JP2001158845A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant resin composition excellent in impact resistance and excellent in chemical resistance and light resistance. SOLUTION: This flame retardant resin composition comprises at least either of two kinds of graft copolymers obtained by carrying out graft polymerization of a composite rubber-like polymer containing an alkyl (meth)acrylate rubber component with a monomer and a flame retardant. The flame retardant resin composition may contain (C) a thermoplastic resin and (C) the thermoplastic resin is preferably a (co)polymer containing at least one kind of a monomer component selected from an aromatic alkenyl compound component, a vinyl cyanide compound component and a (meth)acrylic ester component as a constituent.

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 excellent in light resistance, impact resistance, molding gloss and chemical resistance.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been used for various electric products,
It is used in various fields such as building material parts. Among thermoplastic resins, for example, a styrene-based resin composition has been particularly widely used because of its excellent mechanical properties and electrical properties. However, recently, styrene-based resin compositions used for television sets, CRTs, various computers, OA equipment, home electric appliances, and the like have been required to have extremely high flame retardancy more than before, and acrylonitrile has been required. -Flame-retardant resin materials in which a styrene-based resin such as butadiene-styrene (ABS) resin is made flame-retardant by various methods have been proposed. The most common method of flame retarding a resin material is to knead a flame retardant such as a halogen compound or antimony oxide into the resin. As an index of high flame retardancy, for example, self-extinguishing property (V-0, V-1, V-2 class) based on the United States Underwriters Laboratories (UL) standard 94 is exemplified.

Another important property required for a resin material is light resistance. For example, electrical equipment used outdoors, such as household gas / water meters and outdoor lighting devices, is highly likely to be exposed to sunlight, rainfall, wind, etc., and such electrical equipment has insufficient light resistance. When such a resin material is used, the design property may be impaired due to the deterioration of the resin material, or cracks and cracks may occur.
Therefore, a resin material having excellent light resistance is required for electrical equipment used outdoors. However, a conventional styrene resin to which a halogen compound is added as a flame retardant has a problem that light resistance is poor.

Therefore, it has been widely used to add an ultraviolet absorber or a sterically hindered amine-based light stabilizer to a resin material requiring such light resistance in order to improve the light resistance. Also, Japanese Patent Application Laid-Open No. 9-40828 and
-48900, JP-A-9-59463, JP-A-9-255814, JP-A-9-255842
JP-A-10-7870 discloses that light resistance is improved by using a brominated bisphenol-type epoxy compound having relatively little coloring among halogen compounds or a reaction product thereof as a flame retardant. An approach has been proposed. JP-A-9-235444 and JP-A-11-35789 propose a method for improving the light resistance of a flame-retardant resin material by adding a specific dye, dye or pigment.

[0005]

However, the method of adding an ultraviolet absorber or a sterically hindered amine-based light stabilizer as described above, and Japanese Patent Application Laid-Open Nos. 9-40828 and 9-4.
No. 8900, JP-A-9-59463, JP-A-9-255814, JP-A-9-255842, and JP-A-10-7870, brominated bisphenol-type epoxy compounds or the compounds thereof. A method using a reactant as a flame retardant;
In the method of adding a specific dye, dye or pigment proposed in JP-A-35444 and JP-A-11-35789, light resistance is maintained while maintaining impact resistance, molded appearance, and flame retardancy of a resin material. Although we can improve to some extent,
It was not possible to improve the chemical resistance.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a flame-retardant resin composition having excellent impact resistance, chemical resistance, and light resistance.

[0007]

The present inventors have conducted intensive studies on the light resistance, impact properties, and chemical resistance of a resin composition containing a specific graft copolymer and a flame retardant. In particular, a thermoplastic resin composition containing a graft copolymer having a specific complexed alkyl (meth) acrylate rubber component exhibits good impact properties, flame retardancy, light resistance, and chemical resistance. And arrived at the present invention.

That is, the present invention relates to 100 parts by weight of a resin component comprising the following components (A) and / or (B), 5 to 40 parts by weight of the following component (D), The gist is a flame-retardant resin composition containing 20 parts by weight. (A) An alkyl (meth) acrylate monomer component (a) containing a graft crosslinking agent and a crosslinking agent in the presence of 1 to 30% by weight of a diene rubber (a-1) having a weight average particle diameter of 300 nm or more. -2) Composite rubbery polymer ((a-1) + (a-2)) 2 obtained by emulsion polymerization of 99 to 70% by weight
0 to 80% by weight of at least one monomer selected from the group consisting of aromatic alkenyl compounds, methacrylic esters, acrylic esters and vinyl cyanide compounds (a-
3) A graft copolymer in which 80 to 20% by weight is subjected to emulsion graft polymerization. (B) 0.01 to 10% by weight of a polyfunctional monomer in the presence of 1 to 20% by weight of a polyorganosiloxane (b-1)
Radical polymerization of 99 to 80% by weight of a monomer mixture (b-2) consisting of 60 to 99.9% by weight of an alkyl (meth) acrylate and 0 to 30% by weight of a vinyl monomer copolymerizable therewith; The composite rubbery polymer ((b-
1) + (b-2)) 20 to 80% by weight of at least one monomer (b-3) selected from an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound; Graft copolymer in which weight% is emulsion graft polymerized. (D) Brominated flame retardant (E) Antimony compound The above resin component may further contain a thermoplastic resin (C). Further, the resin component is a component (A) and / or
Or the graft copolymer 30 to 95 comprising the component (B)
% By weight and 70 to 5% by weight of the component (C).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The diene rubber (a-) in the graft copolymer (A) constituting the flame-retardant resin composition of the present invention is used.
1) is a rubbery polymer having diene components such as butadiene and isoprene and a monomer component copolymerizable therewith with a weight average particle diameter of 300 nm or more. When the weight average particle diameter is less than 300 nm, the impact resistance and pigment coloring of the finally obtained flame retardant resin composition decrease. The diene rubber (a-1) having such a weight average particle diameter is, for example, a diene rubber (a-1) which is a thickening agent comprising an acid group-containing copolymer latex.
Obtained by enlarging the particles.

The acid group-containing copolymer latex used as a thickening agent is a copolymer latex containing an acid group-containing monomer and an alkyl acrylate as constituent components of the copolymer. Examples of the acid group-containing monomer include acrylic acid, methacrylic acid, itaconic acid and crotonic acid. As the alkyl acrylate, alkyl acrylates having 1 to 12 carbon atoms in the alkyl group are preferred. The weight ratio of the acid group-containing monomer component in the acid group-containing copolymer is such that the stability of the latex when the diene rubber (a-1) is enlarged is excellent, and the diene rubber ( Since the average particle size of a-1) can be easily controlled to 300 nm or more, it is 3 to 30% by weight, more preferably 10 to 25% by weight in the copolymer. The weight average particle size of the acid group-containing copolymer in the acid group-containing polymer latex is such that the latex has excellent stability when the diene rubber (a-1) is enlarged, The average particle diameter of the system rubber (a-1) is preferably 100 to 200 nm because it can be easily controlled to 300 nm or more. The enlargement is due to the small particle diameter diene rubber (a-a) obtained by emulsion polymerization.
1) It is carried out by adding the acid group-containing copolymer latex to the latex.

The composite rubbery polymer ((a-1) + (a-2)) constituting the graft copolymer (A) is a diene rubber (a-1) 1 having a weight average particle diameter of 300 nm or more. ~ 3
In the presence of 0% by weight, an alkyl (meth) acrylate monomer component (a-2) 9 containing a graft crosslinking agent and a crosslinking agent
It is obtained by emulsion polymerization of 9 to 70% by weight. When the amount of the diene rubber (a-1) is less than 1% by weight, the low-temperature impact characteristics of the finally obtained flame-retardant resin composition decrease, while when it exceeds 30% by weight, the light resistance is poor. May decrease.

