JP2000017029A - Composite rubber-based flame retardant and flame-retardant resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having a high level of impact resistance without using a conventional halogen-based compound such as a bromine / chlorine-based compound, a phosphate compound, or the like. SOLUTION: A composite mainly composed of a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers onto a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber. A rubber-based flame retardant and a flame-retardant resin composition using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant used for a thermoplastic resin and a flame retardant resin composition using the flame retardant.

[0002]

2. Description of the Related Art Conventionally, halogen compounds such as chlorine and bromine compounds have been used to impart flame retardancy to thermoplastic resins, thermoplastic elastomers and the like because of their high ability to impart flame retardancy. Due to environmental problems, it has been desired to reduce the amount of halogen-based compounds such as chlorine and bromine, or to eliminate them.

In order to solve this problem, for example, a polycarbonate / ABS alloy resin is disclosed in Japanese Patent Publication No. 6-7017.
No. 7 has proposed a method using a phosphate compound. However, as shown in the examples of this publication, in order to meet the demand for improved fluidity, for example, if the molecular weight and the blending ratio of polycarbonate or ABS are changed to improve the fluidity, the UL94 test (Anta Lighters Inc.) In this case, drippings (drips) easily occur and the burning time is prolonged.

In order to solve this problem, Japanese Patent Laid-Open Publication No. Hei 6-24
No. 0127, JP-A-7-238218, etc.
Polycarbonate resin or polycarbonate / AB
A method of adding a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer to a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate together with various flame retardants and flame retardant aids to an S alloy resin. Has been proposed. However, even in these prior arts, if polytetrafluoroethylene is not used as a flame-retardant auxiliary, practical use becomes difficult due to the problem of heat resistance, and the blending of polytetrafluoroethylene is premised. Also, since the phosphate ester compound has a relatively low melting point, it oozes to the surface of the material during molding and contaminates the mold surface, or reduces the heat resistance of the material. ing. Further, from the viewpoint of environmental problems, it is desired to reduce the amount of the phosphate ester-based compound used or not to add it.

[0005] Japanese Patent Application Laid-Open Nos.
JP-A-1760, JP-A-9-151315, and JP-A-9-3312 discuss the flame retardancy of a modified polyphenylene ether resin. There is the same problem as the Bonate system.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant resin composition having a high level of impact resistance without using a conventional halogen compound such as a bromine / chlorine compound or a phosphate compound. To provide things.

[0007]

Means for Solving the Problems The present inventors add a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer to a composite rubber composed of a polyorganosiloxane and an alkyl (meth) acrylate rubber. The present inventors have found that it is possible to provide a flame-retardant resin composition having a high level of impact resistance without adding a flame retardant in a thermoplastic resin and / or a thermoplastic elastomer, and have reached the present invention.

That is, the gist of the present invention is as follows.
Composite rubber-based flame retardant containing as a main component a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl monomers onto a composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber And a flame-retardant resin composition using the same.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The polyorganosiloxane used in the composite rubber-based graft copolymer of the present invention is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group.

The dimethylsiloxane used for the production of the polyorganosiloxane includes a dimethylsiloxane-based cyclic body having three or more member rings, and a three- to seven-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 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 a siloxane containing a vinyl polymerizable functional group and capable of bonding to dimethylsiloxane through a siloxane bond. Various alkoxysilane compounds containing a functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-
Methacryloyloxysiloxanes such as methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane; vinylphenylsilanes such as p-vinylphenyldimethoxymethylsilane; and γ -Mercaptosiloxane such as mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane.

These vinyl-polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

As the siloxane crosslinking agent, a trifunctional or tetrafunctional silane crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and the like are used.

The above polyorganosiloxane is produced by mixing a latex obtained by emulsifying a mixture of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group or, if necessary, a mixture containing a siloxane-based crosslinking agent with an emulsifier and water. After homogenization using a homomixer that atomizes by shearing force due to rotation or a homogenizer that atomizes by jet power from a high-pressure generator, polymerize at high temperature using an acid catalyst, and then acidify with an alkaline substance. Neutralize. Examples of the method of adding the acid catalyst used for the polymerization include a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping a latex in which the siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate. Considering the ease of controlling the particle size of the siloxane, a method of dropping a latex in which the siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate is preferable.

