JPH1095911A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Problem] As a resin material having a polycarbonate resin and a SAN-based resin as a matrix, the resin material has a high level of flame retardancy, impact resistance, and excellent fluidity during molding.
Obtain a material that can be used for housing applications such as OA equipment or home electric parts. SOLUTION: At least two kinds selected from the group consisting of a polycarbonate resin (A), an aromatic alkenyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith are used as constituents. Graft copolymer in which a vinyl monomer is graft-polymerized to a composite rubber comprising a copolymer (B), a thermoplastic elastomer (C) substantially containing no gel, a polyorganosiloxane and an alkyl (meth) acrylate rubber. A thermoplastic resin composition comprising the united product (D) and the flame retardant (E).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent flame retardancy, impact resistance and fluidity.

[0002]

2. Description of the Related Art Polycarbonate resins have been used in various industrial applications due to their excellent impact resistance or heat resistance. However, polycarbonate resins have high molding processing temperatures, poor fluidity, or impact strength. Has a drawback such as a large dependency on thickness.

Heretofore, as a method of improving the disadvantages of these polycarbonate resins, ABS resins have been used.
Blending of (acrylonitrile-butadiene-styrene) -based resin is disclosed in JP-B-38-15225,
It is described in JP-B-48-12170. However, in the method of blending an ABS resin with a polycarbonate resin, although it is possible to improve the impact resistance or to lower the molding temperature, the flame retardancy of the resulting blend is insufficient, so that this is improved. In order to add various flame retardants or flame retardant auxiliaries, various methods have been used.

In recent years, however, in housing applications such as OA equipment and home electric parts, resin materials used therefor are required to have a higher level of flame retardancy due to weight reduction, thinning, and complicated shape of the equipment. Fluidity and impact resistance during molding are required.

[0005] Of these, the high flame retardancy of resin materials means that
It is an important requirement that the resin does not drip (drop) in the process of the L burning test, and drip prevention is important in order to prevent fire spread even in an actual fire.

Conventionally, a method of imparting drip prevention to a PC / ABS blend has been disclosed in JP-B-59-366.
No. 57, a method of adding polytetrafluoroethylene, or a method of adding a silicone resin described in JP-A-3-190958 is known.

[0007] However, although these methods are excellent in drip prevention, they cause poor molding appearance or reduced impact resistance due to the added polytetrafluoroethylene or silicone resin, and are economically disadvantageous. Would.

Hitherto, JP-A-6-240127, JP-A-7-179673, and JP-A-7-179673 disclose a method of simultaneously satisfying the drip-preventing property and the impact resistance of a PC / ABS blend and also having an economic advantage. JP-A-7-1
No. 33417 discloses a composite rubber composition obtained by graft-polymerizing a vinyl monomer to a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate together with a PC / ABS blend and various flame retardants and flame retardant aids. A method of adding a graft copolymer is known.

However, in these prior arts, P
Although various known elastic polymers are used as the rubbery polymer to be blended with the C resin, the examples in JP-A-6-240127 disclose ABS.
Only examples using (acrylonitrile-butadiene-styrene) resin are described.
No. 73 and JP-A-7-133417, ABS resin, AAS (acrylonitrile butyl acrylate-styrene) resin and HIPS
Only high-impact polystyrene resins are specifically specified as rubbery polymers.

[0010]

When the ABS resin, the AAS resin or the HIPS resin is blended with the PC resin as a rubbery polymer as described above, all of them are dispersed in a matrix in a spherical form, and thus the resulting blend is obtained. The fluidity at the time of forming the object is low.

On the other hand, when a resin material is used for housing applications such as OA equipment or home electric appliances, good fluidity during molding is required in addition to flame retardancy (drip prevention) and impact resistance of the material. .

An object of the present invention is to provide a resin material having a high level of flame retardancy, impact resistance and excellent fluidity during molding as a resin material having a polycarbonate resin and a SAN-based resin as a matrix. It is an object of the present invention to provide a material that can be used for housing applications such as home appliance members.

