JP6519768B2 - Flame retardant resin composition, molded body 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, heat resistance, impact resistance and color tone without impairing the mechanical properties inherent to a rubber-reinforced styrenic resin, and It relates to an article.

  Conventionally, a flame retardant rubber-reinforced styrene resin has a moldability, a good balance of mechanical properties, and an excellent electrical insulation property. It is used in a wide range of fields. At the time of combustion, a method of flame-retardanting was first adopted as a method of flame-retarding by blending a halogen-based flame retardant such as bromine compound with high flame-retarding efficiency and antimony oxide into a resin to make it flame-retardant. Methods using non-halogen flame retardants have been proposed because of the large amount of smoke and the reduction of environmental impact.

  As a non-halogen flame retardant, for example, typical phosphoric acid esters of phosphorus flame retardants are often used conventionally (see Patent Documents 1 and 2). However, the flame retarding effect of the phosphate ester is extremely low, and in order to impart flame retardancy to the thermoplastic resin, it is necessary to mix the phosphate ester in a large amount, and the heat resistance, impact resistance, and further the gloss or not There was a problem that the color tone decreased. Furthermore, since the phosphate ester bleeds out, there is a problem that mold contamination occurs at the time of molding and a problem that a gas is generated at the time of molding.

  Therefore, as a method for solving these problems, a method of adding a novolac phenol resin and a compound containing a triazine skeleton as a carbonized layer-forming polymer to a hydroxyl group-containing phosphoric acid ester is disclosed (see Patent Document 3). However, this method also has not been able to solve the problem that the mechanical properties inherent to the rubber-reinforced styrene resin, in particular, the impact resistance and the moldability are impaired.

  As a method of suppressing the mechanical property decrease, a method of using a modified phenolic resin is disclosed (see Patent Document 4). However, the method is also insufficient in flame retardancy and can not maintain the inherent heat resistance of the rubber reinforced styrene resin.

JP-A-59-247365 Unexamined-Japanese-Patent No. 7-26093 gazette JP-A-7-70448 JP 2005-36135 A

  Therefore, the problem to be solved by the present invention is to use a non-halogen flame retardant and maintain the mechanical properties of rubber reinforced styrene resin such as impact resistance and color tone, while maintaining the inherent physical properties of rubber reinforced styrene resin The present invention is to provide a rubber-reinforced styrene resin composition excellent in suppression of bleed out, flame retardancy and heat resistance and a molded article thereof.

    The present inventors conducted various studies and found that a rubber-reinforced system obtained by blending a phosphorus atom-containing phenolic oligomer obtained by reacting HCA or a derivative thereof with an o-hydroxybenzaldehyde compound to a rubber-reinforced styrene resin It has been found that a styrene resin composition and a molded article thereof maintain excellent physical properties of a rubber-reinforced styrene resin while suppressing bleed out of the above-mentioned oligomers, and have excellent flame retardancy and heat resistance, It came to complete.

That is, the present invention
A flame retardant resin composition comprising a rubber-reinforced styrenic resin (A) and a phosphorus atom-containing oligomer (B) as essential components, comprising phosphorus atoms relative to 100 parts by mass of the rubber-reinforced styrenic resin (A) The oligomer (B) is contained in the range of 3 to 40 parts by mass, and 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)

Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R is a structural site represented by 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. It relates to a flame retardant resin composition characterized by being represented by

Also, the present invention is
(2) A method for producing a flame-retardant resin composition, which comprises melt-kneading a rubber-reinforced styrene resin (A) and a phosphorus atom-containing oligomer (B), wherein 100 parts by mass of the rubber-reinforced styrene resin (A) is used. Containing the phosphorus atom-containing oligomer (B) in the range of 3 to 40 parts by mass, and 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)

Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R is a structural site represented by 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. The present invention relates to a method for producing a flame-retardant resin composition characterized by

  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, the non-halogen flame retardant is used, and mechanical strength, in particular, the inherent physical properties of rubber reinforced styrene resin such as impact resistance and color tone are maintained, and bleeding out of the non halogen flame retardant is suppressed and difficult It is possible to provide a rubber-reinforced styrene resin composition excellent in flame resistance and heat resistance and a molded article thereof.

  The flame-retardant resin composition of the present invention is a flame-retardant resin composition comprising a rubber-reinforced styrenic resin (A) and a phosphorus atom-containing oligomer (B) as essential components, and the phosphorus atom-containing oligomer (B) ) But 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)

Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R is a structural site represented by 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. It is characterized by being represented by.

・ Rubber reinforced styrene resin (A)
The rubber-reinforced styrene resin (A) (hereinafter sometimes referred to simply as "resin (A)") used in the present invention is an aromatic vinyl monomer and, if necessary, an aromatic vinyl monomer in the presence of a rubbery polymer. A monomer mixture obtained by adding a vinyl monomer copolymerizable with this to a known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.

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

  In addition, as a rubber reinforced styrene resin, a polymer or copolymer containing a styrene monomer (hereinafter sometimes referred to as a (co) polymer) has a grafted structure on a rubbery polymer. And those in which the (co) polymer containing a styrene monomer has a non-grafted structure with the rubbery polymer.

  Specifically, it is obtained by graft polymerization of 95 to 20 parts by mass of a monomer or monomer mixture containing 20% by mass or more of an aromatic vinyl-based monomer with respect to 5 to 80 parts by mass of a rubbery polymer. Vinyl system obtained by polymerizing 10 to 100% by mass of the graft (co) polymer (A-1) to be prepared and a monomer or monomer mixture containing 20% by mass or more of an aromatic vinyl monomer What consists of co-polymer (A-2)-90 mass% is mentioned as a preferable thing.

  As the rubbery polymer, one having a glass transition temperature of 0 ° C. or less is suitable, and a diene rubber is preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, block copolymer of styrene-butadiene, diene rubber such as butyl acrylate-butadiene copolymer, acrylic such as polybutyl acrylate There may be mentioned rubbers, polyisoprenes and ethylene-propylene-diene terpolymers. Among them, the use of polybutadiene or butadiene copolymer is preferred.

  The rubber particle diameter of the rubbery polymer is not particularly limited, but the impact resistance is excellent when the mass average particle diameter of the rubber particles is 0.15 to 0.6 μm, particularly 0.2 to 0.55 μm. It is preferable from Among them, those having a mass average particle diameter of 0.20 to 0.25 μm and a mass ratio of 0.50 to 0.65 μm of 90:10 to 60:40 are impact resistance and thin-walled molded articles It is preferable because the falling weight impact is significantly improved.

  The average mass particle diameter of the rubber particles is the sodium alginate method described in “Rubber Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, PH Biddison” (creamed by the concentration of sodium alginate) The particle size of 50% of the cumulative mass fraction can be determined from the creamed mass ratio and the cumulative mass fraction of the sodium alginate concentration by utilizing the fact that the polybutadiene particle size is different.

  Specific examples of the aromatic vinyl-based monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene and p-t-butylstyrene, and the use of styrene is particularly preferred.

  As monomers other than aromatic vinyl monomers, vinyl chloride cyanide monomers for the purpose of further improving the impact resistance and chemical resistance are also intended to improve the toughness and color tone. When using, (meth) acrylic acid ester type monomers are preferably used respectively.

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

  Further, specific examples of the (meth) acrylic acid ester monomers include methyl, ethyl, propyl, n-butyl and isobutyl esterified products of acrylic acid and methacrylic acid, and methyl methacrylate is particularly preferable. Be

  In addition, other vinyl-based monomers such as maleimide-based monomers such as maleimide, N-methyl maleimide, and N-phenyl maleimide can also be used, if necessary.

  The monomer or monomer mixture used in the above graft (co) polymer (A-1) has an aromatic vinyl monomer content of 20% by mass or more from the viewpoint of the impact resistance of the resin composition Is more preferably 50% by mass or more. In the case of mixing a vinyl cyanide-based monomer, the content is preferably 60% by mass or less, particularly preferably 50% by mass or less, from the viewpoint of molding processability of the resin composition. Moreover, when mixing a (meth) acrylic acid ester type monomer, it is preferable that it is 80 mass% or less from a viewpoint of toughness and impact resistance, and 75 mass% or less is used preferably especially. The total of the blending amounts of the aromatic vinyl monomer, vinyl cyanide monomer and (meth) acrylate monomer in the monomer or monomer mixture is 95 to 20% by mass Is more preferable, and more preferably 90 to 30% by mass.

