JP2001310985A - Flame retardant thermoblastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-halogen flame retardant thermoplastic resin composition having an excellent impact resistance, heat resistance, melt-fluidity and extrusion process stability. SOLUTION: The composition is obtained by blending a rubber-toughened resin (A) obtained by grafting monomer components in the presence of a rubber polymer having a specified particle size distribution and an aromatic polycarbonate (B) having a specified viscosity-average molecular weight of 100 pts.wt. in total with a phosphate ester compound (c) having a specified chemical structure of 8-25 pts.wt. and a polytetrafluoroethylene and a lubricant (D) of 0.1-10 pts.wt. in total.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-halogen flame-retardant thermoplastic resin composition having excellent impact resistance, heat resistance, fluidity, flame retardancy and extrusion production stability.

[0002]

2. Description of the Related Art Conventionally, ABS resins provided with flame retardancy are:
Due to their excellent surface appearance, moldability, and mechanical properties, they are widely used in the fields of electrical and electronic equipment and OA equipment. In recent years, in these products, there has been a tendency to refrain from using halogen-based flame retardants from the standpoint of environmental protection, and flame-retardant materials combining phosphate ester-based flame retardants based on PC (polycarbonate) / ABS alloy resin have been used. Has been launched. However, when a phosphate ester-based flame retardant is combined with a PC / ABS alloy resin, the extrusion production stability is poor and the chemical resistance may be poor. When a polycarbonate resin having a low molecular weight is used in combination with a phosphate ester flame retardant and the extrusion production stability is improved, the impact resistance is reduced even though the extrusion production stability is improved. Further, polytetrafluoroethylene is generally added as an anti-dripping agent, but polytetrafluoroethylene is usually a high molecular weight compound having a molecular weight of 1,000,000 or more.
Difficult to uniformly disperse, lowering the impact strength of the resulting composition,
There is a problem that the strand cannot be stably pulled at the time of pelletization in the extruder.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and can solve the above-mentioned problems by providing impact resistance, heat resistance, fluidity, flame retardancy, and stable extrusion production. An object of the present invention is to provide a non-halogen flame-retardant thermoplastic resin composition having excellent heat resistance.

[0004]

The flame-retardant thermoplastic resin composition of the present invention has the following (A) 10 to 40 parts by weight of a rubber-reinforced resin, and (B) a viscosity-average molecular weight of 16,000 to 3
90 to 60 parts by weight of 0000 aromatic polycarbonate (provided that (A) + (B) = 100 parts by weight)
(C) 8 to 25 parts by weight of a phosphoric ester compound represented by the following general formula (I), and
(D) 10 to 70% by weight of (d1) and (d2) polytetrafluoroethylene (d1) and a lubricant (d2)
90 to 30% by weight [(d1) + (d2) = 10
0% by weight] and a total of 0.1 to 10 parts by weight. (A); in the presence of a rubbery polymer having a particle size distribution in which 15% by weight or less of particles having a particle diameter of 150 nm or less, 60% by weight or more and less than 350 nm and 150% or more and 25% by weight or less of 350 nm or more, A rubber reinforced resin obtained by graft polymerization of a monomer component containing an aromatic vinyl compound and a vinyl cyanide compound as main components.

[0005]

Embedded image

[However, R ¹ , R ² , R ³ and R ⁴
Represents a phenyl group or a xylenyl group each independently selected, X represents an m-phenylene group or a 2,2-bis (4'-phenylene) propane group, and n represents 0.5
１．２1.2. ]

The rubber-reinforced resin (A) according to the present invention comprises a monomer component containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of a rubbery polymer having a specific particle size distribution. Obtained by graft polymerization. The rubber-reinforced resin (A) is obtained by adding a (co) polymer of at least one monomer component selected from the group of the monomer components to a graft copolymer obtained by the graft polymerization. It may be manufactured separately and blended.

Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, ethylene- Butene-1- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, polyurethane rubber, silicone rubber and the like. No. Specific examples of the styrene-butadiene copolymer include a styrene-butadiene random copolymer and a styrene-butadiene block copolymer.
Further, hydrogenated products such as the above-mentioned polybutadiene and styrene-butadiene copolymer can also be used. The above-mentioned rubbery polymer may be used alone or
A mixture of more than one species can be used. Among these, polybutadiene, styrene-butadiene copolymer,
An ethylene-propylene- (non-conjugated diene) copolymer,
Hydrogenated diene (co) polymers and silicone rubbers are preferred.

[0009] The particle size distribution of the rubbery polymer is an important requirement of the present invention. This particle size distribution has a particle size of 150
The rubbery polymer having a particle size of 15 nm or less is 15% by weight or less, preferably 12% by weight or less,
The rubbery polymer having a particle size of less than nm is 60% by weight or more, preferably 65% by weight or more, and the rubbery polymer having a particle diameter of 350 nm or more is 25% by weight or less, preferably 20% by weight or less.
The particle size distribution of the rubbery polymer is significantly related to the orientation of the rubber during molding, and if the particle size distribution is within this range,
Practical impact resistance is improved. Rubber orientation is a phenomenon in which rubber particles are deformed in the flow direction due to shearing stress during molding. When the orientation is increased, the practical impact strength decreases. When the amount of the rubbery polymer having a particle diameter of 150 nm or less is too large, the practical impact strength is reduced because the stress dispersion effect of the rubber particles is reduced. When the amount of the rubbery polymer of 350 nm or more is too large, the orientation is large. As a result, the practical impact resistance decreases, and the flammability evaluation (flame retardancy) also decreases.