The emulsifier used in the production of the polyorganosiloxane is preferably an anionic emulsifier, and an emulsifier selected from sodium alkylbenzenesulfonate, 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.

The method of mixing a siloxane mixture, an emulsifier, water and / or an acid catalyst includes mixing by high-speed stirring and mixing by a high-pressure emulsifying device such as a homogenizer. The method using a homogenizer is a method of mixing a polyorganosiloxane latex. This is a preferable method because the particle size distribution is reduced.

Examples of the acid catalyst used for the polymerization of the 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. Also, n-
When dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, it is possible to reduce poor appearance of the resin composition due to the emulsifier component of the polyorganosiloxane latex.

The polymerization temperature of the polyorganosiloxane is 5
0 ° C. or higher is preferable, and 80 ° C. or higher is more preferable. The polymerization time of the polyorganosiloxane is 2 hours or more, more preferably 5 hours, when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water to form fine particles for polymerization.
In the method of dropping the latex in which the siloxane mixture is finely divided into the aqueous solution of the acid catalyst, it is preferable to hold the latex for about 1 hour after the dropping of the latex.

The termination of the polymerization can be carried out by cooling the reaction solution and neutralizing the latex with an alkaline substance such as caustic soda, caustic potash and sodium carbonate.

The alkyl (meth) acrylate rubber constituting the composite rubber-based graft copolymer is an alkyl (meth)
It is a polymer of acrylate and polyfunctional alkyl (meth) acrylate. The amount of the alkyl (meth) acrylate rubber in the composite rubber-based graft copolymer is not particularly limited.

The composite rubber according to the present invention can be produced by impregnating a polyorganosiloxane latex with an alkyl (meth) acrylate component comprising an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, followed by polymerization. .

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, 2-
Examples thereof include alkyl acrylates such as ethylhexyl acrylate and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate, and these can be used alone or in combination of two or more. Also, in consideration of impact resistance and molded gloss of the resin composition containing the graft copolymer, it is particularly preferable to use n-butyl acrylate.

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, and these can be used alone or in combination of two or more. Preferred Examples Considering the Graft Structure of the Graft Copolymer (Acetone-Insoluble Content, Solution Viscosity of Acetone-Soluble Component) Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate and 1,3-
In this method, butylene glycol dimethacrylate is used in combination.

The composite rubber comprising a polyorganosiloxane and an alkyl (meth) acrylate rubber used in the present invention is prepared by adding the above-mentioned alkyl (meth) acrylate component to a latex of a polyorganosiloxane component and acting with a usual radical polymerization initiator. And polymerized. As a method of adding the alkyl (meth) acrylate, there are a method of mixing 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 speed. In addition,
Considering the impact resistance of the obtained 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-based initiator, or a redox-based 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 sodium salt, Rongalit, and hydroperoxide with ferrous sulfate / ethylenediaminetetraacetic acid is particularly preferable.

The average particle size of the composite rubber is not particularly limited, but is preferably in the range of 0.01 to 0.6 μm. When the average particle size is less than 0.01 μm, the impact resistance of the molded product obtained from the resin composition is deteriorated, and when the average particle size exceeds 0.6 μm, the impact resistance of the molded product from the obtained resin composition is reduced. And the appearance of the molding surface deteriorates.

By subjecting one or more vinyl monomers to radical polymerization in the presence of the composite rubber,
A composite rubber-based graft copolymer is obtained.

The vinyl monomer is not particularly limited. For example, aromatic alkenyl such as styrene, α-methylstyrene, vinyltoluene, methacrylic acid ester such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl Acrylates such as acrylate, ethyl acrylate and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. It is preferable to use one kind of methyl methacrylate or a combination of styrene and acrylonitrile.

