JP2005120199A - Flame-retardant resin composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition having excellent flame retardance and impact resistance. <P>SOLUTION: The flame-retardant resin composition comprises (A) a styrene-based resin and (B) boron oxide and is obtained by mixing 100 parts by mass of (A) the styrene-based resin obtained by polymerizing an aromatic vinyl compound or copolymerizing an aromatic vinyl compound with another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence or absence of a rubber-like polymer with 0.5-100 parts by mass of (B) boron oxide. The flame-retardant resin composition may further comprise 0.1-50 parts by mass of (C) a silicone compound and 0.5-50 parts by mass of (D) a nitrogen-containing compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a flame retardant resin composition that gives a molded article excellent in flame retardancy and impact resistance, and a molded article molded using the flame retardant resin composition as a molding material.

  A flame retardant resin composition obtained by making a composition of a rubber reinforced styrene resin such as ABS resin and HIPS and a polycarbonate resin flame retardant is excellent in mechanical characteristics, physical characteristics, electrical characteristics, and the like. Widely used in the electrical / electronic field, OA / home appliance field, vehicle field, sanitary field, etc.

In order to make these resins flame retardant, halogen flame retardants (see, for example, Japanese Patent No. 3198485), organophosphorus flame retardants (for example, JP-A-9-87337 and JP-A-10-120853). The flame retardant represented by the gazette etc. is used.
In these flame-retardant resin compositions, when a halogen-based flame retardant is used, there are problems such as causing metal corrosion of processing equipment and the like. Further, when a phosphorus-based flame retardant such as a phosphate compound is used, the flame retardant acts as a plasticizer for the resin, so that there are problems such as poor mechanical strength and heat resistance.
Furthermore, Japanese Patent Publication No. 57-1547 discloses a technique of blending a composite metal hydroxide with a styrene resin, but as is apparent from the examples, flame retardancy is improved despite the large amount blended. The effect is low. Moreover, since an inorganic substance is blended in a large amount, the resulting composition has poor impact resistance and fluidity. Japanese Patent Application Laid-Open No. 61-291642 discloses a technique of blending red phosphorus and melamine with an ABS resin. Although it exhibits excellent flame retardancy, it is colored by blending with red phosphorus. Can be used only for these materials, and the range of use is limited. Furthermore, Japanese Patent Application Laid-Open No. 61-291642 discloses a method of blending a phosphorus compound and a novolac resin with an ABS resin. However, when red phosphorus is used, there are the same problems as described above. When a phosphorus compound such as triphenyl phosphate is used, the problem of coloring due to the phosphorus compound can be solved, but there is a problem of yellowing due to the novolak resin.

Japanese Patent No. 3198485 JP-A-9-87337 Japanese Patent Laid-Open No. 10-120853 Japanese Patent Publication No.57-1547 JP 61-291642 A JP 61-291642 A

  The objective of this invention is providing the flame-retardant resin composition excellent in the flame retardance and impact resistance. Another object of the present invention is to provide a molded article comprising the flame retardant resin composition.

As a result of intensive studies to achieve the above object, the present inventor has found a flame retardant resin composition capable of obtaining a molded product having excellent flame resistance and impact resistance by blending boron oxide with ABS resin. The present invention has been completed.
That is, according to one aspect of the present invention, the following (A) component and the following (B) component are included, and 0.5 to 100 parts by mass of the following (B) component is added to 100 parts by mass of the following (A) component. A flame retardant resin composition characterized by being blended is provided.
(A) (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence or absence of a rubbery polymer Styrenic resin,
(B) Boron oxide.
According to the other situation of this invention, the molded article which consists of the said flame-retardant resin composition is provided.

  Since the flame-retardant resin composition of the present invention is constituted by blending (A) a styrene resin with a specific amount of (B) boron oxide, it is possible to obtain a molded article having excellent flame retardancy and impact resistance. .