The gel fraction of the rubbery polymer is preferably 40 to 90% by weight, more preferably 50 to 90% by weight, and particularly preferably 60 to 90% by weight. If the gel fraction is too small, the impact resistance, rigidity, flame retardancy and the like will be reduced, while if the gel fraction is too high, the impact resistance will be reduced. The gel fraction (toluene-insoluble matter) of the rubbery polymer was determined by adding 1 g of the rubbery polymer to 100 ml of toluene, leaving the mixture at room temperature for 48 hours, filtering through a 100-mesh wire gauze, and dissolving the toluene from the dispersed filtrate. Is removed and dried to obtain a toluene-soluble component (g), which can be calculated by the following equation. Gel fraction (%) = [1 (g) -toluene soluble matter (g)]
× 100

The content of the rubbery polymer in the rubber reinforced resin (A) is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and particularly preferably 25 to 50% by weight.
45% by weight. When the content of the rubbery polymer in the component (A) is 10% by weight or more, impact resistance is particularly excellent, and when it is 60% by weight or less, fluidity and flammability evaluation are particularly excellent. If the content of the rubbery polymer in the component (A) is small, the impact resistance tends to decrease. On the other hand, if it is too large, the fluidity and the flame retardancy tend to decrease.

As the aromatic vinyl compound in the monomer component used for the graft polymerization of the component (A), styrene,
α-methylstyrene, o-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, methyl-α-methylstyrene, divinylbenzene, 1,1-
Examples include diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene and the like, with styrene and α-methylstyrene being particularly preferred. When α-methylstyrene is used in the monomer component in an amount of 10 to 50% by weight, preferably 20 to 30% by weight, the heat resistance of the flame-retardant thermoplastic resin composition of the present invention can be particularly improved.

The copolymerization amount of the aromatic vinyl compound is as follows:
(A) Component is preferably 30 to 70% by weight, more preferably 40 to 70% by weight, particularly preferably 45 to 70% by weight.
% By weight.

Examples of the vinyl cyanide compound in the monomer component include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred. The copolymerization amount of the vinyl cyanide compound is preferably 5% in the component (A).
It is preferably from 40 to 40% by weight, more preferably from 10 to 35% by weight, particularly preferably from 10 to 30% by weight. If the copolymerization amount of the aromatic vinyl compound is too large or the copolymerization amount of the vinyl cyanide compound is too small, chemical resistance, flame retardancy, etc. are reduced, while the copolymerization amount of the aromatic vinyl compound is small. If it is too large or the copolymerization amount of the vinyl cyanide compound is too large, the fluidity, impact resistance and the like will be reduced.

As the monomer component, other copolymerizable monomers can be used if necessary.
Examples of the other monomer include an unsaturated acid anhydride, an unsaturated acid, and an imide compound of an unsaturated dicarboxylic acid. Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, with maleic anhydride being preferred. Examples of the unsaturated acid include acrylic acid and methacrylic acid. Examples of imide compounds of unsaturated dicarboxylic acids include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N-
(4-Hydroxyphenyl) maleimide, N-cyclohexylmaleimide, etc. are mentioned, and N-phenylmaleimide is preferable. The monomer components used in the component (A) are used alone or in combination of two or more.

Further, a vinyl monomer having a functional group may be used as the monomer component, if necessary.
Examples of the functional group-containing vinyl monomer include epoxy group-containing unsaturated compounds such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy- 2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1
-Propene, 2-hydroxyethyl acrylate, 2-
Hydroxy group-containing unsaturated compounds such as hydroxyethyl methacrylate and hydroxystyrene; unsaturated carboxylic amides such as acrylamide and methacrylamide; amino groups such as acrylamine, aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate and aminostyrene Unsaturated compounds such as acrylic acid and methacrylic acid; and unsaturated compounds containing an oxazoline group such as vinyl oxazoline. The above functional group-containing vinyl monomers are used alone or in combination of two or more. By copolymerizing these functional group-containing vinyl monomers, when another resin is blended, the interface adhesion (compatibility) with the resin can be increased.

The graft ratio of the rubber-reinforced resin (A) is as follows:
Preferably 60 to 120%, particularly preferably 60 to 90%
%. Here, the graft ratio (%) is a ratio of the monomer component grafted to the rubbery polymer, and is a value determined as follows. That is, (A) the amount of the rubber component of the acetone-insoluble portion of the rubber reinforced resin, for example, when the rubber component is polybutadiene, the absorbance ratio of 967 cm ⁻¹ trans double bond C—H out-of-plane bending vibration by infrared spectroscopy Is obtained from a calibration curve prepared in advance using, and the weight is defined as x, and the weight of the acetone-insoluble component is defined as y. Graft ratio (%) = 100 × (y−x) / x Here, the acetone-insoluble matter was obtained by shaking (A) 1 g of a rubber-reinforced resin in 50 ml of acetone at room temperature for 24 hours with a shaker, and Dissolve the (co) polymer of and centrifuge,
The obtained insoluble matter is obtained by drying at 120 ° C. for 1 hour by vacuum drying. If the graft ratio is too small, the resulting flame retardant thermoplastic resin composition will have poor impact resistance and flame retardancy. On the other hand, if the graft ratio is too high, the fluidity is poor.

