JP2003261875A - Fire retardant, fire retardant composition using the same and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fire retardant excellent in fire-resistant effect, a fire retardant composition using the same and having high fire retardancy and a molded article. <P>SOLUTION: The fire retardant is a phosphorus type fire retardant (A) containing a homopolymer of a phosphorus-containing monomer and/or a copolymer of the phosphorus-containing monomer and other monomer copolymerizable therewith. The other monomer copolymerizable with the phosphorus-containing monomer is preferably at least one monomer selected from a (meth)acrylate monomer, an aromatic alkenyl compound and a vinyl cyanide monomer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant capable of imparting excellent flame retardancy. More specifically, a flame retardant comprising a polymer using a phosphorus-containing vinyl-based monomer having a specific structure and capable of exhibiting excellent flame retardancy even if added in a small amount is blended with the flame retardant. The present invention relates to a flame-retardant resin composition.

[0002]

2. Description of the Related Art In recent years, home electric appliances (household appliances), O
Various synthetic resins are used as members and parts in a wide range of fields including equipment A, building materials and vehicles. Regarding synthetic resins used in these fields, from the viewpoint of preventing the occurrence of fire, etc., and preventing the spread of fire due to the spread of fire,
Normally, a certain level of flame retardancy is required. In addition to the enforcement of the PL Law (Product Liability Law), a high level of flame retardancy of synthetic resins is being demanded year by year in order to prevent the spread of fire due to the spread of fire. Many flame retardants have been developed and studied to meet these demands. Usually, those used as flame retardants for synthetic resins mainly include halogen compounds, phosphorus compounds, etc., and in many cases, in addition to those flame retardants, antimony trioxide, tin oxide, etc. Used as a drug.

When a halogen compound is added to a synthetic resin as a flame retardant, the effect of flame retardancy is great, but there is a problem that a toxic or harmful gas is generated at the time of fire or incineration. Further, antimony trioxide used as a flame retardant aid has problems such as being harmful.

[0004]

Therefore, it is desired to develop a flame-retardant resin containing no halogen compound or containing a relatively small amount of halogen compound. Also,
The flame retardancy of the synthetic resin by the phosphorus compound is lower than that of the halogen compound, so that sufficient flame retardancy cannot be obtained. Therefore, when the flame retardancy of a synthetic resin is measured by the use of a phosphorus compound, it is necessary to increase the addition amount thereof, and thus the heat resistance and mechanical properties of the obtained flame retardant resin are deteriorated. Have a point.

The present invention solves the problems of the above-mentioned respective prior arts, and an object thereof is to provide a flame retardant and a flame retardant resin composition having an excellent flame retarding effect. is there.

[0006]

The gist of the present invention is to provide a homopolymer of a phosphorus-containing vinyl monomer and / or a phosphorus-containing vinyl monomer and another monomer copolymerizable therewith. The phosphorus-based flame retardant (A) contains a copolymer. Further, the gist of the present invention resides in a flame-retardant resin composition obtained by adding the above-mentioned phosphorus-based flame retardant (A) to a thermoplastic resin (B).
Further, the gist of the present invention resides in a molded article obtained by injection molding, extrusion molding or extrusion blow molding of the flame-retardant resin composition described above.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphorus-containing vinyl-based monomer used in the phosphorus-based flame retardant (A) of the present invention (hereinafter simply referred to as the flame-retardant) is not particularly limited, and examples thereof include 2-acryloyloxyethyl. Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, p-styryldiphenylphosphine, diethyl allyl phosphonate and the like can be used.

Although the monomer copolymerizable with the phosphorus-containing vinyl monomer used in the flame retardant (A) is not particularly limited, it may be a (meth) acrylic acid ester monomer or an aromatic monomer. One or more kinds of monomers selected from alkenyl compounds and vinyl cyanide-based monomers are preferably used.
In addition, the "(meth) acryl" in the present invention means acryl and / or methacryl.

As the acrylic acid ester-based monomer, the substituent of the acrylic acid ester may be linear, branched, or cyclic. Specific examples of those having a linear substituent include methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, lauryl acrylate, tridecyl acrylate, and the like. Examples of compounds having a branched substituent include i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and the like. Examples of compounds having a cyclic substituent include cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, and the like.

As the methacrylic acid ester type monomer,
The substituent of the methacrylic acid ester may be linear, branched, or cyclic. Specific examples of those having a linear substituent include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, lauryl methacrylate, tridecyl methacrylate and the like. Examples of compounds having a branched substituent include i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like. Examples of compounds having a cyclic substituent include cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate and the like.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene,
Examples include α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, and 2,4-dimethylstyrene.

Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

In the flame retardant (A), these (meth)
The acrylic ester type monomer, the aromatic alkenyl compound and the vinyl cyanide type monomer may be used alone or in combination of two or more kinds.

The ratio of the phosphorus-containing vinyl-based monomer to these monomers in the flame retardant (A) is 100% by weight of the flame retardant.
Medium, phosphorus-containing vinyl monomer is 100% by mass to 0.01
%, And the above-mentioned monomers are 0 to 99.99% by weight.
When the content of the phosphorus-containing vinyl-based monomer is 0.01% by mass or less, the flame retardancy of the resin composition cannot be improved by adding a small amount.

Further, another type of monomer copolymerizable with the phosphorus-containing vinyl monomer may be used. Examples of such a monomer include vinyl esters such as vinyl acetate; dicarboxylic acid anhydrides such as maleic anhydride; and polyfunctional monomers such as divinylbenzene and allyl methacrylate. These monomers may be used alone or in combination of two or more depending on the purpose. However, as long as they do not impair the flame retardancy of the resin due to the addition of a small amount, which is a function of the flame retardant (A), they are phosphorus-containing vinyl-based single monomers. In a total of 100 parts by weight of the monomer and the copolymerizable vinyl-based monomer, the amount is preferably 10 parts or less, more preferably 10 parts by weight or less.

The polymerization method for obtaining the flame retardant (A) of the present invention is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method.

As the polymerization initiator, for example, t-butyl hydroperoxide, cumene hydroperoxide, organic peroxides such as benzoyl peroxide and lauroyl peroxide, azo compounds or the like may be used alone, or polymerization of dimethylaniline or the like may be used. It can be used in combination with a starting aid, but these specific examples are not limited.

