JP6668589B2 - Flame-retardant resin composition, flame-retardant masterbatch, molded article and method for producing them - Google Patents

Description

  The present invention relates to a flame-retardant resin composition, and more particularly to a flame-retardant resin composition excellent in flame retardancy and moldability without impairing the mechanical properties inherent in a rubber-reinforced styrene resin-containing polycarbonate resin, and a molded article thereof.

  Polymer blend of a polycarbonate resin and a rubber-reinforced styrene resin such as an ABS resin (acrylonitrile / butadiene / styrene copolymer) (hereinafter sometimes referred to as a “resin composition containing a rubber-reinforced styrene resin and a polycarbonate resin”) Has excellent fluidity, and since the molded body using the polymer blend has not only performance such as high impact strength, but also beautiful appearance, there are many products in fields such as electric / electronics and ITE. In particular, it is widely used for the housing of large products such as copiers and printers.

  However, since the polymer blend is derived from ABS resin (acrylonitrile / butadiene / styrene copolymer) and has very high flammability, the strict flame-retardant performance required for insulating materials in the OA field and the electric and electronic fields is required. In order to satisfy this, proposals have been made to increase the flame retardancy using a flame retardant. Furthermore, since the problem of halogen-based flame retardants generating dioxins during combustion has been highlighted, there has been a demand in the market for dehalogenation of flame retardants used. Therefore, as non-halogen flame retardants, flame retardants exhibiting excellent flame retardancy, such as condensed phosphate esters, aluminum phosphinates, and melamine polyphosphate, are commercially available. It has been proposed (for example, see Patent Document 1).

  However, since these non-halogen flame retardants have a low effect of imparting flame retardancy, a large amount of flame retardant is required to obtain the excellent flame retardancy required for insulating materials in the OA field and the electric and electronic fields. It is necessary to add a fuel, and as a result, the thermal stability is inferior, and the appearance defect due to silvery appearance may occur on the product surface, and its improvement has been desired.

JP-A-8-92264

  Therefore, the problem to be solved by the present invention is to use a non-halogen flame retardant, a rubber blend styrene-based resin blended with a polycarbonate resin blended excellent inherent properties, that is, the fluidity of the resin composition, Rubber-reinforced styrene-based resin and polycarbonate resin with excellent flame retardancy while maintaining extrusion stability, molding processability during molding, and mechanical properties such as appearance and impact strength of the obtained molded product An object of the present invention is to provide a resin composition and a molded product thereof.

  As a result of various studies, the inventors of the present application have obtained a phosphorus-containing phenol-based oligomer obtained by reacting HCA or a derivative thereof with an o-hydroxybenzaldehyde compound in a rubber-reinforced styrene-based resin and a polycarbonate resin. The present inventors have found that a resin composition and a molded product thereof have excellent flame retardancy while maintaining excellent mechanical properties such as fluidity and impact strength and appearance, and have completed the present invention.

  That is, the present invention relates to a flame-retardant resin composition containing a polycarbonate resin (A1), a rubber-reinforced styrene-based resin (A2) and a phosphorus atom-containing oligomer (B) as essential components, wherein the polycarbonate resin (A1) And a total of 100 parts by mass of the rubber-reinforced styrene-based resin (A2), wherein the phosphorus atom-containing oligomer (B) is contained in a range of 3 to 20 parts by mass, and the phosphorus atom-containing oligomer (B) is: The following structural formula (1)

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group. The present invention relates to a flame-retardant resin composition represented by the formula:

  The present invention also provides a method for producing a flame-retardant resin composition, which comprises melt-kneading a polycarbonate resin (A1), a rubber-reinforced styrenic resin (A2) and a phosphorus atom-containing oligomer (B), wherein the polycarbonate resin (A1 ) And the rubber-reinforced styrene-based resin (A2) in a total amount of 100 parts by mass, and the phosphorus atom-containing oligomer (B) is contained in the range of 3 to 20 parts by mass, and the phosphorus atom-containing oligomer (B) is , The following structural formula (1)

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group. ), And a method for producing a flame-retardant resin composition.

Further, in the present invention, a step (1) of preparing a flame-retardant masterbatch by melt-kneading a polycarbonate resin (A1), a rubber-reinforced styrene-based resin (A2) and a phosphorus atom-containing oligomer (B) in advance. The method for producing a flame-retardant resin composition further comprising a step (2) of melt-kneading the thermoplastic resin (E) with the flame-retardant masterbatch obtained in the above step,
The phosphorus atom-containing oligomer (B) has the following structural formula (1)

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group. ), And a method for producing a flame-retardant resin composition.

Further, the present invention is a flame-retardant master batch containing, as essential components, a polycarbonate resin (A1), a rubber-reinforced styrene-based resin (A2) and a phosphorus atom-containing oligomer (B),
The phosphorus atom-containing oligomer (B) has the following structural formula (1)

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group. ),
It is characterized by containing the phosphorus atom-containing oligomer (B) at a content ratio of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2). And a flame-retardant masterbatch.

  Furthermore, the present invention relates to a flame-retardant resin composition obtained by melting and kneading the thermoplastic resin (E) with the flame-retardant master batch.

  Furthermore, the present invention relates to a molded article, fiber, film or sheet obtained by molding the flame-retardant resin composition.

    According to the present invention, a polymer blend obtained by blending a rubber-reinforced styrenic resin and a polycarbonate resin using a non-halogen flame retardant has excellent properties inherent in polymer blends, that is, fluidity of resin composition, extrusion stability, and Moldability of rubber-reinforced styrene-based resin and polycarbonate resin having excellent flame retardancy while maintaining mechanical properties such as molding processability, and appearance and impact strength of the obtained molded article, and molding thereof Goods can be provided.

  The flame-retardant resin composition of the present invention is a flame-retardant resin composition containing, as essential components, a polycarbonate resin (A1), a rubber-reinforced styrene resin (A2) and a phosphorus atom-containing oligomer (B). The phosphorus atom-containing oligomer (B) has the following structural formula (1)

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group. ).

・ Polycarbonate resin (A1)
There are no particular restrictions on the polycarbonate resin used in the present invention, and various resins can be used. Usually, an aromatic polycarbonate produced by reacting a dihydric phenol with a carbonate precursor can be used. That is, a product prepared by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method, that is, a reaction of a dihydric phenol with phosgene by a transesterification method of a dihydric phenol with diphenyl carbonate or the like is used. be able to.

  As the dihydric phenol, various ones can be mentioned. In particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy Phenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, Examples include bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, and bis (4-hydroxyphenyl) ketone.

  Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, especially bisphenol A. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate, and specific examples thereof include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.

  The polycarbonate resin may have a branched structure, and as a branching agent, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-vidroxy) Phenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (o-cresol), etc. In addition, phenol, pt-butylphenol, p- t-octylphenol, p-cumylphenol and the like are used.

The polycarbonate resin that can be used in the present invention may be a copolymer having a polycarbonate portion and a polyorganosiloxane portion, or a polycarbonate resin containing this copolymer. Further, it may be a polyester-polycarbonate resin obtained by polymerizing polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. Also, a mixture of various polycarbonate resins can be used. The polycarbonate resin that can be used in the present invention is preferably one that contains substantially no halogen in the structure. In view of mechanical strength and moldability, the viscosity average molecular weight is preferably from 10,000 to 100,000, and particularly preferably from 14,000 to 40,000.
The viscosity-average molecular weight of the polycarbonate resin (A1) component in the present invention is determined by the specific viscosity (ηsp) of a solution obtained by dissolving an aromatic polycarbonate resin in 100 cm ³ of methylene chloride at 20 ° C. using an Ubbelohde viscometer. Is obtained by inserting it into

(Ηsp) / C = [η] + 0.45 × [η] ^2C
[Η] = 1.23 × 10 ⁻⁵ M ^0.83
(However, [η] is the limiting viscosity and C is the polymer concentration.)

・ Rubber reinforced styrene resin (A2)
The rubber-reinforced styrene resin (A2) (hereinafter, may be simply referred to as “resin (A2)”) used in the present invention is prepared by adding an aromatic vinyl monomer and, if necessary, in the presence of a rubbery polymer. It is obtained by subjecting a monomer mixture to which a vinyl monomer copolymerizable therewith is added to known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.

  Specific examples of such a rubber-reinforced styrene resin (A2) include, for example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and MBS resin (methyl methacrylate-butadiene rubber). -Styrene copolymer) and AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer).

  The rubber-reinforced styrene resin has a structure in which a polymer or copolymer containing a styrene monomer (hereinafter, also referred to as a (co) polymer) is grafted on a rubbery polymer. And those having a structure in which a (co) polymer containing a styrene monomer is not grafted to a rubbery polymer.

  Specifically, it is obtained by graft polymerization of 95 to 20 parts by mass of a monomer or a monomer mixture containing 20% by mass or more of an aromatic vinyl monomer with respect to 5 to 80 parts by mass of a rubbery polymer. Of a graft (co) polymer (A2-1) obtained by polymerizing a monomer or monomer mixture containing 20% by mass or more of an aromatic vinyl monomer with 10 to 100% by mass of a vinyl ( (Co) Polymer (A2-2) 0 to 90% by mass is mentioned as a preferable example.

  As the rubbery polymer, those having a glass transition temperature of 0 ° C. or less are suitable, and diene rubbers are preferably used. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, butyl acrylate-butadiene copolymer, and acrylics such as polybutyl acrylate Rubber, polyisoprene, and ethylene-propylene-diene-based terpolymer. Among them, the use of polybutadiene or butadiene copolymer is preferred.

  The rubber particle diameter of the rubbery polymer is not particularly limited, but when the mass average particle diameter of the rubber particles is 0.15 to 0.6 μm, particularly 0.2 to 0.55 μm, the rubber particles have excellent impact resistance. Is preferred. Among them, those having a mass ratio of from 0.20 to 0.25 μm and those having a mass ratio of from 90 to 60:40 having a mass ratio of from 0.50 to 0.65 μm have a high impact resistance and a thin molded product. This is preferable because the falling weight impact is remarkably excellent.