The present invention will be described in detail below.
The styrene resin as the component (A) of the present invention is copolymerized with an aromatic vinyl compound, or an aromatic vinyl compound and the aromatic vinyl compound in the presence or absence of the rubbery polymer (a). One or more styrenic resins obtained by (co) polymerizing monomers (b) composed of other possible vinyl monomers and (co) polymerized in the presence of a rubbery polymer And one or more types of (co) polymerized styrenic resins in the absence of a rubbery polymer may be used. From the viewpoint of improving the flame retardancy and impact resistance aimed by the present invention, the content of the rubbery polymer (a) in the component (A) is from 3 to 80, with the total amount of the component (A) being 100% by mass. It is preferably in the range of mass%, more preferably 5 to 50 mass%, particularly preferably 10 to 30 mass%.
In the present specification, “(co) polymerization” means homopolymerization and / or copolymerization. “(Meth) acryl” means acrylic and / or methacrylic.

The rubbery polymer (a) is not particularly limited, and specific examples thereof include polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, butadiene / (meth) acrylic acid ester copolymer, styrene / Butadiene block copolymers, butadiene-based (co) polymers such as styrene / isoprene-based block copolymers, and parts or complete hydrogenated products of these butadiene-based copolymers, ethylene / propylene copolymers, ethylene / Propylene / non-conjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, acrylic rubber, silicone rubber, silicone / acrylic IPN rubber, etc. These can be used alone or in combination of two or more. Of these, polybutadiene, butadiene / styrene copolymers, styrene / butadiene block copolymers and their hydrogenated products, ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene copolymers, acrylic rubber and silicone Rubber is preferred.

  The gel content of the rubbery polymer is not particularly limited, but when the component (A) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, more preferably 40 to 98. It is 50 mass%, Most preferably, it is 50-95 mass%. Within this range, it is possible to obtain a flame retardant resin composition that gives a molded article that is particularly excellent in flame retardancy and impact resistance.

In addition, the said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was put into 100 ml of toluene, allowed to stand at room temperature for 48 hours, and then filtered through a 100 mesh wire mesh (with a mass of ₁ gram of W) to remove toluene-insoluble matter and the wire mesh at 80 ° C. It is vacuum-dried for a time and weighed (with a mass of ₂ grams), and is calculated by the following formula (1).
Gel content (% by mass) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100 (1)
The gel content can be adjusted by appropriately setting the type and amount of the molecular weight adjusting agent, the polymerization time, the polymerization temperature, the polymerization conversion rate and the like during the production of the rubbery polymer.

  Examples of the aromatic vinyl compound constituting the monomer (b) include styrene, α-methylstyrene, hydroxystyrene, and the like, and these can be used alone or in combination of two or more. . Of these, styrene and α-methylstyrene are preferred.

  Other monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds. , An oxazoline group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, a substituted or unsubstituted amino group-containing unsaturated compound, and the like, each of which is used alone or in combination of two or more. be able to.

  Examples of the vinyl cyanide compound used here include acrylonitrile, methacrylonitrile and the like, and these can be used singly or in combination of two or more.

  Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. They can be used in combination.

Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like, and these can be used alone or in combination of two or more. Further, this maleimide unit may be introduced by a method of copolymerizing maleic anhydride and then imidizing.
Examples of the unsaturated acid compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like. These may be used alone or in combination of two or more. be able to.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples thereof include methyl-1-propene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide and the like, and these can be used alone or in combination of two or more.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used alone or in combination of two or more.

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more.
Examples of the substituted or unsubstituted amino group-containing unsaturated compound include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, There are methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene and the like, and these can be used singly or in combination of two or more.

  The other vinyl monomer copolymerizable with the aromatic vinyl compound is preferably 80% by mass or less, more preferably 70% by mass or less, when the total amount of the monomer (b) is 100% by mass. . Preferred monomer combinations include styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, α-methylstyrene / acrylonitrile, styrene / acrylonitrile / glycidyl methacrylate, styrene / acrylonitrile / 2-hydroxyethyl methacrylate, Styrene / acrylonitrile / (meth) acrylic acid, styrene / α-methylstyrene / acrylonitrile and the like, and these can be used alone or in combination of two or more.

