JP2001055499A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant resin composition having high flame retardancy and excellent in formability, molding appearance, heat resistance and mechanical characteristics. SOLUTION: This flame retardant resin composition comprises (A) a polycarbonate resin, (B) a copolymer having an aromatic alkenyl compound component and a vinyl cyanide compound component as structural units, (C) a graft copolymer obtained by graft copolymerization of a complex polymer ((c-1)+(c-2)) produced from (c-1) an aryl group-containing polyorganosiloxane and (c-2) a vinyl polymer with (c-3) at least one kind selected from the group consisting of an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound, (D) a phosphate-based compound.

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 particularly, to a flame-retardant resin having high flame retardancy and excellent in moldability, appearance, heat resistance and mechanical properties. It relates to a resin composition.

[0002]

2. Description of the Related Art Thermoplastic resins used in home appliances, office automation equipment, building materials and vehicle parts are required to have a high level of flame retardancy year by year in order to prevent the spread of fire due to fire spread. . Conventionally, as a method of imparting flame retardancy to these thermoplastic resins, a method of using a halogen-containing resin such as polyvinyl chloride, a method of mixing and using the resin as a flame retardant, and a method of adding a large amount of a halogen-containing compound A method of adding a halogen-based flame retardant, a method of adding a phosphorus-containing compound (a phosphorus-based flame retardant), and a method of adding a metal hydroxide or the like were common. However, when a flame-retardant thermoplastic resin composition containing a halogen-containing resin or a halogen-based flame retardant is used, there is a problem that a corrosive gas or a toxic gas is generated during combustion or thermal decomposition. There is also a problem with the toxicity of the antimony compound used as a flame retardant aid. In addition, since phosphorus-based flame retardants and metal hydroxides have relatively low flame retardancy-imparting effects, they need to be added in large amounts to make thermoplastic resins flame-retardant. Therefore, when these are added, there are drawbacks such as deterioration of the physical properties inherent to the thermoplastic resin and impairment of the surface appearance of the obtained molded article. Therefore, in order to solve the problems of the conventional flame retardants, various flame retardants have been studied. Among them, silicon compounds such as polyorganosiloxane have low generation of toxic gas and the like. It is widely studied as an environmentally friendly flame retardant.

For example, Japanese Patent Publication No. 3-48947 discloses a silicone resin comprising _0.5 unit of R ₃ SiO (M unit) and a unit of SiO ₂ (Q unit), silicone and II.
It is described that a group A metal salt is effective for making a plastic flame-retardant. Japanese Patent Publication No. Sho 62-60421 states that a polysiloxane resin containing RSiO _1.5 units (T units) in an amount of 80% by weight or more is effective for making a thermoplastic non-silicone polymer flame-retardant. However, in such a method of adding a silicone resin or a polysiloxane resin to a thermoplastic resin to make it flame-retardant, the dispersibility of the added silicone resin or polysiloxane resin in the thermoplastic resin is insufficient. Tokuhei 3-4894
The example of JP-A No. 7 describes that delamination was observed in a resin molded product flame-retarded by adding a silicone resin.

JP-A-10-139964 discloses that a silicone resin having a unit represented by R ₂ SiO _1.0 and RSiO _1.5 and having a weight average molecular weight of 10,000 to 270,000 is a non-silicone resin containing an aromatic ring. It says that it can be made flame-retardant efficiently. However, this silicone resin is inferior in kneading properties such as disturbed ejection of the resin from the kneader when kneading with the non-silicone resin, and in order to improve this, as shown in the examples, silica powder or the like is used. It was necessary to combine inorganic fillers. The resulting flame-retardant resin composition has the drawback that physical properties and moldability are impaired.

[0005] JP-A-5-202280 discloses a flame-retardant polycarbonate resin composition containing a polyorganosiloxane fluid-filler blend.
No. 712 proposes a method of dispersing a silicone resin polymer powder comprising a polyorganosiloxane polymer and a silica filler in an organic resin to make the resin flame-retardant. In these methods, by combining the polyorganosiloxane and the filler, the kneadability with the organic resin, particularly the handleability at the time of kneading, and the flame retardancy are improved, but the surface of the resin molded article due to the use of the filler is improved. The appearance, in particular, the surface smoothness and mechanical properties such as impact resistance were reduced.

[0006] JP-A-63-137964 and JP-A-1-318069 disclose, as a method of using silicone as a flame-resistant additive, a silicone emulsion and an organic thermoplastic polymer dispersion under specific conditions. After mixing
It has been proposed to mix a coagulated and recovered silicone-containing powdery polymer mixture into a thermoplastic resin. In these methods, although the kneading property at the time of adjusting the flame-retardant resin and the handling property of the silicone-containing polymer mixture are excellent, the effect of imparting flame resistance of the silicone-containing polymer mixture is not sufficient, and the heat of the silicone-containing polymer mixture is not sufficient. Dispersibility in a plastic resin is insufficient, and there is a defect that appearance defects such as delamination are likely to occur in a resin molded product.

On the other hand, JP-A-5-339510 and JP-A-8-302211 disclose a method of imparting flame retardancy by adding a polyorganosiloxane resin having a specific structure to a thermoplastic resin. Proposed. However, in these methods, the flame retardancy of the polyorganosiloxane resin used is not sufficient, and it is necessary to use a large amount of another flame retardant such as a phosphate ester, and the resin composition containing such a large amount of flame retardant The product had problems in molding appearance and mechanical properties. Also, as a method of combining a polyorganosiloxane with a thermoplastic resin,
Japanese Patent No. 2558126 discloses a polycarbonate resin obtained by graft-polymerizing a vinyl monomer onto a composite rubber in which a polyorganosiloxane component and an alkyl (meth) acrylate rubber component cannot be separated from each other so that they cannot be separated from each other. Japanese Patent Nos. 2860856, 7-173401 and 7-316409 disclose a method of adding the graft copolymer to a polycarbonate resin, an ABS resin and a polycarbonate resin / ABS resin blend. It is described that the composition is effective in imparting flame retardancy. However, in these methods, the flame retardancy imparting property of the composite rubber-based graft copolymer is not sufficient, and it is necessary to use a large amount of a flame retardant such as a phosphate ester compound or a brominated epoxy compound. As described above, the resin composition containing a large amount of the flame retardant exhibited a decrease in molded appearance and mechanical properties.