[0013]

Means for Solving the Problems The present inventors graft polymerized a vinyl monomer onto a composite rubber comprising a PC resin, a SAN resin, a rubbery polymer, a polyorganosiloxane and an alkyl (meth) acrylate rubber. Of the polymer structure of the rubbery polymer component in the thermoplastic resin composition comprising the grafted polymer and the flame retardant and the impact resistance, flame retardancy and melt fluidity of the thermoplastic resin composition containing the same As a result of the examination, by using a thermoplastic elastomer containing substantially no gel as a rubbery polymer, a thermoplastic resin composition containing the same has both unprecedented excellent impact resistance, flame retardancy and fluidity. The inventors have found that the present invention has been achieved.

That is, the gist of the present invention is as follows.
Polycarbonate resin (A), aromatic alkenyl-based monomer, vinyl cyanide-based monomer and copolymer (B) containing vinyl-based monomer copolymerizable therewith, substantially gel Not containing thermoplastic elastomer (C),
A thermoplastic resin composition comprising a graft copolymer (D) obtained by graft-polymerizing a vinyl monomer onto a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber, and a flame retardant (E).

[0015]

DETAILED DESCRIPTION OF THE INVENTION As the polycarbonate resin (A) according to the present invention, a resin produced by a known method is 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, an ester of a dihydroxy compound with itself or another dihydroxy compound with a bisalkyl or bisallyl carbonate. Examples include an exchange reaction, 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. Typically,
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) according to the present invention has at least two members selected from the group consisting of aromatic alkenyl monomers, vinyl cyanide monomers and vinyl monomers copolymerizable therewith. A copolymer having seeds as a constituent component, examples of aromatic alkenyl monomers include styrene, α
-Methylstyrene, vinyltoluene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like, preferably styrene and α-methylstyrene. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable. Examples of the copolymerizable vinyl monomer include methacrylates such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and glycidyl methacrylate, methyl acrylate and ethyl acrylate. And butyl acrylate and the like, maleimide monomers such as N-phenylmaleimide and N-methylmaleimide, and maleic anhydride.

Preferred examples of the copolymer (B) include a styrene-acrylonitrile copolymer (SAN resin) and a styrene-acrylonitrile-N-phenylmaleimide copolymer.

As a method for producing the copolymer (B), generally known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization are used.

The thermoplastic elastomer (C) which does not substantially contain a gel according to the present invention is a thermoplastic elastomer which does not substantially contain a three-dimensional crosslinked structure, and specifically has a glass transition temperature higher than room temperature. Is a polymer containing a low polymer component and exhibiting fluidity in a molten state.

Specific examples of the substantially gel-free thermoplastic elastomer (C) according to the present invention include, as a hard phase, at least one kind selected from polystyrene, styrene-acrylonitrile copolymer and polyalkyl (meth) acrylate. Containing a polymer component, as a soft phase polybutadiene, polyisoprene, diblock copolymer containing at least one polymer component selected from hydrogenated polybutadiene and polydimethylenesiloxane, triblock copolymer, multi-block copolymer, Polystyrene-based block copolymers such as radial block copolymers and comb-shaped graft copolymers or polystyrene-based comb-shaped graft copolymers, containing an aromatic polyester component such as polybutylene terephthalate and polyethylene terephthalate as a hard phase Polyethylene glycol as a soft phase, a polyether component polytetramethylene glycol, aliphatic polyester, at least one polymer diblock copolymer comprising a component selected from the polylactone and poly dimethylene polysiloxane, triblock copolymer,
Polyester block copolymers such as multi-block copolymers and radial block copolymers, diblock copolymers containing a polyamide component as a hard phase and polyether components such as polyethylene glycol and polytetramethylene glycol as a soft phase , At least one selected from polyamide block copolymers such as triblock copolymers, multiblock copolymers and radial block copolymers, and polystyrene, styrene-acrylonitrile copolymer and polyalkyl (meth) acrylate as a hard phase Polyacrylates such as diblock copolymers, triblock copolymers, multiblock copolymers, radial block copolymers and comb-type graft copolymers containing polybutyl acrylate as a soft phase. Bro Click copolymer or polyacrylate comb-graft copolymer, various polyurethane elastomers, polyvinyl elastomers and polyolefin elastomers chloride.

Considering the balance of fluidity, impact resistance and flame retardancy of the thermoplastic resin composition of the present invention, a preferred example of the substantially gel-free thermoplastic elastomer used is a hard phase. A diblock copolymer containing a polybutadiene (including hydrogenated polybutadiene) or polydimethylsiloxane as a soft phase, a triblock copolymer,
Multi-block copolymer, radial block copolymer and comb-type graft copolymer, more preferably styrene-butadi-entry block copolymer and comb-type graft copolymer having a polydimethylsiloxane main chain / polystyrene side chain structure It is.