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the soluble component of methyl ethyl ketone as a matrix component in the rubber-reinforced resin (A) according to the present invention is preferably 0.2 to 1. 2 dl / g, more preferably 0.2 to 1 dl / g, particularly preferably 0.3 to 1 dl / g
It is 1 dl / g. When the intrinsic viscosity [η] is within the above range, the flame-retardant thermoplastic resin composition of the present invention having particularly excellent impact resistance, heat resistance and fluidity can be obtained. The above graft ratio (%) and intrinsic viscosity [η] are determined based on the types and amounts of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, and the like, and a polymerization time and a polymerization temperature when polymerizing a rubber-reinforced resin. By changing, it can be easily controlled.

The rubber-reinforced resin according to the present invention is obtained by subjecting a monomer component mainly composed of an aromatic vinyl compound and a vinyl cyanide compound to a known emulsion polymerization, solution polymerization, bulk polymerization in the presence of a rubbery polymer. Radical graft polymerization can be performed by polymerization, suspension polymerization, or the like. At this time, a polymerization initiator, a chain transfer agent (molecular weight regulator),
Emulsifiers, water and the like are used. Incidentally, the rubbery polymer and the monomer component used for producing the rubber reinforced resin may be polymerized by adding the monomer component all at once in the presence of the total amount of the rubbery polymer, and may be divided or continuously. It may be added and polymerized. Moreover, you may superpose | polymerize by the method which combined these. Further, the whole or a part of the rubbery polymer may be added during the polymerization to carry out the polymerization.

Examples of the polymerization initiator include organic hydroperoxides represented by cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphoric acid formulations, sulfoxylate formulations and the like. Redox system in combination with a reducing agent, or a persulfate such as potassium persulfate, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO),
Oil-soluble peroxides such as lauroyl peroxide, t-butyl peroxylaurate, t-butyl peroxy monocarbonate are used. Further, the polymerization initiator is
It can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is usually 0.1 to the amount of the monomer component.
1 to 1.5% by weight.

Known chain transfer agents can be used.
Specifically, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, Examples thereof include hydrocarbon salts such as carbon chloride, ethylene bromide, and pentaphenylethane, terpenes, and dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene. The amount of the chain transfer agent to be used is usually 0.05 to 2% by weight based on the amount of the monomer component.

As the emulsifier used in the emulsion polymerization, known emulsifiers can be used. Specifically, sulfates of higher alcohols, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylate, anionic surfactants such as phosphoric acid Agents: Nonionic surfactants such as polyethylene glycol alkyl ester type and alkyl ether type. The amount of the emulsifier to be used is usually 0.1 to the amount of the monomer component.
It is 3 to 5% by weight.

When the rubber-reinforced resin is produced by emulsion polymerization, the powder obtained by coagulation with a coagulant is usually washed with water and then dried to be purified. As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride, and inorganic acids such as sulfuric acid and hydrochloric acid can be used.

The rubber-reinforced resin (A) may be blended, if necessary, with a (co) polymer of at least one monomer component selected from the group of the monomer components. Good. Here, the monomer component of the (co) polymer may have the same composition as the monomer component used for the graft polymerization, or may have a different composition. Further, the (co) polymer may be a combination of several (co) polymer components. The (co) polymer can be obtained by, for example, polymerizing in the same manner as described above. The intrinsic viscosity [η] of the (co) polymer soluble in methyl ethyl ketone (measured in methyl ethyl ketone at 30 ° C.) is preferably 0.2 to 1 dl / g, more preferably 0.3 to 1 dl / g, and particularly preferably 0.3 to 1 dl / g. Preferably 0.3 to
0.8 dl / g. When the intrinsic viscosity [η] is within the above range, it is particularly excellent in impact resistance, heat resistance, and fluidity. The intrinsic viscosity [η] can be controlled in the same manner as described above.

The typical rubber-reinforced resin (A) has the following composition, but the scope of the present invention is as follows:
The present invention is not limited to the following examples unless it exceeds the claims. Acrylonitrile-butadiene-styrene resin Methyl methacrylate-butadiene-styrene resin

Component (A) is added in an amount of 10 to 40 parts by weight based on 100 parts by weight of components (A) and (B) in total.
Preferably 10 to 30 parts by weight, particularly preferably 15 to 3 parts by weight.
0 parts by weight. If the amount of the component (A) is too small, the fluidity decreases, while if it is too large, the flammability evaluation is poor.