The weight average molecular weight of the flame retardant (A) (M
w) and molecular weight distribution (Mw / Mn) are the amount of polymerization initiator, n
It can be adjusted by a chain transfer agent such as octyl mercaptan or t-dodecyl mercaptan, polymerization conditions and the like. These specific examples are not limited as long as the flame retardancy of the resin by the addition of a small amount, which is the function of the flame retardant (A), is not impaired.

The amount of the flame retardant (A) added to 100 parts by mass of the thermoplastic resin (B) is preferably 0.1 to 10 parts by mass.
If it is 0.1 part by mass or more, the flame retardancy of the thermoplastic resin can be improved by adding a small amount, and if it is 10 parts by mass or less, the heat resistance and mechanical properties of the molded product obtained from the flame retardant resin composition. Is not damaged.

The thermoplastic resin (B) capable of improving the flame retardancy by adding the flame retardant (A) is not particularly limited, but is preferably a polycarbonate resin, a polyphenylene ether resin, or a polystyrene resin. If it is one or more thermoplastic resins selected from the group consisting of
The effect is remarkable.

The polycarbonate resin used in the present invention is obtained from dihydroxydiarylalkane and may be optionally branched. These polycarbonate resins are produced by a known method, and are generally produced by reacting a dihydroxy or polyhydroxy compound with phosgene or a diester of carbonic acid.

The dihydroxydiarylalkane is an alkyl group, a chlorine atom, or
Also includes those having a bromine atom. Preferred specific examples of the dihydroxydiarylalkane include 4,4-dihydroxy-2,2-diphenylpropane (bisphenol A), tetramethylbisphenol A and bis- (4-
Hydroxyphenyl) -p-diisopropylbenzene and the like. The branched polycarbonate can be produced, for example, by substituting a part of the dihydroxy compound, for example, about 0.2 to 2 mol% with the polyhydroxy compound. Specific examples of the polyhydroxy compound include:
1,4-bis ^(4, 4,2-dihydroxy-triphenylmethyl) - benzene, phloroglucinol, 4,6
Dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptene, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane, 1,3,5-
Tri (4-hydroxyphenyl) -benzene, 1,1,
1-tri (4-hydroxyphenyl) -ethane, 2,2
-Bis [4,4 ^, -(4,4 ^, -dihydroxyphenyl)
And cyclohexyl] propane.

These polycarbonate resins may be used alone or in admixture of two or more.

The molecular weight and the molecular weight distribution of the polycarbonate resin are not particularly limited and may be appropriately selected depending on the application.

The polyphenylene ether resin used in the present invention is a homopolymer of 1,4-phenylene ether which may have a substituent consisting of 1 to 4 hydrocarbons per repeating unit, or two kinds thereof. The above 1,4-phenylene ether copolymer is shown, and specific examples of such a polyphenylene ether resin include poly (2,6-
Dimethyl-1,4-phenylene) ether, poly (2,
6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2- Methyl-6-propyl-1,
4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, (2,6-dimethyl-1,4-phenylene) ether and (2,3,6)
-Trimethyl-1,4-phenylene) ether copolymer, (2,6-diethyl-1,4-phenylene) ether and (2,3,6-trimethyl-1,4-phenylene) ether Polymer, (2,6-dimethyl-1,
Examples thereof include copolymers of 4-phenylene) ether and (2,3,6-triethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether and , (2,6-dimethyl-1,4
-Phenylene) ether and (2,3,6-triethyl-
Of these, a copolymer with 1,4-phenylene) ether is preferable, and poly (2,6-dimethyl-1,4-phenylene) ether is most preferable.

These polyphenylene ether resins may be used alone or in admixture of two or more.

The molecular weight and the molecular weight distribution of the polyphenylene ether resin are not particularly limited and may be appropriately selected depending on the application.

In the polystyrene resin used in the present invention, the benzene nucleus may be substituted with 1 to 3 halogen atoms or an alkyl group having 1 to 4 carbon atoms, and the α-position has 1 to 4 carbon atoms. Homopolymers or copolymers of (substituted) styrene units that may have an alkyl group, or copolymerization with other copolymerizable vinyl monomers whose styrene units account for 50% by mass or more. It is united. Polystyrene as a specific example of such a polystyrene resin,
Polychlorostyrene, polybromstyrene, poly (α-
Methyl styrene), styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile- Examples thereof include o-methylstyrene copolymer and high-impact polystyrene.

The graft copolymer (C) used in the present invention is a composite rubber composed of a composite rubber component composed of an organosiloxane polymer and a (meth) acrylic acid alkyl ester polymer. The main component is a copolymer obtained by graft-polymerizing the vinyl monomer.

The organosiloxane polymer used in the composite rubber-based graft copolymer (C) of the present invention is not particularly limited, but an organosiloxane polymer containing a vinyl polymerizable functional group is preferable. is there.
Examples of the dimethylsiloxane used for producing the organosiloxane-based polymer include a dimethylsiloxane-based cyclic compound having a 3-membered ring or more, and a 3- to 7-membered ring is preferable. Specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc. These may be used alone or in combination of two or more.

The vinyl-polymerizable functional group-containing siloxane has a vinyl-polymerizable functional group and can be bonded to dimethyl siloxane through a siloxane bond. Considering the reactivity with dimethyl siloxane, vinyl polymerization is possible. 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 -Mercaptosiloxanes 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 kinds. As the siloxane-based crosslinking agent, a trifunctional or tetrafunctional silane-based crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, or tetrabutoxysilane is used.

As a method for producing the above-mentioned organosiloxane polymer, a latex obtained by emulsifying a mixture of dimethylsiloxane and a vinyl-polymerizable functional group-containing siloxane or, if necessary, a mixture containing a siloxane-based crosslinking agent with an emulsifier and water is used. , After homogenizing using a homomixer that atomizes by shearing force due to high-speed rotation, or a homogenizer that atomizes by jetting output from a high pressure generator,
Polymerization is carried out at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance. As the method of adding the acid catalyst used for the polymerization, there are a method of mixing with a siloxane mixture, an emulsifier and water, a method of dropping a latex in which the siloxane mixture is made into fine particles into a hot acid aqueous solution at a constant rate, and the like. Considering the ease of controlling the particle size of the base polymer, a method of dropping the latex in which the siloxane mixture is made into fine particles into a high temperature aqueous acid solution at a constant rate is preferable.