  The average mass particle size of the rubber particles is determined by the sodium alginate method described in “Rubber Age Vol. 88, pp. 484-490 (1960) by E. Schmidt, PH Biddison” (creaming by the concentration of sodium alginate). Utilizing the fact that the particle diameters of polybutadiene differ from each other, the cream mass ratio, the cumulative mass fraction of the sodium alginate concentration, and the particle size of a cumulative mass fraction of 50% are determined.)

  Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, and the like, with styrene being particularly preferred.

  As a monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is used for the purpose of further improving impact resistance and chemical resistance, and for the purpose of improving toughness and color tone. In this case, (meth) acrylate monomers are preferably used.

  Specific examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferably used.

  Further, specific examples of the (meth) acrylic acid ester-based monomer include methyl, ethyl, propyl, n-butyl, and isobutyl esters of acrylic acid and methacrylic acid. Particularly, methyl methacrylate is preferably used. Can be

  Further, if necessary, other vinyl monomers, for example, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide can also be used.

  The monomer or the monomer mixture used in the graft (co) polymer (A2-1) has an aromatic vinyl monomer content of 20% by mass or more from the viewpoint of the impact resistance of the resin composition. Preferably, it is more preferably at least 50% by mass. When a vinyl cyanide-based monomer is mixed, the amount is preferably 60% by mass or less, and particularly preferably 50% by mass or less, from the viewpoint of moldability of the resin composition. When a (meth) acrylate monomer is mixed, the content is preferably 80% by mass or less, particularly preferably 75% by mass or less, from the viewpoint of toughness and impact resistance. The total amount of the aromatic vinyl-based monomer, vinyl cyanide-based monomer and (meth) acrylate-based monomer in the monomer or monomer mixture is 95 to 20% by mass. And more preferably 90 to 30% by mass.

  From the viewpoint of the impact resistance of the resin composition, the mixing ratio of the rubbery polymer and the monomer mixture when obtaining the graft (co) polymer (A2-1) is based on 100 parts by mass of all the graft copolymers. Preferably, the amount of the rubbery polymer is at least 5 parts by mass, more preferably at least 10 parts by mass. In addition, from the viewpoint of the impact resistance of the resin composition and the appearance of the molded article, the amount is preferably 80 parts by mass or less, more preferably 70 parts by mass or less. The proportion of the monomer or monomer mixture is at most 95 parts by mass, preferably at most 90 parts by mass, or at least 20 parts by mass, preferably at least 30 parts by mass.

  The graft (co) polymer (A2-1) can be obtained by a known polymerization method. For example, it can be obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier in the presence of a rubbery polymer latex are continuously supplied to a polymerization vessel and emulsion polymerization is performed. .

The graft (co) polymer (A2-1) contains an ungrafted copolymer in addition to a graft copolymer having a structure in which a monomer or a monomer mixture is grafted on a rubbery polymer. It was done. Although the graft ratio of the graft (co) polymer is not particularly limited, in order to obtain a resin composition having excellent balance of impact resistance and gloss, it is in the range of 20 to 80% by mass, particularly 25 to 50% by mass. It is preferred that Here, the graft ratio is a value calculated by the following equation.
Graft ratio (%) = [<Amount of vinyl copolymer graft-polymerized on rubbery polymer> / <Rubber content of graft copolymer>] × 100

  The properties of the ungrafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.25 to 0.6 dl / g, particularly 0.25 to 0.6 dl / g. A range of 0.5 dl / g is a preferable condition for obtaining a resin composition having excellent impact resistance.

  The vinyl (co) polymer (A2-2) is a copolymer essentially containing an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, and o-ethylstyrene, and styrene is particularly preferably used. One or more of these can be used.

  As a monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is used for the purpose of further improving impact resistance and chemical resistance, and for the purpose of improving toughness and color tone. In this case, a (meth) acrylate monomer is preferably used.

  Specific examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferably used. Specific examples of (meth) acrylate monomers include methyl, ethyl, propyl, n-butyl and isobutyl esters of acrylic acid and methacrylic acid, and in particular, methyl methacrylate is particularly preferably used. .

  Examples of other vinyl monomers that can be copolymerized with these, if necessary, include maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide.

  In the present invention, a vinyl copolymer obtained by copolymerizing a maleimide monomer, that is, a maleimide group-modified vinyl copolymer is used by being contained in a polystyrene resin, so that the heat resistance of the resin composition is improved. Can be improved, and furthermore, the flame retardancy can be specifically improved, so that it can be preferably used.

  From the viewpoint of the impact resistance of the resin composition, the proportion of the aromatic vinyl monomer as a constituent component of the vinyl (co) polymer (A2-2) is preferably 20% by mass or more based on all monomers. Preferably, it is in the range of 50% by mass or more. When a vinyl cyanide monomer is mixed, the content is preferably 60% by mass or less, and more preferably 50% by mass or less, from the viewpoint of impact resistance and fluidity. When a (meth) acrylate monomer is mixed, the content is preferably 80% by mass or less, and more preferably 75% by mass or less, from the viewpoint of toughness and impact resistance. Further, when other vinyl monomers copolymerizable therewith are mixed, the content is preferably 60% by mass or less, particularly preferably 50% by mass or less.

  The properties of the vinyl (co) polymer (A2-2) are not limited, but the intrinsic viscosity [η] measured at 30 ° C. using a methyl ethyl ketone solvent is 0.4 to 0.65 dl / g, particularly Those having a range of 0.45 to 0.55 dl / g, when measured at 30 ° C. using an N, N-dimethylformamide solvent, have a value of 0.35 to 0.85 dl / g, particularly 0.45 dl / g. A range of from 0.7 dl / g to 0.7 dl / g is preferred because a resin composition having excellent impact resistance and moldability can be obtained.

  The method for producing the vinyl (co) polymer (A2-2) is not particularly limited, and may be a conventional method such as bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, and solution-bulk polymerization. A method can be used.

  Further, in the present invention, a modified vinyl polymer containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group and an oxazoline group (hereinafter, a modified vinyl polymer) ) Can also be used. This modified vinyl polymer has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group, a hydroxyl group, an epoxy group, an amino group and It is a polymer containing at least one functional group selected from oxazoline groups. The content of the compound containing these functional groups is not limited, but is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of the modified vinyl polymer.

  There is no particular limitation on the method of introducing a carboxyl group into the modified vinyl polymer, but a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid and itaconic acid or the like. A method of copolymerizing a vinyl monomer having a carboxyl anhydride group with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovaleic acid), α, α′-azobis (α-cyanoethyl) -p A polymerization initiator having a carboxyl group such as benzoic acid and succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-isobutyric acid and 2,3 or 4-mercapto Using a polymerization degree regulator having a carboxyl group such as benzoic acid, a predetermined vinyl monomer is (co) And a copolymer of a (meth) acrylate monomer such as methyl methacrylate or methyl acrylate with an aromatic vinyl monomer and, if necessary, a vinyl cyanide monomer. A method of saponifying with an alkali or the like can be used.

There is no particular limitation on the method for introducing the hydroxyl group, but, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,3-acrylic acid 4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-methacrylic acid Tetrahydroxypentyl, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1- Propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene , 4-dihydroxy-2-butene a vinyl monomer having a hydroxyl group such as, a method of copolymerizing with a predetermined vinyl monomer can be used.

  There is no particular limitation on the method of introducing the epoxy group. A method of copolymerizing a vinyl monomer having a group with a predetermined vinyl monomer can be used. Among them, the epoxy-modified vinyl copolymer in which an epoxy group is introduced by copolymerizing glycidyl methacrylate, when used in a polystyrene resin, the flame retardancy and impact strength of the resin composition of the present invention. Can be improved.

  Although there is no particular limitation on the method of introducing the amino group, for example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethyl methacrylate Amino groups such as aminoethyl, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, and p-aminostyrene And a method of copolymerizing a vinyl monomer having a derivative thereof with a predetermined vinyl monomer.

  The method of introducing the oxazoline group is not particularly limited. For example, a vinyl monomer having an oxazoline group such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline. For example, a method of copolymerizing the polymer with a predetermined vinyl monomer can be used.

  The properties of the modified vinyl polymer are not limited, but the intrinsic viscosity [η] measured at 30 ° C. using a methyl ethyl ketone solvent is 0.2 to 0.65 dl / g, particularly 0.35 to 0.6 dl. / G in the range of 0.3 to 0.9 dl / g, especially 0.4 to 0.75 dl / g, when measured at 30 ° C. using an N, N-dimethylformamide solvent. Those in the range are preferred because a resin composition having excellent flame retardancy, impact resistance, and moldability can be obtained.

  The ratio of the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2) is not particularly limited as long as the effects of the present invention are not impaired, but the ratio of the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2) is not limited. Preferably, the polycarbonate resin (A1) is in the range of 95 to 50 parts by mass, and the rubber-reinforced styrene-based resin (A2) is in the range of 50 to 95 parts by mass, based on 100 parts by mass in total. More preferably, the polycarbonate resin (A1) is in the range of 80 to 60 parts by mass, and the rubber-reinforced styrene-based resin (A2) is in the range of 20 to 40 parts by mass.

.Phosphorus atom-containing oligomer (B)
Next, as described above, the phosphorus atom-containing oligomer (B) used in the present invention has the following structural formula (1)

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an aralkyl group. ), And the content of the component having n of 2 or more in the structural formula (1) is in the range of 5 to 90% based on the peak area in GPC measurement. In the present invention, by using such a phosphorus atom-containing oligomer (B) as a flame retardant component, it is possible to suppress bleeding during melt-kneading and maintain good mold releasability from a mold, and at the same time, to obtain a thin molded product or a molded product. It is capable of dramatically improving the flame-retardant performance of the thin and thin parts of the product.

  The phosphorus atom-containing oligomer (B) thus has the following structural formula (2) in the structural formula (1).