[0008]

As described above, when a silicon compound such as polyorganosiloxane is blended with a thermoplastic resin such as polycarbonate as a flame retardant, high flame retardancy can be exhibited and good kneading properties can be obtained. It was very difficult to maintain and suppress the deterioration of the physical properties of the thermoplastic resin, and to obtain a molded article having an even better appearance.

The present invention has been made in view of the above circumstances, has high flame retardancy, and has good moldability, formability and appearance.
An object of the present invention is to provide a flame-retardant resin composition having excellent heat resistance and mechanical properties.

[0010]

The present inventors have added a polymer containing a polyorganosiloxane to a thermoplastic resin as a flame retardant, and as a result of earnestly studying the flame retardancy of the obtained resin composition, Surprisingly, a graft copolymer obtained by graft-polymerizing a vinyl monomer onto a composite polymer composed of a polyorganosiloxane composed of specific constituents and a vinyl polymer is used for flame retardancy of a polycarbonate resin. Found to be effective. As a result, the content of the flame retardant, which has been conventionally required to exhibit sufficient flame retardancy, can be significantly reduced, whereby the resin composition having both excellent molded appearance and good mechanical properties Was obtained, and reached the present invention. That is, the present invention provides a polycarbonate resin (A), a copolymer (B) containing an aromatic alkenyl compound component and a vinyl cyanide compound component as constituent units, and a polyorganosiloxane (c-1) containing an aryl group. (C-1) + (c-2)), which is selected from aromatic alkenyl compounds, methacrylic esters, acrylic esters and vinyl cyanide compounds. A flame-retardant resin composition comprising a graft copolymer (C) obtained by graft-polymerizing at least one monomer (c-3) and a phosphate compound (D). I do.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a polycarbonate resin (A) produced by a known method can be used. That is, a transesterification reaction between a diester of carbonic acid obtained from a monofunctional aromatic or aliphatic hydroxy compound and a dihydroxy compound, a transalkylation reaction between a dihydroxy compound and a bisalkyl of itself or another dihydroxy compound, or a bisallyl carbonate, Examples of the method include a reaction between a dihydroxy compound and phosgene in the presence of an oxygen binder, and a production method by a reaction between a dihydroxy compound and a bischlorocarbonate of the dihydroxy compound in the presence of an oxygen binder. As a typical production method, there is a production method in which bisphenol A is reacted with carbonyl chloride in the presence of an oxygen binder and a solvent.

The copolymer (B) contains an aromatic alkenyl compound component and a vinyl cyanide compound component as constituent units. The copolymer (B) may contain a vinyl monomer component copolymerizable with an aromatic alkenyl compound component and a vinyl cyanide compound component, if necessary. Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, vinyltoluene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and the like, preferably styrene. ,
α-methylstyrene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred. As the copolymerizable vinyl monomer, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid esters such as glycidyl methacrylate, methyl acrylate, ethyl acrylate,
Examples include acrylates such as butyl acrylate, maleimide compounds such as N-phenylmaleimide and N-methylmaleimide, and maleic anhydride. As a preferred example of the copolymer (B), specifically, styrene-
Acrylonitrile copolymer (SAN resin), styrene-
An acrylonitrile-N-phenylmaleimide copolymer is exemplified. The copolymer (B) can be produced by a known method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

The graft copolymer (C) is a composite polymer ((c-1) + (c-) comprising an aryl group-containing polyorganosiloxane (c-1) and a vinyl polymer (c-2).
2)) is obtained by graft polymerization of at least one monomer (c-3) selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester and a vinyl cyanide compound. The aryl group-containing polyorganosiloxane (c-1) is a polyorganosiloxane containing an aryl group on the side chain and / or the terminal of the polysiloxane. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthalene group and a 4-methyl group. And a nucleus-substituted phenyl group such as a phenyl group, a 4-ethylphenyl group, and a 4-chlorophenyl group. Of these, polyorganosiloxane (c-1) having a phenyl group is preferred because it is easy to produce. When the aryl group-containing polyorganosiloxane (c-1) is used as described above, the resulting flame-retardant resin composition can be obtained in comparison with the case where an aryl group-free polyorganosiloxane, for example, polydimethylsiloxane is used as a constituent unit. Flame retardancy is improved. Therefore, the amount of the phosphate compound (D) to be added to further increase the flame retardancy can be reduced. As a result, the appearance of the molded article of the obtained flame-retardant resin composition can be favorably maintained, and a decrease in physical properties can be suppressed.

The aryl group-containing polyorganosiloxane (c-1) may contain an organic group other than the aryl group on the side chain and / or the terminal of the polysiloxane. Such organic groups include methyl, ethyl, propyl,
Alkyl group such as butyl group, hydroxyl group, methoxy group, alkoxy group such as ethoxy group, mercapto-substituted alkyl group such as mercaptopropyl group, amino-substituted alkyl group such as aminopropyl group, and methacryl group such as γ-methacryloxypropyl group Examples include a substituent, an alicyclic group such as a vinyl group and a cyclohexyl group, a fluoroalkyl group, and an epoxy group-containing substituent. Further, the aryl group-containing polyorganosiloxane (c-1) may have a crosslinked structure or a branched structure via a siloxane bond. The most preferred form of the aryl group-containing polyorganosiloxane (c-1) is a diphenylpolysiloxane having a vinyl polymerizable functional group such as a methacryloxy group, a mercapto group, or a vinyl group on a side chain and / or a terminal, a methacryloxy group,
A diphenylsiloxane-dimethylsiloxane copolymer having a vinyl polymerizable functional group such as a mercapto group or a vinyl group in a side chain and / or a terminal, a methacryloxy group, a mercapto group, a vinyl polymerizable functional group such as a vinyl group as a side chain and And / or terminal phenylmethylpolysiloxane. As described above, when an aryl group-containing polyorganosiloxane (c-1) having a vinyl polymerizable functional group introduced into a side chain and / or a terminal is used, the aryl group-containing polyorganosiloxane (c-1) is produced at the time of production of the graft copolymer (C). It is preferable because a composite polymer ((c-1) + (c-2)) comprising the polyorganosiloxane (c-1) and the vinyl polymer (c-2) can be easily produced.