The emulsifier used in the production of the organosiloxane polymer is preferably an anionic emulsifier, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, etc. used. Particularly, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

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

Examples of the acid catalyst used for the polymerization of the organosiloxane polymer include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. Can be mentioned. These acid catalysts may be used alone or in combination of two or more. Of these, aliphatic-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable, because it is also excellent in stabilizing the organosiloxane polymer latex.
Further, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the poor appearance of the resin composition due to the emulsifier component of the organosiloxane polymer latex can be reduced.

The polymerization temperature of the organosiloxane polymer is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. In addition, the polymerization time of the organosiloxane polymer is
When the acid catalyst is mixed with the siloxane mixture, the emulsifier and water, and finely divided to polymerize, the polymerization is carried out for 2 hours or longer, more preferably 5 hours or longer. Then, it is preferable to hold the latex for about 1 hour after completion of the dropping.

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

The (meth) acrylic acid alkyl ester polymer constituting the graft copolymer (C) is (meth)
It is a polymerized product of an acrylic acid alkyl ester-based monomer and a polyfunctional (meth) acrylic acid alkyl ester-based monomer. The amount of the (meth) acrylic acid alkyl ester-based polymer in the composite rubber-based graft copolymer is not particularly limited.

The composite rubber according to the present invention is composed of an organosiloxane polymer latex and a (meth) acrylic acid alkyl ester-based monomer and a polyfunctional (meth) acrylic acid alkyl ester-based monomer (meth) acrylic. It can be produced by polymerizing after impregnating the acid alkyl ester-based monomer mixed component.

Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate,
Examples include n-propyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like.

Examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate and n-methacrylate. Examples include lauryl and the like.

These may be used alone or in combination of two or more. Considering the impact resistance and molding gloss of the resin composition containing the graft copolymer, it is particularly preferable to use n-butyl acrylate.

Examples of polyfunctional (meth) acrylic acid alkyl ester-based monomers include allyl methacrylate,
Ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butyleneglycol dimethacrylate
And triallyl cyanurate, triallyl isocyanurate and the like.

These may be used alone or in combination of two or more. Considering the graft structure (amount of acetone insoluble matter, solution viscosity of acetone-soluble component) of the graft copolymer, preferred polyfunctional (meth) acrylic acid alkyl ester-based monomers are allyl methacrylate, dimethacrylic acid 1, In this method, 3-butylene glycol is used in combination.

The composite rubber composed of the organosiloxane polymer and the (meth) acrylic acid alkyl ester polymer used in the present invention is prepared by adding the above (meth) acrylic acid alkyl ester monomer to the latex of the organosiloxane polymer. It can be prepared by adding a body component and polymerizing it by allowing an ordinary radical polymerization initiator to act.

As the method of adding the (meth) acrylic acid alkyl ester monomer component, a method of mixing with the latex of the organosiloxane polymer at once and a method of dropping it into the latex of the organosiloxane polymer at a constant rate are added. There is. Considering the impact resistance of the resulting resin composition containing the graft copolymer, a method of mixing with the latex of the organosiloxane polymer at once is preferable.

Further, as the radical polymerization initiator used for the polymerization, a peroxide, an azo type initiator or a redox type initiator in which an oxidizing agent and a reducing agent are combined is used. Among these, a redox initiator is preferable, and a sulfoxylate initiator obtained by combining ferrous sulfate / ethylenediaminetetraacetic acid with a sodium salt / Rongalite / hydroperoxide is particularly preferable.

The average particle size of the composite rubber is not particularly limited, but it is preferably in the range of 0.01 to 0.6 μm. If the average particle size is less than 0.01 μm, the impact resistance of the molded product obtained from the flame-retardant resin composition deteriorates, and if the average particle size exceeds 0.6 μm, the flame-retardant resin composition obtained The impact resistance of the resulting molded article is lowered and the appearance of the molded surface is deteriorated.

By radical-polymerizing one or more vinyl monomers in the presence of the above composite rubber,
A composite rubber-based graft copolymer is obtained. The vinyl-based monomer is not particularly limited, but is, for example, styrene or α-
Aromatic alkenyl such as methylstyrene and vinyltoluene, methacrylic acid alkyl ester such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate, acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate and butyl acrylate, acrylonitrile And vinyl cyanide compounds such as methacrylonitrile. It is preferable to use one kind of methyl methacrylate or to use styrene and acrylonitrile together.

Graft polymerization can be carried out in a single stage or in multiple stages by radical polymerization by adding a vinyl monomer to the latex of the composite rubber. Further, as the radical polymerization initiator used for the polymerization, a peroxide, an azo initiator,
Alternatively, a redox initiator in which an oxidizing agent and a reducing agent are combined is used. Among these, a redox type initiator is preferable, and a sulfoxylate type initiator obtained by combining ferrous sulfate / ethylenediaminetetraacetic acid with a sodium salt / Rongalite / hydroperoxide is particularly preferable.

Further, various chain transfer agents for adjusting the molecular weight and graft ratio of the graft chains can be added to the monomers used in the graft polymerization.

In the graft polymerization, an emulsifier can be added to stabilize the latex of the polymer and to control the average particle size of the graft copolymer. The emulsifier used is not particularly limited,
Preferred examples are cationic emulsifiers, anionic emulsifiers and nonionic emulsifiers, and more preferred examples are a method of using a sulfonate emulsifier or a combination of a sulfate emulsifier and a carboxylate emulsifier.

The particle diameter of the graft copolymer (C) prepared as described above is not particularly limited, but the impact resistance of the flame-retardant resin composition containing the obtained graft copolymer is not limited. Considering both properties and flame retardancy, the average particle size of the composite rubber is preferably in the range of 0.01 to 2 μm. If the average particle size is less than 0.01 μm, the impact resistance of the molded product obtained from the flame-retardant resin composition deteriorates, and if the average particle size exceeds 2 μm, the molded product obtained from the flame-retardant resin composition. Impact resistance is deteriorated and the appearance of the molded surface is deteriorated.

The content of the graft copolymer (C) explained above is 100 parts by mass of the thermoplastic resin (B).
1 to 15 parts by mass is preferable. If it is 1 part by mass or more, the flame retardancy of the flame-retardant resin composition, especially the dripping prevention property, can be improved,
If it is 15 parts by mass or less, the heat resistance and mechanical properties of the molded product obtained from the flame-retardant resin composition will not be impaired.

