JPH07242810A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in fluidity during molding and having a high reflectance of light and excellent flame retardancy by compounding a composition comprising an aromatic polycarbonate, a thermoplastic polyester, etc., with titanium oxide, an organohalogen compound and an inorganic filler. CONSTITUTION:This resin composition is obtained by compounding (A) 100 pts.wt. of a composition comprising 40-90wt.% of an aromatic polycarbonate and 10-60wt.% of a polymer selected from a thermoplastic polyester, a styrene polymer and a methacrylic polymer with (B) 3-20 pts.wt. of titanium oxide, (C) 3-20 pts.wt. of an organohalogen compound having a molecular weight of >=1000 and (D) 0.1-10 pts.wt. of a fibrous inorganic filler having an average fiber diameter of <=4mum and an aspect ratio of >=5. The component D is selected from glass fiber, glass wool, carbon fiber, fibrous magnesium, magnesium borate, silicon carbide whisker, silicon nitride whisker, potassium titanate whisker, fibrous aluminum oxide, needle-shaped titanium oxide and wallastonite. Further, an organophosphorous compound having an average molecular weight of >=500 and phosphorous content of >=8wt.% is compounded in an amount of 3-20 pts.wt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition, and more specifically, one or more selected from (A) aromatic polycarbonate, thermoplastic polyester, styrene-based polymer and methacrylic-based polymer. The present invention relates to a flame-retardant resin composition obtained by adding (B) titanium oxide (C) an organic halogen compound having a molecular weight of 1000 or more and (D) a fibrous inorganic filler having a specific shape to a composition made of a polymer.

The flame-retardant resin composition of the present invention relates to a resin composition having excellent mechanical properties, thermal properties, electrical properties, flame retardancy, and fluidity during molding, and particularly having a high light reflectance,
It is useful in fields requiring a high degree of light reflectance such as backlight reflectors for liquid crystal displays, illuminated bush switches, and reflectors for photoelectric switches.

[0003]

2. Description of the Related Art Conventionally, as the light reflector, a glass-made or resin-molded product which has been metal-plated or coated has been used. The glass reflector is heavy and easily broken. The reflector plate obtained by metal-plating a resin molded product has a problem that the plating cost is high and the total cost is high. Therefore, there has been a demand for a resin molded product that has a low light price and a high light reflectance without the need for post-processing.

As a method for obtaining a resin molded article having a high light reflectance, for example, the method described in JP-A-57-83549 can be considered. In this publication, aromatic polycarbonate (hereinafter abbreviated as PC), a pigment such as titanium oxide, and a silane coupling agent are uniformly blended, and then 28
It is disclosed that pellets are obtained by melt-kneading at 0 ° C. to obtain a molded product having a good hue.

According to the description of JP-A-57-83549, a test piece was molded from a composition consisting of 90 parts by weight of PC, 10 parts by weight of titanium oxide and 1 part by weight of γ-glycidoxypropyltrimethoxysilane. Although the coloring property was certainly good, since the amount of titanium oxide is as large as 10 parts by weight,
The melt viscosity becomes high, and thin molded products (1.6 x 12.7 x
When molding (127 mm), it is necessary to set the resin temperature to 300 ° C. or higher, and as a result, silver often occurs on the surface of the test piece, and only a test piece having extremely low tensile strength and elongation at break can be obtained.

In Japanese Patent Publication No. 63-26140, P
A resin composition is disclosed which comprises C and an end-capped polyorganohydrogen siloxane, titanium oxide, and a stabilizer. The composition described in JP-B-63-26140 also has a high melt viscosity, so that the melt-kneading temperature is 288 ° C. and the molding temperature is 300.
Higher than ℃. When used as a light reflector, the addition ratio of titanium oxide is 3 parts by weight or more, preferably 7 parts by weight or more.
~ 15 parts by weight is required. After melting and kneading PC containing 3 parts by weight or more of titanium oxide at 288 ° C. or higher, the resin temperature is 30
When injection molding is performed at 0 ° C or higher, even if a polyorganohydrogen siloxane having a terminal end or a stabilizer is added, the thermal decomposition accelerating action of PC due to titanium oxide cannot be suppressed, silver is generated on the surface of the molded product, and the commercial value is significantly impaired. It was a thing.

Japanese Patent Publication No. 63-31513 also discloses PC, oligomeric or polymeric hydrocarbon oxysiloxanes,
A resin composition comprising a phosphorus stabilizer and an epoxy stabilizer is disclosed. In this case also, since the melt viscosity is high, 28
Melt kneading at 8 to 316 ° C, pelletizing, and pelletizing
A method of molding at a temperature of 16 ° C. or higher is disclosed.