The alkyl (meth) acrylate in the alkyl (meth) acrylate monomer component (a-2) includes, for example, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
Examples thereof include alkyl acrylates such as 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate, with n-butyl acrylate being particularly preferred. Allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, etc. are mentioned as a graft crossing agent in an alkyl (meth) acrylate monomer component (a-2), and are used individually or in mixture of 2 or more types. Examples of the crosslinking agent in the alkyl (meth) acrylate monomer component (a-2) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. And used alone or in combination of two or more.

The composite rubbery polymer ((a-1) + (a-
2)) is a diene rubber (a-1) latex having a weight average particle diameter of 300 nm or more, and an alkyl (meth) acrylate monomer component (a) containing a graft crosslinking agent and a crosslinking agent.
It is obtained by emulsion polymerization with the addition of -2).
For the emulsion polymerization, a radical polymerization initiator or an emulsifier is used. As the radical polymerization initiator, 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 preferred, and a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalit, and hydroperoxide is particularly preferred. The emulsifier is not particularly limited, but since the stability of the latex during emulsion polymerization is excellent and the polymerization rate can be increased, sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, rosin acid soap, and the like can be used. Various carboxylate salts are preferred. Further, among these, dipotassium alkenyl succinate is preferable because gas generation during high-temperature molding of the finally obtained flame-retardant resin composition can be suppressed.

The composite rubbery polymer ((a-1) + (a-
The particle size distribution of 2)) is not particularly limited, but since the finally obtained flame-retardant resin composition has excellent gloss during high-temperature molding, the proportion of particles having a particle size of less than 100 nm is 5 to 5%.
20% by weight of the composite rubbery polymer ((a-1) + (a
-2)) is preferred. When the proportion of particles having a particle diameter of less than 100 nm is less than 5% by weight, the impact resistance of the finally obtained flame-retardant resin composition tends to decrease. When the proportion exceeds 20% by weight, the gloss of the surface of the molded article when the finally obtained flame-retardant resin composition is molded at a high temperature tends to decrease.

The graft copolymer (A) is obtained by adding a composite rubbery polymer ((a-1) + (a-2)) to an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound. It can be produced by emulsion graft polymerization of at least one selected monomer component (a-3). Among the monomer components (a-3), aromatic alkenyl compounds include, for example, styrene, α-methylstyrene, vinyltoluene and the like, and methacrylates include, for example, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and the like. The acrylic acid ester is, for example, methyl acrylate, ethyl acrylate, butyl acrylate and the like, and the vinyl cyanide compound is, for example, acrylonitrile, methacrylonitrile and the like. Among these, it is preferable to use a mixture of styrene and acrylonitrile as the monomer component (a-3) because the graft copolymer (A) has excellent thermal stability.

The graft copolymer (A) is composed of 20 to 80% by weight of the composite rubbery polymer ((a-1) + (a-2)) and 80 to 80% of the monomer component (a-3). 20% by weight is obtained by emulsion graft polymerization. Emulsion graft polymerization at such a weight ratio is preferred because both the impact resistance and pigment coloring of the finally obtained flame retardant resin composition are excellent. If the amount of the monomer component (a-3) is less than 20% by weight, the pigment coloring of the finally obtained flame-retardant resin composition will be reduced. May decrease. More preferably, in the graft copolymer (A), the composite rubbery polymer ((a-1) + (a-
2)) is 40 to 70% by weight, and the monomer component (a-3) is 60 to 30% by weight. In such a case, the finally obtained flame-retardant resin composition is preferable because it expresses good impact resistance and pigment coloring in a well-balanced manner.

The emulsion graft polymerization for producing the graft copolymer (A) is carried out by a radical polymerization technique using an emulsifier. In addition, various chain transfer agents for controlling the graft ratio and the molecular weight of the graft component can be added to the monomer component (a-3). As the radical polymerization initiator used at this time, a peroxide, an azo initiator, or a redox initiator obtained by combining an oxidizing agent and a reducing agent is used. Redox initiators are preferred among these,
In particular, a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetic acid, Rongalit, and hydroperoxide is preferable. There is no particular limitation on the emulsifier, but various carboxyls such as sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap are used because the stability of the latex during emulsion polymerization is excellent and the polymerization rate is increased. Acid salts are preferred. More preferably, dipotassium alkenyl succinate is preferred because gas generation during high-temperature molding of the finally obtained flame-retardant resin composition can be suppressed.

The graft copolymer (A) latex obtained by emulsion graft polymerization is then introduced into hot water in which a coagulant is dissolved, and is coagulated and solidified. Examples of the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate. Of these, inorganic acids are preferred because of excellent productivity of the graft copolymer (A) and excellent thermal coloring during molding of the finally obtained flame-retardant resin composition. Next, the graft copolymer (A) solidified using the coagulant as described above is redispersed in water or warm water to form a slurry, and the emulsifier residue remaining in the graft copolymer (A) Is eluted in water and washed. After washing, the slurry is dehydrated with a dehydrator or the like, and the obtained solid is dried with a flash dryer or the like to obtain a graft copolymer (A).
Is obtained in the form of particles. The washing conditions at this time are not particularly limited, but it is preferable to wash under conditions where the amount of the emulsifier residue contained in the dried graft copolymer (A) is in the range of 0.5 to 2% by weight. When the amount of the emulsifier residue in the graft copolymer (A) is less than 0.5% by weight, the flowability of the finally obtained flame-retardant resin composition tends to decrease, while the amount exceeds 2% by weight. When the flame-retardant resin composition is molded at a high temperature, the amount of gas generated tends to increase.
The amount of the emulsifier residue in the graft copolymer (A) varies depending on the amount of the emulsifier used, in addition to the above-described conditions for washing the graft copolymer (A). Therefore, the preferable amount of the emulsifier to be used for controlling the amount of the emulsifier residue in the graft copolymer (A) to 0.5 to 2% by weight is 0.1 to 100 parts by weight of the obtained graft copolymer (A). It is 5 to 5 parts by weight, more preferably 0.5 to 1.5 parts by weight.

The weight average particle size of the graft copolymer (A) is not particularly limited, but is preferably 200 to 500 nm because the finally obtained flame-retardant resin composition has excellent impact resistance.
And more preferably 230 to 40
0 nm, more preferably 260-350 nm. Preferred characteristics of the graft copolymer (A) include:
The temperature at which the weight of the graft copolymer (A) decreased by 1% by weight was 300% when subjected to thermogravimetric analysis at a temperature rising condition of 20 ° C./min.
℃ or more. When the temperature is lower than 300 ° C., the amount of gas generated during high-temperature molding of the finally obtained flame-retardant resin composition tends to increase.

The polyorganosiloxane (b-) in the graft copolymer (B) constituting the flame-retardant resin composition of the present invention.
1) is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group. More preferably, 0.3 to 3 mol% of a siloxane unit containing a vinyl polymerizable functional group and 9 dimethylsiloxane units
The polyorganosiloxane is composed of 7 to 99.7 mol%, and further has 1 mol% or less of silicon atoms having three or more siloxane bonds based on all silicon atoms in the polydimethylsiloxane. The size of the polyorganosiloxane (b-1) particles is not particularly limited, but the weight average particle diameter is preferably 200 nm or less because the pigment coloring property of the finally obtained flame-retardant resin composition is excellent. More preferably, it is 100 nm or less.