The tetrafluoroethylene polymer (D) used in the present invention is obtained by polymerizing a monomer containing tetrafluoroethylene as a main component. You may copolymerize with another monomer in the range which does not impair the desired characteristic of a tetrafluoroethylene-type polymer. Examples of the copolymerization component include fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether;
Fluorine-containing (meth) acrylic acid alkyl ester such as (meth) acrylic acid perfluoroalkyl ester; and the like. The amount of the copolymerization component is 10% by weight based on 100% by weight of the total amount of the tetrafluoroethylene and the copolymerization component.
The following is preferable.

The tetrafluoroethylene polymer (D) used in the present invention is preferably one having a fine fibril forming ability.

The tetrafluoroethylene polymer (D) comprises polytetrafluoroethylene (d-1),
(Meth) acrylic acid alkyl ester-based polymer (d) containing 70% by weight or more of a structural unit consisting of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms
It is further preferable that it is a modifier for a thermoplastic resin containing polytetrafluoroethylene consisting of -2).

The (meth) acrylic acid alkyl ester-based polymer (d-2) is a polymer containing 70% by mass or more of structural units consisting of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. 1 to 4 carbon atoms
The (meth) acrylic acid alkyl ester having an alkyl group can be polymerized by radical polymerization, ionic polymerization, or the like. In the present invention, since a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is used, various thermoplastic resins or thermoplastic elastomers are used as compared with conventional polytetrafluoroethylene-containing modifiers. The dispersibility of polytetrafluoroethylene in the inside becomes good. Further, the (meth) acrylic acid alkyl ester-based polymer has no fear of generating a toxic gas at the time of combustion, as compared with a conventional acrylonitrile-styrene-based polymer,
Moreover, the amount of monomers remaining at the end of the polymerization is much less, and the load on the environment is low.

Specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms include:
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like can be mentioned. The alkyl group may be linear or branched. These can be used alone or in combination of two or more. In particular, a polymer containing 50% by mass or more of a structural unit composed of methyl methacrylate is preferable in that a powder having good handleability can be obtained.

When the (meth) acrylic acid alkyl ester-based polymer (d-2) is prepared, another monomer which can be copolymerized with the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is used. The body can be used within a range of 30% by mass or less. Other monomers include vinyl ether type monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate type monomers such as vinyl acetate and vinyl butyrate; olefin type monomers such as ethylene, propylene and isobutylene. A diene monomer such as butadiene, isoprene or dimethylbutadiene;

The weight average molecular weight (Mw) of the alkyl acrylate polymer (d-2) is 20,000.
To 5,000,000 are preferable, and 20,000 to 4,000
More preferably, it is 0000. This Mw is a value measured by gel permeation chromatography.

The polytetrafluoroethylene-containing thermoplastic resin modifier contains the above-mentioned polytetrafluoroethylene (d-1) and a (meth) acrylic acid alkyl ester polymer (d-2) as main components. It consists of About the ratio of both, the total of both is 100% by mass
Based on, polytetrafluoroethylene (d-1)
Is preferably 0.01 to 55 mass%.

The modifier for thermoplastic resin containing polytetrafluoroethylene has, for example, an average particle diameter of 0.05 to 1.0 μm.
In a dispersion liquid in which polytetrafluoroethylene (d-1) particles of m are dispersed, a monomer containing 70% by mass or more of (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is polymerized. After forming the (meth) acrylic acid alkyl ester-based polymer (d-2),
It is obtained by a method of solidifying or spray-drying the solid content in the dispersion [first production method].

Further, for example, the average particle size is 0.05 to 1.0 μm.
A dispersion liquid in which m polytetrafluoroethylene (d-1) particles are dispersed and 70% by mass or more of a structural unit composed of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms (meth) It is obtained by a method [second production method] in which the solid content in the mixed dispersion is coagulated or spray-dried after mixing with the dispersion in which the acrylic acid alkyl ester-based polymer (d-2) particles are dispersed.

The solid contents in the dispersion liquids in the first and second production methods are solidified by, for example, throwing them into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved for salting out. be able to. Also, spray drying is
For example, it can be carried out by directly spraying the aqueous dispersion.

Further, polytetrafluoroethylene (d-
1) In a dispersion liquid in which particles are dispersed, a (meth) acrylic acid alkyl ester is obtained by polymerizing a monomer containing 70% by mass or more of a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. Polymer (d-2)
When the solid content in the dispersion is solidified or spray-dried to obtain the modifier of the present invention after forming
After obtaining a dispersion liquid of (meth) acrylic acid alkyl ester-based polymer (d-2) particles by polymerizing a monomer containing 70% by mass or more of (meth) acrylic acid alkyl ester having an alkyl group of 4 to 4 When the solid content in the dispersion liquid obtained by mixing the dispersion liquid in which the polytetrafluoroethylene (d-1) particles are dispersed is coagulated or spray-dried to obtain the modifier of the present invention, (meth) The average particle diameter of the acrylic acid alkyl ester-based polymer (d-2) particles is 0.05 to 0.15 μm (more preferably 0.05 to 0.15 μm).
It is preferable to carry out the polymerization so that the thickness becomes 1 μm). Moreover, Mw of the (meth) acrylic acid alkyl ester-based polymer (d-2) is 20,000 to 5,000,000.
It is preferable to carry out the polymerization so that it falls within the range of (more preferably 20,000 to 4,000,000).

The weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester polymer (d-2) is
It can be adjusted by the amount of a polymerization initiator, a chain transfer agent such as n-octyl mercaptan or t-dodecyl mercaptan, and polymerization conditions. These specific examples are not limited as long as the function of the modifier for a thermoplastic resin containing polytetrafluoroethylene of the present invention is not impaired.

The dispersion liquid of polytetrafluoroethylene (d-1) particles can be obtained, for example, by emulsion polymerization of a monomer containing tetrafluoroethylene as a main component. Further, as commercially available products (trade name) of the polytetrafluoroethylene (d-1) particle aqueous dispersion, Fluon AD-1 and AD-936 manufactured by Asahi Fluoropolymers; Polyflon D-1 and D manufactured by Daikin Industries, Ltd. -2; Mitsui DuPont Fluorochemicals tetrafluoroethylene 30J and the like.