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, n is a repeating unit of 1 or more, and X is a structural formula shown below. (X1) or (x2)

(In the structural formula (x1) or (x2), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. Represents a structural part). ) As a repeating unit, the flame retardancy of a molded article, particularly the flame retardancy of a thin-walled part, is remarkably improved.

  Here, specific examples of the structural site represented by the structural formula (2) include those represented by the following structural formulas (2-1) to (2-8).

  In the present invention, X in the structural formula (1) is selected from the structural formulas (x1) and (x2), and may be the structural formula (x1) particularly from the viewpoint of flame retardancy. Preferably, therefore, among the structural parts represented by the structural formula (2), the structural formulas (2-1), (2-2), (2-3) corresponding to the structural formula (x-1) ) And (2-4) are preferred.

  In the structural formula (1), Y is a hydrogen atom, a hydroxyl group or a structural site represented by the structural formula (x1) or (x2), and these coexist in the phosphorus atom-containing oligomer. You may. In the present invention, Y is preferably a hydrogen atom or a structural part represented by the structural formula (x1) or (x2) from the viewpoint of heat resistance and flame retardancy. Formula (x1) is preferable.

  Further, as described above, the phosphorus atom-containing oligomer in the above structural formula (1) has n in the range of 1 or more, preferably 1 to 10. Further, when the content of the component having n of 2 or more is in the range of 5 to 90% based on the peak area in GPC measurement, the compatibility with the resin (A) is excellent, and the flame retardancy of the thin portion is low. It is more preferable because it is remarkably excellent.

  Here, the content of a component having n of 2 or more in the structural formula (1) refers to a ratio of a peak area of less than 36.0 minutes in a GPC chart measured under the following conditions.

<GPC measurement conditions>
GPC: The measurement conditions are as follows.
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refraction diameter)
Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40 ° C
Developing solvent tetrahydrofuran
Flow rate 1.0ml / min

  Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC-8020 Model II Version 4.10".

(Used polystyrene)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation

  Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content was filtered through a microfilter (50 μl).

NMR: JNM-ECA500 type nuclear magnetic resonance apparatus manufactured by JEOL Field strength: 500 MHz
Pulse width: 3.25 μsec
Number of integration: 8000 times Solvent: DMSO-d6
Sample concentration: 30 wt%

MS: AXIMA-TOF2 manufactured by Shimadzu Biotech
Measurement mode: linear
Number of accumulation: 50 times Sample composition: sample / DHBA / NaTFA / THF = 9.4 mg / 104.7 mg / 6.3 mg / 1 ml

  In the present invention, when the content of the component having n of 2 or more is 5% or more based on the peak area in the GPC measurement, the compatibility with the resin (A) is good, and the bleed at the time of melt-kneading becomes small. On the other hand, when it is 90% or less, the fluidity during melt-kneading becomes good and the impact strength becomes excellent. Here, the other component is a component in which n is 1. Therefore, in the phosphorus atom-containing oligomer of the present invention, the ratio of the component in which n is 1 is 95 to 10% based on the peak area in GPC measurement. In the present invention, the content of the component having n of 2 or more is preferable in that the compatibility with the resin (A) and the processability can be maintained at a high level, and further excellent flame retardancy can be improved in the cured product. , 40 to 75%, and the content of the component in which n is 1 is preferably in the range of 60 to 25%.

  More specifically, the content of the component where n is 1 is 95 to 10%, the content of the component where n is 2 is 3 to 50%, and the content of the component where n is 3 or more is 1 to 45%. % Is preferable from the viewpoint of solvent solubility. In particular, the content of the component in which n is 1 is 60 to 25%, the content of the component in which n is 2 is 10 to 45%, and n is 3 or more. It is preferable that the content of the component is 10 to 40% from the viewpoint of achieving an excellent balance between workability and flame retardancy.

  Further, as described above, Y in the structural formula (1) is preferably the structural formula (x1), and therefore, in the structural formula (1), Y is the structural formula (x1), and n Is preferably a phosphorus atom-containing oligomer in which the content of two or more components is 40 to 75% and the content of the component in which n is 1 is 60 to 25% from the viewpoint of flame retardancy and heat resistance. In (1), Y is the structural formula (x1), and the content of the component where n is 1 is 95 to 10%, the content of the component where n is 2 is 3 to 50%, and n is 3 or more. Is preferably from 1 to 45% from the viewpoint of preventing bleeding, improving flame retardancy, and excellent compatibility with the resin (A). In particular, Y is a structural formula (x1) And the content of the component with n = 1 is 60 to 25%, the content of the component with n = 2 is 10 to 45%, and Are particularly preferred from the viewpoint that the content of the three or more component is phosphorus atom-containing oligomer is 10 to 40% (B) excellent in these performance balance.

  The phosphorus atom-containing oligomer (B) preferably has a phosphorus atom content in the oligomer of 9 to 12% by mass in view of flame retardancy. The phosphorus atom content is a value measured in accordance with “JIS K01046”.

  The phosphorus atom-containing oligomer (B) described in detail above can be produced by the following production method.

  That is, the phosphorus atom-containing oligomer (B) has the following structural formula (b1-1) or (b1-2)

(Wherein, R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group). b1) and the following structural formula (b2)

Wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group. Compound (b1) / Compound (b2)] at a ratio of 0.01 / 1.0 to 0.99 / 1.0, and reacted at 80 to 180 ° C. in the presence of an acid catalyst. The compound (b2) can be produced by a method in which the compound (b1) is added in a total amount of 1.01 to 3.0 times, based on the charged amount of the compound (b2), and the reaction is carried out at 120 to 200 ° C.

  In the present invention, when the phosphorus atom-containing oligomer (B) is produced by such a method, precipitation of the reaction intermediate can be favorably suppressed, and the molecular weight is easily increased.

Here, in the structural formula (b1-1) or (b1-2), as the alkyl group having 1 to 5 carbon atoms constituting R ² , R ³ , R ⁴ , and R ⁵ , a methyl group, an ethyl group Group, n-propyl group, i-propyl group and t-butyl group, and the compound (b1) used in the present invention is a compound wherein all of R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms. Is preferred from the viewpoint of flame retardancy. Further, the compound (b1) preferably has the structural formula (b1-1) from the viewpoint of excellent flame retardancy of the cured product. On the other hand, R ¹ in the structural formula (b2) in the compound (b2) includes a methyl group, an ethyl group, an n-propyl group, a methoxy group and the like. R ¹ is preferably a hydrogen atom from the viewpoint of excellent flame retardancy.

  Examples of the catalyst that can be used in the method include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acids and the like. The amount of use is preferably in the range of 0.1 to 5.0% by mass with respect to the total weight of the charged raw materials from the viewpoint of preventing a decrease in electrical insulation of the cured product.

  In the reaction, since the compound (b2) is in a liquid state, the reaction can be carried out using the compound (b2) as an organic solvent. However, another organic solvent may be used from the viewpoint of improving workability and the like. Here, examples of the organic solvent used include alcohol-based organic solvents and non-ketone-based organic solvents such as hydrocarbon-based organic solvents. Specifically, examples of the alcohol-based organic solvent include propylene glycol monomethyl ether. Examples of the hydrocarbon organic solvent include toluene and xylene.

  After completion of the reaction, the desired phosphorus atom-containing oligomer (B) can be obtained by drying under reduced pressure.

  The content of the phosphorus atom-containing oligomer (B) in the flame-retardant resin composition used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. The polycarbonate resin (A1) and the rubber-reinforced styrene-based resin are excellent in stability, moldability during molding, and excellent mechanical properties such as appearance, impact strength, and flame retardancy of the obtained molded article. It is preferably in the range of 3 to 20 parts by mass with respect to 100 parts by mass in total of (A2), and more preferably in the range of 8 to 20 parts by mass from the viewpoint of excellent flame retardancy. In addition, from the viewpoint of further improving the appearance of the molded product, the content is most preferably in the range of 8 to 15 parts by mass.

・ Flame retardant (C)
The flame-retardant resin composition of the present invention may contain various flame-retardant auxiliaries (for example, other flame-retardants, antioxidants, stabilizers, and dripping) as needed to improve the flame retardancy and thermal stability. Inhibitor etc.).

(C1 other flame retardants)
In addition, the flame-retardant resin composition of the present invention further provides other flame retardants, for example, a phosphorus-containing compound, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, an alcohol-based flame retardant. Flame retardants, inorganic flame retardants (such as metal oxides and metal hydroxides) (hereinafter sometimes referred to as other flame retardants) and the like may be contained within a range that does not impair the effects of the present invention.

(C1-1) Phosphorus-Containing Compound Phosphorus-Containing Compound Examples of the phosphorus-containing compound include organic phosphorus compounds (eg, monomer-type, dimer-type and trimer-type oligomer-type organic phosphorus compounds, and polymer-type organic phosphorus compounds), and inorganic phosphorus compounds. Can be

(C1-1-1) Organic phosphorus compound Among the organic phosphorus compounds, oligomeric organic phosphorus compounds include phosphoric acid esters, phosphoric acid ester amides, phosphonitrile compounds, organic phosphonic acid compounds (esters, metal salts, etc.), Organic phosphinic acid compounds (esters, metal salts, etc.), polymer type organic phosphorus compounds, phosphine oxides and the like are included.

(C1-1-1-1) Phosphate Esters Phosphate esters include aliphatic phosphate esters [trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate. , phosphoric acid pentaerythritol (e.g., GreatLakes Chemical Co. NH-1197, etc. Bishikurorin esters described in JP-a-2001-106889) of phosphoric acid tri _{C 1-10} alkyl esters such as; corresponding to the phosphate triester Phosphoric acid di-C _1-10 alkyl ester and phosphoric acid mono-C _1-10 alkyl ester], aromatic phosphoric ester [triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, diphenylcresyl phosphate, phosphoric acid] Tri (isopropylphenyl), Phosphoric acid tri C _6-20 aryl esters such as phosphate-diphenylethyl cresyl, aliphatic - aromatic phosphate [methyl diphenyl phosphate, phenyl diethyl phosphate, spirocyclic aromatic phosphoric acid ester (diphenyl pentaerythritol Diphosphate, dicresylpentaerythritol diphosphate, dixylylpentaerythritol diphosphate, etc.).