The thermoplastic resin composition containing such a thermoplastic elastomer containing substantially no gel has high fluidity because the elastomer component forms a laminar or network domain in the flow direction during melt flow. Show,
Further, this thermoplastic elastomer component has an effect of improving the impact resistance of the thermoplastic resin composition.

The graft copolymer (D) according to the present invention comprises:
It is a graft copolymer obtained by graft-polymerizing a vinyl monomer onto a composite rubber comprising a polyorganosiloxane component and an alkyl (meth) acrylate rubber component.

The polyorganosiloxane constituting the graft copolymer (D) according to the present invention is produced by adding a siloxane containing a vinyl polymerizable functional group as a crosslinking agent and a graft crossing agent to dimethylsiloxane and condensing it. be able to.

Examples of the dimethyl siloxane include dimethyl siloxanes having three or more ring members, and those having a three to six member ring are preferred. Specific examples include hexamethylcyclotrisiloxane, octamethyltetracyclosiloxane, decamethylpentacyclosiloxane, dodecamethylhexacyclosiloxane, and the like. These may be used alone or as a mixture of two or more.

The siloxane containing a vinyl polymerizable functional group is not particularly limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethyl siloxane through a siloxane bond. In consideration of the above, various alkoxysilane compounds having a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane,
methacryloxy such as γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane Examples include vinylsiloxanes such as siloxane and tetramethyltetravinylcyclotetrasiloxane, and mercaptosiloxanes such as p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane.

These vinyl polymerizable functional group-containing siloxanes can be used as one kind or as a mixture of two or more kinds. The amount of the siloxane used depends on the impact resistance of the thermoplastic resin composition containing the obtained graft copolymer. In consideration of the molding appearance and the siloxane unit of the polyorganosiloxane, the amount of the siloxane unit having a vinyl polymerizable functional group is 0.2%.
To 3 mol%, more preferably 0.1 to 3 mol%.
A range of 3 to 2% by mole, more preferably 0.3 to 1% by mole is preferred.

As the crosslinking agent, trifunctional and 4-functional
Functional siloxane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane are used.

As a method for producing the polyorganosiloxane constituting the graft copolymer (D) according to the present invention, a mixture comprising the above-mentioned dimethylsiloxane, vinyl-polymerizable functional group-containing siloxane and a crosslinking agent is emulsified with an emulsifier and water. After homogenizing the latex using a homomixer that atomizes by shearing force due to high-speed rotation or a homogenizer that atomizes by jetting power from a high-pressure generator, polymerize at high temperature using an acid catalyst, and then alkalinize. It neutralizes acids with substances.

As a method for adding the acid catalyst used in the polymerization,
There are a method of mixing the siloxane mixture with the emulsifier and water, and a method of dropping the latex in which the siloxane mixture is atomized into a high-temperature acid aqueous solution at a constant speed.The method for controlling the particle diameter of the polyorganosiloxane is easy. Considering this, a method is preferred in which a latex in which the siloxane mixture is atomized is dropped at a constant rate into a high-temperature acid aqueous solution.

As the emulsifier used in the production of the polyorganosiloxane, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. Particularly, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

These emulsifiers are composed of siloxane mixture 10
It is used in the range of about 0.05 to 5 parts by weight with respect to 0 parts by weight. If the amount used is small, the dispersion state becomes unstable, and it tends to be impossible to maintain an emulsified state having a fine particle diameter. If the amount is too large, the coloring of the molded article of the thermoplastic resin composition due to the emulsifier tends to be excessive.

Examples of the acid catalyst used for the polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids, and aliphatic substituted naphthalenesulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. . These acid catalysts are used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable because of excellent stabilizing action of the polyorganosiloxane latex, and n-dodecylbenzenesulfonic acid is particularly preferable. The amount of the acid catalyst used in the production of the polyorganosiloxane is not particularly limited, but the pigment coloring property and the low-temperature impact property of the obtained graft copolymer and the thermoplastic resin composition containing the same are described below. Considering the siloxane mixture 100 parts by weight of 0.5 to 10 parts by weight is preferred,
Further, the amount is preferably 1 to 5 parts by weight, more preferably 1 to 3 parts by weight.