The compounding ratio of the rubbery polymer and the monomer mixture when obtaining the graft (co) polymer (A-1) is 100 parts by mass of the entire graft copolymer from the viewpoint of the impact resistance of the resin composition. The amount of the rubbery polymer is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. Moreover, it is preferable that it is 80 mass parts or less from a viewpoint of the impact resistance of a resin composition, and the external appearance of a molded article, More preferably, it is 70 mass parts or less. The mixing ratio of the monomer or the monomer mixture is 95 parts by mass or less, preferably 90 parts by mass or less, or 20 parts by mass or more, preferably 30 parts by mass or more.

The graft (co) polymer (A-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 emulsifying agent are continuously supplied to a polymerization vessel in the presence of a rubbery polymer latex and emulsion polymerization is performed. .

The graft (co) polymer (A-1) contains a non-grafted copolymer in addition to a graft copolymer having a structure in which a monomer or a mixture of monomers is grafted to a rubbery polymer. It is The graft ratio of the graft (co) polymer is not particularly limited, but in order to obtain a resin composition in which the impact resistance and the gloss are well balanced, it is in the range of 20 to 80% by mass, particularly 25 to 50% by mass. Is preferred. Here, the graft ratio is a value calculated by the following equation.
Graft ratio (%) = [<amount of vinyl copolymer graft-polymerized to rubbery polymer> / <rubber content of graft copolymer> × 100

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

  The vinyl-based (co) polymer (A-2) is a copolymer essentially comprising an aromatic vinyl-based monomer. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyl toluene and o-ethylstyrene, with styrene being particularly preferably used. One or more of these may be used.

  As monomers other than aromatic vinyl monomers, vinyl chloride cyanide monomers for the purpose of further improving the impact resistance and chemical resistance are also intended to improve the toughness and color tone. When using, (meth) acrylic acid ester type monomers are preferably used.

  Specific examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being particularly preferably used. Specific examples of (meth) acrylic acid ester monomers include methyl, ethyl, propyl, n-butyl and isobutyl esterified products of acrylic acid and methacrylic acid, and methyl methacrylate is preferably used. .

  Moreover, as another vinyl-type monomer copolymerizable with these used as needed, maleimide-type monomers, such as maleimide, N- methyl maleimide, and N- phenyl maleimide, are mentioned.

  In the present invention, a vinyl-based copolymer obtained by copolymerizing a maleimide-based monomer, that is, a maleimide-group-modified vinyl-based copolymer is contained in a polystyrene-based resin and used, whereby the heat resistance of the resin composition is obtained. It can be preferably used because it can improve the flame resistance and also can improve the flame retardance specifically.

  The proportion of the aromatic vinyl monomer which is a constituent component of the vinyl (co) polymer (A-2) is 20% by mass or more based on all the monomers from the viewpoint of the impact resistance of the resin composition. Preferably, it is in the range of 50% by mass or more. In the case of mixing a vinyl cyanide-based monomer, from the viewpoint of impact resistance and flowability, the content is preferably 60% by mass or less, more preferably 50% by mass or less. Moreover, when mixing a (meth) acrylic acid ester type monomer, from a viewpoint of toughness and impact resistance, 80 mass% or less is preferable, More preferably, it is the range of 75 mass% or less. Furthermore, in the case of mixing other vinyl monomers copolymerizable with these, 60 mass% or less is preferable, and 50 mass% or less is particularly preferable.

  The characteristics of the vinyl (co) polymer (A-2) are not limited, but the intrinsic viscosity [η] measured at 30 ° C. using methyl ethyl ketone solvent is 0.4 to 0.65 dl / g, particularly Those in the range of 0.45 to 0.55 dl / g or 0.35 to 0.85 dl / g, especially 0.45, as measured at 30 ° C. using N, N-dimethylformamide solvent The thing of -0.7 dl / g is preferable from the resin composition which has the outstanding impact resistance and moldability being obtained.

  There are no particular limitations on the method for producing the vinyl (co) polymer (A-2), and conventional methods such as bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization and solution-mass polymerization may be used. Methods can be used.

  In the present invention, a modified vinyl polymer (hereinafter, modified vinyl polymer) optionally containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group and an oxazoline group ) Can also be used. The modified vinyl polymer has a structure obtained by polymerizing or copolymerizing one or two or more kinds of vinyl monomers, and a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and the like in the molecule. It is a polymer containing at least one functional group selected from oxazoline groups. Although it does not restrict | limit about content of the compound containing these functional groups, It is preferable that it is the range of 0.01-20 mass parts especially per 100 mass parts of modified vinyl polymers.

  There are no particular limitations on the method for introducing a carboxyl group into the modified vinyl polymer, but there may be mentioned carboxyl groups such as acrylic acid, methacrylic acid, maleic acid, monoethyl ester of maleic acid, maleic anhydride, phthalic acid and itaconic acid or A method of copolymerizing a vinyl monomer having a carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovalerate), α, α′-azobis (α-cyanoethyl) -p Polymerization initiators having a carboxyl group such as benzoic acid and peroxide succinate and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto-isobutyric acid and 2,3 or 4-mercapto (Co) a predetermined vinyl monomer using a polymerization degree regulator having a carboxyl group such as benzoic acid And a copolymer of a (meth) acrylate monomer such as methyl methacrylate or methyl acrylate and an aromatic vinyl monomer, and optionally a vinyl cyanide monomer. A method such as saponification with alkali can be used.

The method for introducing the hydroxyl group is also not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3, acrylate 4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5- methacrylate 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-pente , 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.

  The method for introducing the above epoxy group is not particularly limited, but, for example, an epoxy such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether and p-glycidyl styrene For example, a method of copolymerizing a vinyl monomer having a group with a predetermined vinyl monomer can be used. Among them, an epoxy-modified vinyl-based copolymer in which an epoxy group is introduced by copolymerizing glycidyl methacrylate is used in a polystyrene-based resin, and the flame retardancy and impact strength of the resin composition of the present invention are obtained. Can be improved.

  The method for introducing the above amino group is not particularly limited, but, for example, acrylamide, methacrylamide, N-methyl acrylamide, butoxymethyl acrylamide, N-propyl methacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethyl methacrylate Amino group such as aminoethyl, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene and the like And a method of copolymerizing a vinyl-based monomer having a derivative thereof with a predetermined vinyl-based monomer.

  The method for introducing the above oxazoline group is also not particularly limited, but, for example, vinyl-based unit having oxazoline groups such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline A method of copolymerizing a body with a predetermined vinyl monomer can be used.

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

・ 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)

Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R is a structural site represented by 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. And the content of the component in which n is 2 or more in the structural formula (1) is characterized in that it is in the range of 5 to 90% on the basis of 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 at the time of melt-kneading and maintain good releasability from the mold, while using thin molded articles and moldings. It is possible to dramatically improve the flame retardancy performance of thin-walled parts and thin-film parts of products.

  Thus, the phosphorus atom-containing oligomer (B) 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 above 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 It is a structural site represented by Since the structural part represented by is included as a repeating unit, the flame retardance in a molded article, especially the flame retardance in a thin-walled part improves dramatically.

  Here, specific examples of the structural part represented in 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 formula (x1) and the structural formula (x2), but particularly from the viewpoint of flame retardancy, the structural formula (x1) Preferably, among structural sites represented by the structural formula (2), structural formulas (2-1), (2-2), (2-3) corresponding to the structural formula (x-1) are preferable. And (2-4) are preferable.

  Further, in the structural formula (1), Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), but these coexist in the phosphorus atom-containing oligomer May be In the present invention, Y is preferably a hydrogen atom or a structural portion represented by the structural formula (x1) or (x2) from the viewpoint of heat resistance and flame retardancy, and in particular, from the viewpoint of flame retardancy, Y is a structure It is preferable that it is a formula (x1).

  Further, as described above, in the above-mentioned phosphorus atom-containing oligomer, in the above structural formula (1), n is in the range of 1 or more, preferably in the range of 1 to 10. Furthermore, when the content of the component where n is 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 It is more preferable because it becomes remarkably excellent.

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

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

Column: Tosoh Corp. guard column "HXL-L"
+ "TSK-GEL G2000 HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000 HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation "TSK-GEL G3000HXL"
+ Tosoh Corporation "TSK-GEL G4000HXL"

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

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

  Standard: In accordance with the measurement manual of the above-mentioned "GPC-8020 model II version 4.10", the following monodispersed polystyrene having a known molecular weight was used.