In the polyorganosiloxane (b-1), if the siloxane unit having a vinyl polymerizable functional group is less than 0.3 mol%, the polyorganosiloxane (b-
In some cases, the compounding of 1) with the alkyl (meth) acrylate rubber (b-2) becomes insufficient. As a result, the polyorganosiloxane (b-1) bleeds out on the surface of the finally obtained flame-retardant resin composition molded article, and the appearance of the molded article tends to be poor. When the siloxane unit containing a vinyl polymerizable functional group in the polyorganosiloxane (b-1) exceeds 3 mol%, or when silicon atoms having three or more siloxane bonds are all silicon atoms in the polyorganosiloxane. If it exceeds 1 mol%, the impact resistance of the finally obtained flame-retardant resin composition tends to be low. Furthermore, since both the impact resistance and the molded appearance of the finally obtained flame retardant resin composition are excellent, the siloxane unit containing a vinyl polymerizable functional group in the polyorganosiloxane (b-1) is preferably 0.5-2
Mol%, more preferably 0.5 to 1 mol%.

The dimethylsiloxane used in the production of the polyorganosiloxane (b-1) 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, and 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 via a siloxane bond. Considering the reactivity with dimethylsiloxane,
Various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-
Methacryloyloxysiloxane such as methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethyl Examples of the silane include mercaptosiloxanes such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane. These siloxanes containing a vinyl polymerizable functional group can be used alone or as a mixture of two or more.

In order to produce the polyorganosiloxane (b-1), first, if necessary, a siloxane-based crosslinking agent is added to a mixture of dimethylsiloxane and a siloxane containing a vinyl polymerizable functional group. The latex is obtained by emulsification with an emulsifier and water. Next, the latex is made into fine particles by using a homomixer that forms fine particles by shearing force due to high-speed rotation, a homogenizer that forms fine particles by a jetting power of a high-pressure generator, or the like. It is preferable to use a high-pressure emulsifier such as a homogenizer because the particle size distribution of the polyorganosiloxane (b-1) latex becomes small. Then, the finely divided latex is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. The termination of the polymerization is carried out by cooling the reaction solution and further neutralizing the reaction solution with an alkaline substance such as caustic soda, caustic potash and sodium carbonate.

The acid catalyst may be added by a method in which an acid catalyst is previously mixed with a siloxane mixture, an emulsifier, and water, or a method in which a high-temperature acid aqueous solution is dropped at a constant rate into a latex in which the siloxane mixture is finely divided. May be. However, since it is easy to control the particle size of the obtained polyorganosiloxane, 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 polymerization time is at least 2 hours, more preferably at least 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 has been made finer into an aqueous solution of an acid catalyst, it is preferable to hold the latex for about 1 hour after the dropping of the latex.
The polymerization temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.

The siloxane-based crosslinking agent used in producing the polyorganosiloxane (b-1) includes a trifunctional or tetrafunctional silane crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, and the like. Examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and the like. As the emulsifier, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. Among these, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are particularly preferred. These emulsifiers are used in an amount of 0.1 to 100 parts by weight of the siloxane mixture.
It is used in the range of about 05 to 5 parts by weight. If the amount is less than 0.05 part by weight, the amount used is small and the dispersion state becomes unstable, and the emulsified state of a fine particle diameter cannot be maintained. If the amount exceeds 5 parts by weight, the amount used is large, and the color of the emulsifier itself and the deterioration of the thermoplastic resin composition resulting therefrom may greatly affect the color of the molded product.

Examples of the acid catalyst used for the polymerization of the polyorganosiloxane (b-1) include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid and aliphatic substituted naphthalenesulfonic acid, and sulfuric acid, hydrochloric acid and nitric acid. Mineral acids. These acid catalysts are used alone or in combination of two or more. Among them, aliphatic substituted benzenesulfonic acid is preferred, and n-dodecylbenzenesulfonic acid is particularly preferred, because the polyorganosiloxane (b-1) latex is also excellent in stabilizing action. Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the effect of the color of the emulsifier used in the polyorganosiloxane (b-1) latex on the color of the flame-retardant resin composition molded product is reduced. It can be kept small.

The composite rubbery polymer ((b-1) + (b-2)) constituting the graft copolymer (B) is prepared in the presence of 1 to 20% by weight of the polyorganosiloxane (b-1). The monomer mixture (b-2) is obtained by radical polymerization of 99 to 80% by weight. Composite rubbery polymer ((b-1) + (b-
2)) the amount of polyorganosiloxane (b-1) is 1
If the amount is less than 20% by weight, the impact resistance becomes low due to the small amount of the polyorganosiloxane (b-1). If the amount exceeds 20% by weight, the pigment coloring property of the finally obtained flame-retardant resin composition may decrease. is there. Further, since the finally obtained flame-retardant resin composition is excellent in both impact resistance and pigment coloring property, the polyorganosiloxane in the composite rubbery polymer ((b-1) + (b-2)) is used. (B-1) is preferably 6 to
It is 20% by weight, more preferably 10 to 20% by weight.

The monomer mixture (b-2) is composed of 0.01 to 10% by weight of a polyfunctional monomer, 60 to 99.9% by weight of an alkyl (meth) acrylate, and a vinyl copolymerizable therewith. Consists of 0-30% by weight of monomer. Examples of the polyfunctional monomer include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate And polyfunctional alkyl (meth) acrylates. These can be used alone or in combination of two or more. However, since the obtained graft copolymer (B) has excellent impact resistance and gloss at the time of low-temperature molding, allyl methacrylate and 1,3 -Butylene glycol dimethacrylate is preferably used in combination. In addition, the polyfunctional monomer is usually 0.1 to 0.1 in the monomer mixture (b-2).
It is 10% by weight, preferably 0.2 to 5% by weight, more preferably 0.2 to 1% by weight.

Examples of the alkyl (meth) acrylate constituting the monomer mixture (b-2) include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and hexyl. Methacrylate, 2-ethylhexyl methacrylate, n-
Examples include alkyl methacrylates such as lauryl methacrylate. These may be used alone or in combination of two or more. However, it is particularly preferable to use n-butyl acrylate because the finally obtained flame retardant resin composition is excellent in both impact resistance and molding gloss.

The monomer mixture (b-2) may contain, besides the alkyl (meth) acrylate and the polyfunctional monomer, a vinyl monomer copolymerizable therewith. The copolymerizable vinyl monomer is not particularly limited, and for example, the above-described aromatic alkenyl compound and vinyl cyanide compound can be arbitrarily used.

The composite rubbery polymer ((b-1) + (b-
2)) is obtained by adding a monomer mixture (b-2) to a latex of a polyorganosiloxane (b-1) and polymerizing the mixture using a usual radical polymerization initiator. The monomer mixture (b-2) may be mixed with the latex of the polyorganosiloxane (b-1) at a time, or may be dropped at a constant rate into the latex of the polyorganosiloxane (b-1). Is also good. However, since the finally obtained flame-retardant resin composition has excellent impact resistance, a method in which it is mixed with the polyorganosiloxane (b-1) latex 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 initiator is preferable, and a sulfoxylate initiator obtained by combining sodium salt, Rongalit, and hydroperoxide with ferrous sulfate / ethylenediaminetetraacetic acid is particularly preferable.

The graft copolymer (B) is prepared by adding 20 to 80% by weight of the composite rubbery polymer ((b-1) + (b-2)).
80 to 20% by weight of at least one monomer (b-3) selected from an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound
Is obtained by emulsion graft polymerization. If the amount of the monomer (b-3) in the graft polymer (B) is less than 20% by weight, the pigment coloring of the finally obtained flame-retardant resin composition tends to decrease, and 80% by weight. If it exceeds 300, the amount of the composite rubber polymer ((b-1) + (b-2)) will be low, so that the impact resistance tends to be low. Preferably, the monomer (b-3) is 7 since both the pigment coloring property and the impact resistance are excellent.
It is 0 to 30% by weight, more preferably 65 to 35% by weight. The particle diameter of the graft copolymer (B) is such that the weight average particle diameter is 70 to 200 nm because both the impact resistance and the pigment coloring property of the finally obtained flame retardant resin composition are excellent.
And more preferably 100 to 15
0 nm.