As the aromatic polycarbonate resin (B) used in the flame-retardant thermoplastic resin composition of the present invention, those obtained by reacting various dihydroxyaryl compounds with phosgene (phosgene method) or dihydroxyaryl compounds Obtained by the transesterification reaction of diphenyl carbonate with diphenyl carbonate (ester exchange method)
Is mentioned.

Here, the dihydroxyaryl compounds used as the raw materials for the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, and 2,2'-bis (4-hydroxyphenyl) methane. Phenyl) propane, 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, 2,2'-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2'-bis (4-hydroxy-3-bromophenyl ) Propane, 2,2'-bis (4-hydroxy-
3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1,1 '
-Bis (4-hydroxyphenyl) cyclohexane,
4,4'-dihydroxydiphenyl ether, 4,4 '
-Dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,
4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide,
4,4'-dihydroxydiphenylsulfoxide, 4,
4'-dihydroxyphenylsulfoxide, 4,4'-
Dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone,
Examples thereof include 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, hydroquinone, and resorcin, and these are used alone or in combination of two or more. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane, or bisphenol A. A typical aromatic polycarbonate is 2,2'-bis (4-hydroxyphenyl) propane, a polycarbonate obtained by reacting bisphenol A with phosgene.

The aromatic polycarbonate (B) has a viscosity average molecular weight of 16,000 to 30,000, preferably 17,000 to 28,000, and more preferably 1 to 30,000.
8,000-26,000. If the viscosity average molecular weight is too small, flame retardancy and impact resistance will be poor, while if too large, fluidity will be poor. Also, two or more aromatic polycarbonates having different molecular weights can be used. The compounding amount of the component (B) is 90 to 60 parts by weight, preferably 90 to 70 parts by weight, particularly preferably 85 to 70 parts by weight, per 100 parts by weight of the total of the components (A) and (B). (B) If the amount is too small, the evaluation of the flammability is inferior, while if it is too large, the fluidity decreases.

The phosphoric ester compound (C) according to the present invention is represented by the above general formula (I). Here, the phosphate ester compound represented by the above general formula (I) can be used either as a single compound or as a mixture of two or more different phosphate esters. In the phenyl group or xylenyl group in R ^{1 to} R ⁴ , the hydrogen atom of the aromatic ring may be substituted by an alkyl group or the like. X is a divalent organic group derived from resorcinol or bisphenol A, which is a dihydroxy compound, that is, an m-phenylene group or a 2,2-bis (4′-phenylene) propane group. R ¹ , R ² , R ³ and R ^{4 in the} above general formula (I)
Is preferably a xylenyl group, and X is preferably an m-phenylene group. When the component (C) is a mixture, the value of n represents an average value (average degree of polymerization) in the mixture of the condensed phosphate esters. The average degree of polymerization n is 0.5 to 1.2, preferably 0.7
To 1.2, more preferably 0.9 to 1.1. When the average degree of polymerization n is less than 0.5, heat resistance is reduced,
Mold appearance is likely to occur, such as mold contamination and silver on the molded product. On the other hand, a phosphate compound having an average degree of polymerization n of more than 1.2 is difficult to produce and therefore expensive and difficult to use economically.

The compounding amount of the phosphoric acid ester (C) according to the present invention is 8 to 25 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is 10 to 15 parts by weight. If the amount of the (C) phosphate ester is too small, fluidity and flame retardancy are insufficient, while if too large, heat resistance and impact resistance are reduced.

The component (D) according to the present invention comprises polytetrafluoroethylene (d1) and a lubricant (d2),
1) 10 to 70% by weight and (d2) 90 to 30% by weight
[However, (d1) + (d2) = 100% by weight] is blended. Polytetrafluoroethylene (d1) is used as an anti-dripping agent during combustion, and preferably has a number average molecular weight of 1,000,000 or more and more preferably 1.5 million or more. If the number average molecular weight is less than 1,000,000, the effect of preventing dripping may be reduced. The average particle size of the polytetrafluoroethylene (d1) is preferably 100 to 700 μm.
m, particularly preferably 100 to 600 μm. If the average particle size is too small, handling is difficult, and if the average particle size is too large, the anti-dripping effect may be reduced. The particle size distribution of polytetrafluoroethylene is such that particles having a size of 600 μm or more are preferably 30% by weight or less, particularly preferably 25% by weight or less. 600 μm
If the amount of the above particles is too large, flame retardancy and impact resistance are liable to be reduced. The bulk density of polytetrafluoroethylene is
Preferably 100 to 1000 g / l, particularly preferably 3
It is 00 to 900 g / l. If the bulk density is too small or too large, the dispersion state of polytetrafluoroethylene is deteriorated, and the flame retardancy and impact resistance are likely to be reduced. Further, the melting point of polytetrafluoroethylene is preferably from 250 to 350 ° C, particularly preferably from 300 to 340 ° C. If the melting point is too low or too high, the dripping effect tends to decrease. The specific gravity of polytetrafluoroethylene is preferably 1.8 to 2.5, particularly preferably 2 to 2.4. If the specific gravity is too small, the dripping effect is reduced. On the other hand, if the specific gravity is too large, the blending amount needs to be increased, and the impact resistance may be reduced. As a method for producing polytetrafluoroethylene,
Examples include emulsion polymerization and suspension polymerization.