(C1-1-1-2) Phosphate Ester Phosphate Ester Phosphate Ester includes the binding mode of phosphoric acid ester and phosphoric acid amide, and is disclosed in JP-A-2002-226546, JP-A-2001-354684, JP-A-2001-139823, JP-A-2000-327834, JP-A-2000-154277, JP-A-10-175885, JP-A-8-59888, JP-A-63-235363, The phosphoric ester amide described in JP-A-54-19919 can be used.

  The phosphate ester amide is available as a trade name “phosphate ester amide-based flame retardant SP series (for example, SP-601, SP-670, SP-703, etc.)” (manufactured by Shikoku Chemicals Co., Ltd.).

(C1-1-1-3) Phosphonitrile Compound As the phosphonitrile compound, linear and cyclic phenoxyphosphazenes and the like can be used.

(C1-1-1-4) Organic Phosphonic Acid Compound Examples of the organic phosphonic acid (phosphorous acid) compound include, for example, aromatic phosphite (tri-C ₆ phosphite having aryl such as phenyl, cresyl, and xylyl). _-20 aryl esters), aliphatic phosphites (tri-C _1-10 alkyl phosphite wherein alkyl is the alkyl or the like; di- or mono-C ₁ phosphite corresponding to the trialkyl phosphite) _-10 alkyl esters), organic phosphites [e.g., spirocyclic alkyl phosphones such as C _1-6 alkyl phosphonic acid di C _1-6 alkyl wherein alkyl is alkyl as exemplified above (pentaerythritol bis (methyl phosphonate)] Acid ester, etc.), alkyl is the alkyl exemplified above, and aryl is phenyl, The alkyl phosphonic acid diester; Jill, _{C 1-6} alkylphosphonic di _{C 6-10} alkyl phosphonic acid diester, such as aryl and _{C 1-6} alkyl phosphonic acid _{C 1-6} alkyl _{C 6-10} aryl which is xylyl corresponding _{C 6-10} aryl - (including spirocyclic _{C 6-10} aryl phosphonic acid esters, such as pentaerythritol diphenyl _phosphonate) phosphonate _{diester; C 6-10} aryl phosphonic acid monoester (e.g., 10-hydroxy-9,10 - such as dihydro-9-oxa-10-phospha-phenanthrene-10-oxide); corresponding to the phosphonocarboxylic acid esters (the alkyl phosphonic acid diester, such as dimethyl methoxycarbonylmethyl acid C _1-4 alkoxycarbonyl Oki C _1-4 alkyl phosphonic acid diester) includes various phosphonates, such as phosphonocarboxylic acid triester], such as. Further, a metal salt (eg, Ca, Mg, Zn, Ba, or Al salt) of phosphorous acid, a phosphite monoester, or a phosphonocarboxylic acid which may be substituted with an alkyl or aryl group is also included.

(C1-1-1-5) The organic phosphinic acid compound organic phosphinic acid compound, _(such as _{C 1-4} alkyl group) alkyl or _(such as _{C 6-10} aryl group) an aryl group substituted (mono- or di Optionally substituted phosphinic acid esters (C _1-6 alkyl phosphinates such as methyl phosphinate, C _6-10 aryl phosphinates such as phenyl phosphinate, 9,10-dihydro-9-oxa-10-phospho) file phenanthrene-10-oxide, such as _{10-C 1-30} cyclic phosphinic acid esters such as alkyl or _{C 6-20} aryl-substituted 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide), etc. Is included. A metal salt of a phosphinic acid (eg, dimethylphosphinic acid, diethylphosphinic acid, methylethylphosphinic acid, etc.) which may be substituted with an alkyl group or an aryl group (Ca, Mg, Zn, Ba, Al salt, etc.); Phosphinicocarboxylic acid esters (eg, 3-methylphosphinicopropionate, 3-phenylphosphinicopropionate, etc.), and homopolymers and copolymers thereof are also included.

(C1-1-1-6) Polymer-type organic phosphorus compound As the polymer-type organic phosphorus compound, a condensate of a monomer-type organic phosphorus compound other than the polymer-type phosphoric acid ester (C), for example, polyphosphinicocarboxylic acid ester , Polyphosphonamides.

(C1-1-1-7) Phosphine oxide Examples of the phosphine oxide include triphenylphosphine oxide and tricresylphosphine oxide.

(C1-1-2) Inorganic phosphorus compound The inorganic phosphorus compound includes, for example, red phosphorus, (poly) phosphate, and the like.

(C1-1-2-1) Red phosphorus Red phosphorus has a high flame retardant effect, and can impart flame retardancy to a resin even in a small amount. In addition, since the effect can be obtained with a small amount, flame retardancy can be achieved without impairing the properties (for example, mechanical properties and electrical properties) of the resin. As the red phosphorus, red phosphorus that has been subjected to a stabilization treatment (stabilized red phosphorus) is usually preferably used. In particular, red phosphorus obtained by a method of pulverizing red phosphorus without pulverizing it and forming fine particles without forming a highly crushed surface having high reactivity with water or oxygen on the surface of red phosphorus, furthermore, the surface of red phosphorus, Red phosphorus coated alone or in combination with two or more kinds of resins (eg, thermosetting resins, thermoplastic resins), metals, metal compounds (eg, metal hydroxides, metal oxides, etc.) can be used. .

  Normally, stabilized red phosphorus can be used in the form of powder as red phosphorus. The particle diameter of the stabilized red phosphorus is, for example, about 0.01 to 100 μm, preferably about 0.1 to 70 μm, and more preferably about 0.1 to 50 μm.

(C1-2-2) Inorganic salt of (poly) phosphoric acid As the (poly) phosphate, inorganic salts of non-condensed or condensed phosphoric acid such as phosphoric acid, phosphorous acid, hypophosphorous acid, and polyphosphoric acid ( Ammonium, Ca, Mg, Zn, Ba, Al salts) and the like.

(C1-2) Nitrogen-containing flame retardant Nitrogen-containing flame retardant Examples of the nitrogen-containing flame retardant include salts of triazines and cyanuric acid or a derivative thereof, for example, melamine salts of cyanuric acid such as melamine cyanurate; And melem salts, melam salts, melon salts, guanamine salts (eg, guanamine cyanurate, acetoguanamine cyanurate, benzoguanamine cyanurate and the like). These salts can be used alone or in combination of two or more.

(C1-3) Sulfur-containing flame retardant Sulfur-containing flame retardant Examples of the sulfur-containing flame retardant include organic sulfonic acids (alkanesulfonic acid, perfluorosulfonic acid, arylsulfonic acid, sulfonated polystyrene, etc.), sulfamic acid, organic sulfamic acid, Salts such as organic sulfonic acid amides (ammonium salts, alkali metal salts, alkaline earth metal salts, etc.) and the like.

(C1-4) Silicon-containing flame retardant The silicon-containing flame retardant includes (poly) organosiloxane. Examples of the (poly) organosiloxane include homopolymers such as dialkylsiloxane (eg, dimethylsiloxane), alkylarylsiloxane (phenylmethylsiloxane), diarylsiloxane, monoorganosiloxane (eg, polydimethylsiloxane, polyphenylmethylsiloxane) ) Or a copolymer. Examples of the (poly) organosiloxane include a branched organosiloxane [trade name “XC99-B5664” of Toshiba Silicone Co., Ltd., “X-40-9243” and “X-40-9244” of Shin-Etsu Chemical Co., Ltd. , "X-40-9805", compounds described in JP-A-10-139964, etc.], modification having a substituent such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group or an ether group at a molecular terminal or a main chain ( Poly (organosiloxane) (for example, modified silicone) can also be used.

(C1-5) Alcohol-based flame retardant Examples of the alcohol-based flame retardant include polyhydric alcohols (such as pentaerythritol), oligomeric polyhydric alcohols (such as dipentaerythritol and tripentaerythritol), esterified polyhydric alcohols, and substituted alcohols. Alcohols, celluloses (such as cellulose, hemicellulose, lignocellulose, pectocellulose, and adipocellulose), and saccharides (such as monosaccharides and polysaccharides).

(C1-6) Inorganic flame retardant Among the inorganic flame retardants, examples of the metal oxide include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide, and nickel oxide. , Iron oxide, manganese oxide, antimony trioxide, antimony tetroxide, antimony pentoxide and the like. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, tin hydroxide, and zirconium hydroxide. Examples of the metal sulfide include zinc sulfide, molybdenum sulfide, and tungsten sulfide. The inorganic flame retardant also includes expandable graphite.

  These other flame retardants can be used alone or in combination of two or more. The content of the other flame retardant is not particularly limited as long as the effect of the present invention is not impaired, but when used, for example, with respect to a total of 100 parts by mass of the resin (A1) and the resin (A2). , 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and most preferably 0.1 to 20 parts by mass.

(C2 antioxidant or stabilizer)
Further, the flame-retardant resin composition of the present invention may contain an antioxidant or a stabilizer in a range that does not impair the effects of the present invention in order to stably maintain heat resistance for a long period of time. Antioxidants or stabilizers include, for example, phenol (such as hindered phenols), amine (such as hindered amines), phosphorus, sulfur, hydroquinone, quinoline antioxidants (or stabilizers), inorganic Examples include a system stabilizer, a compound having a functional group reactive to an active hydrogen atom (reactive stabilizer), and the like.