The aromatic alkenyl compound used for the monomer (b-3) is, for example, styrene, α-methylstyrene, vinyltoluene and the like, and the methacrylic acid ester is, for example, methyl methacrylate, ethyl methacrylate, 2-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 is preferable because the finally obtained flame-retardant resin composition has excellent thermal stability.

The graft polymer (B) is obtained by adding a monomer (b-3) to a latex of a composite rubbery polymer ((b-1) + (b-2)) and acting with a radical polymerization initiator. By performing the reaction, the resin composition is obtained in one step or in multiple steps. However, since the finally obtained flame-retardant resin composition has excellent impact resistance and pigment coloring property, it is preferable to carry out polymerization in two or more steps.
Various chain transfer agents for adjusting the molecular weight and graft ratio of the graft polymer can be added to the monomer (b-3). Further, at the time of graft polymerization, an emulsifier can be added to stabilize the polymerization latex and further control the average particle size of the graft copolymer (B). The emulsifier is not particularly limited, but is preferably a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, or the like. Further, a method of using a carboxylate emulsifier in combination with a sulfonate emulsifier or a sulfate emulsifier is preferable. After completion of the graft polymerization, the latex is poured into hot water in which a metal salt such as calcium acetate or aluminum sulfate is dissolved, and coagulated and solidified to separate and collect the graft copolymer (B) particles. it can.

The graft copolymer (B) contains 70 to 99% by weight of an insoluble content in an acetone solvent, and the acetone-soluble content is measured as a 0.2 g / 100 cc N, N-dimethylformamide solution at 25 ° C. 0.3 viscosity
It is preferably from 0 to 0.70 dl / g. If the insoluble content in the acetone solvent is less than 70% by weight, the impact resistance of the finally obtained flame-retardant resin composition is reduced, while if it exceeds 99% by weight, the molded gloss is reduced. Also,
When the reduced viscosity measured at 25 ° C. as a 0.2 g / 100 cc N, dimethylformamide solution of acetone-soluble matter is less than 0.30 dl / g, the impact resistance of the finally obtained flame-retardant resin composition Decrease, while 0.70 dl
/ G, the gloss at the time of low-temperature molding tends to decrease. Since both the impact resistance and the gloss at the time of low-temperature molding of the finally obtained flame-retardant resin composition are excellent, the more preferable range of the acetone-insoluble content is 75 to 95% by weight, more preferably 80 to 95% by weight. % By weight. Further, the reduced viscosity of the acetone-soluble component measured at 25 ° C. as a 0.2 g / 100 cc N, N-dimethylformamide solution is more preferably 0.50 to 0.70 dl / g, and still more preferably 0.55 to 0 dl / g. .65 dl / g.

The method for producing the graft copolymer (B) having the above-mentioned acetone-insoluble content and reduced viscosity of the acetone-soluble content is not particularly limited, but the preferred production method is a composite rubbery polymer. ((B-1) + (b-
The following four methods for controlling the conditions when radically polymerizing the monomer (b-3) to 2)) are mentioned. As a first method, the composite rubbery polymer ((b-1) + (b-
There is a method of limiting the amount of the radical polymerization initiator used when polymerizing the monomer (b-3) into 2)). Specifically, when a sulfoxylate-based initiator obtained by combining ferrous sulfate and disodium ethylenediaminetetraacetate, Rongalit and hydroperoxide is used as the radical polymerization initiator, ferrous sulfate and ethylenediaminetetraacetic acid are used. This is a method of reducing the amount of disodium acetate, the amount of Rongalit, or the amount of hydroperoxide used. Increasing the amount of these components tends to increase the amount of acetone-insoluble matter, and tends to reduce the reduced viscosity of the acetone-soluble matter. The second method is a method in which a chain transfer agent such as various mercaptan compounds and styrene dimer is added to the monomer (b-3).
A third method is to limit the polymerization temperature to an appropriate temperature for the radical polymerization initiator used. When the polymerization temperature is low, the number of generated radicals is small, the amount of acetone-insoluble matter is small, and the reduced viscosity of the acetone-soluble matter tends to be high. When the polymerization temperature is high, the number of radicals generated temporarily increases, but the polymerization initiator disappears immediately, and as a result, the amount of acetone-insoluble components is again small, and
The reduced viscosity of the acetone-soluble component tends to increase. 4th
Is a method of adjusting the amount of the emulsifier to be used. When the amount of the emulsifier is small, the amount of the acetone-insoluble component tends to increase, and the reduced viscosity of the acetone-soluble component tends to increase. Conversely, if the amount of emulsifier used is large,
The amount of acetone-insoluble matter tends to decrease, and the reduced viscosity of the acetone-soluble matter tends to decrease. Among the above four methods, the first method that limits the amount of the radical polymerization initiator used is preferable because the amount of the acetone-insoluble component and the reduced viscosity of the acetone-soluble component are easily controlled.

As the thermoplastic resin (C) used in the present invention, polycarbonates are preferred because the finally obtained flame-retardant resin composition exhibits good impact resistance, light resistance and pigment coloring. (Co) polymer comprising at least one monomer component selected from resins, resins such as PBT resins and PET resins, aromatic alkenyl compound components, vinyl cyanide compound components, and (meth) acrylate components. Preferred are copolymers comprising an aromatic alkenyl compound component, a vinyl cyanide compound component and an N-substituted maleimide component. More preferably, a (co) polymer having at least one monomer component selected from an aromatic alkenyl compound component, a vinyl cyanide compound component, and a (meth) acrylate component as a component is preferable. Specific examples of preferred thermoplastic resin (C) include acrylonitrile-styrene copolymer (SAN) resin, polymethyl methacrylate (PMMA) resin, styrene-methyl methacrylate copolymer (MS) resin, polystyrene resin, and acrylonitrile-styrene -Methyl methacrylate terpolymer.

The flame-retardant resin composition of the present invention comprises a resin component containing a graft copolymer (A) and / or a graft copolymer (B), a brominated flame retardant (D), and an antimony compound (E). )including. The resin component may further contain a thermoplastic resin (C). The resin component of the flame-retardant resin composition of the present invention preferably comprises 10 to 90% by weight of the graft copolymer (A) and 90 to 10% by weight of the graft copolymer (B). When the thermoplastic resin (C) is further added, the weight ratio of the graft copolymer (A), the graft copolymer (B) and the thermoplastic resin (C) in the resin component is finally Since the obtained flame-retardant resin composition has excellent impact resistance, rigidity and light resistance simultaneously, the graft copolymer (A) and / or the graft copolymer (B) is 30 to 95% by weight, It is preferable that the content of the plastic resin (C) is 5 to 70% by weight. Further, in the resin component, the graft copolymer composed of 10 to 90% by weight of the graft copolymer (A) and 90 to 10% by weight of the graft copolymer (B) is 40 to 95% by weight, and the thermoplastic resin ( C) is preferably 60 to 5% by weight. The resin component only needs to contain at least one of the graft copolymer (A) and the graft copolymer (B), and may be used alone or in combination.

The brominated flame retardant (D) used in the present invention is not particularly limited, and known brominated flame retardants can be used.
For example, tetrabromobisphenol A and its derivatives, tetrabromobisphenol S, tetrabromophthalic anhydride, hexabromobenzene, brominated diphenyl ether, brominated polycarbonate oligomers and terminal-modified products thereof, brominated epoxy resins (bisphenol A type, novolak type) And terminal-modified products thereof, brominated phenoxy resin, trisbromophenyl phosphate, brominated polystyrene, brominated phenylene ether oligomer and the like are preferably used. Brominated flame retardant (D)
Although it depends on the type of brominated flame retardant used, the bromine content is preferably 10% by weight or more, more preferably about 40 to 85% by weight. It is preferable to use a bromine-based flame retardant (D) having such a bromine content because the resin composition has high flame retardancy. The higher the bromine content ratio, the lower the amount of addition, the more the flame retardancy can be exhibited without impairing the resin properties other than the flame retardancy. Although the amount of the brominated flame retardant (D) depends on the required degree of flame retardancy, it is usually 5 to 100 parts by weight of the resin component.
It is 40 parts by weight, preferably 10 to 35 parts by weight. If the amount is less than 5 parts by weight, the effect of imparting flame retardancy to the resin composition will be insufficient, and if it exceeds 40 parts by weight, impact resistance and heat resistance will decrease.