The lubricant (d2) is used for the purpose of improving the dispersibility of polytetrafluoroethylene. Specific examples of the lubricant (d2) include (1) hydrocarbon-based, for example, liquid paraffin, paraffin wax, microwax and polyethylene wax, (2) aliphatic-based.
Higher alcohols, for example, stearic acid, behenic acid and 12-hydroxystearic acid, (3) esters, for example, esters of polyols and fatty acids such as butyl stearate, monoglyceride stearate, and pentaerythritol, for example, pentaerythritol tetrastearate And glycerides such as hardened castor oil wax and hardened soybean oil wax; esters with monovalent fatty acids such as stearyl stearate; and (4) higher alcohols such as stearyl alcohol. In particular, ester lubricants, for example, esters of glycerides such as hardened castor oil wax and hardened soybean oil wax, esters of polyols such as pentaerythritol and fatty acids, and esters of monovalent fatty acids such as stearyl stearate are preferred. The melting point of the lubricant (d2) is preferably 40 ° C or more, for example, 40 to 150 ° C. Melting point 4
Those having a temperature of less than 0 ° C. are liquid at room temperature, so that it is difficult to uniformly disperse them in the resin composition. These lubricants can be used alone or in combination of two or more, or can be used in combination with other lubricants such as silicone oil.

The mixing ratio of polytetrafluoroethylene (d1) and lubricant (d2) is (d1) / (d2) = 10
~ 70/90 ~ 30 (wt%), preferably (d1) /
(D2) = 30 to 70/70 to 30 (% by weight), more preferably (d1) / (d2) = 40 to 70/60 to 3
0 (% by weight) [where (d1) + (d2) = 1]
00% by weight]. If the blending amount of the lubricant (d2) is small, the necessary amount of the component (D) to be blended for the purpose of preventing dripping will eventually increase, and the polytetrafluoroethylene (d1) will necessarily be blended inevitably. . If the amount of polytetrafluoroethylene (d1) is too large in this way, the desired improvement in impact resistance and the production stability by the extruder cannot be obtained.

In the present invention, the polytetrafluoroethylene (d1) component and the lubricant (d) are preferably used in order to further improve impact resistance, flame retardancy and extrusion production stability.
2) A component obtained by uniformly mixing the components in advance is used as the component (D). However, the polytetrafluoroethylene (d1) component and the lubricant (d2) component can be separately blended or added to the flame-retardant thermoplastic resin composition of the present invention without being mixed. When mixing, high speed mixing over a certain level is necessary, for example, Henschel mixer,
It is performed by a super mixer or the like.

The amount of the composition (D) is 0.1 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
10 to 10 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight. If the amount of the composition (D) is too small, the effect of preventing dripping cannot be obtained, while if it is too large, the impact resistance and the fluidity deteriorate.

In the flame-retardant thermoplastic resin composition of the present invention, the content of a component comprising an organic acid and an oligomer component (hereinafter referred to as “component (E)”) is determined by the content of component (A) and component (B). 3 parts by weight or less, more preferably 2.5 parts by weight or less,
It is more preferably at most 2 parts by weight. When the content of the component (E) is not more than part by weight, the mold molding surface is less contaminated during molding, so the number of times of cleaning the mold molding surface is small, and as a result, continuous molding for a longer time is possible. Becomes In addition, the measuring method of content of an organic acid and an oligomer component can be measured by the method shown in the following example.

The above-mentioned organic acid includes, for example, an emulsifier component such as an emulsifier in a rubbery polymer used as a raw material of the component (A) and an emulsifier used in the production of the component (A).
(A) a component which is released by a coagulant (a strong acid such as sulfuric acid or hydrochloric acid) used in the production of the component to become an organic acid and is present in the component (A); Organic acids used as lubricants can be mentioned. Examples of the organic acid include oleic acid, stearic acid,
Rosin acid and the like.

As a method for keeping the content of the organic acid within the above-mentioned preferred range, a solidification step of recovering the powder of the component (A) from the latex of the component (A) obtained by the emulsion polymerization method includes, for example, chloride Examples thereof include a method using an inorganic salt such as magnesium, magnesium sulfate, and calcium chloride, and a method of alkali-cleaning the powder of the component (A) having a high organic acid content. However, if the above method is implemented, naturally,
The organic acid content does not fall within the above preferred range, and the organic acid content is at the stage of coagulation step or alkali treatment,
Temperature, water amount, treatment time, coagulant amount, coagulant mixing method,
This is achieved by appropriately selecting conditions such as the stirring method and the concentration of the alkali substance. Further, the oligomer component,
Formed during the polymerization of component (A). The composition of the oligomer component is a dimer, a trimer, or the like composed of a monomer used in the polymerization of the component (A). Alternatively, as described above, the case where the above-mentioned monomer is separately polymerized and then added to the component (A) is also included. Examples of a method for keeping the content of the oligomer component within the range of the present invention include a method of lowering the temperature at the time of polymerization, approaching the azeotropic composition, and the like. Further, in the case of the polymerization of (A), it is more effective to perform catalytic polymerization than thermal polymerization.