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

  Sample: A solution obtained by filtering a 1.0% by mass tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl).

NMR: Nippon Denshi JNM-ECA 500 nuclear magnetic resonance apparatus Magnetic field strength: 500 MHz
Pulse width: 3.25 μsec
Number of integration: 8000 times Solvent: DMSO-d6
Sample concentration: 30 wt%

MS: Shimadzu Biotech AXIMA-TOF2
Measurement mode: linear
Integration count: 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 n is 2 or more is 5% or more on the basis of the peak area in the GPC measurement, the compatibility with the resin (A) is good, and bleeding at the time of melt kneading is small. On the other hand, in the case of 90% or less, the flowability at the time of melt-kneading becomes good, and the impact strength is also excellent. Here, the other component is a component in which n is 1, so that in the phosphorus atom-containing oligomer of the present invention, the component in which n is 1 has a ratio of 95 to 10% based on the peak area in GPC measurement. In the present invention, the content of the component of n is 2 or more from the viewpoint that the flame retardancy performance excellent in the cured product can be further improved while maintaining the compatibility with the resin (A) and the processability at a high level. The content of the component in which n is 1 is preferably in the range of 60 to 25%.

  Furthermore, specifically, the content of the component where n is 1 is 95 to 10%, the content of the component for n 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, and in particular, 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 n is 3 or more The content of the component is preferably 10 to 40% from the viewpoint of achieving an excellent balance between processability and flame retardancy.

  In addition, as described above, Y in the structural formula (1) is preferably structural formula (x1). Therefore, in the structural formula (1), Y is structural formula (x1), and n The phosphorus atom containing oligomer whose content of the component of 2 or more is 40 to 75% and the content of the component of n 1 is 60 to 25% is preferable from the point of flame retardancy and heat resistance, and further, the structural formula In (1), Y is a structural formula (x1), and the content of components where n is 1 is 95 to 10%, the content of components where n is 2 is 3 to 50%, and n is 3 or more It is preferable that the content of components of the component is 1 to 45% from the viewpoint of excellent bleeding prevention and flame retardancy improvement, and compatibility with the resin (A). In particular, Y is a structural formula (x1) And the content of the component where n is 1 is 60 to 25%, and the content of the component where n is 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) described above preferably has a phosphorus atom content in the oligomer in a range of 9 to 12% by mass from the viewpoint of flame retardancy. The phosphorus atom content is a value measured in accordance with “JIS Standard K 0102 46”.

  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 of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, or a phenyl group), and the compound (b2) is The compound (b1) / the compound (b2)] is blended in a ratio of 0.01 / 1.0 to 0.99 / 1.0, and the reaction is performed at 80 to 180 ° C. in the presence of an acid catalyst, and The compound (b1) is added in a total amount of 1.01 to 3.0 times the molar amount based on the charged amount of the compound (b2), and the reaction can be carried out at 120 to 200 ° C.

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

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

  Examples of the catalyst that can be used in the above 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, zinc chloride and the like And Lewis acids. The amount used is preferably in the range of 0.1 to 5.0% by mass with respect to the total weight of the charged raw material from the viewpoint of preventing a decrease in the electrical insulation of the cured product.

  The reaction can be carried out using the compound (b2) as an organic solvent because the compound (b2) is in liquid form, but other organic solvents may be used from the viewpoint of improvement of workability and the like. Here, examples of the organic solvent to be used include non-ketone organic solvents such as alcohol-based organic solvents and hydrocarbon-based organic solvents. Specifically, examples of the alcohol-based organic solvents include propylene glycol monomethyl ether and the like. Examples of the hydrocarbon-based organic solvent include toluene and xylene.

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

  The content ratio of the phosphorus atom-containing oligomer (B) used in the present invention in the flame retardant resin composition is not particularly limited as long as the effects of the present invention are not impaired, but mechanical properties, flame retardancy and gloss It is preferable that the range is 3 to 40 parts by mass with respect to 100 parts by mass of the rubber-reinforced styrenic resin (A) from the viewpoint of excellent appearance such as elasticity and color tone, and from the point of excellent heat resistance, 3 More preferably, it is in the range of -30 parts by mass. In addition, from the viewpoint of fluidity at the time of molding, it is preferably in the range of 3 to 25 parts by mass with respect to 100 parts by mass of the rubber-reinforced styrenic resin (A). Most preferably, it is in the range of -20 parts by mass.

· Flame retardant auxiliary (C)
Since the flame retardant resin composition of the present invention improves flame retardancy and thermal stability, various flame retardant assistants (for example, other flame retardants, antioxidants, stabilizers, dripping, etc., as needed. And the like) may be contained.

(C1 Other flame retardants)
In addition, since the flame retardant resin composition of the present invention further imparts flame retardancy, other flame retardants, for example, phosphorus containing compounds, nitrogen containing flame retardants, sulfur containing flame retardants, silicon containing flame retardants, alcohol based Flame retardants, inorganic flame retardants (metal oxides, metal hydroxides, etc.) (hereinafter sometimes referred to as other flame retardants), etc. may be included within the range that does not impair the effects of the present invention.

(C1-1) Phosphorus-containing compound As the phosphorus-containing compound, organic phosphorus compounds (monomer type, dimer type and trimer type oligomer type organophosphorus compounds, polymer type organophosphorus compounds, etc.), inorganic phosphorus compounds and the like are listed. Be

(C1-1-1) Organophosphorus Compounds Among the organophosphorus compounds, oligomeric organophosphorus 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.), polymeric organophosphorus compounds, phosphine oxides, etc. are included.

(C1-1-1-1) Phosphoric acid ester As a phosphoric acid ester, aliphatic phosphoric acid ester [trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate] Phosphoric acid tri C _1-10 alkyl ester such as pentaerythritol phosphate (eg, NH-1197 of Great Lakes Chemical Co., Ltd., bicyclo phosphoric acid ester described in JP-A No. 2001-106889, etc.); corresponding to the phosphoric triester Phosphate di C _1-10 alkyl ester and phosphoric mono C _1-10 alkyl ester etc., aromatic phosphate ester [triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, diphenyl cresyl 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, dicresyl pentaerythritol diphosphate, dixyl pentaerythritol diphosphate etc) and the like.

(C1-1-1-2) Phosphoric Acid Ester Amide Phosphoric acid ester amide includes a binding mode of phosphoric acid ester and phosphoric acid amide, and is disclosed in JP-A-2002-226547, JP-A-2001-354684, and the like. Japanese Patent Application Laid-Open Nos. 2001-139823, 2000-327834, 2000-154277, 10-175985, 8-59888, 63-235363, Japanese Patent Laid-Open Nos. The phosphoric acid ester amides described in JP-A-54-19919 can be used.

  Phosphate ester amide can be obtained under the trade name "Phosphate Ester Amide Flame Retardant SP Series (for example, SP-601, SP-670, SP-703, etc.)" (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

(C 1-1-1-3) Phosphonitrile Compound As the phosphonitrile compound, linear and cyclic phenoxy phosphazene can be used.

(C1-1-1-4) Organic Phosphonic Acid Compound As the organic phosphonic acid (phosphorous acid) compound, for example, aromatic phosphorous acid ester (triC ₆ phosphorous acid whose aryl is phenyl, cresyl, xylyl, etc.) _-20 aryl ester and the like), aliphatic phosphite ester (a phosphite tri C _1-10 alkyl ester in which the alkyl is the alkyl and the like; phosphite di or mono C ₁ corresponding to the phosphite trialkyl ester) _-10 alkyl esters, etc.), organic phosphites [eg, spiro cyclic alkyl phosphonates such as C _1-6 alkyl phosphonic acid di C _1-6 alkyl (pentaerythritol bis (methyl phosphonate) where alkyl is the alkyl as exemplified above] Acid ester, etc., alkyl is the alkyl as 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-phosphonic acid diesters (such as spirocyclic C _6-10 arylphosphonic acid esters such as pentaerythritol diphenylphosphonate); C _6-10 arylphosphonic acid monoesters (eg 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. Also included are phosphorous acid, phosphorous monoesters, metal salts of phosphonocarboxylic acids (such as Ca, Mg, Zn, Ba, and Al salts) which may be substituted with an alkyl or aryl group.