The graft polymerization can be carried out in one step or in multiple steps by adding a vinyl monomer to the latex of the composite rubber and subjecting it to a radical polymerization method. Further, as the radical polymerization initiator used for the polymerization, peroxide, azo-based initiator,
Alternatively, a redox initiator combining an oxidizing agent and a reducing agent is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining sodium salt, Rongalit, and hydroperoxide with ferrous sulfate / ethylenediaminetetraacetic acid is particularly preferable.

Further, 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.

In the graft polymerization, an emulsifier may be added to stabilize the polymerization latex and to control the average particle size of the graft copolymer. The emulsifier to be used is not particularly limited, but preferable examples are a cationic emulsifier, an anionic emulsifier and a nonionic emulsifier, and more preferable examples are a sulfonate emulsifier or a sulfate emulsifier and a carboxylate emulsifier. It is a method used in combination.

The particle diameter of the composite rubber-based graft copolymer prepared as described above is not particularly limited, but the impact resistance and flame retardancy of the resin composition containing the obtained graft copolymer are not limited. In consideration of both properties, the average particle size of the composite rubber is preferably in the range of 0.01 to 2 μm. When the average particle size is less than 0.01 μm, the impact resistance of the molded product obtained from the resin composition deteriorates, and when the average particle size exceeds 2 μm, the impact resistance of the molded product from the obtained resin composition becomes poor. In addition, the molding surface appearance deteriorates.

The thermoplastic resin used in the present invention includes, for example, olefin resins (olefin resins) such as polypropylene (PP) and polyethylene (PE), polystyrene (PS), high impact polystyrene (HIPS), (meth) Styrene resins (St resins) such as acrylic acid ester / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA), ABS, ASA, AES, etc. , Polymethyl methacrylate (PM
MA), an acrylic resin (Ac resin), a polycarbonate resin (PC resin), a polyamide resin (P
A resin), polyester resin (PEs resin) such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), (modified) polyphenylene ether resin (PPE resin), polyoxymethylene resin (POM resin) ), Polysulfone resin (PS
O-based resin), polyarylate-based resin (PAr-based resin),
Engineering plastics such as polyphenylene sulfide resin (PPS resin) and thermoplastic polyurethane resin (PU resin), and PC resin such as PC / ABS / St resin alloy and PA resin such as PA / ABS / St resin alloy, PA such as PA / PP
Resin / polyolefin resin alloy, PC resin such as PC / PBT / PEs resin alloy, olefin resin alloy such as PP / PE, PPE / HIP
P, PPE-based resin alloys such as S, PPE / PBT, and PPE / PA.

Examples of the thermoplastic elastomer used in the present invention include styrene elastomers, vinyl chloride elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, fluorine elastomers,
Examples thereof include 2-polybutadiene, trans 1,4-polyisoprene, and an acrylic elastomer. These may be used alone or in combination. Although not a thermoplastic elastomer, a soft vinyl chloride resin is also included.

In the present invention, the composite rubber-based flame retardant of the present invention is preferably added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin and / or the thermoplastic elastomer. In addition, a conventional flame retardant, a flame retardant auxiliary, a stabilizer, a filler, and the like can be added at the time of compounding, kneading, and molding the resin according to the purpose, as long as the physical properties are not impaired.

Halogen compounds include chlorine flame retardants such as polyvinyl chloride, chlorinated polyethylene, and chlorinated paraffin; bromine flame retardants such as decabromodiphenyl oxide and tetrabromobisphenol A; A halide of a compound can also be regarded as a halogen-based compound.

Phosphate ester compounds are represented by the following formula as a flame retardant.

[0037]

Embedded image

(Where R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom or an organic group, but R ₁ = R ₂ =
R ₃ = R ₄ = excluding hydrogen atoms. A represents a divalent or higher valent organic group, 1 is 0 or 1, m is an integer of 1 or more, and n is 0 or 1.
Represents the above integer. )), But is not limited thereto.