Further, the flame-retardant thermoplastic resin composition of the present invention may contain, if necessary, glass fiber, carbon fiber, wollastonite, talc, mica, kaolin, glass beads,
Fillers such as glass flakes, milled fibers, zinc oxide whiskers, and potassium titanate whiskers can be blended. By blending these fillers, rigidity can be imparted to the flame-retardant thermoplastic resin composition of the present invention. Further, by blending talc or the like, it is possible to impart matting properties to the flame-retardant thermoplastic resin composition of the present invention.

The flame-retardant thermoplastic resin composition of the present invention contains a flame-retardant auxiliary such as an antimony compound, a known coupling agent, an antibacterial agent, a fungicide, an antioxidant, and a weather (light-resistant) agent. And additives such as a plasticizer, a colorant (eg, a pigment and a dye), and an antistatic agent can be blended within a range that does not impair the required performance.

Further, the flame-retardant thermoplastic resin composition of the present invention may contain other (co) polymers according to the required performance. Here, as another polymer,
Polyamide, polyester, polysulfone, polyether sulfone, polyphenylene sulfide, liquid crystal polymer, polyvinylidene fluoride, styrene-vinyl acetate copolymer, polyamide elastomer, polyamide imide elastomer, polyester elastomer, phenol resin, epoxy resin, novolak resin, etc. .

The flame-retardant thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders and the like. A preferred production method is a method using an extruder and a Banbury mixer. When kneading each component, each component may be kneaded at once, or may be added and kneaded in several times. For kneading, kneading may be performed in a multi-stage addition method using an extruder, or kneading using a Banbury mixer, a kneader, or the like, and then, pelletizing using an extruder.

The flame-retardant thermoplastic resin composition of the present invention thus obtained can be prepared by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, foam molding, injection press, press molding, blow molding, etc. It can be molded into molded articles.

The various molded articles obtained by the above molding method are excellent in impact resistance, heat resistance, fluidity, flame retardancy, extrusion production stability, OA / home electric appliances field, electric / electronic / communications field, computer It can be suitably used in the field, miscellaneous goods field, sanitary field, vehicle field and the like.

The flame-retardant thermoplastic resin composition of the present invention is excellent in extrusion production stability.
V-0 flame retardancy of L94 standard is achieved, and excellent Izod impact strength and falling weight impact strength are simultaneously realized. Among them, the falling weight impact strength can be 300 to 550 kgf-mm, more preferably 350 to 520 kgf-mm, and still more preferably 380 to 500 kgf-mm. The heat distortion temperature as an index of heat resistance is preferably 85.
-100 ° C, more preferably 85-95 ° C, even more preferably 88-95 ° C.

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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. In the examples, parts and percentages are by weight unless otherwise specified.

1. Evaluation method Various evaluations in the examples were measured as follows. <1> Particle size of rubbery polymer The particle size of the rubbery polymer was measured by an electron microscope method and an image analysis method. When the rubbery polymer is a latex, after confirming with an electron microscope that the particle size of the latex synthesized in advance in an emulsified state directly indicates the particle size of the dispersed particles in the rubber reinforced resin, The particle size of the dispersed particles was measured by a light scattering method. The measuring device is a laser particle size analysis system LPA-31 manufactured by Otsuka Electronics Co., Ltd.
00, 70 times, using the cumulant method,
The particle size was measured.

<2> Gel fraction (toluene-insoluble content) This is described in the text. <3> Graft ratio This is described in the text. <4> Intrinsic viscosity [η] 1 g of the component (A) is put into 20 ml of methyl ethyl ketone, shaken at room temperature for 2 hours with a shaker to dissolve the free (co) polymer, and the centrifuge is This solution was centrifuged at 15,000 rpm for 30 minutes to obtain a soluble matter excluding insoluble matter after separation and drying. This soluble matter was sufficiently dried with a vacuum dryer. This soluble matter was dissolved in methyl ethyl ketone to prepare five different concentrations. The intrinsic viscosity [η] was determined from the results of measuring the reduced viscosity at each concentration at 30 ° C. using an Ubbelohde viscosity tube. The unit is dl /
g.

<5> Organic Acid Content After the flame-retardant thermoplastic resin composition is dissolved in a solvent (1,4-dioxane), the contained organic acid is methyl-esterified with diazomethane, and the flame ionization detector is used. The organic acid content (%) was measured using a gas chromatography equipped with. <6> Content of oligomer component After dissolving the flame-retardant thermoplastic resin composition in methyl ethyl ketone, the polymer component was reprecipitated with n-pentane, and the supernatant was analyzed by gas chromatography to obtain a dimer and a trimer. From the total, the oligomer component content (%)
Was quantified. <7> Viscosity average molecular weight Aromatic polycarbonate was dissolved in methylene chloride, and five samples having different concentrations were prepared. The intrinsic viscosity value was obtained from the result of measuring the reduced viscosity at each concentration at 20 ° C. using an Ubbelohde viscosity tube. From the obtained intrinsic viscosity value, Ma
The viscosity average molecular weight was calculated using the rk-Houwink equation. The Mark-Houwink constant used is
K is 1.23 × 10 ⁻⁴ and a is 0.83.