As the method for producing the aryl group-containing polyorganosiloxane (c-1), a method in which a siloxane compound containing an aryl group-containing siloxane is emulsion-polymerized is preferable. Specifically, a mixture obtained by adding a siloxane containing no aryl group, a siloxane containing a vinyl polymerizable functional group, a siloxane-based crosslinking agent and / or a branching agent, if necessary, in addition to the aryl group-containing siloxane, is used as an emulsifier. The latex is emulsified with water and water to obtain a latex, and the latex is atomized using a homomixer that atomizes the particles by the shearing force of high-speed rotation or a homogenizer that atomizes the particles with a high-pressure generator. And then neutralizing the acid with an alkaline substance.

Here, the method of adding the acid catalyst includes a method of mixing the acid catalyst with the siloxane mixture, emulsifier and water, and a method of dropping the latex in which the siloxane mixture is finely divided into a high-temperature aqueous acid solution at a constant rate. is there.
The method of mixing the siloxane mixture, emulsifier, water and / or acid catalyst includes mixing by high-speed stirring and mixing by a high-pressure emulsifying device such as a homogenizer, and the method using a homogenizer is used to obtain the resulting polyorganosiloxane (c- This is a preferred method because the particle size distribution of 1) becomes smaller. The polymerization temperature at the time of producing the aryl group-containing polyorganosiloxane (c-1) is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. The polymerization time is 2 hours or more, more preferably 5 hours or more when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water to form fine particles, and more preferably 5 hours or more. Is preferably maintained for about 1 hour after the completion of the dropping of the latex. Termination of the polymerization can be carried out by cooling the reaction solution and further neutralizing the latex with an alkaline substance such as caustic soda, caustic potash, and sodium carbonate. At this time, before the reaction liquid is cooled and neutralized, the polymerization liquid of the aryl group-containing polyorganosiloxane (c-1) is increased by leaving the reaction liquid at a temperature lower than room temperature for 10 hours or more, preferably 15 hours or more, This tends to improve the storage stability of the polymerized latex during the preparation of the graft polymer (C).

The aryl group-containing siloxane used in producing the aryl group-containing polyorganosiloxane (c-1) includes a diphenylsiloxane-based cyclic body having three or more membered rings, a phenylmethylsiloxane-based cyclic body, and the like. Aryl group-containing cyclic siloxane compound, aryl group-containing alkoxysilane compound such as diphenyldimethoxysilane, linear diphenylsiloxane oligomer, linear diphenylsiloxane-dimethylsiloxane oligomer,
Aryl group-containing linear organosiloxane oligomers such as linear phenylmethylsiloxane oligomers, linear phenylmethylsiloxane-dimethylsiloxane oligomers, linear diphenylsiloxane-phenylmethylsiloxane oligomers, and the like. Since the preparation of the organosiloxane (c-1) and the preparation of the graft copolymer (C) containing the same can be easily performed, the aryl group-containing linear organosiloxane having a hydroxyl group and / or an alkoxy group at the terminal is used. It is preferred to use. Specific examples of the aryl group-containing linear organosiloxane having a hydroxyl group and / or an alkoxy group at the terminal include an organosiloxane having a structure represented by the following chemical formula (1) or (2).

[0018]

Embedded image (In the formula, X represents a hydroxyl group or a methoxy group, m represents an integer of 1 or more, and n represents an integer.)

Embedded image (In the formula, X represents a hydroxyl group or a methoxy group, m represents an integer of 1 or more, and n represents an integer.)

The viscosity of the aryl group-containing straight-chain organosiloxane having a hydroxyl group and / or an alkoxy group at the terminal is not particularly limited, but may be selected during the production of the aryl group-containing polyorganosiloxane (c-1). Since the particle size distribution in the latex can be easily controlled and the molecular weight can be easily controlled, the viscosity measured at 25 ° C. is preferably 0.01 to 10 Pa · s, more preferably 0.01 to 10 Pa · s. It is 1 Pa · s, more preferably 0.01 to 0.2 Pa · s. Viscosity is 10Pa
If it exceeds s, the stability of the latex of the aryl group-containing polyorganosiloxane (c-1) may be poor. Examples of the aryl group-containing linear organosiloxane having a hydroxyl group and / or an alkoxy group at a terminal include:
For example, XF40-B619 manufactured by Toshiba Silicone Co., Ltd.
7 (polymethylphenylmethoxysiloxane), YF3
804 (polymethylphenylsiloxane) and XF4
0-B6626 (polymethylphenylmethoxysiloxane) is commercially available. The content of the aryl group in the aryl group-containing linear organosiloxane is not particularly limited. However, since high flame retardancy can be imparted to the obtained flame retardant resin composition, all the silicon atoms in the organosiloxane can be used. When the number of bonding groups other than the bonded siloxane bond is 100, preferably 5 to 95,
More preferably, it is 5 to 50, more preferably 10
~ 40.

Specific examples of siloxane compounds containing no aryl group, which are arbitrarily used in producing the aryl group-containing polyorganosiloxane (c-1), include dimethylsiloxane-based cyclic bodies having three or more ring members. .
Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or as a mixture of two or more. The content of the aryl group in the aryl group-containing polyorganosiloxane (c-1) can be arbitrarily set by using the aryl group-containing organosiloxane and the aryl group-free organosiloxane in combination. The flame retardant resin composition obtained has a high flame retardancy, and the aryl group-containing polyorganosiloxane (c-
Since 1) is easy to produce, the proportion of the aryl group in the organo substituents bonded to all silicon atoms in the aryl group-containing polyorganosiloxane (c-1) is from 1 to 45.
mol%, more preferably 5 to 5 mol%.
The range is 35 mol%.