According to the method of Japanese Patent Publication No. 63-31513, the inventors of the present invention, 100 parts by weight of PC, 3 parts by weight of titanium oxide,
1,3-diphenyltetraethoxydisiloxane 0.4
By weight, a composition comprising 0.1 part by weight of a phosphorus-based stabilizer and 0.1 part by weight of an epoxy-based stabilizer is melt-kneaded to obtain pellets, and an impact test piece and a tensile test piece according to ASTM-D638 are formed. did. Although the obtained test piece had good colorability, a large amount of silver was generated on the surface of the test piece and the elongation at break was as low as 5% or less, which was very low in practicality.

Japanese Unexamined Patent Publication (Kokai) No. 3-247670 discloses a method of adding titanium oxide or the like surface-treated with a copolymer of a polyoxyalkylene derivative and maleic acids to PC. According to the description of the publication, the viscosity average molecular weight of the pellet obtained by adding 1% of the surface-treated titanium oxide to PC was treated for 1 hour in a nitrogen stream at 340 ° C., the decrease in viscosity average molecular weight was about 10%.
It is said to be as low as 00.

The inventors of the present invention also mixed 7 parts by weight of surface-treated titanium oxide with 100 parts by weight of PC according to JP-A-3-247670, melt-kneaded the mixture with a single screw extruder at a cylinder temperature of 280 ° C., and then pelletized it. did. After pre-drying the pellets at 120 ° C. for 7 hours, a test piece was molded at a resin temperature of 300 ° C. This test piece may have a high compounding ratio of titanium oxide, silver is generated on the surface of the test piece, and the light reflectance of the portion where silver is not generated and the portion where silver is not generated are different, and as a resin composition for a reflector, Is inappropriate.

Japanese Unexamined Patent Publication No. 4-159359 discloses that a titanium oxide powder treated with PC, aluminum and a hydrous oxide of silicon, and a composition comprising a specific silicon compound are effective as a reflector. ing. However, the PC itself has a high melt viscosity, and the composition obtained by blending 5 parts by weight or more of the titanium oxide powder treated by the above method with 100 parts by weight of PC has an even higher melt viscosity, resulting in a higher molding temperature. Otherwise, the thin-walled molded product could not be molded.
Even in a PC composition containing 5 parts by weight or more of titanium oxide powder treated by the above method, when molded at a high temperature of 300 ° C. or higher, PC is decomposed, and the light reflectance is lowered due to the generation of silver. Only a molded product having a remarkably low commercial value was obtained due to deterioration of mechanical properties.

In order to lower the resin temperature during molding, a low molecular weight PC having a low melt viscosity, for example, a viscosity average molecular weight of 150.
In a composition in which 5 parts by weight or more of titanium oxide powder and a silane coupling agent or a heat stabilizer are mixed with PC No. 00, silver does not occur, but cracks are likely to occur and mechanical properties are deteriorated. It was great.

Further, recently, a high degree of flame retardancy has been required for the light reflecting plate. For example, the thickness of the test piece is 1.6 mm, and the UL standard No. 94 is V-0, V-1.
Is required. In order to make the PC resin composition flame-retardant, it is generally known that a large amount of an organic halogen compound is added to PC, or a copolymer of bisphenol A and tetrabromobisphenol A is used. When a large amount of organic halogen compound is added to PC, there is a problem that the Izod impact strength and the deflection temperature under load are largely lowered. On the other hand, bisphenol A and tetrabromobisphenol A
In the case of a copolymer with, the fluidity during molding is significantly reduced,
There is a major drawback that it is difficult to form a thin-walled molded product.

[0014]

DISCLOSURE OF THE INVENTION The present invention has a high degree of flame retardancy and excellent fluidity at the time of molding, and by molding at a resin temperature as low as possible, silver is not generated and molding is performed. An object of the present invention is to obtain a resin composition that provides a light-reflecting plate that is uniform throughout the product and has both high light reflectance and excellent physical properties.

[0015]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the inventors of the present invention have conducted various studies and have selected one or more selected from PC, thermoplastic polyester, styrene-based polymer, and methacrylic-based polymer. Molded products obtained from a composition obtained by mixing a resin composition comprising the above polymer with titanium oxide, an organic halogen compound having a molecular weight of 1000 or more, and a fibrous inorganic filler having an average diameter of 4 μm or less and an aspect ratio of 5 or more have silver generation. 500 nm to 700 without
It has been found that it is possible to obtain a light reflector having a light reflectance of 90% or more in the wavelength range of nm, excellent whiteness, and excellent physical properties such as elongation at break and flame retardancy.

That is, the present invention provides (A) PCs 40-9.
100 parts by weight of a resin composition consisting of 0% by weight and 10 to 60% by weight of one or more polymers selected from thermoplastic polyesters, styrene polymers, and methacrylic polymers, (B) titanium oxide 3 to 25 parts by weight, (C) Molecular weight 1
3 to 20 parts by weight of an organic halogen compound of 000 or more,
(D) A flame-retardant resin composition comprising 0.1 to 10 parts by weight of a fibrous inorganic filler having an average diameter of 4 μm or less and an aspect ratio of 5 or more, and further having an average molecular weight of 500 or more and an adjoining content of 8%.
The present invention relates to a flame-retardant resin composition containing 3 to 20 parts by weight of the organic phosphorus compound.