  The component (A) of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a combination of these.

In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used, and any known one can be used.
As polymerization initiators, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, azobisisobutyronitrile, etc. Can be mentioned. Moreover, it is preferable to use redox systems such as various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, etc., as polymerization initiation assistants.
Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, terpinolene and the like.
Examples of the emulsifier include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, potassium salts of higher fatty acids having 10 to 20 carbon atoms, sodium salts, potassium salts of rosin acids, sodium salts Etc. can be used.

  In the emulsion polymerization, the rubbery polymer (a) and the monomer (b) can be used by batch-adding the monomer (b) in the presence of the total amount of the rubbery polymer (a). Alternatively, it may be polymerized by dividing or continuously adding. Moreover, you may add a part of rubber-like polymer (a) in the middle of superposition | polymerization.

  After the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain a powder of the component (A) of the present invention. At this time, two or more kinds of latexes of component (A) obtained by emulsion polymerization may be appropriately blended and then coagulated. As the coagulant used here, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid and citric acid can be used.

When the component (A) is produced by solution polymerization, the solvent that can be used is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, acetone, and the like. Ketones, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like. The polymerization temperature is preferably in the range of 80 to 140 ° C, more preferably 85 to 120 ° C.
In the polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. As the polymerization initiator, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, and the like are preferably used.
When a chain transfer agent is used, for example, mercaptans, α-methylstyrene dimer, terpinolene, etc. can be used.
Moreover, when manufacturing by block polymerization or suspension polymerization, the polymerization initiator, chain transfer agent, etc. which were demonstrated in solution polymerization can be used.
In the polymer component obtained by polymerizing the monomer (b) in the presence of the rubber polymer (a), the monomer (b) is usually grafted to the rubber polymer (a). The copolymerized copolymer and the rubbery polymer (a) ungrafted component (the (co) polymer of the monomers (b)) are included.
The amount of monomer remaining in the component (A) obtained by each polymerization method is preferably 10,000 ppm or less, more preferably 5,000 ppm or less.
The graft ratio of the component (A) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably 40 to 120% by mass. This graft ratio (%) is obtained by the following equation (2).

Graft ratio (mass%) = {(TS) / S} × 100 (2)
In the above formula (2), T is charged with 1 g of component (A) in 20 ml of acetone, shaken with a shaker for 2 hours, and then centrifuged for 60 minutes with a centrifuge (rotation speed: 23,000 rpm). It is the mass (g) of the insoluble matter obtained by separating the insoluble matter and the soluble matter, and S is the mass (g) of the rubbery polymer contained in 1 g of component (A).

In addition, the intrinsic viscosity [η] of the acetone-soluble component of component (A) according to the present invention (measured at 30 ° C. using methyl ethyl ketone as a solvent) is preferably 0.2 to 1.2 dl / g, more preferably Is 0.2 to 1 dl / g, particularly preferably 0.3 to 0.8 dl / g.
The average particle diameter of the grafted rubbery polymer particles dispersed in the component (A) according to the present invention is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,500. It is in the range of ~ 8,000cm. The average particle diameter can be measured by a known method using an electron microscope.

Boron oxide (B) according to the present invention is generally produced from natural minerals, and preferably contains 80% by mass or more of B ₂ O ₃ component. As impurities, silicon oxide, iron oxide, aluminum oxide, calcium oxide, magnesium oxide and the like may be contained, but the content of each is preferably 5% by mass or less. Further, it is preferable from the surface appearance of the final molded product that the boron oxide is used after being pulverized to an average particle size of 1,000 μm or less.