The siloxane containing a vinyl polymerizable functional group optionally used in producing the aryl group-containing polyorganosiloxane (c-1) contains a vinyl polymerizable functional group and is bonded to a diorganosiloxane by a siloxane bond. And various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable in consideration of the reactivity with the diorganosiloxane. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane; p-vinylphenyldimethoxymethylsilane; and γ-mercaptopropyl Mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane; These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

The siloxane crosslinking agent and / or branching agent optionally used in producing the aryl group-containing polyorganosiloxane (c-1) may be a trifunctional or tetrafunctional silane crosslinking agent, for example, a trifunctional silane crosslinking agent. Methoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and the like are used. As an emulsifier optionally used in producing the aryl group-containing polyorganosiloxane (c-1), a usual anionic emulsifier or a nonionic emulsifier is used. As the anionic emulsifier,
Sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium lauryl sulfate, sodium sulfosuccinate, sodium polyoxyethylene alkyl phenyl ether sulfate, N-lauroyl sarcosine soda, dipotassium alkenyl succinate, rosin acid soap and sodium oleate. Of these, use of a sulfonate emulsifier such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate is particularly preferred. As the nonionic emulsifier, polyoxyethylene nonylphenyl ether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, and the like are used. The amount of the emulsifier used is not particularly limited, but in consideration of the stability of the emulsified latex during polymerization and the heat coloring property of the resin composition containing the graft copolymer (C), the amount of the emulsifier used is The range is preferably 0.05 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 2 parts by weight, per 100 parts by weight of the siloxane compound. The acid catalyst optionally used in producing the aryl group-containing polyorganosiloxane (c-1) includes sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid and aliphatic substituted naphthalenesulfonic acid, and sulfuric acid. And mineral acids such as hydrochloric acid, nitric acid and phosphoric acid. Among these, aliphatic substituted benzenesulfonic acid is preferred because of excellent stability of the emulsified latex during polymerization, and normal dodecylbenzenesulfonic acid is particularly preferred.

The content of the aryl group-containing polyorganosiloxane (c-1) in the graft copolymer (C) is not particularly limited, but is necessary for further increasing the flame retardancy of the resulting flame retardant resin composition. Phosphate ester compound (D)
Is low, and as a result, the molding appearance and physical properties of the flame-retardant resin composition are excellent, so that the range of 50 to 99% by weight is preferable. When the content is less than 50% by weight, it is necessary to add a large amount of the phosphoric ester compound (D) in order to develop the flame retardancy of the flame retardant resin composition, whereby the molded appearance and the physical properties tend to be deteriorated. Become. On the other hand, when the content exceeds 99% by weight, the dispersibility of the graft copolymer (C) in the flame-retardant resin composition is reduced, and the molded article tends to have poor appearance. Further, considering the molded appearance, flame retardancy and physical properties of the resin composition, it is more preferably 60 to 99% by weight, more preferably 70 to 95% by weight.

The vinyl polymer (c-2) constituting the graft copolymer (C) is a polymer of a vinyl monomer, preferably a monofunctional vinyl monomer and a polyfunctional vinyl monomer. Is a crosslinkable polymer obtained by copolymerization of Examples of the monofunctional vinyl monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, methacrylates such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate. Such as acrylic acid esters, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile, maleimide compounds such as N-phenylmaleimide, unsaturated acid anhydrides such as maleic anhydride, vinyl halide compounds such as vinyl chloride, ethylene, propylene And unsaturated carboxylic acids such as acrylic acid and methacrylic acid. These can be used alone or in combination of two or more. Among them, the composite polymer ((c
From the ease of forming -1) + (c-2)), it is preferable to use one or more monomers selected from acrylates, methacrylates and aromatic alkenyls. As a polyfunctional vinyl monomer,
Multifunctionality such as allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate Alkyl (meth) acrylate and the like can be mentioned.

The composite polymer ((c-1) + (c-2)) comprising the aryl group-containing polyorganosiloxane (c-1) and the vinyl polymer (c-2) is a polyorganosiloxane (c-1) )) The latex can be prepared by adding a vinyl monomer constituting the vinyl polymer (c-2) to the latex of the component, and polymerizing it by the action of a usual radical polymerization initiator. As a method for adding the vinyl monomer, there are a method of mixing the latex of the aryl group-containing polyorganosiloxane (c-1) at a time and a method of dropping into the latex at a constant speed. It is preferable to use a method of mixing the polyorganosiloxane (c-1) with the latex at a time because high flame retardancy can be imparted to the conductive resin composition. As the radical polymerization initiator used for the polymerization, a peroxide, an azo initiator, or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferable. Composite polymer ((c-1) +
(C-2) The polymerization temperature during the production is not particularly limited, but it is preferably carried out at a temperature of 50 to 90 ° C.

The amount of the aryl group-containing polyorganosiloxane (c-1) in the composite polymer ((c-1) + (c-2)) is not particularly limited. Since high flame retardancy can be imparted and the molded appearance is excellent,
~ 99% by weight is preferred. If the amount is less than 70% by weight, the flame retardancy tends to be low due to the small amount of the polyorganosiloxane (c-1), while if it exceeds 99% by weight, the graft copolymer (C) in the flame retardant resin composition Dispersibility decreases,
The surface appearance of the molded product is likely to deteriorate. Considering both the flame retardancy and the appearance of the molded resin composition, the composite polymer ((c
-1) + (c-2)) in the polyorganosiloxane (c
The amount of -1) is more preferably 80 to 95% by weight.

The graft copolymer (C) is obtained by adding an aromatic alkenyl compound, a methacrylic ester, an acrylate ester and a cyano compound to a composite polymer ((c-1) + (c-2)) produced by emulsion polymerization. It can be produced by graft polymerization of at least one monomer (c-3) selected from vinyl chloride compounds. Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, and vinyl toluene. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and 2-methyl methacrylate.
Ethylhexyl methacrylate and the like. Examples of the acrylate include methyl acrylate, ethyl acrylate and butyl acrylate, and examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Among them, a mixture of styrene and acrylonitrile or methyl methacrylate is preferred because a high flame retardancy can be imparted to the flame retardant resin composition and the appearance of the molded article is excellent.

Here, the graft polymerization is carried out using a composite polymer ((c
-1) + (c-2)), at least one monomer (c-3) selected from an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound is added to the latex, and a radical is added. The polymerization can be carried out in one stage or in multiple stages. In addition, various chain transfer agents for adjusting the molecular weight and the graft ratio of the graft polymer can be added to the monomers used in the graft polymerization. The graft copolymer (C) is obtained by throwing the thus obtained graft copolymer latex into hot water in which a metal salt such as calcium chloride, calcium acetate or aluminum sulfate is dissolved, and then salting and solidifying. And can be recovered in powder form. Although the particle size of the graft copolymer (C) is not particularly limited, the number-average particle size is high because the resulting flame-retardant resin composition can be imparted with high flame retardancy and has excellent physical properties and molded appearance. Is 0.0
It is preferably from 5 to 1.0 μm, more preferably from 0.10 to 0.50 μm.