The polymerization temperature of the polyorganosiloxane is 5
The temperature is preferably 0 ° C or higher, more preferably 80 ° C or higher.

Further, after the polyorganosiloxane is polymerized at a high temperature and then left at a temperature lower than the polymerization temperature, the crosslinking reaction of the polyorganosiloxane proceeds, and the gel content of the resulting polyorganosiloxane increases. The degree of swelling in toluene solvent decreases. The polymerization reaction and the crosslinking reaction can be stopped by cooling the reaction solution and then neutralizing the polymerization latex with an alkaline substance such as sodium hydroxide, sodium hydroxide, and sodium carbonate.

The time of the polymerization reaction is preferably at least 2 hours, more preferably at least 5 hours when the acid catalyst is mixed with the siloxane mixture, emulsifier and water and atomized for polymerization. In the method of dropping the latex in which particles are atomized, it is preferable to hold the latex for 1 hour or more after the dropping of the latex.

The polyorganosiloxane latex thus produced is impregnated with an alkyl (meth) acrylate component composed of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, and then polymerized to form a composite rubber. Obtainable.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Examples thereof include alkyl acrylates such as propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. The use of n-butyl acrylate is particularly preferable.

Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,4 butylene glycol dimethacrylate, triallyl cyanurate, Triallyl isocyanurate and the like can be mentioned. The amount of the polyfunctional alkyl (meth) acrylate used is 0.1 to 20% by weight, preferably 0.2 to 1% by weight in the alkyl (meth) acrylate component.

The alkyl (meth) acrylate and the polyfunctional alkyl (meth) acrylate are used alone or in combination of two or more.

The composite rubber comprising the polyorganosiloxane and the alkyl (meth) acrylate rubber according to the present invention is:
It can be produced by adding the above-mentioned alkyl (meth) acrylate component to the latex of the polyorganosiloxane component and polymerizing it by the action of a usual radical polymerization initiator. As a method of adding the alkyl (meth) acrylate, there are a method of mixing the poly (organosiloxane component) with the latex of the polyorganosiloxane component at a time and a method of dropping into the latex of the polyorganosiloxane component at a constant rate. In consideration of the impact resistance of the obtained thermoplastic resin composition containing the graft copolymer, a method of mixing the latex of the polyorganosiloxane component at a time is preferable.

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-based initiator is preferable, and a sulfoxylate-based initiator obtained by combining sodium salt, longalide, and hydroperoxide with ferrous sulfate / ethylenediaminetetraacetic acid is particularly preferable.

In the radical polymerization, an emulsifier can be added, if necessary. As the emulsifier, nonionic, anionic and cationic emulsifiers are used. Considering the thermal stability when the obtained graft copolymer is blended with a polycarbonate resin-based matrix, a nonionic-anionic emulsifier is preferred, and sodium polyoxyethylene nonylphenyl ether sulfate is more preferred.

The graft copolymer (D) according to the present invention comprises:
It can be produced by graft-polymerizing one or more vinyl monomers onto the composite rubber produced by emulsion polymerization as described above. The vinyl monomer used for the graft polymerization is not particularly limited, but preferred examples are aromatic alkenyl monomers such as styrene, α-methylstyrene and vinyltoluene, and methacrylic acids such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate. Acrylates such as esters, methyl acrylate, ethyl acrylate, and butyl acrylate;
Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. Among these, methyl methacrylate or a mixture of styrene and acrylonitrile is preferable as the monomer used for the graft polymerization in consideration of the thermal stability during molding of the thermoplastic resin composition containing the graft copolymer.

The graft polymerization can be carried out in one step or in multiple steps by adding a monomer to the latex of the composite rubber and using a radical polymerization technique.

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 weight-average particle diameter of the graft copolymer (D) constituting the thermoplastic resin composition according to the present invention is not particularly limited, but considering the impact resistance of the obtained thermoplastic resin composition. It is preferably from 0.05 to 0.50 μm, more preferably from 0.10 to 0.35 μm.