(C2-2) Phenolic antioxidant The phenolic antioxidant includes hindered phenols (hindered phenolic antioxidant), for example, 1,6-hexanediol-bis [3- (3,5- C _2-10 alkylene diol-bis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as di-t-butyl-4-hydroxyphenyl) propionate]; triethylene glycol - bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] di- or Toriokishi _{C 2-4} alkylene diol such as - bis [3- (3,5-di - branched C _3-6 alkyl-4-hydroxyphenyl) propionate]; for example, glycerol tris [3- (3,5-di -t- butyl - - _{C 3-8} alkylene triol such as hydroxyphenyl) propionate] - bis [3- (3,5-di - branched _{C 3-6} alkyl-4-hydroxyphenyl) propionate]; for example, pentaerythritol tetrakis [3- ( C _4-8 alkylenetetraol tetrakis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate such as 3,5-di-t-butyl-4-hydroxyphenyl) propionate And the like.

(C2-3) Amine-based antioxidant The amine-based antioxidant includes a hindered amine, for example, tri- or tetra-C _1-3 alkylpiperidine or a derivative thereof (methoxy, benzoyloxy, phenoxy or the like is substituted at the 4-position). and each may be a 2,2,6,6-tetramethylpiperidine, etc.), bis (tri-, tetra- or _{penta-C 1-3 alkyl-piperidine) C 2-20} alkylene carboxylic acid esters [e.g., bis (2,2,6 , 6-Tetramethyl-4-piperidyl) oxalate, malonate corresponding to oxalate, adipate, sebacate, terephthalate, etc .; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate], 1,2- Bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, phenylnaphthylua Emissions, N, N'-diphenyl-1,4-phenylenediamine, and the like N- phenyl -N'- cyclohexyl-1,4-phenylenediamine.

(C2-4) (Organic) Phosphorus Stabilizer or Antioxidant The phosphorus (organophosphorus) stabilizer or antioxidant includes, for example, triisodecyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite. Phyte, phenyldiisodecyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-t-butylphenyl) ditridecyl phosphite , Tris (branched C _3-6 alkylphenyl) phosphite [for example, tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris ( 2,4-di -t- amyl phenyl) phosphite, etc.], (branched _{C 3-6} alkyl phenyl) Feniruho Fight [e.g., bis (2-t-butylphenyl) phenyl phosphite, etc. 2-t-butylphenyl diphenyl phosphite, tris (2-phenyl) phosphite, bis _{(C 1-9} alkylaryl) pentaerythritol Diphosphite [for example, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.], triphenyl phosphate stabilizers (for example, 4-phenoxy-9-α) -(4-hydroxyphenyl) -p-cumenylo C-3,5,8,10-tetraoxa-4,9-diphosphapyro [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphate, and the like; diphosphonite-based stabilizers (for example, tetrakis ( 2,4-di-t-butyl) -4,4′-biphenylenediphosphonite and the like. The phosphorus-based stabilizer usually has a branched C _3-6 alkylphenyl group (particularly, a t-butylphenyl group). The flame-retardant resin composition of the present invention is preferably used in combination with a phosphorus-based stabilizer or an antioxidant, and is used in a total of 100 parts by mass of the resin (A1) and the resin (A2). By blending the agent (C2-4) in an amount of 0.01 to 10 parts by mass, the light resistance can be dramatically improved. This is because the phosphorus atom-containing oligomer (B) has a structure in which bulky HCA has reacted near the phenolic hydroxyl group, and when hydrogen is donated to the peroxide radical generated by autoxidation, the phenolic hydroxyl group itself becomes It is considered that steric hindrance results in phenoxy radical having low activity.

(C2-5) Hydroquinone-based antioxidant The hydroquinone-based antioxidant includes, for example, 2,5-di-t-butylhydroquinone, and the quinoline-based antioxidant includes, for example, 6-ethoxy-2. , 2,4-trimethyl-1,2-dihydroquinoline and the like, and the sulfur-based antioxidants include, for example, dilauryl thiodipropionate, distearyl thiodipropionate and the like.

(C2-6) Inorganic stabilizer (inorganic metal or mineral stabilizer)
Inorganic stabilizers (inorganic metal or mineral stabilizers) include hydrotalcite, zeolites and alkaline earth metal compounds.

(C2-6-1) Hydrotalcite Examples of the hydrotalcite include hydrotalcites described in JP-A-60-1241 and JP-A-9-59475, for example, the following formula [M ^{_{2+ 1-X M 3+ X (}} OH) 2] X + [a N- X / n · mH 2 O] X- ( ^{wherein, M 2+} is ^{Mg 2+, Mn 2+, Fe 2+} , divalent metals such as ^{Co 2+} indicates ^{ion, M 3+} is ^{Al 3+,} Fe ^{3+, .A} showing a trivalent metal ion such as ^{Cr 3+ n-is _{CO 3 2-, OH -, HPO}} 4 2-, SO 4 2- n -valent (such as In particular, it represents a monovalent or divalent anion. X is 0 <x <0.5, and m is 0 ≦ m <1). In addition, hydrotalcite is available from Kyowa Chemical Industry Co., Ltd. as "DHT-4A", "DHT-4A-2", "Alkamizer" and the like.

(C2-6-2) Zeolite Examples of the zeolite include, but are not particularly limited to, a zeolite described in Japanese Patent Application Laid-Open No. 7-62142 [a minimum unit cell of which is a crystalline aluminosilicate of alkali and / or alkaline earth metal. Zeolites which are acid salts (A-type, X-type, Y-type, L-type and ZSM-type zeolites, mordenite-type zeolites; natural zeolites such as chabazite, mordenite and faujasite, etc.) can be used. The A-type zeolite is referred to as “zeolam series (A-3, A-4, A-5)”, “zeostar series (KA100P, NA-100P, CA-100P)”, etc., and X-type zeolite. Are available as "Zeolam Series (F-9)" and "Zeostar Series (NX-100P)", and Y-type zeolites are available as "HSZ Series (320NAA)" from Tosoh Corporation and Nippon Chemical Industry Co., Ltd. Available.

(C2-6-3) Alkaline earth metal compound Examples of the alkaline earth metal compound include oxides (such as magnesium oxide), hydroxides (such as magnesium hydroxide and calcium hydroxide), and carbonates [magnesium carbonate , (Soft / colloidal / heavy) calcium carbonate], and organic carboxylate (eg, magnesium acetate, calcium acetate, magnesium stearate, calcium stearate, calcium 12-hydroxystearate) and the like.

  These inorganic stabilizers can be used alone or in combination of two or more.

(C2-7) Reactive stabilizer The reactive stabilizer includes a compound having a functional group reactive to an active hydrogen atom. The compound having a functional group reactive to an active hydrogen atom is selected from a cyclic ether group, an oxetane group, an acid anhydride group, an isocyanate group, an oxazoline group (ring), an oxazine group (ring), a carbodiimide group, and the like. Further, compounds having at least one kind of functional group can be exemplified.

(C2-7-1) Compound having a cyclic ether group The compound having a cyclic ether group includes a compound having an epoxy group or an oxetane group. Examples of the compound having an epoxy group include an alicyclic compound such as vinylcyclohexene dioxide, a glycidyl ester compound such as glycidyl versatate, and a glycidyl ether compound (hydroquinone diglycidyl ether, biphenol diglycidyl ether, bisphenol-A diamine). Glycidyl ether), a glycidylamine compound, an epoxy group-containing vinyl copolymer, an epoxidized polybutadiene, an epoxidized diene monomer-styrene copolymer, triglycidyl isocyanurate, and an epoxy-modified (poly) organosiloxane.

(C2-7-2) Compound having an oxetane group Examples of the compound having an oxetane group include di [1-ethyl (3-oxetanyl)] methyl isophthalate and di [1-ethyl (3-oxetanyl) terephthalate. Oxetanyl ester compounds such as methyl esters, oxetanyl ether compounds {e.g., alkyl oxetanyl compounds such as di [1-ethyl (3-oxetanyl)] methyl ether and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane; Aryl oxetanyl compounds such as 3-ethyl-3- (phenoxymethyl) oxetane, aralkyl oxetanyl ether compounds such as 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bisphenol-A di [ 1-ethyl (3-o Bisphenol-type oxetane resins such as cetanyl) methyl ether, mono- to poly [1-ethyl (3-oxetanyl)] methyl-etherified phenol novolak, and mono- to poly [1-ethyl (3-oxetanyl)] methyl-etherified cresol novolak And oxetane-modified (poly) organosiloxanes such as [3- (triethoxysilyl) propoxy] methyloxetane, and derivatives having the oxetanyl units {for example, [1- Ethyl (3-oxetanyl)] methyl derivative}, and corresponding alkyl oxetanylmethyl derivative {for example, [1-methyl (3-oxetanyl)] methyl derivative}.

(C2-7-3) Compound having an acid anhydride group Examples of the compound having an acid anhydride group include olefin resins having a maleic anhydride group (for example, ethylene-maleic anhydride copolymer, maleic anhydride Modified polypropylene, etc.).

(C2-7-4) Compound Having Isocyanate Group Examples of the compound having an isocyanate group include aliphatic isocyanates such as hexamethylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, aromatic isocyanates such as diphenylmethane isocyanate, and the like. Modified isocyanate (for example, trimer of isophorone diisocyanate) and the like.

(C2-7-5) Compound having an oxazoline group Examples of the compound having an oxazoline group include 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) and 2,2 ′-(1, Examples thereof include bisoxazoline compounds such as 4-phenylene) -bis (2-oxazoline) and vinyl resins having an oxazoline group (for example, vinyloxazoline-modified styrene resins and the like).

(C2-7-6) Compound having an oxazine group Examples of the compound having an oxazine group include bisoxazine compounds such as 2,2′-bis (5,6-dihydro-4H-1,3-oxazine). No.