Furthermore, what processed the surface of boron oxide can also be used. The treatment method is not particularly limited, but (1) a method in which a treatment agent is dissolved in a solvent, applied to boron oxide and dried, and (2) after immersing boron oxide in an organic solvent solution in which the treatment agent is dissolved in a solvent. Method of taking out and drying, (3) Method of mixing boron oxide and treatment agent with a mixer and attaching the treatment agent to the surface of boron oxide, (4) Method of coating the treatment agent on the surface of boron oxide particles by impact-type impacting means, etc. (5) There is a method in which a thermosetting resin or the like is coated on the surface of boron oxide, cured on the surface, and coated. The method (4) using the impact hitting means can be carried out using a commercially available apparatus such as a hybridization system of Nara Machinery Co., Ltd., for example.
Examples of the surface treatment agent include silane coupling agents, titanate coupling agents, coupling agents such as aluminum couplings, silicone oils such as hydrogen silicone oils, triazine derivatives and cyanuric acid or isocyanuric acid. Salt, fluorine-containing polymer such as polytetrafluoroethylene, epoxy resin, urea resin, unsaturated polyester resin, polymer such as phenol resin, melamine resin, ketone resin, alkyd resin, metal hydroxide such as magnesium hydroxide, There are silica and the like, and these surface treatment agents can be used alone or in combination of two or more.

  The usage-amount of the said (B) component in the flame-retardant resin composition of this invention is 0.5-100 mass parts with respect to 100 mass parts of (A) component of this invention, Preferably it is 1-80. The weight is more preferably 3 to 70 parts by weight, and particularly preferably 5 to 50 parts by weight. If the amount is less than 0.5 parts by weight, the flame retardancy is not improved. Decrease significantly.

  The silicone compound that is the component (C) of the present invention has a structural unit represented by the general formula (I) and a repeating structural unit represented by the general formula (II) as essential components, and is a repeating unit represented by the general formula (III). Those containing 80 mol% or less of the structural unit or the repeating structural unit represented by the general formula (IV) are preferable, and the shape is oily, gum-like, varnish-like, powdery, rubber-like, or pellet-like Can be used.

In the formula, R ^{1 to} R ⁶ are an alkyl group having 1 to 14 carbon atoms, a substituted alkyl group having 1 to 14 carbon atoms, an alkoxyl group having 1 to 14 carbon atoms, an aryl group, an alkyl group-substituted aryl group and / or an alkylene group-substituted aryl group. It is at least one selected from the group consisting of a group, hydrogen, and a (meth) acryl group. Usually, 5 mol% or more of R ^{1 to} R ⁶ is preferably an aryl group such as a phenyl group, more preferably 10 mol% to less than 80 mol% is an aryl group, and more preferably 30 mol% to less than 80 mol%. Is particularly preferably an aryl group. Moreover, when R < ¹ > -R < ⁶ > is a (meth) acryl group, it is preferable at the point of a flame retardance.

The silicone compound of the present invention is preferably a branched polyorganosiloxane composed of the above general formulas (I), (II) and (III), wherein R ^{1 to} R ⁶ have less than 20 to 80 mol% of 6 to 12 carbon atoms. What is an aryl group is more preferable, and phenylmethyl polysiloxane in which the aryl group is a phenyl group and R ^{1 to} R ⁶ other than the phenyl group are methyl groups is particularly preferable.

In addition, polyorganosiloxane side chain, both ends, one end, side chain end can be modified with amino group, epoxy group, carboxyl group, phenol group, etc. Is particularly preferred.
In addition, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include a trifluoropropyl group. Examples of the alkoxyl group include a methoxy group and an ethoxy group, and examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.

  Although the weight average molecular weight of the silicone compound which is (C) component of this invention is not specifically limited, It is the polystyrene conversion value measured using gel permeation chromatography (GPC), and is the range of 300-1,000,000. Things are usually used.

  The silicone compound of the present invention is produced by a general production method. To illustrate the production method, the unit constituting the general formula (III) or the unit constituting the general formula (II) and the general formula (III) ) And / or co-hydrolyzing organohalosilane in water at a proportion corresponding to the proportion of units constituting the general formula (IV), and subjecting the resulting hydrolysis product to a condensation reaction, followed by alkali metal hydroxide It can be dehydrated and produced by an equilibration reaction with a catalyst. For example, it can be produced by a method described in JP-A No. 5-247212.