The resin component in the present invention is PC40-90.
Wt% and thermoplastic polyester, styrenic polymer,
It is composed of 10 to 60% by weight of one or more polymers selected from methacrylic polymers, and when the proportion of PC is lower than 40% by weight, the deflection temperature under load and the impact strength are largely decreased, which is not preferable. On the other hand, if the PC content is more than 90% by weight, the fluidity will drop significantly and the resin temperature during molding will be 300 ° C.
And silver is liable to occur, impairing practicality, which is not preferable. Therefore, the ratio of PC is set to the above range,
The blending ratio of one or more polymers selected from thermoplastic polyesters, styrene polymers, and methacrylic polymers is 10 to 60% by weight.

The viscosity average molecular weight of PC is 18,000.
˜28,000, preferably 20,000 to 26.0
00. When the viscosity average molecular weight of PC is lower than 18,000, the mechanical properties are largely deteriorated, and when it exceeds 28,000, the melt viscosity is too high, and the resin temperature during molding becomes higher than 300 ° C., which is not preferable. The resin temperature at the time of molding is slightly different depending on the injection molding machine, but in general, the resin temperature is often 5 to 20 ° C. higher than the cylinder set temperature.

As the PC used in the present invention, one obtained by a conventionally known manufacturing method is used. That is, in the presence of an organic solvent inert to the reaction, an aqueous alkali solution, a dihydric phenol compound and phosgene are reacted, and then a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added to perform polymerization. Polymerization method, a pyridine method or the like in which a dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is introduced to directly produce PC. In the above reaction, when necessary, Molecular weight regulators, branching agents, etc. are used.

Specific examples of the dihydric phenol compound used in the production of PC include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4
-Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-
Hydroxy-3-methylphenyl) propane, 1,1-
Bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane , Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane;
Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4′-dihydroxydiphenyl ether, 4, Dihydroxydiaryl ethers such as 4'-dihydroxy-3,3'-dimethyldiphenyl ether; 4,4'-Dihydroxy-3,3'-dimethyldiphenyl sulfides such as dihydroxydiaryl sulfides; Dihydroxy diaryl sulfoxides such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxy-
Dihydroxydiarylsulfones such as 3,3′-dimethyldiphenylsulfone may be used alone or in combination of two or more.

As the thermoplastic polyester of the present invention, aliphatic polyester, aromatic polyester, wholly aromatic polyester and the like can be used. Specifically, a polycondensate obtained from a dicarboxylic acid or its derivative and a divalent or higher polyhydric alcohol or a polyhydric phenol compound;
Examples include polymers obtained from dicarboxylic acids or their derivatives and cyclic ether compounds; polycondensates of metal salts of dicarboxylic acids and dihalogen compounds; ring-opening polymers of cyclic ester compounds. The term "dicarboxylic acid derivative" as used herein means an acid anhydride, an ester, an acid halide or the like. The dicarboxylic acid may be aliphatic or aromatic.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p
-Phenylenediacetic acid, m-phenylenediglycolic acid,
p-phenylenediglycolic acid, diphenyldiacetic acid, diphenyldi-p, p'-dicarboxylic acid, diphenylether-p, p'-dicarboxylic acid, diphenyl-m, m-
Dicarboxylic acid, diphenyl ether-4,4'-diacetic acid, diphenylmethane-p, p'-dicarboxylic acid, diphenylethane-p, p'-dicarboxylic acid, benzohenone-4,4'-dicarboxylic acid, naphthalene-1,4- Dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-
Dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyric acid, 1,2-diphenoxypropane-p, p'-dicarboxylic acid, 1,3-diphenoxypropane-p, p'-dicarboxylic acid, 1, 4-diphenoxybutane-p, p'-dicarboxylic acid, 1,5-diphenoxypentane-dicarboxylic acid, 1,6-diphenoxyhexane-dicarboxylic acid, p- (p-carboxyphenoxy) benzoic acid, 1,2 -Bis (2-methoxyphenoxy) -ethane-p, p'-dicarboxylic acid, 1,3-bis (2-methoxyphenoxy) -propane-p, p'-
Dicarboxylic acid etc. are mentioned.

Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, adipic acid, cork acid, mazelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid and fumaric acid. Examples of preferred dicarboxylic acids are aromatic dicarboxylic acids, more preferably terephthalic acid, isophthalic acid,
Naphthalene-2,6-dicarboxylic acid may be mentioned.

As the polyhydric alcohol having a valence of 2 or more, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butane-1,4-diol, 2, 2-dimethylpropane
1,3-diol, cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, tetramethylene glycol, pentamethylene glycol,
Hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol and the like can be mentioned.