(C2-7-7) Compound having a carbodiimide group Examples of the compound having a carbodiimide group include polyarylcarbodiimides such as poly (phenylcarbodiimide) and poly (naphthylcarbodiimide), poly (2-methyldiphenylcarbodiimide), and poly ( 2,6-diethyldiphenylcarbodiimide), poly (2,6-diisopropyldiphenylcarbodiimide), poly (2,4,6-triisopropyldiphenylcarbodiimide), poly (2,4,6-trit-butyldiphenylcarbodiimide), etc. Poly [4,4'-methylenebis (2,6-diethylphenyl) carbodiimide], poly [4,4'-methylenebis (2-ethyl-6-methylphenyl) carbodiimide], poly [4 4 ' Poly [alkylenebis (alkyl or cycloalkylaryl) carbodiimide] such as -methylenebis (2,6-diisopropylphenyl) carbodiimide] and poly [4,4'-methylenebis (2-ethyl-6-methylcyclohexylphenyl) carbodiimide]. Is mentioned.

  These reactive stabilizers can be used alone or in combination of two or more.

  These antioxidants and / or stabilizers can be used alone or in combination of two or more. The content of the antioxidant and / or the stabilizer is not particularly limited as long as the effect of the present invention is not impaired. When used, for example, the resin (A1) and the resin (A2) may have a total content of 100% by mass. The range is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and most preferably 0.1 to 10 parts by mass with respect to parts.

  Among these antioxidants and stabilizers, from the viewpoint of hydrolysis resistance, it is preferable to combine an inorganic stabilizer and a reactive stabilizer, and the ratio (mass ratio) of both is determined as inorganic stabilizer / reaction. Sex stabilizer = 95/5 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 50/50.

  Phosphoric acids (for example, inorganic phosphoric acid such as phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, and polyphosphoric acid) exemplified in the specific flame-retardant auxiliary for the resin (A1) and the resin (A2); When an organic phosphoric acid such as phosphonocarboxylic acid or nitrogen-containing phosphoric acid is added, the thermal stability is further improved.

(C3 anti-dripping agent)
Further, the flame-retardant resin composition of the present invention may contain an anti-dripping agent such as a fluororesin as long as the effect of the present invention is not impaired. With the anti-dripping agent, dripping of the fire and the melt during combustion can be suppressed. The fluororesin includes homo- or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, and perfluoroalkylvinyl ether; the fluorine-containing monomers, ethylene, propylene, and acrylate. And other copolymerizable monomers. Examples of such a fluorine-based resin (fluorine-containing resin) include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene. Copolymers such as an ethylene-perfluoroalkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, and an ethylene-chlorotrifluoroethylene copolymer are exemplified. These fluororesins can be used alone or in combination of two or more.

  The fluororesin may be used in the form of particles, and the average particle size may be, for example, about 10 to 5000 μm, preferably about 100 to 1000 μm, and more preferably about 100 to 700 μm.

  The content of the fluorine-based resin is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 100 parts by mass of the resin (A1) and the resin (A2) in total. Is 0.1 to 3 parts by mass.

・ Additive (D1) / filler (D2)
Furthermore, the flame-retardant resin composition of the present invention may contain an additive (D1) and a filler (D2) as other components according to the purpose. Other additives (D1) include ultraviolet absorbers, heat stabilizers, stabilizers such as weathering stabilizers, lubricants, release agents, coloring agents, plasticizers, nucleating agents, impact modifiers, sliding agents, and the like. Can be Further, the flame retardant resin composition of the present invention may be modified with a filler (D2) in order to further improve mechanical strength, rigidity, heat resistance, electrical properties and the like. The filler (D2) includes a fibrous filler and a non-fibrous filler (a plate-like filler, a granular filler, and the like). When these additives (D1) and fillers (D2) are used, the proportion of the additives (D1) or fillers (D2) in the flame-retardant resin composition is within a range that does not impair the effects of the present invention. Although not particularly limited, when used, for example, the range of 1 to 60% by mass is preferable in the flame-retardant resin composition of the present invention, the range of 1 to 50% by mass is more preferable, and the range of 1 to 45% by mass is more preferable. Is most preferable.

(D2-1 fibrous filler)
Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, potassium titanate fiber, metal fiber, and high-melting organic fiber (for example, aliphatic or aromatic polyamide, aromatic Group polyester, fluorine resin, acrylic resin such as polyacrylonitrile, etc.). Preferred fibrous fillers include glass fibers and carbon fibers.

(D2-2 Non-fibrous filler)
Among the non-fibrous fillers, examples of the plate-like filler include glass flakes, mica, graphite, and various metal foils. Examples of the particulate filler include carbon black, silicon carbide, silica, quartz powder, glass beads, glass powder, milled fiber (for example, milled glass fiber), calcium silicate, aluminum silicate, kaolin, talc, clay, and silica. Silicates such as algae earth and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; sulfuric acids of metals such as calcium sulfate and barium sulfate Salts, metal powders and the like. Preferred non-fibrous fillers include particulate or platy fillers, especially glass beads, milled fibers, kaolin, talc, mica, and glass flakes.

  Particularly preferred fillers (D2) include glass fibers, for example, glass fibers having high strength and rigidity (such as chopped strands).

  When using these fillers (D2), it is desirable to use a sizing agent or a surface treatment agent, if necessary. Such sizing agents or surface treatment agents include functional compounds. Examples of the functional compound include an epoxy-based compound, a silane-based compound, a titanate-based compound, preferably an epoxy-based compound, particularly a bisphenol A-type epoxy resin and a novolak-type epoxy resin.

  The filler (D2) may have been subjected to convergence treatment or surface treatment with the sizing agent or surface treatment agent. Regarding the timing of the treatment, the treatment may be performed simultaneously with the addition of the filler, or may be performed before the addition. The amount of the functional surface treating agent or sizing agent used in combination is 5% by mass or less, preferably about 0.05 to 2% by mass, based on the filler.

  The phosphorus atom-containing oligomer (B) of the present invention can make the resin highly flame-retardant, probably because it promotes carbonization of the resin surface during combustion. Further, by using in combination with a polymer type phosphoric ester or an aromatic resin, it is possible to further impart flame retardancy to the flame retardant resin composition of the present invention even in a small amount, This is preferable because it does not cause out-out or decrease in heat resistance.

(D3 polymer compound)
(D3-1 resin)
In addition, the flame-retardant resin composition of the present invention may be a polyester resin or a polyether ketone resin based on 100 parts by mass of the resin (A1) and the resin (A2) in a range that does not impair the effects of the present invention. It is preferable to further mix 1 to 100 parts by mass of a polyarylene sulfide resin typified by a polyether resin, a polyimide resin, a polyamide resin, a polyphenylene sulfide resin, or a polyarylene ether resin typified by a polyphenylene ether resin. A polyarylene ether resin is a preferred resin from the viewpoint of improving flammability and heat resistance.
The polyphenylene ether resin that can be used in the present invention includes the following general formula (p-1)

(However, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon groups, and may be the same or different from each other.) A homopolymer and / or a copolymer comprising a bonding unit. Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferable, and the method for producing such a polyphenylene ether resin is not particularly limited, and for example, it is described in U.S. Patent No. 3,306,874. It can be easily produced, for example, by oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine according to the method as a catalyst. In addition, US Pat. No. 3,306,875 and US Pat. No. 3,257,357, U.S. Pat. No. 3,257,358 and JP-B-52-17880, The PPE used in the present invention has a reduced viscosity ηSP / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.20. It is preferably in the range of from 0.70 dl / g to 0.70 dl / g, and more preferably in the range of from 0.30 to 0.60 dl / g. Adjustment of the amount of catalyst at the time of producing the polyphenylene ether resin can be mentioned.

(D3-2 silicone compound)
In addition, the flame-retardant resin composition of the present invention is a composition that does not easily drop (drip) during burning by itself, but as long as the silicone compound is further added within a range that does not impair the effects of the present invention. This is preferable because the effect of suppressing dropping (drip) of droplets during combustion, suppression of flame spread during combustion, and improvement in impact resistance can be further enhanced. The silicone compound that can be used in the present invention refers to a silicone resin and / or a silicone oil.

  As the silicone resin that can be used in the present invention, the following general formulas (s-1) to (s-4)

(Here, R ²¹ represents a unit selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group, respectively) Examples include polyorganosiloxanes comprising chemically bonded siloxane units selected from a mixture. Further, those having a viscosity of about 200 to 300,000,000 centipoise at room temperature (23 ° C.) are preferred. It is not limited to this as long as it is a silicone resin.

  As the silicone oil that can be used in the present invention, the following general formula (s-5)

(Here, R ²² represents an alkyl group or a phenyl group, and i is an integer of 1 or more.). The silicone oil that can be used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited to the above silicone oil.

  As the silicone compound that can be used in the present invention, a silicone resin and / or a silicone oil can be used, but a silicone oil is preferred from the viewpoint of improving flame retardancy and impact resistance.

  The amount of the silicone compound to be added is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, based on 100 parts by mass of the resin (A1) and the resin (A2) in total. And more preferably 0.1 to 5 parts by mass.

-Method for producing flame-retardant resin composition The flame-retardant resin composition of the present invention further requires the polycarbonate resin (A1), the rubber-reinforced styrene resin (A2), and a phosphorus atom-containing oligomer (B). The flame retardant aid (C), the additive (D1), the filler (D2), and the polymer compound (D3) may be used in a range that does not impair the effects of the present invention, such as a tumbler or a Henschel mixer. After pre-mixing using various mixers in advance, use a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a mixer such as a kneader, and set the resin set temperature to the melting point or higher. It can be melt-kneaded. Alternatively, the components may be prepared by preliminarily mixing the components or by premixing only some of the components and supplying the extruder using a feeder to melt-knead the components. Further, when the components (C), (D1), (D2), and (D3) are added, if these components are brittle such that they are easily broken by melt-kneading, the components (A1), (A2) or (A2) A method in which the component (B) is batch-fed into the upstream portion, the components (C), (D1), (D2), and (D3) are added after the middle stream and melt-kneaded with the resin component is also used. It is preferable from the point of target strength. The resin composition after the melt-kneading is subjected to a molding process described later, but may be once in the form of pellets or powder for storage or distribution. The form in that case may be a known form such as a pellet or a powder, as long as the effects of the present invention are not impaired. The pellet is not particularly limited, but is preferably a pellet from the viewpoint of handleability. The pellets can be produced according to a conventional method. For example, it is preferable that the pellets are extruded into strands from the apparatus used for the melt-kneading, and then cooled with water and cut to form pellets.