(C1-1-1-5) Organic Phosphinic Acid Compound In the organic phosphinic acid compound, an alkyl group (such as a C _1-4 alkyl group) or an aryl group (such as a C _6-10 aryl group) is substituted (monosubstituted or disubstituted). (Optionally substituted) phosphinic acid ester (C _1-6 alkyl of phosphinic acid such as methyl phosphinate, C _6-10 aryl of phosphinic acid such as phenyl phosphinate, 9, 10-dihydro-9-oxa-10-phos Phaphenanthrene-10-oxide, cyclic phosphinic acid esters such as 10-C _1-30 alkyl or C _6-20 aryl substituted -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Is included. And metal salts (such as Ca, Mg, Zn, Ba, and Al salts) of phosphinic acids (eg, dimethylphosphinic acid, diethylphosphinic acid, methylethylphosphinic acid, etc.) optionally substituted with an alkyl group or an aryl group; Also included are phosphinico carboxylic acid esters (e.g., 3-methyl phosphinico propionic acid ester, 3-phenyl phosphinico propionic acid ester, etc.), and homopolymers and copolymers thereof.

(C1-1-1-6) Polymer-Type Organophosphorus Compound As the polymer-type organophosphorus compound, a condensate of a monomer-type organophosphorus compound other than the polymer-type phosphate ester (C), for example, polyphosphinico carboxylic acid ester And polyphosphonic acid amides.

(C1-1-1-7) Phosphine Oxide As the phosphine oxide, triphenyl phosphine oxide, tricresyl phosphine oxide and the like can be mentioned.

(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 red phosphorus, normally, red phosphorus (stabilized red phosphorus) subjected to stabilization treatment is preferably used. In particular, red phosphorus obtained by a method of pulverizing red phosphorus without pulverizing it and forming fine particles without forming a crushed surface having high reactivity with water and oxygen on the red phosphorus surface, and further, the surface of red phosphorus, Red phosphorus etc. covered by resin (for example, thermosetting resin, thermoplastic resin), metal, metal compound (for example, metal hydroxide, metal oxide etc.) etc. alone or in combination of 2 or more types can be used .

  As red phosphorus, stabilized red phosphorus can usually be used in powder form. 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 salts of (poly) phosphoric acid As (poly) phosphates, inorganic salts of non-condensed or condensed phosphoric acid such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc. Ammonium, Ca, Mg, Zn, Ba, Al salt etc. are mentioned.

(C1-2) Nitrogen-Containing Flame Retardant Nitrogen-Containing Flame Retardant As a nitrogen-containing flame retardant, salts of triazines and cyanuric acid or derivatives thereof, for example, melamine salts of cyanuric acid such as melamine cyanurate; corresponding to melamine salts These include melem salts, melam salts, melon salts, guanamine salts (eg, guanamine cyanurate, acetoguanamine cyanurate, benzoguanamine cyanurate, etc.) 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 As the sulfur-containing flame retardant, organic sulfonic acid (alkanesulfonic acid, perfluorosulfonic acid, arylsulfonic acid, sulfonated polystyrene, etc.), sulfamic acid, organic sulfamic acid, And salts such as organic sulfonic acid amides (ammonium salts, alkali metal salts, alkaline earth metal salts and the like) and the like.

(C1-4) Silicon-containing flame retardant The silicon-containing flame retardant includes (poly) organosiloxane. Examples of (poly) organosiloxanes include homopolymers such as dialkylsiloxanes (eg, dimethylsiloxane etc.), alkyl aryl siloxanes (eg phenylmethylsiloxane), diarylsiloxanes, monoorganosiloxanes (eg, polydimethylsiloxane, polyphenylmethylsiloxane Etc.) or copolymers and the like. Further, as (poly) organosiloxane, branched organosiloxane [trade name “XC99-B5664” of Toshiba Silicone Co., Ltd., trade name “X-40-9243” of Shin-Etsu Chemical Co., Ltd., “X-40-9244” , “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 the molecular terminal or main chain Poly) organosiloxanes (for example, modified silicone etc.) can also be used.

(C1-5) Alcohol-Based Flame Retardant As the alcohol-based flame retardant, polyhydric alcohol (such as pentaerythritol), oligomeric polyhydric alcohol (such as dipentaerythritol or tripentaerythritol), esterified polyhydric alcohol, substituted Alcohols (cellulose, hemicellulose, lignocellulose, pectocellulose, adipocellulose, etc.), saccharides (monosaccharides, polysaccharides, etc.) and the like.

(C1-6) Inorganic Flame Retardant Among the inorganic flame retardants, metal oxides include, for example, molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, copper oxide, zinc oxide, aluminum oxide, nickel oxide Iron oxide, manganese oxide, antimony trioxide, antimony tetraoxide, antimony pentoxide and the like. Examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, tin hydroxide and zirconium hydroxide. Examples of the metal sulfide include zinc sulfide, molybdenum sulfide, tungsten sulfide and the like. The inorganic flame retardants also include expandable graphite and the like.

  These other flame retardants can be used singly or in combination of two or more. The content of the other flame retardant is not particularly limited as long as the effects of the present invention are not impaired, but when it is used, for example, 0.01 to 50 parts by mass of 100 parts by mass of the resin (A) The range is preferable, the range of 0.05 to 30 parts by mass is more preferable, and the range of 0.1 to 20 parts by mass is the most preferable.

(C2 antioxidant or stabilizer)
In addition, 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 maintain heat resistance stably for a long period of time. Antioxidants or stabilizers include, for example, phenol type (such as hindered phenols), amine type (such as hindered amines), phosphorus type, sulfur type, hydroquinone type, quinoline type antioxidant (or stabilizer), inorganic A system stabilizer, a compound having a functional group reactive to an active hydrogen atom (reactive stabilizer), and the like are included.

(C2-2) Phenolic Antioxidants Phenolic antioxidants include hindered phenols (hindered phenolic antioxidants), for example, 1,6-hexanediol-bis [3- (3,5- (5) C _2-10 alkylenediol-bis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as di-t-butyl-4-hydroxyphenyl) propionate]; eg, Di or trioxy _C2-4 alkylene diol-bis [3- (3,5-di-branched) such as triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] 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] ] Is preferable.

(C2-3) Amine Antioxidants Amine antioxidants include hindered amines such as tri- or tetra-C _1-3 alkylpiperidine or derivatives thereof (methoxy, benzoyloxy, phenoxy etc. are substituted at 4-position) Optionally (2,2,6,6-tetramethylpiperidine etc.), bis (tri, tetra or penta C _1-3 alkyl piperidine) C _2-20 alkylene dicarboxylic acid ester [eg, 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, phenylnaphthyl acid Emissions, N, N'-diphenyl-1,4-phenylenediamine, and the like N- phenyl -N'- cyclohexyl-1,4-phenylenediamine.

(C2-4) (Organic) phosphorus-based stabilizers or antioxidants Examples of phosphorus-based (organophosphorus-based) stabilizers or antioxidants include triisodecyl phosphite, tris nonyl phenyl phosphite, and diphenyl isodecyl phosphite. Phyto, phenyldiisodecyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4'-butylidene bis (3-methyl-6-t-butylphenyl) ditridecyl phosphite Tris (branched _C3-6 alkylphenyl) phosphite [eg, 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 [eg, 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 (eg, 4-phenoxy-9-α) -(4-hydroxyphenyl) -p-cumenilo Di-3,5,8,10-tetraoxa-4,9-diphosphapyr [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphate etc., diphosphonite stabilizers (eg tetrakis 2,4-di-t-butyl) -4,4'-biphenylene diphosphonite and the like. The phosphorus-based stabilizer usually has a branched _C3-6 alkylphenyl group (in particular, t-butylphenyl group). The flame retardant resin composition of the present invention preferably uses a phosphorus-based stabilizer or an antioxidant in combination, and the phosphorus-based antioxidant (C2-based) is used per 100 parts by mass of the rubber-reinforced styrenic resin (A). The light resistance can be dramatically improved by blending 0.01 to 10 parts by mass of 4). This is because the phosphorus atom-containing oligomer (B) has a structure in which bulky HCA is reacted in the vicinity of the phenolic hydroxyl group, and when hydrogen is donated to the peroxide radical generated by autoxidation, the phenolic hydroxyl group itself is It is believed that steric hindrance results in a less active phenoxy radical.

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

(C2-6) Inorganic stabilizers (inorganic metal or mineral stabilizers)
Inorganic stabilizers (inorganic metal or mineral stabilizers) include hydrotalcite, zeolite, alkaline earth metal compounds and the like.