7 units of a structural unit composed of an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is used.
The dispersion liquid of (meth) acrylic acid alkyl ester-based polymer (d-2) particles containing 0% by mass or more is a single amount containing 70% by mass or more of (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. The body is obtained by emulsion polymerization, miniemulsion polymerization, or the like. The emulsifier that can be used for these polymerizations is not particularly limited, and various conventionally known emulsifiers can be used. For example, anionic surfactants such as fatty acid salts, alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl phosphate ester salts, dialkyl sulfosuccinates; polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, glycerin Nonionic surfactants such as fatty acid esters; cationic surfactants such as alkylamine salts can be used. These emulsifiers can be used alone or in combination.

Depending on the type of emulsifier used, the p
When H is on the alkaline side, an appropriate pH is added to prevent hydrolysis of the (meth) acrylic acid alkyl ester.
Modifiers can be used. Examples of the pH adjuster include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, and the like.
Examples thereof include potassium dihydrogen phosphate-boric acid and disodium hydrogen phosphate-citric acid.

The polymerization initiator used for the polymerization of the (meth) acrylic acid alkyl ester includes, for example, a water-soluble initiator or an oil-soluble initiator alone or a redox type. Specific examples of water-soluble initiators include inorganic initiators such as persulfates. Specific examples of the oil-soluble initiator include organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide and lauroyl peroxide; and azo compounds. Specific examples of the redox-based initiator include a combination of the above-mentioned inorganic initiator with sulfite, bisulfite, thiosulfate, etc., and the above-mentioned organic peroxide or azo compound combined with thorium formaldehyde sulfoxylate, etc. There are things like However, it is not limited to these specific examples.

The content of the modifier for the polytetrafluoroethylene-containing thermoplastic resin is such that the polytetrafluoroethylene (d-1) is added to 100 parts by mass of the thermoplastic resin (B).
Content of 0.001 to 20 parts by mass is preferable. If the polytetrafluoroethylene-containing thermoplastic resin modifier (D) of the present invention is used in an amount within this range, the polytetrafluoroethylene component is uniformly dispersed in the thermoplastic resin (B), and the mechanical properties and Flame resistance, especially dripping prevention property, is improved.

The thermoplastic resin composition of the present invention contains a plasticizer, depending on its purpose, as long as its characteristics are not impaired.
Stabilizers, fillers, impact modifiers, lubricants, processing aids, foaming agents, pigments, antifogging agents, antibacterial agents, antistatic agents, conductivity imparting agents, surfactants, crystal nucleating agents, heat resistance improvers. Various additives such as the above can be added.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, and 2
-Ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl Phthalates such as decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl phthalate; tricresyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, 2-ethylhexyl Diphenyl phosphate, cresyl diphenyl phosphate, etc. Phosphoric acid ester plasticizer; di -2
-Adipic ester plasticizer such as ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl-normal nonyl adipate, diisooctyl adipate, diisonormal octyl adipate, dinoroctyl adipate, didecyl adipate; dibutyl Sebacate ester plasticizers such as sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, butylbenzyl sebacate; azelaine such as di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate Acid ester plasticizers; triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl citrate tributyl, acetyl citrate tri-2-ethylhexyl Citric acid ester plasticizers; glycolic acid ester plasticizers such as methylphthalylethyl glycolate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate; tributyl trimellitate, tri-normalhexyl trimellitate, Tri-2-ethylhexyl trimellitate, tri-
Trimellitic acid ester plasticizers such as normal octyl trimellitate, tri-isooctyl trimellitate and tri-isodecyl trimellitate; phthalic acid isomerizations such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate Ester plasticizers; ricinoleic acid ester plasticizers such as methyl acetyl ricinoleate and butyl acetyl ricinoleate; polyester plasticizers such as polypropylene adipate, polypropylene sebacate and modified polyesters thereof; epoxidized soybean oil, epoxy butyl stear Rate, epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, 2-
Examples thereof include epoxy-based plasticizers such as ethylhexyl epoxy torrate. These may be used alone or in combination of two or more as required.

Examples of the stabilizer include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate; potassium, magnesium, barium, zinc, cadmium, lead. Metal such as 2 ethylhexanoic acid,
Metal soap 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,
Organotin-based stabilizers derived from ester groups and fatty acid salts, maleates, and sulfides; Ba-Zn-based, Ca-Zn-based stabilizers
System, Ba-Ca system, Ca-Mg-Sn system, Ca-Zn-
Complex metal soap stabilizers such as Sn-based, Pb-Sn-based, Pb-Ba-Ca-based; metals such as barium and zinc; branched fatty acids such as 2-ethylhexanoic acid, isodecanoic acid and trialkylacetic acid; oleic acid; Metals derived from usually two or more organic acids such as ricinoleic acid, unsaturated fatty acids such as linoleic acid, alicyclic acids such as naphthenic acid, carboxylic acids, benzoic acid, salicylic acid and aromatic acids such as substituted derivatives thereof. Salt stabilizers: these stabilizers are dissolved in an organic solvent such as petroleum hydrocarbons, alcohols, glycerin derivatives and the like, and further phosphites, epoxy compounds, color-developing inhibitors, transparency improvers, light stabilizers, Metallic stabilizers such as metal salt liquid stabilizers containing antioxidants and stabilizing aids such as lubricants; epoxy resin, epoxidized soybean oil, epoxidized vegetable oil, epoxidized fatty acid Epoxy compounds such as glycol ester,
Phosphorus is substituted with an alkyl group, an aryl group, a cycloalkyl group, an alkoxyl group, etc., and an organic phosphite ester having a dihydric alcohol such as propylene glycol, hydroquinone, an aromatic compound such as bisphenol A, BHT, sulfur or methylene Hindered phenol such as bisphenol dimerized with a group, an ultraviolet absorber such as salicylate, benzophenone, benzotriazole, a light stabilizer of a hindered amine or nickel complex salt, carbon black, an ultraviolet shielding agent such as rutile titanium oxide, Polyhydric alcohols such as trimerolpropane, pentaerythritol, sorbitol and mannitol, nitrogen-containing compounds such as β-aminocrotonic acid esters, 2-phenylindole, diphenylthiourea and dicyandiamide Sulfur-containing compounds such as key thio dipropionate ester, acetoacetic ester, dehydroacetic acid, keto compounds such as β Jiketon, organosilicon compound,
Examples include non-metallic stabilizers such as borate esters. These can be used alone or in combination of two or more.