  (C) component of this invention is 0.1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-30 mass parts, More preferably, it is 0.5-20 mass parts, Especially Preferably it is 0.5-10 mass parts, if it is less than 0.1 mass part, the flame retardance of (A) + (B) component cannot be improved, and if it exceeds 50 mass parts, impact resistance will be inferior.

As the nitrogen-containing compound which is the component (D) of the present invention, those exemplified in the following (1) to (3) can be preferably used.
(1) Triazine derivative; specific examples thereof include melamine, melamine: formaldehyde = 1: 1 to 1: 6 (molar ratio), methylol melamine containing 1 to 6 methylol groups obtained by reacting both, and the methylol Melamine resin obtained by heat-curing melamine in acidic solution, modified melamine resin heat-cured by adding urea, phenol and alcohol simultaneously when resinating methylol melamine, by neutralization reaction of sulfuric acid and melamine Obtained melamine sulfate, benzoguanamine, methylolated benzoguanamine obtained by reacting both with benzoguanamine: formaldehyde = 1: 1 to 1: 4 (molar ratio) and the methylolated benzoguanamine obtained by heat curing in an acidic solution. Resinous material, acetoguanamine, acetoguanamine: hol Aldehyde = 1: 1 to 1: resinous material methylolated acetoguanamine and said methylolated acetoguanamine obtained by reacting both obtained by heat curing in an acidic solution and the like at 4.

  (2) (Iso) cyanuric acid derivatives; specific examples thereof include melamine cyanurate, melamine isocyanurate obtained by neutralization reaction of (iso) cyanuric acid and melamine, triallyl cyanurate, triallyl isocyanurate, trimeta Examples include allyl isocyanurate.

(3) Imidazolidinone derivatives; specific examples thereof are obtained by subjecting methylolates obtained by reacting both ethyleneurea or ethylenethiourea: formaldehyde = 1: 1 to 1: 2 to heat condensation in an acidic solution. A resinous material is mentioned.

  The component (D) of the present invention is 0.5 to 50 parts by mass, preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, particularly 100 parts by mass of the component (A) of the present invention. Preferably it is 3-20 mass parts, and if it is less than 0.5 mass part, the effect which improves the flame retardance of (A) + (B) component or (A) + (B) + (C) component will be acquired. If the amount exceeds 50 parts by mass, the impact resistance is poor.

  Moreover, a fluororesin powder and / or a metal oxide can be mix | blended with the flame-retardant resin composition of this invention from the objective of improving a flame retardance further. The fluororesin powder used here is a fluoroethylene resin (a polymer of monomers in which ethylene hydrogen atoms are substituted with one or more fluorine atoms). As a specific example, polyfluoroethylene is used. , Polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene / fluoropropylene copolymer, polyvinylidene fluoride, and the like. The preferred weight average molecular weight is usually 500,000 or more, more preferably 1,000,000 or more. It is. The average particle size is preferably 10 to 600 μm. In addition, the fluororesin powder used in the present invention can be improved in dispersibility with polyethylene wax, organic acid, organic acid metal salt or the like. It is preferable to use the said fluororesin powder in 0.01-5 mass parts with respect to 100 mass parts of (A) component of this invention.

  Examples of the metal oxide include magnesium oxide, aluminum oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, zinc oxide, tin oxide, and the like. ) It is preferably used in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the component.

The flame-retardant resin composition of the present invention can be prepared by kneading each component by a method using various extruders, a Banbury mixer, a kneader, a continuous kneader, or the like, or a method combining these. A preferable production method is a method using an extruder, particularly preferably a method using a multi-screw extruder, a method using a Banbury mixer or a continuous kneader, and a method combining these.
Furthermore, when each component is kneaded, these components may be kneaded in a lump, or may be kneaded in multiple stages.

A well-known inorganic filler can be mix | blended with the flame-retardant resin composition of this invention. As the inorganic filler used here, glass fiber, glass flake, milled glass, glass beads, hollow glass, carbon fiber, carbon fiber milled fiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite, mica, There are kaolin, montmorillonite, hextrite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, plate alumina, silica, plate silica, and organically treated smectite. These may be used alone or in combination of two or more. They can be used in combination. In addition, for the purpose of improving the dispersibility of the inorganic filler, a surface treated with a known coupling agent can be used. Known coupling agents include silane coupling agents, aluminum coupling agents, titanate coupling agents and the like.
Moreover, organic fillers, such as an aramid fiber, a phenol fiber, and a polyester fiber, can also be mix | blended.
These fillers are usually used in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the flame retardant resin composition of the present invention.

