardancy, fluidity, impact resistance, and heat resistance. I know that

[0069]

[Table 1]

[0070]

Examples 4 to 7 (a) Thermoplastic resin The above HIPS and PPE-MB were used. (B) Phosphorus-containing flame retardant organic phosphorus compound The above-mentioned FR, poly-FR and triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name TPP) (hereinafter referred to as TPP) were used.

Red phosphorus A commercially available resin-coated red phosphorus powder [Nova Excel 150 (hereinafter referred to as RP), manufactured by Rin Kagaku Kogyo Co., Ltd.] was used. (C) Drip suppression resin The silicone resin Si-1 described above was used. (D) Triazine skeleton-containing compound The MC was used. (E) Higher fatty acid amide The above EBS was used. (F) Preparation and evaluation of composition Example 1 except that the compounding ratio was changed to that shown in Table 2.
~ 3 The same experiment as in Comparative Examples 1 to 5 was repeated. The results are shown in Table 2 together with Example 1.

According to Table 2, the composition containing the hydroxyl group-containing aromatic phosphoric acid ester has extremely excellent balance characteristics of drip resistance, flame retardancy, fluidity, impact resistance and heat resistance. I understand.

[0073]

[Table 2]

[0074]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is a thermoplastic resin composition in which the dropping of fire species during combustion is extremely small and the flame resistance, impact resistance, heat resistance, and fluidity are excellent.
This composition is suitable for home electric appliance parts, office automation equipment parts, etc., and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 is a silicone resin containing a vinyl group (Si-
1) and a vinyl group-free silicone resin (Si-
It is the figure which showed the infrared absorption spectrum of 2).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 85:02)

Claims (1)

[Claims] 1. A thermoplastic resin (A), a phosphorus-containing flame retardant which is (B) an organic phosphorus compound and / or red phosphorus, and (C) a non-softening and vinyl group-containing silicone resin and / or poly. A drip-resistant flame-retardant heat-resistant and impact-resistant resin composition comprising a phosphazene drip suppressing resin.