In the above formula, examples of the organic group include an alkyl group, a cycloalkyl group and an aryl group which may or may not be substituted. When substituted, the number of substituents is not limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkoxyl group, an alkylthio group, an aryl group, an aryloxy group, and an arylthio group.
Further, a group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or a group obtained by combining these substituents by an oxygen atom, a nitrogen atom, a sulfur atom, or the like (eg, an arylsulfonylaryl group) May be a substituent. In addition, a divalent or higher valent organic group is one of the hydrogen atoms bonded to a carbon atom from the above organic groups.
It means a divalent or higher valent group formed by removing more than one group. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols such as biphenyl and bisphenol A, and the relative positions of the two or more free valences are arbitrary. Particularly preferred examples include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxybiphenyl, p,
p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like.

Specific examples of the phosphoric ester compound include:
Trimethyl phosphate, Triethyl phosphate, Tributyl phosphate, Trioctyl phosphate, Tributoxyethyl phosphate, Triphenyl phosphate, Tricresyl phosphate, Trixyl phosphate, Cresyl diphenyl phosphate, Xyl diphenyl phosphate, Octyl diphenyl phosphate, Diisopropyl phenyl phosphate, Monophosphates such as diphenyl-2-ethylcresyl phosphate, tris (isopropylphenyl) phosphate, diphenyl methylphosphonate, diethyl phenylphosphonate, resorcinyl diphenyl phosphate, and bisphenol A bisphosphate, hydroquinone bisphosphate; Resorcinol bisphosphate, trioxybenze Polyphosphates such as bisphenol A-bis (dicresyl phosphate), phenylene bis (diphenyl phosphate), phenylene bis (ditolyl phosphate), phenylene bis (dixylyl phosphate), which are triphosphates and the like. Fate. Preferred are triphenyl phosphate, trixyl phosphate, phenylene bis (diphenyl phosphate), and phenylene bis (dixylyl phosphate), and more preferred is triphenyl phosphate.

Polytetrafluoroethylene can be added as a flame retardant aid, if necessary. 0.00 parts by weight of the thermoplastic resin and / or the thermoplastic relastomer
It is preferable to add in the range of 1 to 5 parts by weight. 0.00
If the amount is less than 1 part by weight, the effect of the addition is not obtained. If the amount exceeds 5 parts by weight, the impact resistance is reduced and the appearance is poor. The properties of polytetrafluoroethylene are as follows: average particle size of 0.05 to 1000 μm, density of 1.2 to 2.3 g / cm ³ , 65 to 76% by weight
Those having a fluorine content of are preferred. Tetrafluoroethylene addition form may be added as powder,
It may be added as a powder co-coagulated with the composite rubber-based graft copolymer. Further, tetrafluoroethylene particles may be added to particles of a (meth) acrylate (co) polymer or an acrylonitrile-styrene copolymer. It may be added in a supported structure.

[0042] Metal oxides and metal carbonates can also be used as flame retardant aids. By using these, it is possible to further improve the flame retardancy of the silicone component. That is, silicone has a cracking property at the time of combustion, and a volatile low-molecular cyclic substance is generated. Although this ring is relatively flammable, the addition of a metal catalyst creates a highly crosslinked product before cracking of the silicone backbone occurs, which forms a three-dimensional curtain on the surface in contact with oxygen,
Cut off oxygen supply and extinguish self. As the metal catalyst, platinum or the like is used, but metal oxides and metal carbonates are preferable from an industrial viewpoint.

The metal oxide is used as a flame retardant aid. Examples thereof include titanium oxide, cobalt oxide, nickel oxide, copper oxide, aluminum oxide, zinc oxide, iron oxide, and antimony trioxide. preferable.

The metal carbonate is used as a flame retardant aid, and examples thereof include cobalt carbonate, nickel carbonate, copper carbonate, aluminum carbonate, and zinc carbonate, with cobalt carbonate being most preferred.

When a metal hydroxide is used as a flame retardant or a flame retardant auxiliary, magnesium hydroxide, aluminum hydroxide and hydrotalcite are particularly preferably used. Average particle size of 10 from the viewpoints of aggregation, toughness, water resistance, and flame retardancy
Those having a surface treatment with a fatty acid metal salt, a silane coupling agent, a titanate coupling agent, or the like at 〜5000 nm are more preferred.