The graft copolymer (D) according to the present invention comprises:
The graft copolymer latex produced as described above is put into hot water in which a metal salt such as calcium chloride, calcium acetate or aluminum sulfate is dissolved, and the graft copolymer is separated and recovered by salting out and coagulating. be able to. Of these, calcium salts such as calcium chloride and calcium acetate are particularly preferable as a coagulant to be used in consideration of the thermal stability when the obtained graft copolymer is blended with a polycarbonate resin matrix.

The amount of each component used in the thermoplastic resin composition of the present invention is not particularly limited. However, in consideration of the mechanical properties and heat resistance of the obtained thermoplastic resin composition, the polycarbonate resin (A) 1 to 99 parts by weight, copolymer (B) 1 to 99 parts by weight, thermoplastic elastomer (C) 0.01 to 40 parts by weight, graft copolymer (D)
The range of 0.01 to 40 parts by weight is preferred. In particular, when the amount of the thermoplastic elastomer (C) is less than 0.01 part by weight, the fluidity of the thermoplastic resin composition decreases, and when it exceeds 40 parts by weight, heat resistance and rigidity tend to decrease. . When the amount of the graft copolymer (D) is less than 0.01 part by weight, the impact resistance of the thermoplastic resin composition decreases, and when the amount exceeds 40 parts by weight, heat resistance and rigidity decrease. Tend to.

The flame retardant (E) according to the present invention refers to a conventionally known flame retardant and a mixture of a flame retardant auxiliary and a flame retardant which are used in combination with the flame retardant to promote the flame retarding action.

Examples of such a flame retardant include a phosphate ester compound, a polyphosphate compound, a halogenated compound, a metal hydroxide, an antimony oxide compound, a guanidine-based flame retardant and a zirconium-based flame retardant. Considering the mechanical strength of the obtained thermoplastic resin composition, phosphate ester compounds, halogenated compounds and antimony oxide compounds are preferred, and phosphate ester compounds and halogenated compounds are more preferred.

Specific examples of the phosphate compound include:
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.

Specific examples of the halogenated compound include tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclododecane, octabromodiphenyl ether, bistribromophenoxyethane,
Ethylene bistetrabromophthaleimide, tribromophenol, various halogenated epoxy oligomers obtained by the reaction of halogenated bisphenol A with epihalohydrin, carbonate oligomers containing halogenated bisphenol A as constituents, halogenated polystyrene, chlorinated polyolefins and Examples thereof include polyvinyl chloride and the like, and preferred are tetrabromobisphenol A and epoxy oligomers and carbonate oligomers containing tetrabromobisphenol A as a constituent.

Further, specific examples of antimony oxide include:
Antimony pentoxide and antimony trioxide are mentioned.

These flame retardants (E) can be used alone or in combination of two or more.

The blending amount of the flame retardant (E) can be changed according to the required level of flame retardancy and is not particularly limited. However, in the standard test represented by the UL-94 vertical combustion test, The range of 0.1 to 30 parts by weight is preferable in consideration of the pass / fail of the above, the heat resistance of the thermoplastic resin composition, and the mechanical properties. The thermoplastic resin composition of the present invention can contain polytetrafluoroethylene (F) if necessary. Polytetrafluoroethylene has an action as an anti-drip agent at the time of combustion.
It is preferable to add 0.5 to 1.0 part by weight. As the polytetrafluoroethylene, a commercially available powder or slurry can be used.

The thermoplastic resin composition of the present invention comprises the above polycarbonate resin (A), copolymer (B), thermoplastic elastomer (C), graft copolymer (D), flame retardant (E) and Can be produced by extruding polytetrafluoroethylene (F) according to a 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 thermoplastic resin composition containing the graft copolymer may further contain a dye, a pigment, a stabilizer, a reinforcing agent, a filler, and the like, if necessary.

Hereinafter, the present invention will be described with reference to examples. In Reference Examples, Examples and Comparative Examples, "parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.
Means

The weight-average particle diameter of the polyorganosiloxane in the latex in Reference Example and the graft copolymer in Example was DLS-700 manufactured by Otsuka Electronics Co., Ltd.
It was determined by a dynamic light scattering method using a mold.

The measurement of the Izod impact strength in the examples and comparative examples was carried out by a method according to ASTM D258 (test piece thickness: 3.2 mm).