(C2-6-1) Hydrotalcite As the hydrotalcite, hydrotalcites described in JP-A 60-1241 and JP-A 9-59475, for example, the following formula [M ^{2 +} _1-X M3 ⁺ _X (OH) ₂ ] ^{X +} [AN ^- _{X / n} · _m H ₂ O] ^X- (wherein, M ²⁺ is a divalent metal such as Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ^2+, etc. indicates ^{ion, M 3+} is ^{Al 3+,} Fe ^{3+, .A} showing a trivalent metal ion such as ^{Cr 3+ n-it} is _{^{CO 3 2-, OH -, HPO}} 4 2-, SO 4 2- n -valent (such as In particular, a monovalent or divalent anion is shown, x is 0 <x <0.5, and m is a hydrotalcite compound represented by 0 ≦ m <1. In addition, hydrotalcite is available from Kyowa Chemical Industry Co., Ltd. as "DHT-4A", "DHT-4A-2", "alkamizer" etc.

(C2-6-2) Zeolite The above-mentioned zeolite is not particularly limited, but, for example, the zeolite described in JP-A-7-62142 [crystalline aluminosilicate having a minimum unit cell of alkali and / or alkaline earth metal] And zeolites (A-type, X-type, Y-type, L-type and ZSM-type zeolites, mordenite zeolites; natural zeolites such as chabazite, mordenite, faujasite, etc.) and the like can be used. In addition, A-type zeolite can be used as "Zeolam series (A-3, A-4, A-5)", "Zeostar series (KA100P, NA-100P, CA-100P)", etc. As “Zeolam series (F-9)”, “Zeostar series (NX-100P)”, etc., Y-type zeolite is “HSZ series (320NAA)” etc. from Tosoh Corporation, Nippon Chemical Industry Co., Ltd. It is available.

(C2-6-3) Alkaline Earth Metal Compound As the alkaline earth metal compound, for example, oxides (such as magnesium oxide), hydroxides (such as magnesium hydroxide and calcium hydroxide), carbonate [magnesium carbonate (Soft / colloid / heavy) calcium carbonate etc.], organic carboxylates (magnesium acetate, calcium acetate, magnesium stearate, calcium stearate, calcium 12-hydroxystearate etc) can be used.

  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 cyclic ether group, oxetane group, acid anhydride group, isocyanate group, oxazoline group (ring), oxazine group (ring), carbodiimide group, etc. And compounds having at least one functional group.

(C2-7-1) Compound Having Cyclic Ether Group The compound having a cyclic ether group includes a compound having an epoxy group and an oxetane group. Examples of the compound having an epoxy group include alicyclic compounds such as vinylcyclohexene dioxide, glycidyl ester compounds such as versatic acid glycidyl ester, glycidyl ether compounds (hydroquinone diglycidyl ether, biphenol diglycidyl ether, bisphenol-A Glycidyl ether etc.), glycidyl amine compound, epoxy group-containing vinyl copolymer, epoxidized polybutadiene, epoxidized diene-based monomer-styrene copolymer, triglycidyl isocyanurate, epoxy-modified (poly) organosiloxane and the like.

(C2-7-2) Compound Having an Oxetane Group As a compound having an oxetane group, for example, di [1-ethyl (3-oxetanyl)] methyl ester of isophthalic acid or di [1-ethyl (3-oxetanyl) terephthalic acid An oxetanyl ester compound such as methyl ester, an oxetanyl ether compound {eg, an alkyl oxetanyl compound such as di [1-ethyl (3-oxetanyl)] methyl ether or 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 resin such as cetanyl) methyl ether, mono to poly [1-ethyl (3-oxetanyl)] methyl etherified phenol novolak, mono to poly [1-ethyl (3-oxetanyl)] methyl etherified cresol novolak, etc. Novolak-type oxetane resin etc.}, oxetane-modified (poly) organosiloxanes such as 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl oxetane, and derivatives having the oxetanyl unit {e.g. Alkyl oxetanyl methyl derivatives corresponding to ethyl (3-oxetanyl)] methyl derivatives} {eg, [1-methyl (3-oxetanyl)] methyl derivatives} and the like.

(C2-7-3) Compound Having Acid Anhydride Group As a compound having an acid anhydride group, for example, an olefin resin having a maleic anhydride group (for example, ethylene-maleic anhydride copolymer, maleic anhydride) And modified polypropylene etc.).

(C2-7-4) Compound Having an Isocyanate Group As the compound having an isocyanate group, for example, aliphatic isocyanate such as hexamethylene diisocyanate, alicyclic isocyanate such as isophorone diisocyanate, aromatic isocyanate such as diphenylmethane isocyanate, and the like A modified product of isocyanate (for example, trimer of isophorone diisocyanate etc.) and the like can be mentioned.

(C2-7-5) Compound Having an Oxazoline Group As a compound having an oxazoline group, for example, 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) or 2,2 ′-(1,1) Examples thereof include bisoxazoline compounds such as 4-phenylene) -bis (2-oxazoline), and vinyl resins having an oxazoline group (for example, vinyl oxazoline-modified styrene resins).

(C2-7-6) Compound Having an Oxazine Group As a compound having an oxazine group, for example, bisoxazine compounds such as 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), etc. It can be mentioned.

(C2-7-7) Compound Having Carbodiimide Group As a compound having a carbodiimide group, for example, polyarylcarbodiimides such as poly (phenylcarbodiimide), poly (naphthylcarbodiimide), poly (2-methyldiphenylcarbodiimide), poly ( 2,6-diethyldiphenylcarbodiimide), poly (2,6-diisopropyldiphenylcarbodiimide), poly (2,4,6-triisopropyldiphenylcarbodiimide), poly (2,4,6-tri t-butyldiphenylcarbodiimide), etc. Polyalkylaryl carbodiimides, poly [4,4'-methylenebis (2,6-diethylphenyl) carbodiimide], poly [4,4'-methylenebis (2-ethyl-6-methylphenyl) carbodiimide], poly [4,4 4 ' -Poly [alkylene bis (alkyl or cycloalkyl aryl) carbodiimide] such as-methylene bis (2, 6-diisopropyl phenyl) carbodiimide], poly [4, 4 '-methylene bis (2-ethyl 6-methyl cyclohexyl phenyl) carbodiimide], etc. Can be 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 effects of the present invention are not impaired, but when it is used, for example, 100 parts by mass of the rubber-reinforced styrenic resin (A) The range of 0.01 to 15 parts by mass is preferable, the range of 0.05 to 10 parts by mass is more preferable, and the range of 0.1 to 10 parts by mass is most preferable.

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

  Phosphorus acids (for example, inorganic phosphoric acid such as phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, polyphosphoric acid, etc .; exemplified in the section of the specific flame retardant auxiliary to the rubber-reinforced styrenic resin (A); phosphono acid The addition of a carboxylic acid, an organic phosphoric acid such as nitrogen-containing phosphoric acid, etc.) further improves the thermal stability.

(C3 anti-dripping agent)
Furthermore, to the flame retardant resin composition of the present invention, a dripping inhibitor such as a fluorine resin may be added within the range not to impair the effects of the present invention. By the anti-drip agent, it is possible to suppress the dripping of the heat species and the melt at the time of combustion. As the fluorine-based resin, homopolymers or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether, etc .; the above-mentioned fluorine-containing monomers and ethylene, propylene, acrylate And copolymers with copolymerizable monomers such as As such a fluorine-based resin (fluorine-containing resin), for example, homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride and the like; tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoro Examples of such copolymers include ethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. These fluorine resins can be used singly or in combination of two or more.

  The fluorine-based resin may be used in the form of particles, and the average particle diameter 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 0.1 with respect to 100 parts by mass of the rubber-reinforced styrenic resin (A). -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 UV absorbers, heat stabilizers, stabilizers such as weathering stabilizers, lubricants, mold release agents, coloring agents, plasticizers, nucleating agents, impact modifiers, sliding agents, etc. Be Furthermore, 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 fibrous fillers and non-fibrous fillers (plate-like fillers, powdery particulate fillers, etc.). When the additive (D1) or the filler (D2) is used, the ratio of the additive (D1) or the filler (D2) in the flame retardant resin composition is in a range that does not impair the effects of the present invention. Although not particularly limited, when used, for example, a range of 1 to 60% by mass is preferable in the flame retardant resin composition of the present invention, a range of 1 to 50% by mass is more preferable, and 1 to 45% by mass Is most preferable.