-Flame-retardant masterbatch and method for producing the same The flame-retardant resin composition of the present invention contains the polycarbonate resin (A1), the rubber-reinforced styrene-based resin (A2) and the phosphorus atom-containing oligomer (B) as described above. The flame-retardant resin composition can be produced by directly melt-kneading, but contains the polycarbonate resin (A1) and / or the rubber-reinforced styrene resin (A2) and the phosphorus atom-containing oligomer (B) at a high concentration. A flame-retardant masterbatch is produced by melt-kneading, and a thermoplastic resin (E) such as the polycarbonate resin (A1) and / or the rubber-reinforced styrene resin (A2) is added to the obtained flame-retardant masterbatch. ) Can be obtained by diluting and compounding and melt-kneading. The details will be described below.

  More specifically, the above components (A1), (A2) and (B) are preliminarily mixed with a mixer such as a V-type blender, a ribbon blender or a Henschel mixer as required, and then kneaded in a single screw extruder. Using a known mixer such as a mixer, an open roll mixer, a pressurized kneader, a Banbury mixer, a twin-screw extruder or the like, melt kneading is performed with the resin set temperature equal to or higher than the melting point. Among them, the twin-screw extruder is preferable in view of kneading properties and productivity. After the melt-kneading, the mixture is processed into pellets or the like according to a conventional method to obtain the flame-retardant master batch of the present invention. The content ratio of the phosphorus atom-containing oligomer (B) in the flame-retardant masterbatch is not particularly limited as long as the effect of the present invention is not impaired, but the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2 ) Is preferably melt-kneaded to contain the phosphorus atom-containing oligomer (B) in a range of 3 to 20 parts by mass, and is melt-kneaded to be contained in a range of 8 to 20 parts by mass. Is more preferable.

  The flame-retardant resin composition of the present invention can be obtained by further adding a thermoplastic resin (E) as a diluting resin to the flame-retardant master batch thus obtained, and melt-kneading the mixture. By obtaining the flame-retardant resin composition via the master batch in this manner, the phosphorus-containing oligomer (B), which is a flame-retardant component, can be stably and uniformly dispersed, and can be added at a higher concentration. An excellent flame retardant effect can be imparted to the molded article.

  Here, the thermoplastic resin (E) for a diluting resin that can be used in the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, the polycarbonate resin (A1) and the rubber-reinforced styrene resin (A2) or a polymer compound (D3), that is, a polycarbonate resin, a rubber-reinforced styrene resin, a polyester resin, a polyether ketone resin, a polyether resin, a polyimide resin, a polyamide resin, a polyarylene sulfide resin, a polyarylene ether resin, Silicone compounds and the like can be mentioned, and among them, polycarbonate resin and polyarylene ether resin are preferable. When the flame-retardant master batch containing the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2) is melt-kneaded with the thermoplastic resin (E), the polycarbonate resin (A1) and the rubber-reinforced styrene-based styrene-based resin are melt-kneaded. As the resin (A2) and the thermoplastic resin (E), the same type of resin or different types of resins may be used depending on the purpose. However, the same type of resin may be used from the viewpoint of compatibility. preferable.

  In order to produce a flame-retardant resin composition from the flame-retardant master batch of the present invention, the polycarbonate resin (A1) and the rubber-reinforced styrene resin (A2) in the finally obtained flame-retardant resin composition )), The thermoplastic resin (E) for a diluting resin is adjusted and added so as to contain the phosphorus atom-containing oligomer (B) in a ratio of 3 to 20 parts by mass with respect to a total of 100 parts by mass. There is no particular limitation if it is melt-kneaded. For example, when the thermoplastic resin (E) is the polycarbonate resin (A1) and / or the rubber-reinforced styrene-based resin (A2), the polycarbonate resin (A1) and / or the rubber in the flame-retardant masterbatch is used. The thermoplastic resin (E) such that the phosphorus atom-containing oligomer (B) is 3 to 20 parts by mass with respect to a total of 100 parts by mass of the reinforced styrenic resin (A2) and the thermoplastic resin (E) for a dilution resin. Is preferably added. When the thermoplastic resin (E) is a resin other than the polycarbonate resin (A1) and / or the rubber-reinforced styrene resin (A2), the polycarbonate resin (A1) and / or the polycarbonate resin in the flame-retardant masterbatch is used. With respect to 100 parts by mass of the rubber-reinforced styrene-based resin (A2), 1 to 100 parts by mass of the thermoplastic resin (E) for the diluting resin and 3 to 20 parts by mass of the phosphorus atom-containing oligomer (B) are used. It is preferable to add a thermoplastic resin (E). The method of melt-kneading is not particularly limited, and for example, the same method as the method for producing the master batch can be employed.

  When producing the flame-retardant masterbatch, together with the polycarbonate resin (A1), the rubber-reinforced styrene-based resin (A2) and the phosphorus atom-containing oligomer (B), or the flame-retardant masterbatch When diluting into a batch, together with the thermoplastic resin (E), the flame retardant aid (C), the additive (D1), the filler (D2), and the polymer compound (D3) are used to make the effects of the present invention. It can also be blended within a range that does not impair.

-Molded article / use The flame-retardant resin composition of the present invention obtained as described above is melt-kneaded in a molding machine and subjected to extrusion molding, injection molding, calender molding, hollow molding, vacuum molding, pressure molding, etc. Flame-retardant resin molded articles can be produced by various known molding methods.

  As a specific example of the flame-retardant resin molded article obtained by molding the flame-retardant resin composition of the present invention, it is possible to use in various applications where high flame retardancy is required, particularly, a film , Sheets, fibers and the like. Specifically, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, Plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer related parts, etc. VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as audio and compact discs, lighting parts, refrigerator parts, air conditioners Home, office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, oil-less bearings, stern bearings, underwater, represented by parts, typewriter parts, word processor parts, etc. Various bearings such as bearings, motor parts, mechanical parts such as lighters, typewriters, etc., optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machine parts; alternator terminals, alternator connectors, ICs Regulators, various valves such as exhaust gas valves, various fuel related / exhaust / intake systems pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, Air gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump Impellers, turbine vanes, parts related to wiper motors, dust distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, fuel related solenoid valves coils, fuse connectors, horn terminals, electrical equipment Parts insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake pipe Ston, solenoid bobbin, engine oil filter, ignition device case, personal computer, printer, display, CRT display, fax, copy, word processor, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive, etc. It is useful for electrical and electronic equipment parts such as housings, chassis, relays, switches, case members, transformer members, coil bobbins, automobile parts, mechanical parts, and various other uses.

  The thickness of the sheet or film obtained by molding the flame-retardant resin composition of the present invention into a sheet or film shape varies depending on the use, and can be any thickness. It is preferably from 10 to 150 μm, more preferably from 20 to 100 μm, particularly preferably from 30 to 70 μm.

  A molded article obtained by molding the flame-retardant resin composition of the present invention, particularly a film, sheet, or fiber formed into a sheet, film, or fiber is a rubber-reinforced styrene resin having mechanical strength and transparency. In addition, it is possible to suppress the bleed out of the phosphorus atom-containing oligomer (B), which is a flame retardant component, and to exhibit excellent flame retardancy and heat resistance while maintaining various physical properties inherent in the polycarbonate resin-containing resin composition. it can.

  In addition, the term of the sheet or film in the present invention is not particularly used to strictly distinguish between the sheet and the film, but is used to clarify that both are included, and as long as it has the features of the present invention. , Sheets and films can be interpreted as broadly as possible, and the term sheet includes what is called a plate or plate as long as it has the features of the present invention. In addition, when it is necessary to distinguish between a sheet and a film, the sheet is usually used when the thickness is about 0.5 to 5 mm, and the film is usually used when the thickness is about 5 to 500 μm. used.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Polycarbonate resin (A1) / ABS resin (A2)>
A-1: Polycarbonate resin containing 30% by mass of ABS resin (“MULTILON T-3750” manufactured by Teijin Limited)
A-2: Polycarbonate resin ("Panlite L1225WP" manufactured by Teijin Limited)
<Phosphorus atom-containing oligomer>
B-1: A phosphorus atom-containing oligomer was produced by the following method.
In a flask equipped with a thermometer, a cooling pipe, a fractionating pipe, a nitrogen gas introducing pipe, and a stirrer, 1220 g (10.0 mol) of 2-hydroxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene were added. 1512 g (7.0 mol) of -10-oxide (hereinafter abbreviated as “HCA”) and 22.3 g (0.19 mol) of oxalic acid were charged, and the temperature was raised to 120 ° C. and reacted for 1 hour. Next, 1728 g (8.0 mol) of HCA was added, the temperature was raised to 180 ° C., and the mixture was reacted for 3 hours. Then, the water was removed by heating under reduced pressure, and the following structural formula

4100 g of a phosphorus atom-containing oligomer (B-1) having a structural unit represented by the following formula was obtained. The obtained phosphorus atom-containing oligomer has a softening point of 138 ° C. (B & R method), a melt viscosity (measuring method: ICI viscometer, measuring temperature: 180 ° C.) of 66 dPa · s, and a hydroxyl equivalent of 428 g / eq. The phosphorus content was 10.5%, and the component ratio of n = 2 or more was 49.0%.

<Phosphorus flame retardant>
B-2: Condensed phosphate ester (“PX-202” manufactured by Daihachi Chemical Co., Ltd.)
B-3: Condensed phosphonic acid ester ("Nonen 73" manufactured by Marubishi Yuka Kogyo Co., Ltd.)
B-4: Aluminum phosphinate ("EXOLIT OP-930" manufactured by Clariant Co., Ltd.)
B-5: Melamine polyphosphate ("MELAPUR 200/70" manufactured by Ciba Specialty Chemicals Co., Ltd.)