A nitrogen-containing organic compound can be used as a flame retardant auxiliary. For example, isocyanuric acid, melamine, cyanuric acid, melamine cyanurate, tris (2-hydroxyethyl) isocyanurate, triallyl cyanurate, 1,3,5-triacryloylhexahydro-S-triazine, trimethallyl isocyanurate and the like Organic nitrogen compounds are exemplified.

Examples of the plasticizer include alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, and pyromet; Adipate, dioctyl adipate, disiononyl adipate, dibutyl azelate, dioctyl azelate, alkyl esters of fatty acid polybasic acids such as diisononyl azelate, phosphate esters such as tricresyl phosphate, adipic acid, azelaic acid, sebacic acid, Polycarboxylic acids such as phthalic acid and ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,
A polyester-based plasticizer such as a polycondensate having a molecular weight of about 600 to 8,000 with a polyhydric alcohol such as 4-butylene glycol, the end of which is sealed with a monohydric alcohol or a monocarboxylic acid; epoxidized soybean oil; Epoxy plasticizers such as epoxidized linseed oil, epoxidized tall oil fatty acid-2-ethylhexyl, and chlorinated paraffin.

As the stabilizer, for example, tribasic lead sulfate,
Lead-based stabilizers such as dibasic lead phosphite, basic lead sulfite and lead silicate, metals such as potassium, magnesium, barium, zinc, cadmium and lead and 2-ethylhexanoic acid,
Metallic soap-based stabilizers derived from fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid, alkyl groups, ester groups and fatty acids Organotin stabilizer derived from salt, maleate, sulfide-containing, Ba-Zn based, Ca-Zn
System, Ba-Ca-Sn system, Ca-Mg-Sn system, Ca-
Composite metal soap stabilizers such as Zn-Sn, Pb-Sn, and Pb-Ba-Ca, metal groups such as barium and zinc, and branched fatty acids such as 2-ethylhexanoic acid, isodecanoic acid, and trialkylacetic acid, and oleic acid Metals derived from two or more organic acids, usually unsaturated fatty acids such as ricinoleic acid and linoleic acid, aliphatic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid, and their substituted derivatives Salt-based stabilizers, these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, and glycerin derivatives, and phosphites, epoxy compounds, color inhibitors, transparency improvers, light stabilizers, and antioxidants Metal stabilizers, such as metal salt liquid stabilizers, which contain stabilizing aids such as antioxidants, plate-out inhibitors, and lubricants, as well as epoxy resins and epoxy resins. Soybean oil, epoxidized vegetable oils, epoxy compounds such as epoxidized fatty acid alkyl esters,
Organic phosphites in which phosphorus is substituted with an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, and the like, and having an aromatic compound such as a dihydric alcohol such as propylene glycol, hydroquinone, and bisphenol A; UV absorbers such as hindered phenols such as bisphenol dimerized with methylene groups, salicylic acid esters, benzophenone, and benzotriazole; light stabilizers such as hindered amines or nickel complex salts; and UV shielding agents such as carbon black and rutile-type titanium oxide. Polyhydric alcohols such as trimerolpropane, pentaerythritol, sorbitol and mannitol, β-aminocrotonates, nitrogen-containing compounds such as 2-phenylindole, diphenylthiourea and dicyandiamide; Sulfur-containing compounds such as Ruki thio dipropionate ester, acetoacetic ester, dehydroacetic acid, keto compounds such as β Jiketon, organosilicon compound,
Non-metallic stabilizers such as borate esters may be used, and these may be used alone or in combination of two or more.

Examples of the filler include inorganic materials such as clay, talc, mica, carbon black, graphite, glass beads, glass fiber, carbon fiber and metal fiber, organic fibers such as polyamide, and silicone. And natural organic substances such as wood flour.