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

(D2-2 fibrous filler)
Among the non-fibrous fillers, examples of plate-like fillers include glass flakes, mica, graphite, various metal foils and the like. Particulate fillers include carbon black, silicon carbide, silica, quartz powder, glass beads, glass powder, milled fibers such as milled glass fibers, calcium silicate, aluminum silicate, kaolin, kaolin, talc, clay, silica Algal earth, silicates such as wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; sulfuric acid of metals such as calcium sulfate and barium sulfate Salt, metal powder, etc. are included. Preferred non-fibrous fillers include particulate or plate-like fillers, in particular glass beads, milled fibers, kaolin, talc, mica and glass flakes.

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

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

  The filler (D2) may be subjected to convergence treatment or surface treatment by the above-mentioned convergence agent or surface treatment agent. Regarding the timing of the treatment, the treatment may be carried out simultaneously with the addition of the filler, or may be treated in advance before the addition. The amount of the functional surface treatment agent or focusing agent used in combination is 5% by mass or less, preferably about 0.05 to 2% by mass, with respect to the filler.

  The phosphorus atom-containing oligomer (B) of the present invention can highly flame-retardant the resin, probably to promote carbonization of the resin surface at the time of combustion. Further, by using it in combination with a polymer type phosphoric ester, an aromatic resin or the like, it is possible to further impart flame retardance to the rubber-reinforced styrene resin (A) -containing resin composition even in a small amount. It is preferable because it does not cause bleed out and heat resistance decrease.

(D3 polymer compound)
(D3-1 resin)
Further, the flame retardant resin composition of the present invention is a polyester resin, a polyether ketone resin, a polyether resin with respect to 100 parts by mass of the rubber-reinforced styrenic resin (A) within the range not impairing the effects of the present invention. It is preferable to further blend 1 to 100 parts by mass of a polyarylene sulfide resin represented by a polyimide resin, a polyamide resin, a polyphenylene sulfide resin, and a polyarylene ether resin represented by a polyphenylene ether resin, and further flame retardancy and heat resistance A polyarylene ether resin is mentioned as a preferable resin from a viewpoint which can be made to improve property.
As polyphenylene ether resin which can be used for this invention, 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 or substituted hydrocarbon group, and may be the same or different from each other). It is a homopolymer and / or copolymer consisting of bonding units. Specific examples of this polyphenylene ether resin are preferably poly (2,6-dimethyl-1,4-phenylene ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, etc. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferred, and the method for producing such polyphenylene ether resin is not particularly limited, and, for example, described in US Pat. No. 3,306,874. It can be easily prepared, for example, by oxidative polymerization of 2,6-xylenol, using a complex of cuprous salt and amine according to the method as a catalyst, and further, US Patent 3,306,875, US Patent U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358 and Japanese Patent Publication No. 52-17880, It can be easily produced by the method described in Japanese Patent Application Laid-Open No. 50-51197. The reduced viscosity ηSP / C (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the above PPE used in the present invention is 0.20. It is preferably in the range of -0.70 dl / g, more preferably in the range of 0.30 to 0.60 dl / g, as a means for satisfying the above-mentioned requirements for the reduced viscosity of the polyphenylene ether resin, Adjustment of the amount of catalysts at the time of manufacture of polyphenylene ether resin etc. can be mentioned.

(D3-2 silicone compound)
Further, the flame retardant resin composition of the present invention is a composition which is hard to drop droplets by itself (drip), but if the effect of the present invention is not impaired, if the silicone compound is further added It is preferable because it is possible to further enhance the effect of suppressing the dripping of droplets during combustion (drip), suppressing the fuel spread during combustion, and improving the impact resistance. The silicone compounds that can be used in the present invention refer to silicone resins and / or silicone oils.

  As a silicone resin which can be used for this invention, the following general formula (s-1)-(s-4)

(Here, R ²¹ represents a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or an allyl group, respectively) and these units Mention may be made of polyorganosiloxanes consisting of chemically bonded siloxane units selected from mixtures, and furthermore those having a viscosity of about 200 to 300,000,000 centipoise at room temperature (23 ° C.), As long as it is a silicone resin, it is not limited to it.

  As a silicone oil which can be used for this invention, 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 is preferably one having a viscosity of 0.65 to 100,000 centistokes, but is not limited as long as it is the silicone oil described above.

  Although silicone resins and / or silicone oils can be used as silicone compounds that can be used in the present invention, silicone oils are preferred in terms of improving flame retardancy and impact resistance.

  The amount of the silicone compound added is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass with respect to 100 parts by mass of the rubber-reinforced styrenic resin (A). It is more preferable that it is in the range of 0.1 to 5 parts by mass.

Method for Producing Flame Retardant Resin Composition The flame retardant resin composition of the present invention comprises the rubber-reinforced styrenic resin (A) and the phosphorus atom-containing oligomer (B), and, if necessary, the effects of the present invention Using various mixers such as a tumbler or Henschel mixer, for example, with a flame retardant auxiliary (C), an additive (D1), a filler (D2), and a polymer compound (D3), as long as the After preliminarily mixing, the resin can be melt-kneaded at a resin setting temperature of the melting point or more using a mixer such as a Banbury mixer, a roll, Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like. Alternatively, each component may be pre-mixed, or only some components may be pre-mixed and supplied to an extruder using a blender for melt-kneading. When components (C), (D1), (D2) and (D3) are further added and the component is brittle, such as those components are easily broken by melt-kneading, components (A) to (B) The mechanical strength of the resin composition obtained is also a method in which the components are collectively charged to the upstream portion, and the components (C), (D1), (D2) and (D3) are added in the middle stream and thereafter to melt blend it with the resin component. It is preferable from The resin composition after melt-kneading is subjected to a molding process described later, but may be once made into a pellet or powder form for storage and circulation. The form in that case may be a well-known form such as a pellet or a powder, as long as the form of the present invention is not impaired, and a pellet is preferable from the viewpoint of handleability of the thing without limitation. The pellets can be produced according to a conventional method, and for example, after extrusion in the form of a strand from the apparatus used for the melt-kneading, it is preferable to carry out water cooling and cutting to obtain pellets.

Flame Retardant Masterbatch and Method for Producing the Same As described above, the flame retardant resin composition of the present invention comprises the rubber-reinforced styrenic resin (A) and the phosphorus atom-containing oligomer (B). Although it can be produced by direct melt-kneading, it is produced by melt-kneading a flame-retardant masterbatch containing the rubber-reinforced styrenic resin (A) and the phosphorus atom-containing oligomer (B) at a high concentration by melt-kneading It is also possible to dilute and blend a thermoplastic resin (E) such as a rubber-reinforced styrenic resin and the like to the flame-retardant masterbatch and melt-knead it. The details will be described below.

  More specifically, the components (A) and (B) described above are premixed by a mixer such as a V-type blender, a ribbon blender, or a Henschel mixer as necessary, and then a single-screw extrusion kneader, open Using a known mixer such as a roll mixer, a pressure type kneader, a Banbury mixer, or a twin-screw extrusion kneader, melt kneading is performed with the resin set temperature being equal to or higher than the melting point. Among these, a twin-screw extrusion type kneader is preferable in terms of kneadability and productivity. After melt-kneading, by processing into pellets etc. according to a conventional method, the flame-retardant masterbatch of the present invention is obtained. 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 content is 100 parts by mass of the rubber-reinforced styrenic resin (A) It is preferable to melt-knead so that the said phosphorus atom containing oligomer (B) may be contained in 5-50 mass parts, and it is more preferable to melt-knead so that it may be contained in 7-40 mass parts.

  The flame-retardant resin composition of the present invention is obtained by further adding and melting-kneading a thermoplastic resin (E) as a dilution resin to the thus obtained flame-retardant masterbatch. By thus obtaining the flame retardant resin composition via the masterbatch, the phosphorus atom-containing oligomer (B), which is a flame retardant component, can be stably dispersed uniformly, and it is possible to add a high concentration, An excellent flame retardant effect can be imparted to the molded body.