Examples of preferred polyhydric alcohols are ethylene glycol, propane-1,2-diol, propane-
Examples thereof include 1,3-diol, butane-1,3-diol, butane-1,4-diol, and more preferably, ethylene glycol and butane-1,4-diol. As the polyhydric phenol compound, hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (4
-Hydroxyphenyl) propane, 1,1- (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) Phenyl) ketone, 4-
Examples thereof include hydroxyphenyl-3-hydroxyphenyl ketone.

Examples of the cyclic ether compound include ethylene oxide and propylene oxide, and examples of the cyclic ester compound include ε.
-Caprolactone, δ-valerolactone and the like can be mentioned. The dihalogen compound to be reacted with the metal salt of dicarboxylic acid means a compound obtained by substituting the hydroxyl group of the polyhydric alcohol or the polyhydric phenol compound with a halogen atom such as chlorine or bromine. The heat-deprived polyester used in the resin composition of the present invention is produced by a known method using the above raw materials, for example, a method such as a transhalogenation method, direct dehydration condensation, dehalogenation metal by interfacial polycondensation or the like. To be done.

Among these, preferred thermoplastic polyesters include polyethylene terephthalate (hereinafter abbreviated as PET), polypropylene terephthalate, polybutylene terephthalate (hereinafter abbreviated as PBT), polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethanol terephthalate. And so on. Further, a copolyester such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate can be used. Of these, particularly preferred are PET and P.
It is BT.

The thermoplastic polyester used in the present invention has an intrinsic viscosity measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethylene mixed at a weight ratio of 6: 4, of 0.3 or more, usually 0.6 to 1 .5 is preferable,
If it is less than 0.3, the mechanical strength such as elongation at break is lowered, which is not preferable. If the polymer has a high molecular weight such that the intrinsic viscosity exceeds 1.5, the melt viscosity of the composition is high, the molding temperature is high, and the resin composition is thermally decomposed, which is not preferable.

As the styrene-based polymer in the present invention, polystyrene and high impact polystyrene (HI
PS), acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, acrylate / styrene / acrylonitrile copolymer, acrylonitrile / ethylene / styrene copolymer, and styrene / maleic acid copolymer are commercially available polymers. To be done.

The methacrylic polymer in the present invention is a methacrylic acid or methacrylic acid ester polymer, or a copolymer of methacrylic acid or another vinyl monomer copolymerizable with methacrylic acid ester,
Specifically, for example, polymethylmethacrylate,
Copolymers such as polyethylmethacrylate, polybutylmethacrylate, polypropylmethacrylate, and methylmethacrylate / styrene copolymer are exemplified.

The titanium oxide used in the present invention preferably has a rutile type crystal structure produced by the chlorine method from the viewpoint of the light resistance of the resin composition. The titanium oxide surface may be treated with zinc, aluminum or silica. Further known silane-based coupling agents, for example, those treated with cetyltrimethoxysilane, γ-aminopropyltrimethoxysilane, methylhydrogenforisiloxane, or organosilane compounds containing methylhydrogenforisiloxane and zirconium salt. Can be used.

Titanium oxide having a particle size of 0.05 to 5 μm, preferably 0.1 to 1 μm is preferably used. When the particle size of titanium oxide is smaller than 0.05 μm, the light reflectance decreases, while when it exceeds 5 μm, irregularities on the surface of the molded product are conspicuous, causing poor appearance, and mechanical properties, especially elongation at break. Is greatly reduced, which is not preferable.

Titanium oxide is added in an amount of 3 to 25 parts by weight, preferably 7 to 15 parts by weight, based on 100 parts by weight of the resin component. When the compounding ratio of titanium oxide is lower than 3 parts by weight, a thin-walled molded product is not preferable because light rays are transmitted therethrough and the reflectance is lowered. Further, if it exceeds 25 parts by weight, the melt viscosity becomes extremely high, and the resin temperature at the time of molding becomes 3
The temperature exceeds 00 ° C, and P due to titanium oxide
There is a risk that the decomposition of C is promoted, which is not preferable.

As the fibrous inorganic filler which is one of the compounding ingredients in the present invention, those having an average diameter of 4 μm or less and an aspect ratio of 5 or more are suitably used. Examples of such fibrous inorganic filler include glass fiber, glass wool, carbon fiber, and fibrous magnesium (for example, manufactured by Ube Industries, Ltd.
Mosheige), magnesium borate, silicon carbide whiskers, silicon nitride whiskers, graphite, potassium titanate whiskers, fibrous aluminum oxide, acicular titanium oxide,
Examples include wollastonite and ceramic fibers (for example, Ibiwool, Ibiwool). As these inorganic fibrous fillers, those treated with various coupling agents such as silane, organic compounds having an oxazoline ring, and other surface-treating agents can be preferably used, and those obtained by converging with known converging agents may be used. .