The amount of at least one monomer (c-3) selected from aromatic alkenyl compounds, methacrylates, acrylates and vinyl cyanide compounds constituting the graft copolymer (C) is particularly limited. Not to be added, but 0.1 to 30% by weight based on the graft copolymer (C)
It is preferable that When the amount of the monomer (c-3) is less than 0.1% by weight, the resulting flame-retardant resin composition tends to have a reduced molded appearance, while when the amount exceeds 30% by weight, the flame-retardant property tends to be low. Show. In consideration of both the flame retardancy and the molded appearance of the obtained flame retardant resin composition, the preferred range of the monomer (c-3) is 1 to 30% by weight, more preferably 1 to 30% by weight.
-20% by weight, more preferably 1-15% by weight.

As the phosphate compound (D),
Trimethyl phosphate, Triethyl phosphate, Tributyl phosphate, Trioctyl phosphate, Tributoxyethyl phosphate, Triphenyl phosphate, Tricresyl phosphate, Cresyl phenyl phosphate, Octyl diphenyl phosphate, Diisopropyl phenyl phosphate, Tris (chloroethyl) phosphate, Alkoxy substituted bisphenol A Examples include polyphosphates such as bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, and trioxybenzene triphosphate, and preferred are triphenyl phosphate and various polyphosphates. The phosphate compound (D) is added to appropriately adjust the flame retardancy of the flame retardant resin composition. The content of the phosphate compound (D) in the flame-retardant resin composition is determined according to the required flame-retardant level. Even when the content of the acid ester compound (D) is small, high flame retardancy can be exhibited. When the content of the phosphate ester compound (D) is large, the flame retardancy of the obtained flame retardant resin composition is improved, but deterioration of physical properties such as impact resistance and heat resistance and poor appearance of the molded article occur. On the other hand, when the content of the phosphate compound (D) is small, the flame retardancy tends to decrease. Considering the physical properties, molded appearance, and flame retardancy of the flame-retardant resin composition, the preferred content of the phosphate compound (D) is determined by the resin component, that is, the polycarbonate resin (A) and the copolymer (B). For a total of 100 parts by weight of the graft copolymer (C),
0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.
Parts by weight, more preferably 1 to 10 parts by weight.

In the flame-retardant resin composition of the present invention, at least one monomer selected from aromatic alkenyl compounds, methacrylic esters, acrylic esters and vinyl cyanide compounds may be added to the rubbery polymer if necessary. It may contain a graft polymer (E) obtained by graft polymerization. Examples of the rubbery polymer constituting the graft copolymer (E) include polybutadiene, butadiene-styrene copolymer, ethylene-propylene-diene copolymer, acrylic rubber, polyisoprene, polyurethane rubber, and polydimethylsiloxane. Can be Specific examples thereof include an ABS graft polymer, an AES graft polymer, and an ASA graft polymer. When the graft copolymer (E) is blended with the flame-retardant resin composition, the impact resistance, chemical resistance, fluidity, weather resistance, and the like of the flame-retardant resin composition can be appropriately adjusted. be able to. The content of the graft copolymer (E) is not particularly limited, but considering the flame retardancy of the obtained flame retardant resin composition, the resin component, that is, the polycarbonate resin (A) and the copolymer (B) The amount is preferably 50 parts by weight or less, more preferably 3 parts by weight, based on 100 parts by weight of the total of the graft copolymer (C).
0 parts by weight or less, more preferably 10 parts by weight or less.
Further, if necessary, a non-drip agent such as polytetrafluoroethylene may be added to the flame-retardant resin composition.

The flame-retardant resin composition of the present invention comprises a polycarbonate resin (A), a copolymer (B), a graft copolymer (C), and a phosphate compound (D), if necessary. It can be produced by extruding the copolymer (E) with an ordinary known kneading apparatus. Examples of the molding machine used for kneading include an extruder, an injection molding machine, a blow molding machine, a calender molding machine, and an inflation molding machine. The flame-retardant resin composition contains a dye, a pigment,
Stabilizers, reinforcing agents, fillers and the like can be added. In addition, a flame retardant other than the phosphate compound can be used in combination with the flame retardant resin composition in order to supplement the flame retardancy.
Specific examples of the flame retardant include red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, phosphoric anhydride, polyvinyl chloride, brominated epoxy compound, brominated polycarbonate, brominated bisphenol and the like. Examples include halogen compounds, metal oxides such as antimony trioxide and zinc oxide, nitrogen-containing compounds such as melamine, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. The use of the flame-retardant resin composition of the present invention is not particularly limited, but various electric and electronic parts such as connectors, electric wire covering materials, sockets, personal computer housings, battery cases, mobile phone housings, printer housings, copier housings. OA equipment such as body and facsimile housing, communication equipment parts, automobile interior parts such as various building materials parts, sheet materials, instrument panel parts, tableware, vacuum cleaner housing, television housing, home appliance parts such as air conditioner housing, syringes, catheters, etc. It is suitable for use in medical materials and the like.

[0033]

EXAMPLES The present invention will be described below with reference to examples. In addition,
In Reference Examples, Examples and Comparative Examples, "parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.
Means (Reference Example 1) Polyorganosiloxane latex (S-
Production of 1) 95 parts of terminal methoxydiphenyldimethylsiloxane (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%) and 5 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and after stirring, 200 parts of distilled water was added and 1 part was added using a homomixer.
After preliminary stirring at 000 rpm, the mixture was treated four times with a homogenizer at a pressure of 40 MPa to emulsify and disperse to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and left at 20 ° C. After 16 hours, the pH of the latex was adjusted with a 5% aqueous sodium hydroxide solution. Neutralized to 7.4, polymerization was completed and polyorganosiloxane latex (S-
1) was obtained. The polyorganosiloxane latex (S-1) thus obtained had a solid content of 29.1% and an absorbance of 0.58. In addition, latex (S-1)
The weight average molecular weight of the polyorganosiloxane contained therein is 160
The refractive index measured at 20 ° C. was 1.515. Table 1 shows the above results, phenyl content and number average molecular weight.
Shown in

In Reference Example 1, the absorbance, weight average molecular weight, phenyl content, and refractive index were measured by the following methods. Absorbance The polyorganosiloxane latex (S-1) adjusted to a solid concentration of 0.5 g / L was measured at a wavelength of 700 nm using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation.
It measured on condition of. Weight average molecular weight The polyorganosiloxane latex (S-1) was precipitated and recovered in isopropyl alcohol, and dried under vacuum at room temperature.
It was measured using GPC manufactured by TERS and determined from the retention time in terms of standard polystyrene. -Phenyl content The polyorganosiloxane latex (S-1) was precipitated and recovered in isopropyl alcohol, dried in vacuo at room temperature, and analyzed by NMR (GSX-400, manufactured by JEOL Ltd.) of a heavy acetone solution. The molar amount of the methyl group (M) and the phenyl group (P) bonded to the silicon atom was determined, and the content of the phenyl group was determined from the following formula. Phenyl content (mol%) = P / (P + M) × 100 Refractive index Polyorganosiloxane latex (S-1) was precipitated and collected in isopropyl alcohol, and dried under vacuum at room temperature. Abbe refraction manufactured by Shimadzu Corporation 20 using a rate meter
The temperature was measured at ° C.