The antimony compound (E) used in the present invention improves the flame retardancy of the resin composition, and known compounds can be used. For example, antimony salts such as antimony trioxide, antimony pentoxide, and sodium antimonate and the like can be mentioned. As these antimony compounds, those having a surface treated are also industrially available, and those having been subjected to a surface treatment may be used. The amount of the antimony compound (E) to be used is 1 to 20 parts by weight based on 100 parts by weight of the resin component. When the amount is less than 1 part by weight, the flame retardancy imparting due to the synergistic effect with the brominated flame retardant (D) is insufficient, and when the amount exceeds 20 parts by weight, the impact resistance of the finally obtained flame retardant resin composition decreases. I do.

The polytetrafluoroethylene (F) used in the present invention improves the flame retardancy of the resin composition. The composition is not particularly limited, and known compositions can be used. One million or more polytetrafluoroethylene (F) is preferred. If the molecular weight of polytetrafluoroethylene (F) is less than 1,000,000, a high degree of flame retardancy, for example, UL94 standard (Underwriters, USA)
Laboratories) A large amount of addition is required to satisfy the test, and as a result, the moldability and mechanical strength of the finally obtained flame-retardant resin composition are reduced. Polytetrafluoroethylene (F) is added in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the resin component. 0.001
If the amount is less than 10 parts by weight, drip at the time of combustion tends to occur, and high flame retardancy tends to be insufficient. If the amount is more than 0.5 part by weight, moldability, appearance of a molded article, heat resistance, The impact properties tend to decrease.

The chlorinated polyethylene (F) used in the present invention is intended to improve the flame retardancy of the resin composition. The type of the chlorinated polyethylene (F) is not particularly limited, and known types can be used. It is preferably 20 to 70% by weight, and more preferably 30 to 50% by weight. The amount of the chlorinated polyethylene (F) is 0.1 to 10 parts by weight based on 100 parts by weight of the resin component.
If the amount is less than 0.1 part by weight, drip during combustion is likely to occur, and high flame retardancy tends to be insufficient.
If the amount exceeds the weight part, the moldability, the appearance of the molded product, the heat resistance, and the impact resistance tend to decrease.

The benzotriazole compound (G) used in the present invention improves the light resistance of the resin composition, and known compounds can be used. For example, 2- (5-
Methyl-2-hydroxyphenyl) benzotriazole, 2- (3-tetrabutyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2,
2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like. The amount of the benzotriazole-based compound (G) is 0.1 to 3.0 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 0.1 part by weight, the light resistance of the finally obtained flame retardant resin composition tends to deteriorate, and if it exceeds 3 parts by weight, the heat resistance tends to decrease.

The silicone oil (H) used in the present invention improves the flame retardancy of the resin composition, and includes, for example, polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrodienesiloxane and the like. Further, the carbon number of the alkyl group is usually 1
A modified silicone oil obtained by subjecting the alkyl group of the polydialkylsiloxane of 18 to 18 to an epoxy modification, an alkyl modification, an amino modification, a carboxyl modification, and an alcohol modification can also be used. The viscosity of the silicone oil (H) used is usually 1 to 25 at a temperature of 25 ° C.
10,000 cSt, preferably 5 to 5000 cS
t, more preferably 10 to 2000 cSt. If the viscosity is less than 1 cSt, the effect of improving the intended flame retardancy is poor, while if it exceeds 10,000 cSt, the compatibility with the resin is reduced. The silicone oil (H) is used in an amount of 0.001 to 0.5 part by weight, preferably 0.005 to 0.2 part by weight, based on 100 parts by weight of the resin component. If the silicone oil (H) is less than 0.001 part by weight, the flame retardant resin composition finally obtained tends to drip and the flame retardancy deteriorates. On the other hand, if it exceeds 0.5 parts by weight, the impact resistance of the flame-retardant resin composition may decrease, or the silicone oil (H) may bleed out on the surface of the molded product.

The flame-retardant resin composition of the present invention comprises a graft copolymer (A) and / or a graft copolymer (B),
Brominated flame retardant (D), antimony compound (E), and, if necessary, thermoplastic resin (C), chlorinated polyethylene (F), polytetrafluoroethylene (G), benzotriazole compound (H), Silicone oil (I)
Can be produced by melt-kneading using an extruder or a kneader such as a Banbury mixer, a pressure kneader, or a roll. The obtained flame-retardant resin composition is as it is, or, if necessary, after blending a dye, a pigment, a stabilizer, a reinforcing agent, a filler, another flame retardant, a foaming agent, a lubricant, a plasticizer, etc. It can be used as a raw material for producing molded articles. The flame-retardant resin composition is formed into a target molded product by various molding methods such as an injection molding method, an extrusion molding method, a blow molding method, a compression molding method, a calendar molding method, and an inflation molding method. Examples of industrial applications of such a flame-retardant resin composition include vehicle parts, in particular, various exterior / interior parts used without painting, wall materials, building material parts such as window frames, tableware,
Home appliance parts such as toys, vacuum cleaner housings, television housings, air conditioner housings, interior members, ship members, communication device housings, and the like.

[0047]

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. The percentages and parts in the following examples are based on weight unless otherwise specified. (Reference Example 1) Production of diene rubber latex (G-1) The following components were charged into a 10 L stainless steel autoclave, and the temperature was raised to 50 ° C. Deionized water 145 parts Disproportionated potassium rosinate 1.0 part Potassium oleate 1.0 part Sodium formaldehyde sulfoxylate dihydrate 0.4 part Anhydrous sodium sulfate 0.1 part Tertiary decyl mercaptan 0.3 part 0.5 parts of diisopropylbenzene hydroperoxide 26.2 parts of 1,3-butadiene 1.4 parts of styrene Subsequently, 0.5 parts of sodium pyrophosphate, 0.005 parts of ferrous sulfate, and ion-exchanged water Was added to start a polymerization. At a polymerization temperature of 57 ° C., 1,
A mixture consisting of 68.6 parts of 3-butadiene and 3.6 parts of styrene was dropped and supplied by a pressure pump. Then, when the polymerization conversion reached 40%, 0.3 parts of normal dodecyl mercaptan was added, and the polymerization was further continued.
After 8 hours, the remaining 1,3-butadiene was removed to obtain a diene rubber latex (G-1) having a solid content of 40.2%, a polymerization conversion of 97%, and a weight average particle diameter of 70 nm.

Reference Example 2 Synthesis of Acid-Containing Copolymer Latex (K-1) for Enlargement In a reactor equipped with a cooling pipe, a jacket heater and a stirrer, the following components were added under a nitrogen stream. The internal temperature was raised to 65 ° C. while charging and stirring. Potassium oleate 2.2 parts Sodium dioctyl sulfosuccinate (70% solution) 3.6 parts Sodium formaldehyde sulfoxylate dihydrate 0.3 parts Ferrous sulfate heptahydrate 0.003 parts Disodium ethylenediaminetetraacetate 0.009 parts Ion-exchanged water 200 parts To this, a mixture consisting of 81.5 parts of n-butyl acrylate, 18.5 parts of methacrylic acid, and 0.5 part of cumene hydroperoxide was added over 2 hours. After the addition was completed, the polymerization was continued at the same temperature for 2 hours. The polymerization conversion was 98%, and an acid group-containing copolymer latex (K-1) for enlargement having an average particle diameter of 150 nm was obtained.