When the resin component, the organic halogen compound, the fibrous inorganic filler and the titanium oxide are blended, a known coupling agent such as a silane coupling agent is separately added to 0.3 parts by weight with respect to 100 parts by weight of the fibrous inorganic filler. ~ 30
It is also possible to blend by weight. By this, the surface of the fibrous inorganic filler and titanium oxide is highly coated, the direct contact between the fibrous inorganic filler and titanium oxide and the resin component is reduced, and the direct contact between the PC component and the fibrous inorganic filler and titanium oxide is performed. Thermal contact can be avoided as much as possible, and thermal decomposition of the PC component during high temperature molding can be suppressed.

In the present invention, the addition of the above-mentioned fibrous inorganic filler is carried out by dropping the molten resin ignited during the combustion test.
It is effective in preventing so-called dropping. To effectively prevent the molten resin from falling, the fibrous inorganic filler used has an average diameter of 4 μm or less and an aspect ratio of 5
The above are preferred. When the aspect ratio of the fibrous inorganic filler is less than 5, the effect of preventing the molten resin from catching fire from dropping is small, which is not preferable.

The mixing ratio of the fibrous inorganic filler is 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin component. When the compounding ratio of the fibrous inorganic filler is lower than 0.1 part by weight, the effect of preventing the molten resin from catching fire from dropping is small, and when it exceeds 10 parts by weight, the impact strength is lowered and the flame-retardant resin composition This is inconvenient because the specific gravity of is high. Further, if the average diameter of the fibrous inorganic filler exceeds 4 μm, the fibrous inorganic filler is raised on the surface of the molded product and the light reflectance is lowered, which is not preferable.

For the purpose of further improving the light reflectance of the light reflector formed from the flame-retardant resin composition of the present invention, a carbonate oligomer from bisphenol A, polycaprolactone, an acrylic elastic polymer, and terminal glycidyl of polycaprolactone. A derivative, 12-caprolactone, an organopolysiloxane, a copolyestercarbonate, and a polyester oligomer can also be blended. The mixing ratio thereof is 2 to 50 with respect to 100 parts by weight of the resin composition.
Parts by weight are preferred. If the blending ratio is less than 2 parts by weight, the effect of improving the light reflectance is small, and if it exceeds 50 parts by weight, the deformation temperature under load and the impact strength of the obtained molded article must be largely reduced.

The flame-retardant resin composition of the present invention was prepared according to UL standard 94.
When it is desired to make it flame-retardant to VC-0 or V-1 or more, the organic halogen compound having a molecular weight of 1000 or more is blended in an amount of 3 to 25 parts by weight, preferably 7 to 15 parts by weight. As such an organic halogen compound, a carbonate oligomer having a polymerization degree of 3 to 25 using tetrabromobisphenol A as a starting material, a brominated polystyrene, a brominated epoxy compound, or the like can be blended. If the blending amount of the organic halogen compound is less than 3 parts by weight, the target flame retardancy cannot be obtained. On the other hand, if the blending amount of the organic halogen compound exceeds 25 parts by weight, mechanical strength is lowered and thermal stability at the time of molding is lowered, which is not preferable. Further, if the molecular weight of the organic halogen compound is lower than 1000, it volatilizes during the melt-kneading and pollutes the working environment, which is not preferable.

Further, an antimony compound, a zirconium compound or the like can be blended as a flame retardant aid.
In addition, the resin component 100 is added to prevent dripping of the fired resin.
It is also possible to mix 2 parts by weight or less of polytetrafluoroethylene having a molecular weight of 1,000,000 or more with respect to parts by weight.

The flame-retardant resin composition of the present invention may further contain a flame retardant. Examples of such a flame retardant include an organic phosphorus compound having an average molecular weight of 500 or more and a neighboring content of 8% by weight or more. Examples of such an organic phosphorus compound include phenyl resorcinol polyphosphate and phenyl cresyl disclosed in JP-A-57-207461, JP-A-57-207462 and JP-A-5-170996.・ Resorcin polyphosphate, tetraphenyl resorcin diphosphate,
Phenyl tricresyl resorcin diphosphate,
Triphenyl, cresyl, resorcin, diphosphate and the like can be preferably used.

When the flame retardant used has an average molecular weight of less than 500, for example, an organophosphorus compound such as triphenyl phosphate or tricresyl phosphate, the organophosphorus compound in the molded article is applied to the surface of the molded article. Bleed out. This bleed-out phenomenon is not preferable in the present invention because it not only causes a defective appearance of the molded product, but also cracks occur at the edges of the molded product with a large residual strain, which significantly reduces the practicality. When the phosphorus content in the organic phosphorus compound is lower than 8% by weight, the target flame retardancy, that is, the test according to UL Standard No. 94,
In order to obtain a composition ranked -0 or V-1, it is necessary to increase the addition rate of the organic phosphorus compound, and as a result, heat resistance such as load deflection temperature is lowered, which is not preferable.