  The thermoplastic resin (E) for the dilution 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, but, for example, the rubber-reinforced styrene resin (A) and the polymer compound (D3), that is, the rubber-reinforced styrene resin, polyester resin, polyether ketone resin, polyether resin, polyimide resin, polyamide resin, polyarylene sulfide resin, polyarylene ether resin, silicone compound, etc., among which And polycarbonate resins and polyarylene ether resins are preferred. The rubber-reinforced styrenic resin (A) and the thermoplastic resin (E) are intended to melt and knead a thermoplastic resin (E) with a flame-retardant masterbatch containing the rubber-reinforced styrenic resin (A). Depending on the kind of resin used, different kinds of resins may be used, but from the viewpoint of compatibility, it is preferable to use the same kind of resin.

  In order to produce a flame-retardant resin composition from the flame-retardant masterbatch of the present invention, 100 parts by mass of the rubber-reinforced styrenic resin (A) in the finally obtained flame-retardant resin composition, There is no particular limitation as long as the thermoplastic resin (E) for dilution resin is adjusted and added so as to contain the above-mentioned phosphorus atom-containing oligomer (B) in a proportion of 3 to 40 parts by mass, and melt-kneaded. For example, when the thermoplastic resin (E) is the rubber-reinforced styrene resin (A), the rubber-reinforced styrene resin (A) in the flame retardant masterbatch and the thermoplastic resin (E) for dilution resin It is preferable to add a thermoplastic resin (E) so that the said phosphorus atom containing oligomer (B) may be 3-40 mass parts with respect to a total of 100 mass parts of. When the thermoplastic resin (E) is a resin other than the rubber-reinforced styrenic resin (A), for a dilution resin relative to 100 parts by mass of the rubber-reinforced styrenic resin (A) in the flame retardant masterbatch It is preferable to add a thermoplastic resin (E) so that 1-100 mass parts of thermoplastic resin (E) and 3-40 mass parts of said phosphorus atom containing oligomers (B) may become. The method of melt-kneading is not particularly limited, and, for example, the same method as the method of producing the master batch can be employed.

  In addition, when manufacturing the said flame-retardant masterbatch, it dilutes with said said rubber-reinforced styrenic resin (A) and a phosphorus atom containing oligomer (B), or when diluting to the said flame-retardant masterbatch Combining the above-mentioned flame retardant auxiliary (C), additive (D1), filler (D2), and polymer compound (D3) together with the plastic resin (E) within the range that does not impair the effects of the present invention You can also.

Molded article / use According to 100 parts by mass of the rubber-reinforced styrenic resin (A) obtained as described above, the content of the phosphorus atom-containing oligomer (B) in the range of 3 to 40 parts by mass. The flame retardant resin composition is melt-kneaded in a molding machine to produce a flame retardant resin molded product by various known molding processing methods such as extrusion molding, injection molding, calendar molding, hollow molding, vacuum molding, pressure molding and the like. can do.

  As a specific example of the flame-retardant resin molded product obtained by molding and processing the flame-retardant resin composition of the present invention, it can be used in various applications where high flame retardancy is required, and in particular, in particular, It can be suitably used for applications such as films, sheets, and fibers. Specifically, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, varicon cases, optical pickups, oscillators, various terminal plates, transformers, Plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, LCDs, FDD carriages, FDD chassis, motor brush holders, parabola antennas, computer related parts etc. Electrical and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio and compact discs, lighting parts, refrigerator parts, airco Parts such as parts, typewriter parts, word processor parts, etc. Home, office electrical products parts, office computer related parts, telephone related parts, facsimile related parts copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater Various bearings such as bearings, motor parts, mechanical parts represented by lighters, typewriters etc., optical devices represented by microscopes, binoculars, cameras, watches etc., precision machine related parts; alternator terminals, alternator connectors, IC Regulators, various valves such as exhaust gas valves, various pipes related to fuel, exhaust system and intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, Air gas sensor, coolant 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 Impeller, Turbine vane, Wiper motor related parts, Distributer, Starter switch, Starter relay, Wire harness for transmission, Window-osher nozzle, Air conditioner panel switch board, Coil for fuel related solenoid valve, Connector for fuse, Connector for horn, Horn terminal Parts insulating plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake Stone, solenoid bobbin, engine oil filter, igniter 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 various applications such as housings, chassis, relays, switches, case members, transformer members, electric and electronic parts such as coil bobbins, automobile parts, mechanical parts and the like.

  The thickness of the sheet or film obtained by forming the flame-retardant resin composition of the present invention into a sheet or film varies depending on the application and can be any thickness, but usually 5 to 200 μm, Preferably, it is 10 to 150 μm, more preferably 20 to 100 μm, and particularly preferably 30 to 70 μm.

  Molded articles obtained by forming the flame-retardant resin composition of the present invention, in particular films or sheets or fibers obtained by forming into sheet-like or film-like or fiber-like form, are resins (A) such as mechanical strength and transparency. Can suppress bleed out of the phosphorus atom-containing oligomer (B), which is a flame retardant component, and can exhibit excellent flame retardancy and heat resistance satisfying UL-94 / VTM-0 while maintaining the physical properties of .

  In addition, the term "sheet or film" in the present invention is not used to specifically distinguish between sheet and film, and is used to clarify that both are included, as long as they have the features of the present invention. The term "sheet" or "film" can be interpreted as broadly as possible, and the term "sheet" is intended to include what is referred to as a plate or plate as long as it has the features of the present invention. When it is necessary to distinguish between a sheet and a film, the sheet is usually used when its thickness is about 0.5 to 5 mm, and the film is usually when its thickness is about 5 to 500 μm. used.

  The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples.

<Rubber reinforced styrene resin>
A-1: A graft (co) polymer was produced by the following method. The grafting rate is determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer, and the mixture was refluxed for 4 hours. After centrifuging this solution for 30 minutes at 8,000 rpm (centrifugal force 10,000 G (98 × 10 ³ m / s ² )), insolubles were filtered. The insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.

Graft ratio = [(n)-(m) x L] / [(m) x L] x 100
Here, L means the rubber content of the graft copolymer.

  40 parts of a monomer mixture consisting of 70% of styrene and 30% of acrylonitrile was added in the presence of 60 parts (solid content converted) of polybutadiene latex (average rubber particle diameter 0.3 μm, gel content 85%) and emulsion polymerization was added. The obtained graft copolymer was coagulated with sulfuric acid and then dried to obtain a powder.

  The graft ratio of the obtained graft copolymer was 36%, and it contained 18.1% of a non-graftable copolymer consisting of 70% of styrene structural unit and 30% of acrylonitrile. In addition, the intrinsic viscosity of methyl ethyl ketone soluble component was 0.34 dl / g.

A-2-1: A vinyl-based copolymer was produced by the following method.
A monomer mixture consisting of 70% styrene and 30% acrylonitrile was subjected to suspension polymerization to prepare a vinyl copolymer <A-2-1>. The limiting viscosity of the methyl ethyl ketone soluble component of the obtained vinyl copolymer <A-2-1> was 0.53 dl / g.

A-2-2: A vinyl copolymer was produced by the following method.
A monomer mixture consisting of 69.7% of styrene, 30% of acrylonitrile and 0.3% of glycidyl methacrylate was subjected to suspension polymerization to prepare a vinyl copolymer <A-2-2>. The limiting viscosity of the methyl ethyl ketone soluble component of the obtained vinyl copolymer <A-2-2> was 0.54 dl / g.

A-2-3: A vinyl copolymer was produced by the following method.
A monomer mixture consisting of 51% of styrene, 9% of acrylonitrile and 40% of N-phenylmaleimide was solution-polymerized in a cyclohexanone solvent to prepare a vinyl-based copolymer <A-2-3>. The limiting viscosity of the methyl ethyl ketone soluble component of the obtained vinyl copolymer <A-2-3> was 0.59 dl / g.

<Phosphorus atom-containing oligomer>
B-1: A phosphorus atom-containing oligomer was produced by the following method.
Thermometer, condenser, fractionation pipe, nitrogen gas inlet pipe, flask attached with stirrer, 1220 g (10.0 mol) of 2-hydroxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 1512 g (7.0 mol) of -10-oxide (hereinafter abbreviated as "HCA") and 22.3 g (0.19 mol) of oxalic acid were charged, the temperature was raised to 120 ° C, and the reaction was allowed to proceed for 1 hour. Then, 1728 g (8.0 mol) of HCA was added, and the temperature was raised to 180 ° C. to react for 3 hours. Then, the water is removed under heating and reduced pressure, and the following structural formula

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

<Phosphorus antioxidant>
C-1: Tris (2,4-di-t-butylphenyl) phosphite) "IRGAFOS 168" manufactured by BASF was used.