The spiral flow length of the thermoplastic resin compositions in Examples and Comparative Examples was measured using an injection molding machine IS-100EN manufactured by Toshiba Machine Co., Ltd.
Using a cavity-shaped mold of (width) × 2 mm (thickness) × 800 mm (length), set the cylinder temperature to 260
° C., mold temperature 80 ° C., was determined by measuring the length of the injection molded shaped articles in the flow direction in the condition of the injection pressure 1000 kg / cm ^2.

The flame retardancy of the thermoplastic resin compositions in Examples and Comparative Examples was measured by a method conforming to the UL94 / 5V method A, and the test pieces were applied to a burner five times to determine the combustion and glowing times. The measurement and the observation of the presence or absence of dripping (measuring the number of drip test pieces) were performed. In addition, the thickness of the test piece was 2.5 mm.

[0064]

【Example】

(Reference Example 1) Composite rubber-based graft copolymer (S-1)
Production of 97.5 parts of octamethyltetracyclosiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. To this was added 0.67 parts of sodium dodecylbenzenesulfonate and 200 parts of distilled water in which 1 part of dodecylbenzenesulfonate was dissolved, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then added to a homogenizer at 300 kg / cm ^2. Once to obtain a stable premixed organosiloxane latex. This mixed solution was transferred into a reactor equipped with a cooling pipe, a jacket heater and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and then allowed to stand at 30 ° C .; To pH 7
Neutralized. The degree of polymerization of the obtained polyorganosiloxane was 88%, and the average particle diameter of the polyorganosiloxane in the latex was 0.21 μm.

Next, 100 parts of the above-mentioned polyorganosiloxane latex and sodium polyoxyethylene alkylphenyl ether sulfate (manufactured by Kao Corporation) were placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device. 0.8 part of Emal NC-35) was collected, and 120 parts of distilled water was added and mixed. Then, the mixture was composed of 37.5 parts of n-butyl acrylate, 2.5 parts of allyl methacrylate and 0.3 part of tertiary butyl hydroperoxide. The mixture was added.

The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. When the internal liquid temperature reaches 60 ° C., ferrous sulfate 0.00
01 parts, ethylenediaminetetraacetic acid disodium salt 0.0
An aqueous solution in which 003 parts and 0.20 part of Rongalid were dissolved in 3 parts of distilled water was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 2 hours to complete the polymerization of the acrylate component to obtain a latex of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

After the liquid temperature inside the reactor dropped to 60 ° C.,
A mixed solution of 9 parts of acrylonitrile, 21 parts of styrene, and 0.3 part of tertiary butyl hydroperoxide was dropped and polymerized for about 1 hour. After the completion of the dropping, the mixture was held for 2 hours to complete the graft polymerization to the composite rubber. The polymerization rate of the obtained composite rubber-based graft copolymer was 97.9%, and the weight average particle diameter was 0.30 μm. Next, 150 parts of an aqueous solution in which 5% by weight of calcium acetate was dissolved was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer was gradually dropped into this, and solidified. Next, the precipitate was separated, washed and dried to obtain a graft copolymer (S-1).

Reference Example 2 Production of Polydimethylsiloxane Comb Graft Copolymer (G-1) 25 parts of side-chain mercapto-modified silicone oil (Shin-Etsu Silicone KF2001 manufactured by Shin-Etsu Chemical Co., Ltd.), 75 parts of styrene And azobisisobutyronitrile 0.2
After charging 5 parts to a separable flask and blowing nitrogen gas for 30 minutes, while keeping the inside of the flask under a nitrogen atmosphere, the flask was immersed in a water bath at 80 ° C., stirred for 8 hours, and then rapidly cooled. The reaction was stopped. Analysis of this reaction solution by gas chromatography showed that the polymerization conversion of styrene was 30%. Next, the reaction solution was poured into a large amount of methanol, and a precipitate was collected. The collected precipitate was dried at 60 ° C. overnight,
Vacuum drying was performed at 20 ° C. overnight to obtain a polymer (G-1).
The obtained polymer (G-1) was put into a chloroform or toluene solvent and stirred, and then the polymer components were dissolved in the respective solvents.

(Examples 1 to 3 and Comparative Examples 1 to 7) In Examples and Comparative Examples, the following components were used.