Examples 1 to 5 and Comparative Examples 1 to 8 Production of Flame Retardant Masterbatch After premixing the raw materials with a Henschel mixer so as to have the composition ratios shown in Tables 1 and 2, a sintered filter having an aperture of 25 μm was prepared. The mixture was melt-kneaded in a mounted twin-screw extruder with a diameter of 30 mm (a set temperature of 250 ° C.), and then a strand was obtained, cut and pelletized to produce a master batch. At that time, a resin pressure rise value during continuous operation for one hour was measured. Table 1 shows the results. In the production of a masterbatch using the twin-screw extruder, extrusion stability during continuous operation for one hour was evaluated according to the following criteria.

(Extrusion stability)
：: The state of the kneaded material was stable and could be extruded without any problem.
Δ: Although the viscosity of the kneaded material and the pulsation phenomenon and foaming slightly occurred, the strand could be pulled and sampling could be performed.
X: The viscosity of the kneaded material, the pulsation phenomenon and the foaming were remarkable, the strand could not be drawn, and sampling was impossible.

(Intrinsic viscosity)
Regarding the master batches (MB1-1) to (MB6-1) from which sampling was possible or the resin composition obtained using the same, phenol / 1,1,1,2,2-tetrachloroethane (mass ratio 1/1) ) Was dissolved at 110 ° C. to a concentration of 1.00 × 10 ⁻² kg / L using the mixed solvent described above, and then cooled to 30 ° C., and a fully automatic solution viscometer (“2CH DJ504” manufactured by Sentech Co., Ltd.) was used. )) Was used to measure the intrinsic viscosity. The measurement was performed by measuring the falling seconds of only the sample solution having a concentration of 1.00 × 10 ⁻² kg / L and the solvent alone, and calculating by the following equation.
IV = [(1 + 4KH · ηsp) 0.5-1] / (200KH · C)
(Here, ηsp = η / η0-1, where η is the number of seconds the sample solution has fallen, η0 is the number of seconds the solvent has fallen, C is the polymer solution concentration (kg / L), and KH is Huggins constant. KH was 0.33.)

(Examples 6 to 19, Comparative Examples 9 to 16)
Using the polycarbonate resin composition pellets (master batch) (MB1-1) to (MB6-1) that could be sampled, dilution was performed so that the composition ratio (flame retardant concentration) shown in Tables 3 to 6 was obtained. After dry blending using the pellets of the polymer for use (E), a bar-shaped test piece having a thickness of 2 mm and a bar-shaped test piece having a thickness of 3 mm were prepared using an injection molding machine.

The molding by the injection molding machine was performed under the following conditions.
Molding machine: Roboshot S-2000i manufactured by FANUC
Molding conditions: cylinder temperature 260 ° C, mold temperature 70 ° C, injection speed 50mm / sec, screw rotation speed 80rpm, back pressure 3MPa, holding pressure 50MPa, holding pressure time 5sec, cooling time 10sec

Mold 1 (2 mm thick bar-shaped test piece): 13 mm wide x 135 mm long x 2 mm thick Mold for bar-shaped test piece Mold 2 (3 mm thick bar-shaped test piece): 13 mm wide x 135 mm long × 3 mm thick bar-shaped test piece mold

<Polymer for dilution (E)>
E-1: Polycarbonate resin containing 30% by mass of ABS resin (“MULTILON T-3750” manufactured by Teijin Limited)
E-2: Polycarbonate resin ("Panlite L1225WP" manufactured by Teijin Limited)

(Evaluation of flame retardancy (vertical combustion))
Each of the obtained flame-retardant resin compositions was molded at a set temperature (260 ° C.) using an injection molding machine to prepare a bar-shaped test piece having a thickness of 2 mm. The obtained bar-shaped test piece was evaluated by a method based on the UL94 vertical combustion test standard.

(Evaluation of flame retardancy (critical oxygen index))
Each of the obtained flame-retardant resin compositions was molded at a set temperature (260 ° C.) using an injection molding machine to prepare a bar-shaped test piece having a thickness of 3 mm. After cutting the obtained bar-shaped test piece in half in the longitudinal direction, it was evaluated by a method based on JIS-K7201.

(Evaluation of mechanical properties (flexural strength))
Each of the obtained flame-retardant resin compositions was molded at a set temperature (260 ° C.) using an injection molding machine to prepare a bar-shaped test piece having a thickness of 3 mm. The obtained bar-shaped test piece was evaluated by a method based on ASTM-D790.

(Evaluation of mechanical properties (Izod impact strength))
Each of the obtained flame-retardant resin compositions was molded at a set temperature (260 ° C.) using an injection molding machine to prepare a bar-shaped test piece having a thickness of 3 mm. After the obtained bar-shaped test piece was cut in half in the transverse direction, it was notched and evaluated by a method based on ASTM-D256.

(Evaluation of moldability)
At the time of injection-molding 10 bar-shaped test pieces having a thickness of 3 mm, the drawing at the time of resin measurement in an injection molding machine and the obtained bar-shaped test pieces were observed and evaluated according to the following criteria. .
・ ・ ・: No molten resin leaked from the nozzle at the time of resin measurement, and drawing did not occur. Further, no stringing was observed in the sprue portion of the bar-shaped test piece, and the sprue was completely broken and continuous molding was possible.
Δ: Molten resin did not leak from the nozzle during resin measurement, and drawing did not occur. Moreover, stringing was observed in the sprue portion of the bar-shaped test piece, no sprue break occurred, and continuous molding was impossible.
X: Molten resin leaked from the nozzle during resin measurement, and drawing occurred. Moreover, stringing was observed in the sprue portion of the bar-shaped test piece, no sprue break occurred, and continuous molding was impossible.

Claims (13)

A flame-retardant resin composition containing a polycarbonate resin (A1), a rubber-reinforced styrenic resin (A2), and a phosphorus atom-containing compound and an oligomer (B) as essential components, wherein the polycarbonate resin (A1) and the rubber-reinforced resin are used. The phosphorus-containing compound and oligomer (B) are contained in the range of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the styrene-based resin (A2), and the phosphorus-containing compound and oligomer (B) are: The following structural formula (1)
(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; n is a repeating unit in the range of 1 to 10; Is the following structural formula (x1) or (x2)
Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. A flame-retardant resin composition represented by the formula: A method for producing a flame-retardant resin composition comprising melt-kneading a polycarbonate resin (A1), a rubber-reinforced styrenic resin (A2), and a phosphorus atom-containing compound and an oligomer (B), wherein the polycarbonate resin (A1) and the rubber The phosphorus-containing compound and oligomer (B) are contained in the range of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the reinforced styrenic resin (A2), and the phosphorus-containing compound and oligomer (B) are , The following structural formula (1)
(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; n is a repeating unit in the range of 1 to 10; Is the following structural formula (x1) or (x2)
Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. A method for producing a flame-retardant resin composition, characterized in that: A step (1) of preparing a flame-retardant masterbatch by melt-kneading a polycarbonate resin (A1), a rubber-reinforced styrene-based resin (A2), and a phosphorus atom-containing compound and an oligomer (B) in advance; A method for producing a flame-retardant resin composition, further comprising a step (2) of melt-kneading a thermoplastic resin (E) to the obtained flame-retardant master batch,
The phosphorus atom-containing compound and the oligomer (B) are represented by the following structural formula (1)
(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; n is a repeating unit in the range of 1 to 10; Is the following structural formula (x1) or (x2)
Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. A method for producing a flame-retardant resin composition, characterized in that: In the step (1), a phosphorus atom-containing compound and an oligomer (B) are melted in a range of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2). The method for producing a flame-retardant resin composition according to claim 3, which is kneaded. In the step (2), the thermoplastic resin (E) is selected from the group consisting of a polycarbonate resin, a rubber-reinforced styrene resin, a polyester resin, a polyether ketone resin, a polyether resin, a polyimide resin, a polyamide resin, and a polyarylene ether resin. The method for producing a flame-retardant resin composition according to claim 3, which is at least one selected from the group consisting of: A flame-retardant master batch containing a polycarbonate resin (A1), a rubber-reinforced styrene-based resin (A2), a phosphorus atom-containing compound and an oligomer (B) as essential components,
The phosphorus atom-containing compound and the oligomer (B) are represented by the following structural formula (1)
(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group; n is a repeating unit in the range of 1 to 10; Is the following structural formula (x1) or (x2)
Wherein Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2); and in the structural formula (x1) or (x2), ^{2, R 3, R 4,} R 5 are, each independently, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group. ),
The total content of the polycarbonate resin (A1) and the rubber-reinforced styrene resin (A2) is 100 parts by mass, and the phosphorus atom-containing compound and the oligomer (B) are contained at a content ratio of 3 to 20 parts by mass. A flame-retardant masterbatch characterized by the following. A flame-retardant resin composition obtained by melt-kneading the thermoplastic resin (E) with the flame-retardant master batch according to claim 6. The thermoplastic resin (E) is the polycarbonate resin (A1) and / or the rubber-reinforced styrene resin (A2), and the polycarbonate resin (A1) and the rubber-reinforced styrene resin ( The flame-retardant resin composition according to claim 7, wherein the phosphorus atom-containing compound and the oligomer (B) are in a range of 3 to 20 parts by mass with respect to 100 parts by mass in total of A2) and the thermoplastic resin (E). The thermoplastic resin (E) is a thermoplastic resin other than the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin (A2), and the polycarbonate resin (A1) and the rubber-reinforced styrene-based resin in a flame-retardant masterbatch are used. The thermoplastic resin (E) is in a range of 1 to 100 parts by mass and the phosphorus atom-containing compound and oligomer (B) are in a range of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the resin (A2). Flame-retardant resin composition. A molded article obtained by molding the flame-retardant resin composition according to claim 1. A fiber obtained by molding the flame-retardant resin composition according to claim 1. A film or sheet obtained by molding the flame-retardant resin composition according to claim 1. A method for producing a molded article for molding the flame-retardant resin composition according to claim 1.