Reference Example 3 Graft Copolymer (A-1)
Production of diene rubber latex (G-1) prepared in Reference Example 1
To 100 parts (as solid content), 2.1 parts (as solid content) of the acid group-containing copolymer latex (K-1) for enlargement prepared in Reference Example 2 were added with stirring, and further stirred for 30 minutes. To obtain an enlarged diene rubber latex. The weight average particle diameter of the diene rubber after the enlargement is 380.
nm. Next, in a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 10 parts of an enlarged diene rubber latex (as a solid content) 10 parts dipotassium alkenyl succinate 0.3 parts ion-exchanged water 175 parts butyl Acrylate 40 parts Allyl methacrylate 0.16 part 1,3-butylene glycol dimethacrylate 0.08 part Tertiary butyl hydroperoxide 0.1 part was charged. The atmosphere in the reactor was replaced with nitrogen, and the temperature of the jacket heater was raised to 60 ° C. When the internal liquid temperature reached 50 ° C., an aqueous solution dissolved in ferrous sulfate heptahydrate 0.00015 part disodium ethylenediaminetetraacetate 0.00045 part Rongalite 0.24 part ion-exchanged water 5 parts After the addition, the internal temperature was raised to 75 ° C. to start radical polymerization. This state was maintained for one hour to complete the polymerization of the acrylate component to obtain a latex of a composite rubbery polymer of a diene rubber and a butyl acrylate rubber which was enlarged. The composite rubbery polymer latex sampled in a small amount had a weight average particle diameter of 300 nm, and the weight of particles having a particle diameter of less than 100 nm was 8%. Next, an aqueous solution comprising 0.15 parts of Rongalite, 0.65 parts of dipotassium alkenyl succinate, 10 parts of ion-exchanged water, and then 6.3 parts of acrylonitrile 18.7 parts of styrene 0.11 part of tertiary butyl hydroperoxide Was added dropwise over 1 hour to carry out polymerization. Five minutes after the completion of the dropping, an aqueous solution consisting of ferrous sulfate heptahydrate 0.001 part ethylenediaminetetraacetic acid disodium salt 0.003 part Rongalit 0.15 part ion-exchanged water 5 parts was added, and then acrylonitrile 6.3. 1 part of styrene 18.7 parts of tertiary butyl hydroperoxide 0.19 parts of a mixture consisting of 0.014 parts of normal octyl mercaptan was dropped and polymerized over 1 hour. After completion of the dropwise addition, the temperature was maintained at 75 ° C. for 10 minutes and then cooled. When the internal temperature reached 60 ° C., 0.2 parts of an antioxidant (Antage W500 manufactured by Yoshitomi Pharmaceutical Co., Ltd.) 0.2 parts alkenyl succinic acid An aqueous solution consisting of 0.2 parts of dipotassium and 5 parts of ion-exchanged water was added. By the above operation, a latex of a graft copolymer (A-1) in which acrylonitrile and styrene were graft-polymerized to a composite rubber polymer of an enlarged diene rubber and butyl acrylate rubber was obtained. The weight average particle size of the polymer in the obtained latex was 325 nm. Next, the graft copolymer (A-1) latex was added to a 0.6% aqueous sulfuric acid solution heated to 45 ° C., 1.2 times the total latex, while stirring, to coagulate the polymer. Next, the liquid temperature was raised to 65 ° C. and maintained for 5 minutes, and then the liquid temperature was further raised to 90 ° C. and maintained for 5 minutes. Next, after the precipitate was separated, the recovered substance was poured into 10 times the volume of distilled water and stirred for 10 minutes to wash. This dispersion was dehydrated with a centrifugal dehydrator and further dried at 80 ° C. for 16 hours to obtain a graft copolymer (A-1). The residual emulsifier residue in the graft copolymer (A-1) was 1.3%, and the acetone-insoluble content was 82%.
%, The reduced viscosity of the acetone-soluble component is 0.65 dl / g,
The temperature at which the weight of the graft polymer was reduced by 1% was 320 ° C.

Reference Example 4 Production of Polyorganosiloxane (L-1) Latex 98 parts of octamethylcyclotetrasiloxane 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. To this was added an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of ion-exchanged water, and 10,000
After stirring at 2 revolutions per minute for 2 minutes, the homogenizer was used for 200 minutes.
One pass at a pressure of kg / cm ² gave a stable premixed organosiloxane latex. Meanwhile, a reagent injection container,
10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were charged into a reactor equipped with a cooling pipe, a jacket heater and a stirrer to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after completion of the addition, the temperature was maintained for 1 hour, and the mixture was cooled. The reaction was then neutralized with aqueous sodium hydroxide.
The polyorganosiloxane thus obtained (L-
1) The latex was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. The weight average particle diameter of the polyorganosiloxane (L-1) in the latex was 50 nm.

Reference Example 5 Graft copolymer (B-
Production of 1) 45.2 parts of polyorganosiloxane latex (L-1) produced in Reference Example 4 in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, and a stirrer Emal NC-35 ( Polyoxyethylene alkyl phenyl ether sulfate (manufactured by Kao Corporation) 0.2 part Ion-exchange water 148.5 parts After adding and mixing, n-butyl acrylate 42 parts allyl methacrylate 0.3 part 1,3-butylene glycol di A mixture consisting of 0.1 part of methacrylate and 0.11 part of t-butyl hydroperoxide 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 temperature of the solution reached 60 ° C., an aqueous solution consisting of 0.00075 parts of ferrous sulfate heptahydrate, 0.000225 parts of ethylenediaminetetraacetic acid disodium salt, 0.20022 parts of Rongalite, and 10 parts of ion-exchanged water was added. , Radical polymerization was started.
The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component, thereby obtaining a latex of a composite rubbery polymer of polyorganosiloxane (L-1) and butyl acrylate rubber. After the temperature of the liquid inside the reactor had dropped to 70 ° C., an aqueous solution consisting of 0.25 parts of Rongalite and 10 parts of ion-exchanged water was added, and then 2.5 parts of acrylonitrile and 7.5 parts of styrene and 7.5 parts of t-butyl hydroperoxide. 05 parts of the mixture was added dropwise over 2 hours to carry out polymerization. After completion of the dropping, the temperature of 60 ° C. was maintained for 1 hour, and then ferrous sulfate heptahydrate 0.001 part ethylenediaminetetraacetic acid disodium salt 0.003 part Rongalit 0.2 part Emar NC-35 (Kao Corporation )) An aqueous solution consisting of 0.2 parts of ion-exchanged water 10 parts was added, and then a mixture consisting of acrylonitrile 10 parts styrene 30 parts t-butyl hydroperoxide 0.2 parts was dropped and polymerized over 2 hours. After completion of the dropwise addition, the temperature of 60 ° C. was maintained for 0.5 hour, then 0.05 parts of cumene hydroperoxide was added, and the temperature of 60 ° C. was further maintained for 0.5 hour, followed by cooling. To this latex, 0.5 part of latemul ASK (dipotassium alkenyl succinate; manufactured by Kao Corporation) was added, and acrylonitrile and acrylonitrile were added to a composite rubber polymer composed of polyorganosiloxane (L-1) and butyl acrylate rubber. A polymerization latex of a graft copolymer (B-1) obtained by graft-polymerizing styrene was obtained. The weight average particle size of the graft copolymer (B-1) in the latex is
It was 120 nm. Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 1% was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer (B-1) was gradually dropped into the mixture, and solidified. Next, the precipitate was separated, washed, and then centrifuged (H-1 manufactured by Domestic Centrifuge Co., Ltd.).
Using 30E), dehydration treatment was performed at 1800 rpm for 2 minutes. Next, it was dried at 85 ° C. for 24 hours to obtain a graft copolymer (B-1). The acetone insoluble content in the graft copolymer (B-1) was 85%, and the reduced viscosity of the acetone-soluble component was 0.58 dl / g.