In addition, MBS, ABS, AES, NB
Impact strength modifiers such as R, EVA, acrylic rubber, composite rubber graft copolymers, processing aids such as (meth) acrylate copolymers, liquid paraffin, pure hydrocarbons such as low molecular weight polyethylene, Halogenated hydrocarbons,
Fatty acids such as higher fatty acids, oxy fatty acids, fatty acid amides such as fatty acid amides, polyhydric alcohol esters of fatty acids such as glycerides, fatty alcohol esters of fatty acids (ester wax), metallic soaps, fatty alcohols,
Polyhydric alcohol, polyglycol, polyglycerol,
Ester such as partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester of polyglycerol, (meth) acrylate copolymer, etc.
These lubricants, chlorinated paraffin, aluminum hydroxide,
Flame retardants such as antimony trioxide and halogen compounds; heat-resistant improvers such as (meth) acrylate-based copolymers, imide-based copolymers, styrene-acrylonitrile-based copolymers, release agents, crystal nucleating agents, and fluids A property improving agent, a colorant, an antistatic agent, a conductivity-imparting agent, a surfactant, an antifogging agent, a foaming agent, an antibacterial agent, and the like can be added.

Further, at the time of kneading, a crosslinking agent and a crosslinking assistant can be added as necessary to impart crosslinkability, and the crosslinking treatment is carried out at the time of kneading by appropriate selection of the crosslinking agent and at an appropriate stage thereafter. be able to. Examples of the crosslinking agent include organic peroxides having a half-life temperature lower than the maximum temperature during kneading by 20 ° C. or more. For example, dicumyl peroxide, 1,
1-bis (t-butylperoxy) -3.3.5-trimethylcyclosiloxane, 2.5-dimethyl-2.5-
Di (t-butylperoxyhexane), t-butylperoxy-3.5.5-trimethylhexanoate, di-
t-butyl diperoxyisophthalate and the like. Examples of the crosslinking aid include triallyl fumarate, vinyl silane, maleated EPDM, and the above-mentioned triallyl isocyanurate.

The method for producing the flame-retardant resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt mixing method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include, in particular, an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

The flame-retardant resin composition of the present invention can be produced by extruding and molding with a usual known kneading machine. Such molding machines include extruders,
Examples include an injection molding machine, a blow molding machine, a calender molding machine, and an inflation molding machine.

The flame-retardant resin composition of the present invention may further comprise a dye, a pigment, a stabilizer, a reinforcing agent such as glass fiber and carbon fiber, a filler such as talc and mica, a flow improver, if necessary. An antistatic agent, a conductivity-imparting agent, an antifogging agent, a foaming agent, an antibacterial agent and the like can be added.

The use of the molded article obtained from the flame-retardant resin composition of the present invention is not particularly limited.
For example, copiers, fax machines, printers, desktop / notebook / tower / server computers,
Housing and chassis parts for various OA / information / home appliances such as PDAs, mobile phones / PHS, TVs, VCRs, audio equipment, housings for PHS exchanges, telephone exchanges, etc., housings and duct hoses for indoor and outdoor units for air conditioners / coolers Covers, housings for home appliances,
Applications that require flame retardancy, such as electric wires, cables, display parts, and various building materials are listed.

[0056]

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

The following raw materials were used in the production of the resin compositions in Examples and Comparative Examples.

Polycarbonate resin (PC resin): Iupilon S-2000FN manufactured by Mitsubishi Engineering-Plastics Corporation Polyphenylene ether resin (PPE resin): Japan G
E Plastics Co., Ltd. Intrinsic viscosity (chloroform 25 ° C.) 0.48 dl / g poly (2,6-dimethyl-1,4-phenylene) ether ・ Polystyrene resin (PS resin): Sumitomo Chemical Co., Ltd. Sumibrite M-140 manufactured by Toyobo Co., Ltd .: Perprene S2000 (Reference Example 1) Polyorganosiloxane latex (L
Preparation of -1) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. 100 parts of the above mixed siloxane was added to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were dissolved, and 10,000 was mixed with a homomixer.
After pre-stirring at 300 rpm,
The mixture was emulsified and dispersed at a pressure of kg / cm ² 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 while mixing and stirring, and allowed to stand at 20 ° C.
After 8 hours, the pH of this latex was neutralized to 7.4 with an aqueous sodium hydroxide solution to complete the polymerization, thereby obtaining a polyorganosiloxane latex. The polymerization rate of the obtained polyorganosiloxane was 89.5%, and the average particle size of the polyorganosiloxane was 0.16 μm.