Component (A) (PC resin): Iupilon S2000F manufactured by Mitsubishi Engineering-Plastic Corporation Component (B) (SAN resin): A mixture of 70 parts of styrene and 30 parts of acrylonitrile was polymerized by a suspension polymerization method. , A SAN resin having a reduced viscosity (ηSP / C) of 0.60 measured in a dimethylformamide solution Component (C) (C-1): Styrene-butadi entry block copolymer (Califlex TR1011 manufactured by Showa Gel Co., Ltd.); (C-2): Comb graft copolymer (G-1) produced in Reference Example 2 (C-3): ABS graft copolymer (polybutadiene content 50%, styrene content 35) %, Acrylonitrile content 15%, gel content 72% measured in acetone solvent
(C-4): AAS (acrylonitrile-butyl acrylate-styrene) graft copolymer (butyl acrylate rubber content 50%, styrene content 35%, acrylonitrile content 15%, measured in acetone solvent. AAS graft copolymer having a gel content of 68%) Component (D) (composite rubber-based graft copolymer): Reference Example 1
Component (E) (flame retardant) (E-1): phenylresorcinol polyphosphate (CR733S, manufactured by Daihachi Chemical Co., Ltd.) (E-2): Tribromobisphenol A (E-3): antimony trioxide Component (F): polytetrafluoroethylene (manufactured by Du Pont-Mitsui Fluorochemicals: 30J) The above (A), (B), (C), (D), (D) Each component of E) and (F) was mixed in the ratio (weight ratio) shown in Table 1,
It was shaped by a twin-screw extruder set at a cylinder temperature of 240 ° C. to produce pellets. Next, the pellets were injection molded at a cylinder set temperature of 240 ° C. and a mold temperature of 80 ° C. to obtain test pieces for physical properties and a combustion test. From each of the obtained test pieces, Izod impact strength, UL94 / 5V (A
Method) The results of the flame retardancy test are shown in Table 1. The spiral flow length was measured using the obtained pellets.
Table 1 shows the results.

[0071]

[Table 1]

The following is clear from the examples and comparative examples.

1) The thermoplastic resin compositions of Examples 1 to 5 exhibit high Izod impact strength, excellent flame retardancy satisfying UL94 / 5VB acceptance criteria, and have a high spiral flow length.

2) The thermoplastic resin composition of Comparative Example 1, which does not contain the composite rubber-based graft copolymer, exhibits high fluidity, but has low impact resistance and generates a drip during a combustion test, so that UL-94. It does not satisfy the acceptance criteria of / 5 VB, which is not preferable.

3) The thermoplastic resin compositions of Comparative Examples 2 to 4 exhibit high Izod impact strength and excellent flame retardancy satisfying the UL94 / 5VB acceptance criteria, but have a small spiral flow length and large molded articles or It is not preferable because injection molding of a thin molded product becomes difficult.

[0076]

As described above, the present invention has the following remarkable effects, and its industrial value is extremely large.

1) The thermoplastic resin composition of the present invention has an excellent balance of impact resistance, flame retardancy and fluidity.

2) In particular, the balance between flame retardancy and fluidity is determined by the conventionally known graft copolymer containing a composite rubber composed of polyorganosiloxane and acrylate rubber, thermoplastic resin composed of polycarbonate resin and SAN resin. It is a very high level that cannot be obtained with a resin composition, and its utility value as a material for housing various industrial materials, particularly OA equipment or home electric parts, is extremely high.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 25/12 C08L 25/12 27/18 27/18 33/20 33/20 51/00 51/00 (72) Inventor Yanagi Akira Kase 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Central Research Laboratory

Claims (2)

[Claims] 1. A composition comprising at least two components selected from the group consisting of a polycarbonate resin (A), an aromatic alkenyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith. A copolymer (B), a thermoplastic elastomer substantially free of gel (C),
A thermoplastic resin composition comprising a graft copolymer (D) obtained by graft-polymerizing a vinyl monomer onto a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber, and a flame retardant (E). 2. A composition comprising at least two components selected from the group consisting of a polycarbonate resin (A), an aromatic alkenyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith. A copolymer (B), a thermoplastic elastomer substantially free of gel (C),
Graft copolymer (D) in which a vinyl monomer is graft-polymerized on a composite rubber composed of polyorganosiloxane and alkyl (meth) acrylate rubber, flame retardant (E)
And a thermoplastic resin composition comprising polytetrafluoroethylene (F).