When the flame-retardant resin composition of the present invention is required to have a high impact resistance, the following elastomers 1 to 1 are used.
It can be blended in the range of 0 parts by weight. If the compounding ratio of the elastomer is less than 1 part by weight, the effect of improving the impact resistance is small and 1
If it exceeds 0 parts by weight, the deflection temperature under load and the elastic modulus decrease largely, which is not preferable.

Specific examples of the elastomer used in the present invention include styrene / butadiene rubber, ethylene / propylene / diene copolymer (EPDM), ethylene / vinyl acetate copolymer, polyacrylic acid ester, polyisoprene, Hydrogenated polyisoprene, polyester / polyether copolymers, polyamide elastomers such as those sold by Toray Industries under the Pebax trade name, and Grelax A products from Dainippon Ink and Chemicals Inc. Polyamide elastomers sold under the name, ethylene / butene 1 copolymer, styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, ethylene / propylene copolymer, ethylene / propylene / ethylidene Norbornene copolymer, thermoplastic polyester elas Hydrogenated styrene / ethylene / butylene / styrene block copolymer (hereinafter abbreviated as SEBS) sold under the trade name of “Clayton G” by Maru, Shell Chemical Co., Ltd., “Mitsui Petrochemical Co., Ltd.” Ethylene-α as sold under the trade name "Tufmer"
Olefin copolymers and propylene-α olefin copolymers, ethylene methacrylic acid-based special elastomers such as those sold by Mitsui DuPont Polychemicals Co., Ltd., and Takeda Yakuhin Co., Ltd. sells them under the brand name "Stafloyd". A core-shell type elastomer with a core core made of rubber and a shell layer made of hard resin, and a core-shell type elastomer such as that sold by Mitsubishi Rayon Co., Ltd. under the brand name of "METABLEN S" are used. it can. A core / shell type elastomer whose core layer is made of silicone rubber and shell layer is made of acrylic rubber or acrylic resin, also sold by Mitsubishi Rayon Co., Ltd., grade name S2001 or RK.
120 or the like can be added. Further, a block copolymer composed of a polystyrene phase and a hydrogenated polyisoprene phase as sold under the trade name of "Septon" by Kuraray Co., Ltd. can be used.

In the flame-retardant resin composition of the present invention, if necessary, known heat stabilizers such as phenol type, phosphite type, thioether type, hindered phenol type, epoxy type, zinc sulfide, zinc oxide, etc. And antioxidants can be used. In addition, antistatic agents, plasticizers, lubricants,
Release agent, ultraviolet absorber, that is, benzotriazole-based compound, benzophenone-based compound, aromatic benzoate-based compound, cyanoacrylate-based compound, oxalic anilide-based compound, sterically hindered piperidine derivative or high molecular weight piperidine as a light stabilizer Derivatives and the like can also be added.

The flame-retardant resin composition of the present invention can be produced by the equipment and method generally used for producing a thermoplastic resin composition. For example, (1) components constituting the flame-retardant resin composition of the present invention are collectively mixed, melt-kneaded with a uniaxial or biaxial extruder, and pelletized. (2) With a single-screw or twin-screw extruder having two or more raw material input ports, polymer components other than PC, titanium oxide, and a silane coupling agent are input from the first raw material input port, and after melt-kneading The remaining raw materials are charged from the second raw material charging port, melt-kneaded and pelletized. (3) Polymer components other than PC, titanium oxide, and a silane coupling agent are melt-kneaded, pelletized, and then the remaining components are additionally blended into the pellets, and the mixture is melt-kneaded to pelletize. As the melt kneader, a single-screw or twin-screw extruder can be preferably used.

Raw materials used in Examples and Comparative Examples of the present invention are as follows.

PC is a product of Mitsubishi Gas Chemical Co., Inc., with a viscosity average molecular weight of 25,000 and 20,000, and a trade name of Iupilon S1000 (P
C1) and Iupilon S3000 (abbreviated as PC2) were used.

The thermoplastic polyester has an intrinsic viscosity of 0.
Polyethylene terephthalate (hereinafter abbreviated as PET) 5 and polybutylene terephthalate (hereinafter abbreviated as PBT) having an intrinsic viscosity of 1.2 were used.

As the styrene-based polymer, an acrylonitrile / butadiene / styrene copolymer (hereinafter abbreviated as ABS) (Mitsui Toatsu Co., Ltd./Santac GT15) is used as an acrylate / styrene / acrylonitrile copolymer (hereinafter abbreviated as ASA) ( Hitachi Chemical Co., Ltd., Vitax V67
01A), acrylonitrile / styrene copolymer (hereinafter abbreviated as AS) (Electrochemical Co., Ltd./AS-S), polymethylmethacrylate (hereinafter abbreviated as PMMA) (Mitsubishi Rayon Co., Ltd./Acrypet MF), respectively. used.