  The flame retardant resin composition of the present invention is blended with known light resistance (weather) agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, dyes, antibacterial agents, antifungal agents, and foaming agents. be able to.

  Further, the flame retardant resin composition of the present invention includes other known polymers such as polycarbonate resin, PMMA, polypropylene, polyethylene, polyamide resin, thermoplastic polyester resin, polyamide elastomer, polyester elastomer, polyphenylene ether, polyphenylene. Sulfide, epoxy resin, phenol resin, LCP, polyurethane, phenoxy resin, urea resin, and the like can be appropriately blended.

  The flame-retardant resin composition of the present invention thus prepared is obtained as a molded product by a known molding method such as injection molding, press molding, sheet extrusion molding, vacuum molding, profile extrusion molding, foam extrusion molding, or the like. be able to. Examples of the molded products formed by these methods include the following.

Various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickup parts, oscillators, various terminal boards, transformers, plugs, printed wiring boards, Electrical and electronic parts such as tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts.
Household and office appliances represented by VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, sound parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, etc. parts.
Office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jig related parts.
Sanitary-related parts such as toilet seats, tank covers, casings, kitchen parts, washstand-related parts, bathroom-related parts.
Housing and housing related parts such as window frames, furniture, flooring, and wall materials.
Optical equipment and precision equipment related parts such as microscopes, binoculars, cameras and watches.
Various valves such as alternator terminals, alternator connectors, IC regulators, exhaust gas valves, various valves related to fuel, exhaust systems, and intake systems.
Air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant 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, distributor, starter switch, starter relay, wiper harness for transmission, window washer nozzle , Air conditioner panel switch board, fuel related solenoid valve co Rubobin, fuse connector, horn terminal, insulating plates for electric equipment, step motor roller, a lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case.
PC, printer, display, CRT display, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive and other storage device housing, chassis, relay, switch, case member, transformer member, coil bobbin, etc. Electronic equipment parts. Various other uses.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the examples, parts and% are based on mass unless otherwise specified. Various measurements in the examples and comparative examples were based on the following methods.

[1] Evaluation method (1) Gel content of rubbery polymer;
(2) Average particle diameter of rubbery polymer latex;
The average particle size of the rubbery polymer latex used for forming the component (A) was measured by a light scattering method. The measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mummant method was used with 70 times integration. In addition, it confirmed with the electron microscope that the particle diameter of the dispersion-grafted rubber-like polymer particle in (A) component was substantially the same as the latex particle diameter.
(3) Graft ratio of component (A): According to the method described above.
(4) The intrinsic viscosity [η] of the acetone-soluble component of component (A);

(5) Flame retardancy (Flame retardance-1) Limit oxygen index (LOI)
LOI was measured according to ASTM D-2863. The higher the value, the more difficult it is to burn, and it was used as an index of flame retardancy.
(Flame Retardancy-2) Self-extinguishing Using a limiting oxygen index measuring device and a test piece, the presence or absence of self-extinguishing was observed at an oxygen concentration of 25%. Those that automatically extinguish after ignition (self-extinguishing) are highly flame retardant. Evaluated according to the following criteria:
: Fire extinguishes within 5 seconds after ignition.
○: Burns for 5 seconds or more, but self-extinguishing.
×: No self-extinguishing property.
(6) Impact resistance Based on ISO test method 179, the Charpy impact strength (KJ / m ² ) with notch was measured.