<8> Impact Resistance (Izod Impact Strength) Using an injection molding machine J100E-C5 manufactured by Nippon Steel Works, the cylinder temperature was 220 ° C., the mold temperature was 50 ° C., and the JI was used.
A No. 2 test piece of SK7110 was molded and the Izod impact strength was measured. The unit is kgf-cm / cm. <9> Heat Deformation Temperature (HDT) Using a test piece having a width of 12.8 mm, a height of 12.8 mm and a length of 128 mm, a heat distortion temperature of 18.5 kgf / cm ² and a bending stress of 18.5 kgf / cm ² in accordance with JIS K7207 ° C). <10> Fluidity (melt flow rate, MFR) Measured according to JIS K7210. Measurement temperature is 24
The temperature is 0 ° C., the load is 98 N, and the unit is g / 10 minutes.

<11> Drop Weight Impact Strength Servo Pulser EH, a high-speed impact tester manufactured by Shimadzu Corporation
Using F-2H-20L, the breaking energy of a test piece having a thickness of 50 × 80 × 2.4 mm was measured. The measurement conditions were as follows: test specimen holder diameter 30 mmφ, impact rod tip 12.7 mmR,
The impact speed was 3.1 m / s. The unit is kgf-mm
It is. <12> Flammability evaluation (flame retardancy) 127 mm long according to the method specified in UL94 standard
A vertical combustion test was performed on a test piece having a width of 12.7 mm and a thickness of 2.5 mm. As the evaluation results, “V-0” was a vertical test result and passed V-0, and “BN” was a combustion (bur)
ning), and "D" indicates a dripping mismatch. <13> Extrusion production stability Using an NVC50 extruder manufactured by Nakatani Machinery Co., Ltd., the product was pelletized at a cylinder set temperature of 220 ° C. and indicated by the following evaluation criteria. Good; stable extrusion production was possible. Poor; strand breaks at both ends of the extruder die occurred.

2. Reference Example 1 [Preparation of rubbery polymer] Polybutadiene latex shown in Table 1 was used as rubbery polymers (a) to (c).

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[Table 1]

3. Reference Example 2 [Preparation of Component (A)] At the compounding ratios shown in Table 2, rubbery polymers (a) to (c),
Emulsion polymerization using styrene and acrylonitrile monomer components as monomer components, and graft copolymers (A-1-2) and (A'-1-6) having different graft ratios
I got Further, at the compounding ratio shown in Table 2, solution polymerization was carried out using only the monomer components to obtain a copolymer (a-1). Table 2 shows the evaluation results of the obtained graft copolymer and the copolymer.

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[Table 2]

4. Reference Example 3 [Preparation of aromatic polycarbonate (B) component] As the component (B), the following aromatic polycarbonates (B-1 to 3) and (B'-1 to 2) were used. (B-1): a polycarbonate having a viscosity average molecular weight of 18,000 (B-2): a polycarbonate having a viscosity average molecular weight of 23,000 (B-3): a polycarbonate having a viscosity average molecular weight of 28,000 (B'-1) ): Polycarbonate having a viscosity average molecular weight of 15,000 (B′-2): polycarbonate having a viscosity average molecular weight of 31,000

5. Reference Example 4 [Preparation of phosphate ester compound (C) component] As the component (C), the following phosphate esters (C-1 to C-1)
3) and (C'-1 to 2) were used. (C-1): a phosphoric ester compound of the above general formula (I) wherein R ^{1 to} R ⁴ are a phenyl group, X is a 2,2-bis (4′-phenylene) propane group, and n is 1.1. (C-2): R ^{1 to} R ^{4 in} the general formula (I) are 2,6-
A phosphoric ester compound in which a xylenyl group, X is a m-phenylene group, and n is 1.0. (C-3): A phosphate compound in which R ^{1 to} R ^{4 in} the general formula (I) are a phenyl group, X is a 2,2-bis (4′-phenylene) propane group, and n is 0.6. (C'-1): Triphenyl phosphate [R ^{1 to} R ^{4 in the} above general formula (I) are phenyl groups and n is 0). (C'-2): a phosphoric ester compound of the above general formula (I) in which R ^{1 to} R ⁴ are a phenyl group, X is a 2,2-bis (4′-phenylene) propane group, and n is 0.3.

6. Reference Example 5 [Preparation of component (D)] As component (d1), Hostaflon TF1620 (trade name, manufactured by Dyneon Co., Ltd.)
Particle size distribution: 25% by weight or less of particles having a particle size of 600 μm or more, bulk density of 850 g / l, melting point of 327 ° C., specific gravity of 2.1
5, molecular weight 7,000,000) and (D2) a hydrogenated castor oil wax was used to prepare (D-1-4) and (D'-1-2) shown below. (D-1): 50 parts of (d1) and 50 parts of (d2)
Mix for 5 minutes with Henschel mixer. (D-2): 20 parts of (d1) and 80 parts of (d2)
Mix for 5 minutes with Henschel mixer. (D-3): 70 parts of (d1) and 30 parts of (d2)
Mix for 5 minutes with Henschel mixer. (D-4): 50 parts of (d1) and 50 parts of (d2)
Mix for 5 minutes with Henschel mixer. (D'-1): 80 parts of (d1) and 20 parts of (d2) were mixed with a Henschel mixer for 5 minutes.