As a copolymer of 60% by weight of methyl methacrylate and 40% by weight of styrene as a methacrylic polymer (hereinafter abbreviated as MS), Estyrene 600 manufactured by Nippon Steel Chemical Co., Ltd. was used.

Hydrogenated styrene / ethylene / butylene / styrene block copolymer (hereinafter referred to as SEB) as an elastomer.
(Abbreviated as S), Shell Chemical's Kraton G1651 was used.

Titanium oxide is a type manufactured by Ishihara Sangyo Co., Ltd., a particle size of 0.25 to 0.40 μm, and the main treatment agent is Al.
R-820 (hereinafter abbreviated as Ti1) which is Si and Zn, particle size of 0.25 to 0.40 μm, and R whose main processing agent is Al
-615 (hereinafter abbreviated as Ti2) was used.

As the silane coupling agent, γ-aminopropyltrimethoxysilane was used (hereinafter abbreviated as silane).

As a flame retardant, tetrabromobisphenol A manufactured by Mitsubishi Gas Chemical Co., Inc. was used as a starting material, and a carbonate oligomer (hereinafter abbreviated as TBA) having a degree of polymerization of 10 and tribumophenol at both ends was used as a flame retardant. Antimony tetroxide from Mikuni Seiren Co., Ltd. as a fuel aid (hereinafter abbreviated as antimony)
It was used.

Phenylcresyl.
Resorcin polyphosphate (hereinafter abbreviated as phosphorus compound) was used.

As a fibrous inorganic filler having an average diameter of 4 μm or less and an aspect ratio of 5 or more, which has an effect of preventing dropping during a combustion test, aminosilane-treated glass fiber “E-FMW800” (average diameter of 0. 8μ
m, length 5 to 100 μm) (hereinafter abbreviated as FMW), acicular titanium oxide “FTL200” manufactured by Ishihara Sangyo Co., Ltd. (average diameter 0.05 to 0.15 μm, fiber length 4 to 12 μm)
(Hereinafter abbreviated as needle-like titanium), Otsuka Chemical Co., Ltd. potassium titanate fiber “Tismo” (average diameter 0.2 to 0.5 μm)
Then, a fiber length of 10 to 20 μm) (hereinafter abbreviated as Tismo) was used.

[0058]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 PC1; 60 parts by weight, ABS; 40 parts by weight, Ti1; 4
Parts by weight, TBA: 15 parts by weight, antimony; 3 parts by weight,
And FMW; 2 parts by weight are mixed by a tumbler, and a single screw extruder with a screw diameter of 30 mm sets the cylinder temperature to 25.
The mixture was melt-kneaded at 0 ° C. and a screw rotation speed of 150 rpm, and then pelletized. After drying the pellets at 110 ° C. for 5 hours, an injection molding machine (SG125 manufactured by Sumitomo Heavy Industries, Ltd.) was used to mold temperature 70 ° C., resin temperature 260 ° C., injection pressure 9
3.2 at ASTM-D638 standard type 1 at 8 Mpa
mm mm tensile test pieces were molded. 100 x 100 x 2 mm square plate 127 x 12.7 x under the same conditions as the tensile test piece
A 1.6 mm flammability test piece was molded.

The tensile elongation at break (hereinafter abbreviated as elongation) is A
According to STM-D638, five tests were conducted at a pulling rate of 5 mm / min and a test temperature of 23 ° C., and the average value was taken. The average value was 25%.

The light ray reflectance (hereinafter abbreviated as reflectance%) is
Shimadzu Corporation UV256-FW type, reflectance meter, measured in the wavelength range of 400 to 700 nm, 500 to 7
The lowest reflectance in the wavelength range of 00 nm was 91%. A reflectance of 90% or more was passed.

The hue is Z-10 manufactured by Nippon Denshoku Industries Co., Ltd.
100 × 100 × 2mm with 0DP color measuring instrument
Measured with a square plate. L value = 93.9, a value = −0.52, b
A value = 2.5 was obtained. The b value <3.0 was regarded as acceptable.

The appearance of the molded product was visually observed by inspecting the combustion test piece, and A was a test piece having no silver, B was a test piece in which a minute silver was generated, C was a test piece in which a small silver was generated, and C was a large silver. The obtained test piece was designated as D, and A and B were designated as passed. The appearance of the test piece obtained here is A
Met.

The combustion test is carried out in accordance with UL standard No. 94, and the flame-retardant materials having higher flame retardance are V-0, V-1, V-2, H.
In the present invention, it is classified into B and V-0 or V-1.
Was accepted. The result obtained here was V-0.

Comparative Example 1 A test piece was obtained by pelletizing in the same manner as in Example 1 except that 1 part by weight of Ti1 was used. As a result of performing the test under the same conditions, the elongation was 28% and the reflectance was 84%, which was unacceptable. The hue is L value = 92.5, a value = −0.38, b value = 4.5.
The molded product appearance was A, and the flammability was V-0.