[2] Flame Retardant Resin Composition Component (1) (A) Component (1-1) Production Example A1; ABS resin A glass flask having an internal volume of 7 L equipped with a stirrer was subjected to ion exchange water 75 in a nitrogen stream. Part, potassium rosinate 0.5 part, t-dodecyl mercaptan 0.1 part, polybutadiene latex (average particle diameter: 3500 kg, gel content: 85%) 40 parts (solid content), styrene 15 parts, acrylonitrile 5 parts In addition, the temperature was raised with stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerizing for 1 hour, 50 parts of ion exchange water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of t-dodecyl mercaptan and 0.01 part of cumene hydroperoxide for 3 hours. The polymerization was continued for 1 hour, and the polymerization was continued for 1 hour. Then, 0.2 part of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) was added to complete the polymerization. . The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a styrene resin A1. The graft ratio of this A1 was 68%, and the intrinsic viscosity [η] of the acetone soluble component was 0.45 dl / g.

(1-2) Production Example A2: AS resin Two jacketed polymerization reaction vessels equipped with a ribbon wing with an internal volume of 30 L were connected to each other, purged with nitrogen, and then 75 parts of styrene and 25 parts of acrylonitrile in the first reaction vessel. 20 parts of toluene were continuously added. A solution of 0.12 part of t-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator. Continuously fed. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by a pump provided outside the first reaction vessel, and the same amount as that of styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator was taken out. Supplied to the eye reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and had an intrinsic viscosity [η] of 0.48. Styrene resin A2 was obtained.

(2) (B) Component B1; As the boron oxide, a product with an average particle size of 250 μm manufactured by Nippon Electric Works Co., Ltd. was used.
B2: B1 boron oxide surface-treated with methyl hydrogen silicone oil KF99 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

(3) Component (C) The following polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. was used as the silicone compound.
C1; X-40-9805 (trade name of methylphenyl silicone resin)
C2; X-40-9805-64 (trade name of methylphenyl silicone resin)
C3; KR-511 (trade name of methylphenyl silicone oligomer)

(4) Component (D) As a melamine cyanurate, MC-640 (trade name) manufactured by Nissan Chemical Industries, Ltd. was used.

(5) Other ingredients (E)
E1: As polytetrafluoroethylene, Hostaflon TF1620 (trade name) manufactured by Sumitomo 3M Limited was used.
E2: Fine particle titanium oxide TTO-51 (C) (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used.

Examples 1 to 14, Comparative Examples 1 and 2
After mixing with a Henschel mixer at the blending ratio shown in Table 1, the mixture was melt-kneaded using a twin-screw extruder (cylinder setting temperature 220 ° C.) and pelletized. After the obtained pellets were sufficiently dried, test pieces for evaluation were produced by an injection molding machine (cylinder setting temperature 210 ° C.). Using this test piece, flame retardancy and impact resistance were evaluated by the above methods.

From the results shown in Table 1, the following is clear.
The molded articles of Examples 1 to 14 of the present invention are excellent in both flame retardancy and impact resistance.
On the other hand, Comparative Example 1 is an example in which the amount of component (B) used in the present invention is small outside the scope of the invention, and the flame retardancy is poor. Comparative Example 2 is an example in which the amount of the component (B) used in the present invention is large outside the scope of the invention, and the impact resistance is greatly inferior.

The flame retardant resin composition of the present invention has excellent flame retardancy and impact resistance, and is used in the vehicle field, electrical / electronic field, communication field, OA / home appliance field, etc. where high performance is required. Useful as various parts.

Claims (4)

A flame retardancy comprising the following (A) component and the following (B) component, and blending 0.5 to 100 parts by mass of the following (B) component with respect to 100 parts by mass of the following (A) component: Resin composition.
(A) (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence or absence of a rubbery polymer Styrenic resin,
(B) Boron oxide.   Furthermore, the flame-retardant resin composition of Claim 1 formed by mix | blending 0.1-50 mass parts of (C) silicone compounds with respect to 100 mass parts of said (A) component.   Furthermore, the flame-retardant resin composition of Claim 1 or 2 formed by mix | blending 0.5-50 mass parts of (D) nitrogen-containing compounds with respect to 100 mass parts of said (A) component. The molded article which consists of a flame-retardant resin composition of any one of Claims 1-3.