Reference Example 2 Preparation of polyorganosiloxane latex (S-2) 76.3 parts of methoxydiphenyldimethylsiloxane terminated (XF40-B6197 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 34 mol%), octamethylcyclotetrasiloxane (TSF-40 manufactured by Toshiba Silicone Co., Ltd.
4) 18.7 parts and γ-methacryloyloxypropyldimethoxymethylsilane 5 parts were mixed to obtain 100 parts of a siloxane mixture. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonate were added to the siloxane mixture, and the mixture was stirred.
After adding 00 parts and preliminarily stirring with a homomixer at 10,000 rpm, the mixture was emulsified and dispersed by treating with a homogenizer four times at a pressure of 40 MPa to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and left at 20 ° C. After 16 hours, the pH of the latex was adjusted with a 5% aqueous sodium hydroxide solution. After neutralization to 7.4, the polymerization was completed to obtain a polyorganosiloxane latex (S-2). The polyorganosiloxane latex (S-2) thus obtained had a solid content of 28.6% and an absorbance of 0.31. The weight average molecular weight of the polyorganosiloxane in the latex (S-2) was 67000,
The refractive index measured at 0 ° C. was 1.491. Table 1 shows the results, the phenyl content and the number average molecular weight. In addition,
Absorbance, weight average molecular weight, phenyl content, and refractive index were measured in the same manner as in Reference Example 1.

(Reference Example 3) Production of polyorganosiloxane latex (S-3)
And the amount of octamethylcyclotetrasiloxane was changed to 38 parts, polymerization was carried out in the same manner as in Reference Example 2 to obtain a polyorganosiloxane latex (S-3). The polyorganosiloxane latex (S-3) thus obtained had a solid content of 29.0% and an absorbance of 0.11. The weight average molecular weight of the polyorganosiloxane in the latex (S-3) is 110,000,
The refractive index measured at 20 ° C. was 1.469. Table 1 shows the results, the phenyl content and the number average molecular weight. The absorbance, weight average molecular weight, phenyl content and refractive index were measured in the same manner as in Reference Example 1.

(Reference Example 4) Preparation of polyorganosiloxane latex (S-4)
And the amount of octamethylcyclotetrasiloxane was changed to 57 parts, polymerization was carried out in the same manner as in Reference Example 2 to obtain a polyorganosiloxane latex (S-4). The polyorganosiloxane latex (S-4) thus obtained had a solid content of 29.4% and an absorbance of 0.07. The weight average molecular weight of the polyorganosiloxane in the latex (S-4) is 154000,
The refractive index measured at 20 ° C. was 1.448. Table 1 shows the results, the phenyl content and the number average molecular weight. The absorbance, weight average molecular weight, phenyl content and refractive index were measured in the same manner as in Reference Example 1.

(Reference Example 5) Preparation of polyorganosiloxane latex (S-5) 75.6 parts of methoxyphenylmethylsiloxane at terminal (XF40-B6626 manufactured by Toshiba Silicone Co., Ltd .: diphenylsiloxane content = 47 mol%), octamethylcyclotetrasiloxane (TSF-404 manufactured by Toshiba Silicone Co., Ltd.)
19.4 parts and γ-methacryloyloxypropyldimethoxymethylsilane 5 parts were mixed to obtain 100 parts of a siloxane mixture. Next, sodium dodecylbenzenesulfonate and dodecylbenzenesulfonate were added in 1 part each.
Parts of the siloxane mixture, and after stirring, 200 ml of distilled water
Then, the mixture was preliminarily stirred at 10,000 rpm with a homomixer, and then treated four times with a homogenizer at a pressure of 40 MPa to emulsify and disperse to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then left at 20 ° C.
Six hours later, the pH of this latex was neutralized to 7.4 with a 5% aqueous sodium hydroxide solution to complete the polymerization, and a polyorganosiloxane latex (S-5) was obtained. The polyorganosiloxane latex (S-
The solid content of 5) was 30.0%, and the absorbance was 0.43. The weight average molecular weight of the polyorganosiloxane in latex (S-5) was 17000,
Was 1.510. Table 1 shows the results, the phenyl content and the number average molecular weight. The absorbance, weight average molecular weight, phenyl content and refractive index are shown in Reference Example 1.
The measurement was performed in the same manner as described above.

Reference Example 6 Production of Polyorganosiloxane Latex (T-1) 95 parts of octamethylcyclotetrasiloxane (TSF-404 manufactured by Toshiba Silicone Co., Ltd.) and 5 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed.
100 parts of a siloxane mixture were obtained. Next, 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were added to the siloxane mixture, and the mixture was stirred.
After preliminary stirring at 00 rpm, the mixture was
The mixture was emulsified and dispersed by treating at a pressure of 0 MPa four times to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and left at 20 ° C. After 16 hours, the pH of the latex was adjusted with a 5% aqueous sodium hydroxide solution. After neutralization to 7.4, the polymerization was completed to obtain a polyorganosiloxane latex (T-1). The polyorganosiloxane latex (T-1) thus obtained had a solid content of 29.4% and an absorbance of 0.08. The weight average molecular weight of the polyorganosiloxane in the latex (T-1) is 21,000.
0 and the refractive index measured at 20 ° C. was 1.409. Table 1 shows the results, the phenyl content and the number average molecular weight. The absorbance, weight average molecular weight, phenyl content,
The refractive index was measured in the same manner as in Reference Example 1.