Examples of the filler include carbonates such as ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, talc, wollastonite and zeolite. , Silica, zinc oxide, magnesium oxide, carbon black, graphite, glass beads,
In addition to inorganic materials such as glass fibers, carbon fibers, and metal fibers, organic fibers such as polyamide, organic materials such as silicone, and natural organic materials such as wood flour can be mentioned. These can be used alone or in combination of two or more.

Examples of impact modifiers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene. -Styrene-based graft copolymer, acrylonitrile-styrene-butadiene-based copolymer rubber, acrylonitrile-styrene-butadiene-based graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber , Styrene-ethylene-butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPD
M), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silicone rubber, and the like. As the diene of the ethylene-propylene-diene copolymer rubber (EPDM), 1,4-hexanediene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene and the like are used. These impact modifiers can be used alone or in combination of two or more.

As the lubricant, for example, liquid paraffin,
Natural paraffin, micro wax, synthetic paraffin,
Pure hydrocarbons such as low molecular weight polyethylene; halogenated hydrocarbons; fatty acids such as higher fatty acids and oxyfatty acids; fatty acid amides such as fatty acid amides and bis fatty acid amides; fatty acids such as lower alcohol esters of fatty acids and glycerides Esters such as polyhydric alcohol ester, polyglycol ester of fatty acid, fatty alcohol ester of fatty acid (ester wax); metal soap, fatty alcohol,
Polyhydric alcohol, polyglycol, polyglycerol,
Examples thereof include partial esters of fatty acids and polyhydric alcohols, partial esters of fatty acids and polyglycols, and partial esters of polyglycerols.

Examples of the processing aid include (meth) acrylic acid ester-based copolymers, (meth) acrylic acid ester-styrene copolymers, (meth) acrylic acid ester-
Styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene- (meth) acrylate copolymer, acrylonitrile-styrene-α-styrene copolymer, acrylonitrile-styrene-maleimide copolymer Examples include coalescence.

The flame retardant (A), the graft copolymer (C) and the tetrafluoroethylene polymer (D) of the present invention may be blended with the thermoplastic resin (B) by, for example, extrusion kneading, roll kneading, etc. It can be performed by melt-kneading by a conventionally known method. Further, the flame retardant (A), the graft copolymer (C) and the tetrafluoroethylene polymer (D) of the present invention and a part of the thermoplastic resin (B) are mixed to prepare a masterbatch. It is also possible to perform multi-stage mixing such as further adding and mixing the rest of the thermoplastic resin (B).

The molding process of the flame retardant resin composition containing the flame retardant of the present invention includes, for example, calender molding, thermoforming, extrusion blow molding, foam molding, extrusion molding, injection molding,
Examples include melt spinning. Of these, extrusion blow molding, extrusion molding, and injection molding are preferable.

Examples of useful molded articles obtained by using the flame-retardant resin composition to which the modifier of the present invention is added include, for example, extrusion molded sheets, films and profile molded articles; extrusion blow molding and injection molding. Examples include hollow molded bodies and injection molded bodies. Specific examples thereof include bumpers of automobiles, spoilers and side moldings, and housings of office automation equipment.

[0084]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In each description, "part" means mass part and "%" means mass%. Also,
Various physical properties were measured by the following methods.

(1) Particle size measurement: A dispersion of modifier particles was diluted with distilled water and used as a sample for measurement using a CHDF2000 type particle size distribution meter manufactured by MATEC, USA. The measurement conditions were standard conditions recommended by MATEC.
That is, using a dedicated particle separation capillary type cartridge and carrier liquid, the liquidity is almost neutral and the flow rate is 1.
4 ml / min, pressure about 4000 psi and temperature 35
With the temperature kept at 0 ° C, 0.1 ml of a diluted latex sample having a concentration of about 3% was used for the measurement. As a standard particle size substance,
A total of 12 points of monodisperse polystyrene with a known particle size manufactured by DUKE, USA were used within the range of 0.02 μm to 0.8 μm.

(2) Flammability test: In accordance with UL94 standard
A vertical combustion test was carried out. A test piece having a thickness of 1.3 mm was used.

<Production Example 1: Flame Retardant (A-1)> Phosphorus-containing vinyl monomer (diphenyl-2-methacryloyloxyethyl phosphate, MR-260 manufactured by Daihachi Chemical Co., Ltd.) 10
0 part was placed in a reaction vessel equipped with a stirring blade and a nitrogen inlet, and stirred under a nitrogen stream for 30 minutes to perform nitrogen substitution in the reaction vessel and the phosphorus-containing vinyl-based monomer. Then
Benzoyl peroxide and dimethylaniline were added, and the mixture was stirred for 5 minutes, then the stirring was removed and the polymerization was started at room temperature. After 4 hours from the initiation of polymerization, polymerization was carried out at 100 ° C. for 3 hours to obtain a phosphorus-containing vinyl polymer (A-1).

<Production Example 2: Flame retardant (A-2)> Phosphorus-containing vinyl monomer (diphenyl-2-methacryloyloxyethyl phosphate, MR-260 manufactured by Daihachi Chemical Co., Ltd.) 75
And 25 parts of methyl methacrylate were placed in a reaction vessel equipped with a stirring blade and a nitrogen inlet, and stirred under a nitrogen stream for 30 minutes to perform nitrogen substitution of the reaction vessel and the phosphorus-containing vinyl monomer. Next, benzoyl peroxide and dimethylaniline were added, and the mixture was stirred for 5 minutes and then the stirring was removed to start the polymerization at room temperature. After 4 hours from the initiation of polymerization, polymerization was carried out at 100 ° C. for 3 hours to obtain a phosphorus-containing vinyl polymer (A-2).

<Production Example 3: Graft copolymer (C-1)
> (1) Organosiloxane polymer latex (L-
Production 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-mentioned mixed siloxane was added to 200 parts of distilled water in which 1 part of each of sodium dodecylbenzene sulfonate and dodecylbenzene sulfonic acid was dissolved, and 10,000 was added by a homomixer.
After pre-stirring at rpm, 300 with homogenizer
It was emulsified and dispersed at a pressure of kg / cm @ 2 to obtain a latex of an organosiloxane monomer. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, and then at 20 ° C.
After 48 hours, the pH of this latex was neutralized to 7.4 with an aqueous sodium hydroxide solution, and the polymerization was completed to obtain an organosiloxane polymer latex. The polymerization rate of the obtained organosiloxane-based polymer was 89.5%, and the average particle size of the organosiloxane-based polymer was 0.1.
It was 6 μm.