7. Examples 1 to 11 and Comparative Examples 1 to 13 After the above components were mixed in a mixing ratio shown in Tables 3 to 6 using a Henschel mixer for 3 minutes, Nakatanani Machine Co., Ltd.
Was extruded at a cylinder set temperature of 220 to 250 ° C. using an NVC type extruder with a 50 mm vent to obtain pellets. The obtained pellets were sufficiently dried, and injection-molded at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C. using an injection molding machine J100E-C5 manufactured by Nippon Steel Works to obtain various test pieces for evaluation. . This test piece was evaluated by the above evaluation method. The evaluation results are shown in Tables 3 to 6.

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[Table 3]

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[Table 4]

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[Table 5]

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[Table 6]

Effects of Examples As is clear from Examples 1 to 11 in Tables 3 and 4, all of the flame-retardant thermoplastic resin compositions of the present invention have impact resistance, heat resistance, fluidity and flame retardancy. Excellent extrudability and extrusion production stability.
On the other hand, as is clear from Tables 5 and 6, Comparative Examples 1 and 2
This is an example in which the ratio of the rubber particle diameter in the component (A) of 150 nm or less is outside the range of the present invention, and the falling weight impact strength is inferior. Comparative Examples 3 and 4 have a rubber particle diameter of 35 in the component (A).
This is an example in which the ratio of 0 nm or more is out of the range of the present invention, and the falling weight impact strength and the flame retardancy are inferior. Comparative Example 5
(B) the amount of the component (A) is small outside the scope of the present invention;
This is an example in which the amount of the component is increased outside the range of the present invention, and the fluidity is poor. Comparative Example 6 is an example in which the amount of the component (A) is large outside the range of the present invention, and the amount of the component (B) is small outside the range of the present invention, and the flame retardancy is inferior.

Comparative Example 7 is an example in which the viscosity average molecular weight of the component (B) is low outside the range of the present invention, and the falling weight impact strength is inferior. Comparative Example 8 is an example in which the viscosity average molecular weight of the component (B) is large outside the range of the present invention, and the fluidity is poor. Comparative Example 9,
No. 10 is an example where the polymerization degree of the component (C) is small outside the range of the present invention, and the heat resistance is inferior. Comparative Example 11 is an example in which the blending amount of the component (C) is out of the range of the present invention and is small, and the flame retardancy is poor. Comparative Example 12 is an example in which the blending amount of the component (C) is large outside the range of the present invention, and the heat resistance is inferior. Comparative Example 13
In the compounding ratio of (d1) and (d2) of the component (D),
This is an example in which the component (d1) is large and the component (d2) is small.
Poor drop impact strength, flame retardancy, and extrusion production stability.

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The flame-retardant thermoplastic resin composition of the present invention comprises:
It is non-halogen and has excellent impact resistance, heat resistance, fluidity, flame retardancy and extrusion production stability. Then, the molded article can be suitably used in the OA / home electric appliance field, the electric / electronic / communication field, the computer field, the sundries field, the sanitary field, the vehicle field, and the like.

Continued on the front page (72) Inventor Keigo Higaki 1-18-1 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. (72) Inventor Hiroaki Miyazaki 1-1-18 Kyobashi 1-Chome, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F term (reference) 4J002 AE03Z AE05Z BB03Z BD15Y BN14W BN15W BN16W CG01X CP03Z EF056 EH057 EW066 FD17Z FD177 GN00 GQ00

Claims (2)

[Claims] 1. The following (A) 10 to 40 parts by weight of a rubber reinforced resin, and (B) a viscosity average molecular weight of 16,000 to 3
90 to 60 parts by weight of 0000 aromatic polycarbonate (provided that (A) + (B) = 100 parts by weight)
(C) 8 to 25 parts by weight of a phosphoric ester compound represented by the following general formula (I), and (D) polytetrafluoroethylene (d1) and a lubricant (d2) based on 0 parts by weight, d1) 10 to 70% by weight and (d2)
90 to 30% by weight [(d1) + (d2) = 10
0% by weight] and a total of 0.1 to 10 parts by weight. (A); in the presence of a rubbery polymer having a particle size distribution in which 15% by weight or less of particles having a particle diameter of 150 nm or less, 60% by weight or more and less than 350 nm and 150% or more and 25% by weight or less of 350 nm or more, A rubber reinforced resin obtained by graft polymerization of a monomer component containing an aromatic vinyl compound and a vinyl cyanide compound as main components. Embedded image Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from a phenyl group or a xyenyl group,
X represents an m-phenylene group or a 2,2-bis (4'-phenylene) propane group, and n is 0.5 to 1.2. ] 2. The polytetrafluoroethylene (d)
The flame-retardant thermoplastic resin composition according to claim 1, wherein 1) and the lubricant (d2) are blended in advance.