[0040]

[Table 1]

Reference Example 7 Graft copolymer (A-
Preparation of 1) The polyorganosiloxane latex (S-1) prepared in Reference Example 1 was solidified in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater, and a stirrer to a solid content of 90%.
A portion was collected, 100 parts of distilled water was added, and after purging with nitrogen, the temperature was raised to 50 ° C., and 4.9 parts of methyl methacrylate, 0.1 part of allyl methacrylate and diisopropylbenzene hydroperoxide (manufactured by NOF Corporation) (Park Mill P) was mixed and stirred for 30 minutes, and the mixed solution was permeated into the polyorganosiloxane particles.
Then, ferrous sulfate 0.001 part, ethylenediaminetetraacetic acid disodium salt 0.003 part, Rongalit 0.2
A mixed solution of 4 parts and 10 parts of distilled water was charged to start radical polymerization, and then kept at an internal temperature of 70 ° C. for 2 hours to complete the polymerization to obtain a composite polymer latex. A mixed solution of 0.1 part of diisopropylbenzene hydroperoxide (Parkmill P, manufactured by NOF Corporation) and 5 parts of methyl methacrylate was added to this composite polymer latex at 70 ° C. for 10 minutes.
Then, the mixture was kept at 70 ° C. for 2 hours to complete the graft polymerization to the composite polymer. Further, the solid content of the obtained graft copolymer latex was 18.5%,
The absorbance was 0.76. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% by weight of calcium chloride, coagulated, separated, washed, and dried at 80 ° C. for 16 hours to obtain a white powdery graft copolymer. Polymer (A-
1) was obtained. Table 2 shows the polymerization conditions and the physical properties of the graft copolymer. The absorbance was measured in the same manner as in Reference Example 1.

(Reference Examples 8 to 11) Graft copolymer (A)
-2) Production of (A-5) The polyorganosiloxane latex used was converted to (S-
Except having changed to 2) to (S-5), a white granular graft copolymer (A-2) to (A-
5) was obtained. Table 2 shows the polymerization conditions and the physical properties of the graft copolymer. The absorbance was measured in the same manner as in Reference Example 1.

Reference Example 12 Graft copolymer (A-
Preparation of 6) The polyorganosiloxane latex (S-1) prepared in Reference Example 1 was solidified in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer.
A portion was collected, 200 parts of distilled water was added, the atmosphere was replaced with nitrogen, the temperature was raised to 50 ° C., and the temperature was raised to 50 ° C. Park Mill P) 0.6 part of the mixture was charged and stirred for 30 minutes.
This mixture was permeated into the polyorganosiloxane particles. Next, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.24 part of Rongalit and 10 parts of distilled water was charged to start radical polymerization. After holding for a while, the polymerization was completed to obtain a composite polymer latex. To the composite polymer latex, diisopropylbenzene hydroperoxide (Parkmill P, manufactured by NOF Corporation) was added.
A mixture of 2 parts and 10 parts of methyl methacrylate was heated to 70 ° C.
For 10 minutes, and then maintained at 70 ° C. for 2 hours to complete the graft polymerization to the composite polymer. The solid content of the obtained graft copolymer latex was 18.0.
%, Absorbance was 0.56. Next, the obtained graft copolymer latex was dropped into 400 parts of hot water containing 1.5% of calcium chloride, coagulated, separated, washed, and dried at 80 ° C. for 16 hours to obtain a white powdery graft copolymer. Merging (A-
6) was obtained. Table 2 shows the polymerization conditions and the physical properties of the graft copolymer. The absorbance was measured in the same manner as in Reference Example 1.

Reference Example 13 Graft copolymer (B-
Production of 1) The polyorganosiloxane latex used was converted to (T-
A white granular graft copolymer (B-1) was obtained in the same manner as in Reference Example 7, except that the procedure was changed to 1). The solid content of the latex containing the graft copolymer (B-1) is 18.
The absorbance was 5%, and the absorbance was 0.11. Table 2 shows the polymerization conditions and the physical properties of the graft copolymer. The absorbance was measured in the same manner as in Reference Example 1.

[0045]

[Table 2] In Table 2, MMA indicates methyl methacrylate, and AMA indicates allyl methacrylate.

Examples 1 to 16 Graft copolymers (A-1) to (A-6) produced in Reference Examples 7 to 12, polycarbonate resin (Iupilon S2000FN; manufactured by Mitsubishi Engineering-Plastics Corporation), It comprises 29% of an acrylonitrile component and 71% of a styrene component.
An acrylonitrile-styrene copolymer having a reduced viscosity of 0.60 dl / g measured from an N-dipolycarbonate resin methylformamide solution at 25 ° C., triphenyl phosphate (TPP manufactured by Daihachi Chemical Co., Ltd.), and a rubber content of 6
0% ABS graft polymer and polytetrafluoroethylene (F201L; manufactured by Daikin Industries, Ltd.)
Was weighed in the amounts shown in Tables 3 and 4 and mixed thoroughly using a Henschel mixer. A twin screw extruder (PCM) in which these mixtures were set at a barrel temperature of 280 ° C.
-30; manufactured by Ikegai Iron and Steel Co., Ltd.) to produce pellets. Tables 3 and 4 show the kneadability evaluation results at that time. The obtained pellet was 100 mm × 1 by an injection molding machine set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C.
A flat plate having a thickness of 00 mm and a thickness of 3 mm was formed. Tables 3 and 4 show the evaluation results of the appearance of the molded plate. Further, the obtained pellets were heated at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C.
A test piece was prepared by an injection molding machine set at ℃, and the deflection temperature under load and the Izod impact strength were measured using the test piece. The results are shown in Tables 3 and 4. Next, a rod-shaped molded plate of 125 mm × 12.5 mm × 3.2 mm thick and 125 mm × 12.5 mm × 1.6 mm thick was molded by an injection molding machine set at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. . Using this, a UL94 vertical combustion test was performed. The results are shown in Tables 3 and 4.