(2) Composite rubber-based graft copolymer (C-
1) Production of the above-mentioned organosiloxane polymer latex (L-
276 parts of 1) and 99 parts of water were placed in a separable flask equipped with a stirrer, and after nitrogen replacement, the temperature was raised to 50 ° C.,
A mixed solution of 8.8 parts of n-butyl acrylate, 0.2 parts of allyl methacrylate and 0.1 part of tert-butyl hydroperoxide was charged and stirred for 30 minutes, and this mixed solution was permeated into the organosiloxane polymer particles. Let Then, ferrous sulfate 0.002 parts, ethylenediaminetetraacetic acid disodium salt 0.006 parts, Rongalit 0.26
A mixed solution of 1 part and 5 parts of distilled water was charged to start radical polymerization, and then the internal temperature was maintained at 70 ° C. for 2 hours to complete the polymerization, to obtain a composite rubber latex. A part of this latex was sampled and the average particle size of the composite rubber was measured to be 0.18.
was 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 and found to be 97.3% by weight. To this composite rubber latex, a mixed solution of 0.06 parts of tert-butyl hydroperoxide and 11 parts of methyl methacrylate was added.
The mixture was added dropwise at 0 ° C. for 30 minutes and then kept at 70 ° C. for 4 hours to complete the graft polymerization on the composite rubber. The obtained graft copolymer latex was dropped into a heated aqueous solution of calcium acetate, coagulated, separated and washed, and then 75
After drying at 16 ° C. for 16 hours, a powdery composite rubber-based graft copolymer was obtained.

<Production Example 4: Polytetrafluoroethylene-containing thermoplastic resin modifier (D-1)> Polytetrafluoroethylene particle dispersion (Fluon AD936 manufactured by Asahi Fluoropolymers, solid content concentration 63.0%, 83.3 parts containing 5% of polyoxyethylene alkylphenyl ether with respect to polytetrafluoroethylene, distilled water 1
16.7 parts was added to obtain a polytetrafluoroethylene particle dispersion liquid (d-1) having a solid content of 26.2%. This dispersion liquid (d-1) contains 25% polytetrafluoroethylene particles and 1.2% polyoxyethylene alkylphenyl ether.

80 parts of this dispersion liquid (d-1) (20 parts of polytetrafluoroethylene), 165 parts of distilled water, and 1.5 parts of dipotassium alkenylsuccinate are provided with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet. The atmosphere in the reaction vessel was replaced with nitrogen by charging the reaction vessel with a nitrogen gas stream. Then, when the temperature of the inside of the system was raised to 55 ° C. and the temperature of the inside liquid became 55 ° C., a mixed liquid consisting of 0.1 part of potassium persulfate and 5 parts of distilled water was added, and further, methyl methacrylate 64 Parts, 9 parts of n-butyl methacrylate 16 parts
Polymerization was carried out by dropwise addition over 0 minutes. After completion of dropping, the polymerization was completed by holding for about 45 minutes. Solid particles were not separated through a series of operations, and a uniform particle dispersion was obtained.

On the other hand, 150 parts of an aqueous solution having a calcium acetate content of 7% was heated to 70 ° C. and stirred. 100 parts of the previously prepared particle dispersion was gradually dropped into this aqueous solution to precipitate a solid. Next, this precipitate was separated, filtered, and dried to obtain a polytetrafluoroethylene-containing thermoplastic resin modifier (D-1).

The average particle diameter of the (meth) acrylic acid alkyl ester polymer in this particle dispersion is 0.0
It was 8 μm. Further, the weight average molecular weight (Mw) of the (meth) acrylic acid alkyl ester-based polymer measured by gel permeation chromatography is 2,
It was 600,000.

<Production Example 5: modifier for polytetrafluoroethylene-containing thermoplastic resin (D-2)> In the same manner as in Production Example 1, a polytetrafluoroethylene particle dispersion liquid (d-) having a solid content of 26.2%. 1) was obtained. This dispersion liquid (d-1) 2
00 parts (polytetrafluoroethylene 50 parts), distilled water 35 parts, methyl methacrylate 40 parts, n-butyl acrylate 10 parts, t-butyl hydroperoxide 0.2.
Parts and 0.5 part of n-octyl mercaptan as a chain transfer agent are charged into a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and the atmosphere in the reaction vessel is replaced with nitrogen by passing a nitrogen stream. I went. Then, when the temperature of the system was raised to 60 ° C. and the internal liquid temperature reached 60 ° C., 0.0005 part of iron (II) sulfate, 0.0015 part of disodium ethylenediaminetetraacetate, and Rongalite salt of 0.3 Part and 5 parts of distilled water were added to initiate a radical polymerization. This state was maintained for 90 minutes to complete the polymerization. Solid particles were not separated through a series of operations, and a uniform particle dispersion was obtained. Thereafter, precipitation, separation, filtration and drying were carried out in the same manner as in Production Example 1 to give a polytetrafluoroethylene-containing thermoplastic resin modifier (D-
2) was obtained.

The average particle diameter of the (meth) acrylic acid alkyl ester polymer in this particle dispersion is 0.1.
It was 0 μm. The Mw of the (meth) acrylic acid alkyl ester polymer was 47,000.

<Production Example 6: Polytetrafluoroethylene-containing thermoplastic resin modifier (D-3)> In the same manner as in Production Example 1, a polytetrafluoroethylene particle dispersion liquid (d-) having a solid content of 26.2% was used. 1) was obtained.

On the other hand, in a reaction vessel equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, 225 parts of distilled water, 80 parts of methyl methacrylate, 20 parts of n-butyl acrylate, and 0.8 parts of sodium dodecylbenzene sulfonate. The atmosphere in the reaction vessel was replaced with nitrogen by charging a part of the reactor and passing a nitrogen stream. After that, when the temperature of the inside of the system was raised to 60 ° C. and the internal liquid temperature reached 60 ° C., iron (II) sulfate was adjusted to 0
0005 parts, disodium ethylenediaminetetraacetic acid
A mixture of 0015 parts, 0.3 parts of Rongalite salt and 5 parts of distilled water was added to initiate polymerization. The liquid temperature rose to 95 ° C. by the start of the polymerization. After that, the liquid temperature is 8
When the temperature had dropped to 0 ° C., this state was maintained for 90 minutes to complete the polymerization, to obtain an aqueous dispersion of (meth) acrylic acid ester-based polymer particles (d-2). The solid content concentration of this aqueous particle dispersion (d-2) was 30.4%. The average particle size of the (meth) acrylic acid alkyl ester-based polymer in the particle dispersion liquid (d-2) is 0.08.
was μm. The (meth) acrylic acid alkyl ester-based polymer Mw was 50,000.