Reference Example 2 Production of Composite Rubber Graft Copolymer (C-1)
76 parts and 99 parts of water were placed in a separable flask equipped with a stirrer, purged with nitrogen, heated to 50 ° C., and charged with 8.8 parts of n-butyl acrylate and 0.2 parts of allyl methacrylate.
And a mixture of 0.1 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane particles. Then, sulfuric acid 1
A mixture of 0.002 part of iron, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalit and 5 parts of distilled water was charged to start radical polymerization, and then kept at 70 ° C. for 2 hours to carry out polymerization. Upon completion, a composite rubber latex was obtained. A part of this latex was sampled and the average particle diameter of the composite rubber was measured to be 0.18 μm.
The latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured.
7.3%.

A mixture of 0.06 part of tert-butyl hydroperoxide and 11 parts of methyl methacrylate was added dropwise to this composite rubber latex at 70 ° C. for 30 minutes, and then maintained at 70 ° C. for 4 hours to form a composite rubber. The graft polymerization of was completed. The obtained graft copolymer latex was dropped into a heated aqueous calcium acetate solution, coagulated, separated, washed, and then dried at 75 ° C. for 16 hours to obtain a powdery composite rubber-based graft copolymer.

(Examples 1-3 and Comparative Examples 1-3) Table 1
0.5 parts each of an oxidation stabilizer (Adeka Argus Chemical Co., Ltd., AO-60, AO-412S) was mixed with the polycarbonate resin-based (PC-based) and polyester-based elastomers, and the mixture was heated to 250 ° C. The mixture was supplied to a screw extruder and kneaded to obtain pellets. The polyphenylene ether resin (PPE) was kneaded at 270 ° C.

The obtained pellets were processed with a 20 mmφ, 35 oz. Screw in-line molding machine.
PE system has a cylinder temperature of 270 ° C, a mold temperature of 60 ° C,
Each test piece was prepared in a molding cycle of 35 seconds.

Evaluation contents: Izod impact test: Izod impact test having a thickness of 6.35 mm and UL94 combustion test in accordance with ASTM: D256, and a sample having a thickness of 3.2 mm were provided.

Table 1 shows the above measurement results.

[0065]

[Table 1]

From the above Examples and Comparative Examples, the following became clear.

Table 1 shows that the examples of the present invention are superior to the comparative examples in flame retardancy, and that the flame retardancy, impact resistance and heat resistance are balanced at a high level.

[0068]

The composite rubber flame retardant of the present invention has high flame retardancy and impact resistance. When this is added to a thermoplastic resin composition, high flame retardancy, impact resistance, and heat resistance can be achieved without adding a halogen compound, a phosphate ester compound, and an impact modifier, and the It is possible to provide a low-impact flame-resistant high-impact material at a relatively low cost. The composite rubber-based flame retardant of the present invention is also useful as a non-drip agent.

Continued on the front page F term (reference) 4J002 AC041 AC061 BB031 BB121 BC031 BC061 BC071 BD121 BG041 BG061 BH011 BN061 BN071 BN121 BN141 BN151 BN212 BN222 FD001 CB001 CF061 CF071 CF161 CG001 CH071 FD02 FD170 FD180 FD200 FD310 FD320 GL00 GQ00 GQ01 4J026 AA45 AA46 AA47 AA61 AA63 AB44 AC15 AC18 AC31 AC32 AC36 BA05 BA06 BA27 BA31 BB01 BB02 DA04 DA07 DA09 DA10 DA11 DA12 DA13 DA16 DB10 DB12 DB13 DB16 DB08 GA08

Claims (2)

[Claims] 1. A composite mainly composed of a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers onto a composite rubber composed of a polyorganosiloxane and an alkyl (meth) acrylate rubber. Rubber flame retardant. 2. A flame-retardant resin composition comprising the composite rubber-based flame retardant according to claim 1 and a thermoplastic resin and / or a thermoplastic elastomer.