Reference Example 6 Graft Copolymer (X-1)
In a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirring device, dipotassium alkenylsuccinate 0.1 part ion-exchanged water 175 parts n-butyl acrylate 50 parts allyl methacrylate 0.20 parts 1,3 -Butylene glycol dimethacrylate 0.1 part Tertiary butyl hydroperoxide 0.1 part was charged. 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 reached 50 ° C., an aqueous solution consisting of ferrous sulfate heptahydrate 0.00015 part disodium ethylenediaminetetraacetate 0.00045 part Rongalit 0.24 part ion-exchanged water 5 parts was added. After raising the internal temperature to 75 ° C,
Radical polymerization was started. Keep this state for one hour,
The polymerization of the acrylate component was completed to obtain a latex of butyl acrylate rubber. The weight average particle diameter of the composite rubber polymer measured by sampling a small amount of this acrylate rubber polymer latex was 270 nm, and the weight of particles less than 100 nm based on the total weight was 3%. Less than,
Graft polymerization was carried out in the same manner as described in (Reference Example 3) except that the total amount of dipotassium alkenylsuccinate was adjusted, and a graft copolymer (X) obtained by graft-polymerizing acrylonitrile and styrene onto butyl acrylate rubber was used. -1) latex was obtained. The weight average particle diameter of the graft copolymer (X-1) in the obtained latex is 2
It was 95 nm. Further, in the same manner as described in (Reference Example 3), the graft copolymer (X-
The collection treatment of 1) was performed to obtain graft copolymer (X-1) particles. The amount of the residual emulsifier residue in the graft copolymer (X-1) was 1.6%, the amount of the acetone-insoluble component was 78%, the reduced viscosity of the acetone-soluble component was 0.61 dl / g, and the weight of the graft copolymer was 1 The% decrease temperature was 330 ° C.

(Reference Example 7) Graft copolymer (X-2)
Preparation of the diene polymer latex (G-
1) In 100 parts (as solid content), add the acid group-containing copolymer (K-1) latex 1.2 for enlargement prepared in Reference Example 2.
Parts (as solids) are added with stirring and an additional 30 parts
Stirring was continued for minutes to obtain an enlarged diene rubber latex. The weight average particle diameter of the polymer after enlargement is 310 nm
Met. Next, in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, 60 parts of enlarged diene rubber latex (as solid content) 60 parts sodium hydroxide 0.10 part Dextrose 0.45 parts A mixture consisting of 135 parts of exchanged water (including water in the enlarged diene rubber latex) was heated to 50 ° C. Thereafter, an aqueous solution consisting of 0.01 parts of ferrous sulfate heptahydrate, 0.02 parts of anhydrous sodium pyrophosphate, 5 parts of ion-exchanged water, 12 parts of acrylonitrile, 28 parts of styrene, 0.7 part of t-dodecyl mercaptan, 0.7 part of cumene A mixture consisting of 0.2 parts of hydroperoxide was added dropwise over 180 minutes, during which the internal temperature was adjusted to 50 to 65 ° C. Immediately after the completion of the dropwise addition, 0.1 part of cumene hydroperoxide was added, and the mixture was kept at an internal temperature of 65 ° C. for 1 hour, and then cooled. The weight average particle size of the polymer in the obtained latex was 330 nm. An antioxidant (Antage W-400 manufactured by Yoshitomi Pharmaceutical Co., Ltd.) 0.2 part 25% potassium rosinate aqueous solution 0.8 part Ion-exchanged water 2.0 part was added to the obtained diene rubber-based graft polymer latex. Is added to a 1% aqueous sulfuric acid solution heated to 60 ° C., which is 1.6 times the amount of the graft polymer latex, and further kept at 90 ° C. for 5 minutes, washed and dried to obtain a diene rubber. -Based graft copolymer (X
-2) was obtained. The residual emulsifier residue amount in the graft copolymer (X-2) was 1.1%, the acetone-insoluble content was 83%,
The reduced viscosity of the acetone-soluble component is 0.35 dl / g, and the temperature at which the weight of the graft copolymer (X-2) decreases by 1% is 3
It was 10 ° C.

Various physical properties in the reference examples were measured by the following methods. (1) Weight average particle diameter of (co) polymer in latex Measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCES. (2) The particle diameter in the composite rubbery polymer is 100 n
m weight ratio of particles less than m
It was measured using a submicron particle size distribution analyzer CHDF-2000 manufactured by MATEC APPLIED SCIENCES.
The particle size weight of nm or less was determined. (3) Acetone insoluble content in graft copolymer About 2.5 g (weighed) of the graft copolymer and 80 ml of acetone were placed in a flask equipped with a cooling tube and a heater, and heated at 65 ° C. for 3 hours using a heater. An extraction process was performed. After cooling, the inner solution was treated with a centrifuge of Hitachi Koki Co., Ltd. at 15,000 rpm for 30 minutes to separate acetone-insoluble components, and then the precipitate after removing the supernatant was dried. The weight was measured and calculated by the following equation (1). Acetone insoluble matter (% by weight) = dry weight of precipitate after separation / weight of graft copolymer before acetone extraction × 100 (1) (4) Reduced viscosity of acetone-soluble component in graft copolymer In the above (3), the acetone solvent was evaporated under reduced pressure from the supernatant obtained by separating the acetone-insoluble component by centrifugation to precipitate and recover the acetone-soluble component. Next, the solution viscosity of a solution obtained by dissolving 0.2 g of this acetone-soluble component in 100 cc of N, N-dimethylformamide is
It was measured at 25 ° C. using an automatic viscometer (manufactured by Sun Electronics Co., Ltd.). Then, the reduced viscosity of the acetone-soluble component was determined from the solvent viscosity measured under the same conditions. (5) Amount of emulsifier residue in graft copolymer The emulsifier residue contained in the graft copolymer was methyl-esterified with methanol and hydrochloric acid in an acetone solvent, and then filtered. Then, the residue obtained by removing the solvent in the filtrate under reduced pressure is dissolved in n-hexane, washed with water, and then subjected to gas chromatography (Shimadzu Corporation).
GC-14B). (6) Measurement of Temperature at which Weight of Graft Copolymer Decreases by 1% The temperature was measured at a temperature rising condition of 20 ° C./min using “TG / DTA200” manufactured by Seiko Instruments Inc.

(Examples 1-4 and Comparative Examples 1-2) Graft copolymer (A-1) produced in Reference Example 3, Reference Example 5
The graft copolymer (B-1) produced in the above, the graft copolymers (X-1) produced in Reference Examples 6 and 7 and (X-1)
-2) an acrylonitrile-styrene copolymer (SAN resin) comprising 29% of an acrylonitrile component and 71% of a styrene component and having a reduced viscosity of 0.60 dl / g measured at 25 ° C. from an N, N-dimethylformamide solution; One-terminal modified tetrabromobisphenol A ("SR-T104" manufactured by Sakamoto Yakuhin Co., Ltd.) as a brominated flame retardant
N "), antimony trioxide, chlorinated polyethylene (" Daisorac E-230 "manufactured by Daiso Corporation), polytetrafluoroethylene (D201, Daikin Industries, Ltd.)
L), "Adecastab LA-36" manufactured by Asahi Denka Kogyo Co., Ltd. as a benzotriazole-based compound was weighed with the resin formulation shown in Table 1, and calcium stearate and ethylenebisstearylamide were added to 100 parts of the resin component. After adding 1.0 part and 0.2 part, respectively, they were mixed using a Henschel mixer, and the mixture was heated to 200 ° C. in a degassing extruder (PCM-30 manufactured by Ikeigai Iron Works Co., Ltd.).
And kneaded to obtain pellets. Table 1 shows the results of Izod impact strength, melt flow rate (MI), Rockwell hardness, molded gloss, flame retardancy, and chemical resistance measured using the obtained pellets. In addition, white colored pellets were prepared in the same manner as described above except that 3 parts of titanium oxide (CR60-2: manufactured by Ishihara Sangyo Co., Ltd.) was added in place of the carbon black to be used in the above-mentioned resin composition. Was used to form a white-colored molded plate. Table 1 shows the light resistance test results using the white colored plate.