In the examples, kneadability, evaluation of molded appearance,
The deflection temperature under load, Izod impact strength, and UL94 vertical combustion test were performed by the following methods. Kneadability When the resin composition was kneaded and extruded with a twin-screw extruder and formed into pellets, the state of discharge of the resin from the die opening of the extruder was evaluated by visual observation. The evaluation criteria at that time are as follows. ：: good (smooth discharge of resin from die opening) △: slightly poor (discharge of resin from die opening is sometimes disturbed) ×: defective (discharge of resin from die opening is difficult to pelletize) ・ Molding Appearance evaluation Injection molding using a 100 mm × 100 mm × thickness 3 mm injection mold was performed using an injection molding machine J8 manufactured by Japan Steel Works, Ltd.
Using 5LS-II, cylinder set temperature 280 ° C,
The molding was performed under the conditions of a mold temperature of 80 ° C. and an injection speed of 50%. The surface of the obtained molded plate was visually observed, and the appearance of the molded product was evaluated according to the following criteria. ：: good, Δ: cloudy, ×: cloudy, low gloss ・ Load deflection temperature Measured according to ASTM D648, load 1.82M
It was measured under the condition of Pa. -Izod impact strength: Specimen thickness is measured in accordance with ASTM D256.
The measurement was performed under the conditions of 4 mm (with a notch) and a measurement temperature of 23 ° C.・ Vertical combustion test (UL94V) Based on UL94 of the U.S. Underriders Laboratories (UL) standard, evaluation was made based on the burning time and the drip property during the burning test using a 3.2 mm thick injection molded test piece. .

[0048]

[Table 3] In the table, PC indicates a polycarbonate resin.

[0049]

[Table 4] In the table, PC indicates a polycarbonate resin.

Comparative Examples 1-2 Pellets were prepared in the same manner as in Example 1 except that the graft copolymer (B-1) produced in Reference Example 13 was used. The same evaluation as in Example 1 was performed. Table 4 shows the results.

[Comparative Examples 3 to 8] Polycarbonate resin (Iupilon S2000FN; manufactured by Mitsubishi Engineering-Plastics Corporation), acrylonitrile component 29%
And a reduced viscosity of 0.6% as measured at 25 ° C. from an N, N-dimethylformamide solution comprising
Acrylonitrile-styrene copolymer of 0 dl / g, triphenyl phosphate (TP manufactured by Daihachi Chemical Co., Ltd.)
P) and polytetrafluoroethylene (F201L; manufactured by Daikin Industries, Ltd.) were weighed at the respective compounding amounts shown in Table 4, and were sufficiently mixed using a Henschel mixer.
The mixture was shaped by a twin-screw extruder (PCM-30; manufactured by Ikegai Iron & Steel Co., Ltd.) set at a barrel temperature of 280 ° C. to produce pellets. This resin composition was evaluated in the same manner as in Example 1. Table 4 shows the results.

From the examples and comparative examples, the following has become clear. 1) From the comparison between Examples 1 to 12 and Comparative Examples 4 to 7 and the comparison between Examples 13 to 16 and Comparative Example 8, the resin composition containing the graft copolymer containing the aryl group-containing polyorganosiloxane as a constituent component In comparison with the resin composition of the comparative example not containing this, the resin composition had a higher Izod impact strength, a shorter burning time in a UL burning test, and better flame retardancy. 2) The resin compositions of Examples 1 to 16 all had good resin kneading properties, molded appearance, impact resistance, heat resistance, and good flame retardancy. Such a resin composition having excellent moldability, physical properties, and flame retardancy has high utility value as various industrial materials. 3) The resin compositions of Comparative Examples 1 to 3 containing a graft copolymer containing a polyorganosiloxane containing no aryl group as a component are inferior in flame retardancy when the content of triphenyl phosphate is small, while the triphenyl phosphate content is low. When the phosphate content was high, the moldability, the appearance, the impact resistance and the heat resistance were poor. These resin compositions cannot simultaneously satisfy moldability, physical properties, and flame retardancy, and have low industrial utility value. 4) The resin compositions containing no graft copolymer of Comparative Examples 4 to 7 are inferior in flame retardancy when the content of triphenyl phosphate is small, and are poor in moldability and processing when the content of triphenyl phosphate is large. The appearance, impact resistance and heat resistance were poor. These resin compositions cannot simultaneously satisfy moldability, physical properties, and flame retardancy, and have low industrial utility value.

[0053]

As described above, the flame-retardant resin composition of the present invention has high flame retardancy and excellent physical properties such as moldability, molding appearance, heat resistance and mechanical properties. . In particular, the balance between flame retardancy, impact resistance and heat resistance is at an extremely high level that cannot be obtained with conventional polycarbonate resin / SAN resin-based polymer alloys containing phosphoric acid esters, and is made of various industrial materials, especially OA equipment and home electric parts. Is extremely useful as a housing material.

Continued on the front page F term (reference) 4J002 BC06X BG04X BG05X BG06X BG07X BG09X BG10X BH01X BH02X BN07Z BN12Z BN15Z CG00W CP17Y EW046 FD010 FD030 FD090 FD136

Claims (6)

[Claims] 1. A polycarbonate resin (A), a copolymer (B) containing an aromatic alkenyl compound component and a vinyl cyanide compound component as constituent units, an aryl group-containing polyorganosiloxane (c-1) and vinyl The composite polymer ((c-1) + (c-
2)) a graft copolymer (C) obtained by graft-polymerizing at least one monomer (c-3) selected from an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound; And a phosphoric ester compound (D). 2. The copolymer according to claim 1, wherein the copolymer (B) further contains, as a constitutional unit, a vinyl monomer component copolymerizable with an aromatic alkenyl compound component and a vinyl cyanide compound component. The flame-retardant resin composition according to the above. 3. The rubbery polymer further includes a graft polymer (E) obtained by graft-polymerizing at least one monomer selected from an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound. The flame-retardant resin composition according to claim 1 or 2, wherein: 4. An aryl group-containing polyorganosiloxane (c-1) obtained by emulsion polymerization of a siloxane compound containing an aryl group-containing linear organosiloxane having a hydroxyl group and / or an alkoxy group at a terminal. The flame-retardant resin composition according to any one of claims 1 to 3, wherein 5. The method according to claim 1, wherein the proportion of the aryl group in the organo substituent bonded to all silicon atoms in the aryl group-containing polyorganosiloxane (c-1) is 1 to 45 mol%. 5. The flame-retardant resin composition according to any one of 4. 6. The ratio of the aryl group-containing polyorganosiloxane (c-1) in the graft copolymer (C) is from 50 to 50.
The flame-retardant resin composition according to any one of claims 1 to 5, wherein the content is 99% by weight.