<Polyphenylene ether resin>
D-1: A high molecular weight polyphenylene ether resin was produced by the following method.
The inside of the stainless steel reactor, which has an oxygen blowing inlet at the bottom of the reactor and has a cooling coil and stirring blades inside, is sufficiently replaced with nitrogen, and then 54.8 g of cupric bromide and 1110 g of di-n-butylamine And 8.75 kg of 2,6-xylenol were dissolved in a mixed solvent of 20 liters of toluene, 16 liters of n-butanol and 4 liters of methanol and charged into the reactor. While stirring, oxygen was continuously blown into the reactor, and polymerization was performed for 180 minutes while controlling the internal temperature at 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A methanol / hydrochloric acid mixed solution was added thereto to decompose the remaining catalyst in the polymer, and the catalyst was sufficiently washed with methanol and then dried to obtain powdery polyphenylene ether. The reduced viscosity SP SP was 0.55 dl / g. Moreover, SP value is 8.67.

D-2: A low molecular weight polyphenylene ether resin was produced by the following method.
The same experiment as <D-1> was repeated except shortening polymerization time to 90 minutes in manufacture of said <D-1>. The reduced viscosity η sp / C was 0.41 dl / g. Moreover, SP value is 8.67.

<Silicone-based compound>
D-3: A silicone resin “DC 4-7081” manufactured by Toray Dow Corning Silicone Co., Ltd. was used.
D-4: A silicone oil "SH200 (1000 cs)" manufactured by Toray Dow Corning Silicone Co., Ltd. was used.

<Phosphorous flame retardants>
-PX-200: A phosphorus-based flame retardant "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. was used.
PFR: A phosphorus-based flame retardant "Resorcinol bis (diphenyl phosphate)" manufactured by ADEKA was used.
FR-1: A hydroxyl group-containing phosphorus compound was produced by the following synthesis method.
A hydroxyl group-containing aromatic phosphoric acid ester (FR-1) was produced according to Patent Document 3 Examples. That is, 122.7 parts by mass of phenol (molar ratio: 2.0) and 0.87 parts by mass of aluminum chloride (molar ratio: 0.01) are placed in a flask and 100 parts by mass of phosphorus oxychloride at 90 ° C. (molar ratio: 1.0) Was dripped over 1 hour. To the formed intermediate, 71.7 parts by mass of resorcin (molar ratio 1.0) was added, and further reacted. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. The reaction product was then cooled and washed with water to remove the catalyst and chlorine to obtain a phosphoric acid ester mixture (hereinafter referred to as FR-1). This mixture was analyzed by GPC (gel permeation chromatography) to find that diphenyl resorcinyl phosphate, triphenyl phosphate, and the following formula

And a mass ratio of 54.2 / 18.3 / 27.5, respectively.
Fr-1: A hydroxyl group-free aromatic phosphoric acid ester "CR741C" manufactured by Daihachi Chemical Industry Co., Ltd. was used.
<Triazine compound>
MC: "melamine cyanurate MC610" manufactured by Nissan Chemical Industries, Ltd. was used.
<Novolak resin>
PSM-4362: "Resitop PSM-4326" manufactured by Gunei Chemical Industry Co., Ltd. was used.
<Modified phenolic resin>
EPOXY: A compound synthesized by the following method was used.
While applying a nitrogen gas purge to a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 104 parts of a phenol novolac resin having a solution viscosity of 205 mm ² / s at 25 ° C. of a 50% by weight n-butanol solution (hydroxyl group 1. 0 equivalent), 370 parts (4.0 moles) of epichlorohydrin, 42 parts of n-butanol, and 2.3 parts of tetraethylbenzylammonium chloride were dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 82 parts (1.0 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours, and then stirred for 0.5 hours under the same conditions Continued. During this time, the azeotropically distilled distillate was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was performed while returning the oil layer to the reaction system. Thereafter, the unreacted epichlorohydrin was distilled off under reduced pressure. To the crude epoxy resin thus obtained, 550 parts of methyl isobutyl ketone and 55 parts of n-butanol were added and dissolved. Further, 15 parts of a 10% aqueous solution of sodium hydroxide was added to this solution and reacted at 80 ° C. for 2 hours, and washing with 100 parts of water was repeated three times until the pH of the washing solution became neutral. Then, the system was azeotropically dewatered by azeotropic distillation, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 144 parts of the target denatured phenol resin. The epoxy equivalent of the obtained modified phenolic resin is 185 g / eq, and the solution viscosity of 50% by weight 1,4-dioxane solution at 25 ° C. is 48 mm ² / s (measured using a viscometer No. 200), and air The residual carbide content at 600 ° C. according to TGA measurement when the temperature was raised at 40 ° C./min in an atmosphere was 37%.

Examples 1 to 9 and Comparative Examples 1 to 3
Each component is mixed at the compounding ratio shown in the table, and pelletized by melt-kneading and extruding at 220 to 270 ° C. using a vented 30 mm diameter twin screw extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) A polymer was produced. Subsequently, each test piece was shape | molded by the injection molding machine (Sumitomo Heavy Industries, Ltd. make, pro mat 40/25) by injection pressure lower limit pressure +1 Mpa, and the physical property was measured on condition of the following.

(1) Flame retardancy: With respect to the test piece for flame retardancy evaluation of 1.6 mm thickness obtained by injection molding, the flame retardance of five test pieces was evaluated according to the evaluation standard defined in UL94. The flame retardancy level decreases in the order of V-0> V-1> V-2> HB.

(2) Impact resistance: Impact resistance was evaluated according to ASTM D256-56A.

(3) Heat resistance: The heat resistance was evaluated according to ASTM D648 (load: 1.82 MPa).

(4) Color tone: The color tone of the test piece was visually judged. (◎: white, ○: slightly yellow, :: pale yellow, ×: yellow)

  The measurement results of flame retardancy, impact resistance, heat resistance and color tone of each sample are summarized in Table 1.

Claims (10)

A flame retardant resin composition comprising a rubber-reinforced styrenic resin (A) and a phosphorus atom-containing oligomer (B) as essential components, comprising phosphorus atoms relative to 100 parts by mass of the rubber-reinforced styrenic resin (A) The oligomer (B) is contained in the range of 3 to 40 parts by mass, and 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 structure shown below Formula (x1) or (x2)
Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R is a structural site represented by 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. A flame retardant resin composition characterized by being represented by   In addition to the rubber-reinforced styrenic resin (A) and the phosphorus atom-containing oligomer (B), a phosphorus stabilizer or an antioxidant is further added in an amount of 0.01 to 10 based on 100 parts by mass of the rubber-reinforced styrenic resin (A) The flame retardant resin composition according to claim 1, which is contained in the range of parts by mass. The flame retardant resin composition according to claim 1 or 2, wherein the content of the component in which n is 2 or more in the structural formula (1) is in the range of 5 to 90% based on the peak area in GPC measurement. A method for producing a flame retardant resin composition, comprising melt-kneading a rubber-reinforced styrenic resin (A) and a phosphorus atom-containing oligomer (B), comprising: phosphorus atoms relative to 100 parts by mass of the rubber-reinforced styrenic resin (A) Containing oligomer (B) in a range of 3 to 40 parts by mass, and 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 structure shown below Formula (x1) or (x2)
Y is a hydrogen atom, a hydroxyl group or a structural moiety represented by the structural formula (x1) or (x2), and in the structural formula (x1) or (x2), R is a structural site represented by 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. A method for producing a flame-retardant resin composition, characterized in that In addition to the rubber-reinforced styrenic resin (A) and the phosphorus atom-containing oligomer (B), a phosphorus stabilizer or an antioxidant is further added in an amount of 0.01 to 10 based on 100 parts by mass of the rubber-reinforced styrenic resin (A) The method for producing a flame-retardant resin composition according to claim 4, wherein the resin composition is added and melt-kneaded in the range of parts by mass. The method for producing a flame retardant resin composition according to claim 4 or 5, wherein the content of the component in which n is 2 or more in the structural formula (1) is in the range of 5 to 90% based on the peak area in GPC measurement. . The molded object obtained by shape | molding the flame-retardant resin composition of Claim 1. A fiber obtained by molding the flame-retardant resin composition according to claim 1. The film or sheet obtained by shape | molding the flame-retardant resin composition of Claim 1. The manufacturing method of the molded object which shape | molds the flame-retardant resin composition of Claim 1.