(1) Measurement of Izod impact strength Measured by a method according to ASTM D256 at 23 ° C.
The measurement was performed after leaving the Izod test piece under the atmosphere for 12 hours or more. (2) Measurement of melt flow rate (MI) According to a method in accordance with ASTM D1238, barrel temperature 2
The test was performed under the conditions of 00 ° C. and a load of 49N. (3) Measurement of Surface Hardness (Rockwell Hardness) Measurement was performed by a method based on ASTM D785. (4) Molding gloss 100 mm x 100 mm x 3 mm plate was molded using an injection molding machine J85-ELII manufactured by Nippon Steel Works Co., Ltd. under the conditions of cylinder set temperature 200 ° C, mold temperature 60 ° C, and injection speed 50%. The measurement was performed using the obtained molded plate. (5) Flame retardancy A test specimen having a thickness of 1/16 inch was set at a cylinder set temperature of 200 using an injection molding machine SAV-60 manufactured by Yamashiro Seiki Co., Ltd.
C., and a mold temperature of 60.degree. C., and the specimen was continuously in contact with a flame until a drip occurred according to a vertical test method of UL-94 standard to measure a drip start time, and the UL-94 was measured. Grade was determined. (6) Chemical resistance A 2 mm-thick press-formed plate of the resin composition is formed in advance, and a 35 mm × 120 mm specimen is cut out from the plate to obtain a long diameter of 12 mm.
It is attached to a 1/4 elliptical jig having a diameter of 0 mm and a minor diameter of 40 mm.
After the chemical was applied to the surface of the specimen, it was covered with a polyethylene film and exposed to the chemical at 25 ° C. for 4 hours. Thereafter, the surface condition of the specimen was observed, and the maximum stress-strain value at which cracks did not occur was used as an index of chemical resistance. The following were used as chemicals. Isopropyl alcohol Dioctyl phthalate (DOP) Myopet (registered trademark) manufactured by Kao Corporation (7) Light resistance A white colored plate of 100 mm x 100 mm x 3 mm was subjected to black panel temperature 63 ° C with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). , Cycle conditions 60 minutes (rainfall: 12
Min), and evaluated by the degree of discoloration (ΔE) measured by the color difference meter after the treatment for 500 hours in the above-mentioned manner and the gloss retention rate calculated by the following equation (2). Gloss retention (%) = gloss after exposure for 500 hours / gloss before exposure × 100 (2)

[0057]

[Table 1]

The following has been made clear from the examples and comparative examples. 1) The resin compositions containing the graft copolymer (A-1) and / or the graft copolymer (B-1) of Examples 1 to 4 all have high Izod impact strength, good molded appearance and flame retardancy. , Light and chemical resistance. 2) The resin composition of Comparative Example 1 containing only the acrylic rubber-based graft copolymer (X-1) to which no specific composite rubbery polymer is applied has excellent flame retardancy and molded appearance,
Although it exhibited light resistance and chemical resistance, it was inferior in impact resistance. Therefore, the industrial value of this resin composition is low. 3) The resin composition of Comparative Example 2 containing only the diene rubber-based graft copolymer (X-2) to which no specific composite rubbery polymer was applied was excellent in impact resistance and molded appearance,
Despite showing flame retardancy, it was inferior in light resistance and chemical resistance.
Therefore, the utility value of this resin composition is low.

[0059]

As described above, the flame-retardant resin composition of the present invention comprises two types of graft copolymers (A) and (B).
A brominated flame retardant (D)
And the antimony compound (E), it is excellent not only in flame retardancy but also in impact strength, light resistance and chemical resistance. Therefore, the flame retardant resin composition of the present invention has an extremely large utility value in industry.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/16 C08L 101/00 (72) Inventor Hisaya Yokohama 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayo F-term (reference) at Ohtake Works 4J002 BB244 BC06Y BD154 BG03Y BG05Y BG07Y BG09Y BN20X BN21W BN22W CF05Y CG01Y CP035 CP095 DE097 EB046 EB136 EU178 FD048 FD135 GQ00 4J026 AC15 BA04 BA03 BA06 DA06 DB13 DB16 FA02 GA09

Claims (11)

[Claims] 1. The following component (A) and / or (B)
With respect to 100 parts by weight of the resin component containing the
A flame-retardant resin composition comprising 5 to 40 parts by weight of component and 1 to 20 parts by weight of component (E). (A) An alkyl (meth) acrylate monomer component (a) containing a graft crosslinking agent and a crosslinking agent in the presence of 1 to 30% by weight of a diene rubber (a-1) having a weight average particle diameter of 300 nm or more. -2) Composite rubbery polymer ((a-1) + (a-2)) 2 obtained by emulsion polymerization of 99 to 70% by weight
0 to 80% by weight, 80 to 20% by weight of at least one monomer (a-3) selected from an aromatic alkenyl compound, a methacrylate, an acrylate and a vinyl cyanide compound
Is a graft copolymer obtained by emulsion graft polymerization. (B) 0.01 to 10% by weight of a polyfunctional monomer in the presence of 1 to 20% by weight of a polyorganosiloxane (b-1)
Radical polymerization of 99 to 80% by weight of a monomer mixture (b-2) consisting of 60 to 99.9% by weight of an alkyl (meth) acrylate and 0 to 30% by weight of a vinyl monomer copolymerizable therewith; The composite rubbery polymer ((b-
1) + (b-2)) 20 to 80% by weight of at least one monomer (b-3) selected from an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester and a vinyl cyanide compound; weight%
Is a graft copolymer obtained by emulsion graft polymerization. (D) Brominated flame retardant (E) Antimony compound 2. The flame-retardant resin composition according to claim 1, wherein the resin component further contains a thermoplastic resin (C). 3. The resin composition according to claim 2, wherein the resin component comprises 30 to 95% by weight of the component (A) and / or (B) and 70 to 5% by weight of the component (C). Flame retardant resin composition. 4. The diene-based rubber (a-1) is one which has been enlarged by an enlarger comprising an acid group-containing copolymer latex. Flame-retardant resin composition. 5. The flame-retardant resin composition according to claim 1, wherein the graft copolymer (B) has a weight average particle diameter of 70 to 200 nm. 6. The thermoplastic resin (C) is a (co) polymer containing at least one monomer selected from an aromatic alkenyl compound, a vinyl cyanide compound and a (meth) acrylate. 3. The method according to claim 2, wherein
6. The flame-retardant resin composition according to any one of claims 1 to 5. 7. The method according to claim 1, wherein 0.1 to 10 parts by weight of chlorinated polyethylene (F) is further added to 100 parts by weight of the resin component. Flammable resin composition. 8. The method according to claim 1, wherein 0.001 to 0.5 parts by weight of polytetrafluoroethylene (G) is further added to 100 parts by weight of the resin component. The flame-retardant resin composition according to the above. 9. The flame-retardant resin composition according to claim 8, wherein the molecular weight of the polytetrafluoroethylene (G) is 1,000,000 or more. 10. The method according to claim 1, wherein 0.1 to 3.0 parts by weight of the benzotriazole compound (H) is further added to 100 parts by weight of the resin component. The flame-retardant resin composition according to the above. 11. The method according to claim 1, wherein 0.001 to 0.5 parts by weight of silicone oil (I) is further added to 100 parts by weight of the resin component. Flame retardant resin composition.