Examples 2 to 7 Test pieces were prepared in the same manner as in Example 1 except that the molding temperature and the composition ratio of the composition were set as shown in Table 1. The results are shown in Table 1.

Comparative Examples 2 to 7 Test pieces were prepared in the same manner as in Examples 2 to 7 except that the content of the composition was shown in Table 2, and the test was conducted under the same conditions. The results are shown in Table 2.

Example 8 ASA: 40 parts by weight, Ti1: 10 parts by weight, γ-aminopropyltrimethoxysilane (silane type); 0.05 parts by weight were mixed in a tumbler and the mixture was mixed with a single screw extruder having a screw diameter of 30 mm. The mixture was melt-kneaded at a cylinder setting temperature of 240 ° C. and a screw rotation speed of 150 rpm, and then pelletized. 50 parts by weight of these pellets, 50 parts by weight of PC1, TBA;
15 parts by weight, antimony; 5 parts by weight, and needle-shaped titanium; 7 parts by weight were mixed, mixed with a tumbler, and then set at a cylinder temperature of 260 with a single screw extruder having a screw diameter of 30 mm.
After melt-kneading at ℃ and screw rotation speed of 150 rpm, pelletization was performed. After drying the pellets at 110 ° C. for 5 hours,
Using an injection molding machine (Sumitomo Heavy Industries Ltd. SG125 type), mold temperature 90 ° C, resin temperature 270 ° C, injection pressure 98
3.2 m of ASTM-D638 standard type 1 in Mpa
An m-thick tensile test piece was molded. 1 under the same conditions as the tensile test piece
00 × 100 × 2 mm square plate, 127 × 12.7 × 1.
A 6 mm flammability test piece was molded. The physical property test was carried out in accordance with Example 1 to find that the elongation was 32% and the reflectance% was 91.
%, L value = 94.2, a value = −0.28, b value = 2.
0, the appearance of the molded product was A, and the flammability was V-0.

Example 9 ASA; 40 parts by weight, PC1; 60 parts by weight, Ti1; 1
0 parts by weight, γ-aminopropyltrimethoxysilane (silane type); 0.05 parts by weight, TBA; 15 parts by weight, antimony; 5 parts by weight, and needle titanium; A single-screw extruder having a diameter of 30 mm melt-kneaded at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 150 rpm, and then pelletized to prepare a test piece. Hereinafter, as a result of a physical property test performed according to Example 1, the elongation is 29%, the reflectance% is 90%, and the L value = 93.
5, a value = -0.32, b value = 2.5, the appearance of the molded product was B, and the flammability was V-0.

Comparative Example 8 Pellets were obtained in the same manner as in Example 9 except that 30 parts by weight of Ti1 was used. A test piece was prepared and a physical property test was conducted in accordance with Example 1 except that the resin temperature was 310 ° C. As a result, elongation was 8%, reflectance% was 86%, L value = 93.8, a value =
-0.43, b value = 4.8, appearance C of molded product, flammability is V
It was -2.

[0071]

INDUSTRIAL APPLICABILITY The present invention relates to a resin composition having excellent mechanical properties, thermal properties, electrical properties, flame retardancy and fluidity at the time of molding, and particularly having a high light reflectance, and a backlight for liquid crystal display. It can be used in fields that require a high degree of light reflectance such as display plates, illuminated bush switches, and photoelectric switch reflectors.

[0072]

[Table 1]

[0073]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 33/02 LHR 33/10 LHU LJA 67/02 LNZ // (C08L 69/00 67:02 101 : 04 85:02) (72) Inventor Hisashi Kuwahara 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastics Center (72) Inventor Shinya Miya, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Chome 6-2 Sanryo Gas Chemical Co., Ltd. Plastics Center

Claims (3)

[Claims] 1. (A) Aromatic polycarbonate 40 to 9
100 parts by weight of a composition consisting of 0% by weight and 10 to 60% by weight of one or more polymers selected from thermoplastic polyesters, styrene polymers, and methacrylic polymers.
(B) Titanium oxide 3 to 25 parts by weight, (C) Molecular weight 100
A flame-retardant resin composition comprising 3 to 20 parts by weight of an organic halogen compound of 0 or more and (D) 0.1 to 10 parts by weight of a fibrous inorganic filler having an average diameter of 4 μm or less and an aspect ratio of 5 or more. 2. A fibrous inorganic filler having an average diameter of 4 μm or less and an aspect ratio of 5 or more is glass fiber, glass wool, carbon fiber, fibrous magnesium, magnesium borate, silicon carbide whiskers, silicon nitride whiskers, graphite,
The flame-retardant resin composition according to claim 1, which is a potassium titanate whisker, fibrous aluminum oxide, acicular titanium oxide, wollastonite, or ceramic fiber. 3. The flame-retardant resin composition according to claim 1, which contains 3 to 20 parts by weight of an organic phosphorus compound having an average molecular weight of 500 or more and a neighboring content of 8% by weight or more.