200 parts of the polytetrafluoroethylene particle dispersion (d-1) prepared above (50 parts of polytetrafluoroethylene) and an aqueous dispersion of (meth) acrylate polymer particles (d-2) 164. 5 copies ((meta)
Acrylic ester-based polymer (50 parts), a stirring blade,
It was added to a reaction vessel equipped with a condenser, a thermocouple, and a nitrogen inlet, and the liquid temperature inside was heated to 80 ° C. and stirred.
Stirring was continued for 1 hour in a state where the internal liquid temperature was 80 ° C. to obtain a mixed liquid of both dispersions. Thereafter, precipitation, separation, filtration and drying were carried out in the same manner as in Production Example 1 to obtain a polytetrafluoroethylene-containing thermoplastic resin modifier (D-3).

Examples 1 to 11 and Comparative Examples 1 and 2 In the Examples and Comparative Examples, the following were used.

(A) Flame Retardant Polymers (A-1) to (A-2) produced in Production Examples 1 and 2
It was used. In addition, triphenyl phosphate (TPP manufactured by Daihachi Chemical Co., Ltd.) was used as (A-3).

(B) Thermoplastic resin B-1: Polycarbonate (PC) resin: Iupilon S- manufactured by Mitsubishi Engineering Plastics Co., Ltd.
2000F, B-2: Polyphenylene ether (PPE) -based resin: The polyphenylene ether-based resin used is poly (2,6-
It was dimethyl-1,4-phenylene) ether, and the reduced viscosity was 0.59 when measured with a Ubbelohde viscometer using a 0.1% chloroform solution at 25 ° C. B-3: Polystyrene (PSt) resin: G440K manufactured by Nippon Polystyrene Co., Ltd.

(C) Graft Copolymer The graft copolymer (C-1) produced in Production Example 3 was used.

(D) Tetrafluoroethylene-based polymer Polytetrafluoroethylene-containing thermoplastic resin modifier D-1 to D-3 or D-4 prepared in Production Examples 4 to 6
(Asahi Glass Co., Ltd .: Fluon CD-1) was used.

The respective components shown in Table 1 were mixed in respective proportions (mass ratios), and the results were shaped using a co-directional twin-screw extruder (PCM-30 manufactured by Ikegai Seisakusho Co., Ltd.) set to a cylinder temperature of 280 ° C. Then, pellets were prepared. Then, using this pellet, an injection molding machine (S by Yamashiro Seisakusho Co., Ltd.) was set for the flammability test at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C.
Injection molding was performed with AV-60) to obtain a test piece.

Table 1 shows the results of a vertical burning test according to the UL-94 standard for the obtained test pieces.

[0107]

[Table 1]

[0108]

As described above, according to the present invention, a flame-retardant resin composition having excellent flame retardancy can be obtained. In addition, since it is possible to provide a thermoplastic resin molded product having excellent flame retardancy, its utility value in the field of housing materials for office automation equipment, home electric appliances and the like is enormous.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 27/18 C08L 27/18 43/02 43/02 51/00 51/00 69/00 69/00 71 / 12 71/12 101/00 101/00 (72) Inventor Koichi Ito 3816 Noborito, Tama-ku, Kawasaki-shi, Kanagawa Mitsubishi Rayon Co., Ltd. Tokyo Technical and Information Center F-term (reference) 4F071 AA22 AA27 AA33 AA34 AA39 AA50 AA51 AA67 AA77 AE07 AF47 AH07 AH10 AH16 BA01 BB05 BB06 BC07 4H028 AA46 AA48 BA06 4J002 AA011 BC031 BC041 BC061 BC071 BC091 BC111 BD154 BG045 BG055 BG065 BN123 BN141 BN173 BQ002 CG011 CG031 CH061 CH071 CN00 FD010 FD020 FD030 FD132 FD170 GQ00 4J100 AB02Q AB03Q AB07P AB07Q AB16Q AG04Q AK32Q AL03Q AL04Q AL05Q AL08P AL08Q AL11Q AL75Q AM02Q AP07P BA04P BA05Q BA62P BA64P BA65P BC43P BC43Q CA01 CA04 JA28 JA57

Claims (8)

[Claims] 1. A phosphorus flame retardant containing a homopolymer of a phosphorus-containing vinyl monomer and / or a copolymer of a phosphorus-containing vinyl monomer and another monomer copolymerizable therewith. (A). 2. The other monomer copolymerizable with the phosphorus-containing vinyl monomer is a (meth) acrylic acid ester monomer,
The phosphorus-based flame retardant (A) according to claim 1, which is one or more kinds of monomers selected from aromatic alkenyl compounds and vinyl cyanide-based monomers. 3. The thermoplastic resin (B) according to claim 1 or 2.
A flame-retardant resin composition comprising the phosphorus-based flame retardant (A) described. 4. The flame-retardant resin composition according to claim 3, wherein the thermoplastic resin (B) is at least one resin selected from a polycarbonate resin, a polyphenylene ether resin, and a polystyrene resin. object. 5. A graft copolymer comprising the flame-retardant resin composition according to claim 3 or 4 and further containing a composite rubber component comprising an organosiloxane polymer and a (meth) acrylic acid alkyl ester polymer. A flame-retardant resin composition to which C) is added. 6. A flame-retardant resin composition obtained by further adding the tetrafluoroethylene polymer (D) to the flame-retardant resin composition according to claim 3. 7. A tetrafluoroethylene polymer (D)
Is a (meth) acrylic acid alkyl ester-based polymer (70% by weight or more of a constitutional unit consisting of polytetrafluoroethylene (d-1) and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms ( d-2)
A flame-retardant resin composition comprising a modifier for a thermoplastic resin containing polytetrafluoroethylene. 8. A molded article obtained by injection molding, extrusion molding or extrusion blow molding of the flame-retardant resin composition according to any one of claims 3 to 7.