KR20050036683A - Flame-retardant resin composition and molded article - Google Patents

Abstract

This invention contains the following component (A) and a component (B), and provides the flame-retardant resin composition characterized by mix | blending the following component (B) with 0.5-100 mass parts with respect to 100 mass parts of following component (A). do:

(A) a styrene resin formed by (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; And

(B) boron oxide.

Moreover, 0.1-50 mass parts of (C) silicone compounds and / or 0.5-50 mass parts of (D) nitrogen-containing compounds can be contained further.

Description

Flame Retardant Resin Compositions and Molded Products {FLAME-RETARDANT RESIN COMPOSITION AND MOLDED ARTICLE}

The present invention relates to a flame retardant resin composition providing 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.

Rubber-reinforced styrene-based resins such as ABS resin and HIPS, and flame-retardant resin compositions obtained by flame-retardant compositions of these and polycarbonate resins are excellent in mechanical, physical and electrical properties. It is widely used in the field, the vehicle field, and the sanitary field.

For flame retardation of these resins, see halogen-based flame retardants (see, for example, Japanese Patent No. 3198485), organophosphorus flame retardants (see, for example, Japanese Patent Application Laid-Open No. 9-87337 and Japanese Patent Application Laid-Open No. 10-120853). Flame retardants represented by) are used.

In these flame-retardant resin compositions, when a halogen-based flame retardant is used, there is a problem such as causing metal corrosion of processing equipment. Moreover, when phosphorus flame retardants, such as a phosphate compound, are used, there exists a problem of reducing mechanical strength, heat resistance, etc. by making a flame retardant act as a plasticizer of resin.

Further, Japanese Patent Application Laid-Open No. 57-1547 discloses a technique for blending a composite metal hydroxide with a styrene resin, but as is apparent from the examples, when a large amount of this is blended, the effect of improving the flame retardancy is relatively low. In addition, since the inorganic substance is blended in a large amount, the impact resistance and fluidity of the resulting composition are inferior. Japanese Unexamined Patent Publication No. 61-291642 discloses a technique for blending red phosphorus and melamine in ABS resins, which shows excellent flame retardancy, but can be used only as a black-based material because it is colored due to the formulation of red phosphorus. There is no use range. In addition, Japanese Patent Application Laid-Open No. 61-291642 discloses a method of blending a phosphorus compound and a novolak resin in an ABS resin. However, when using a red phosphorus, there are the same problems as described above. When used, the coloring problem due to the phosphorus compound can be solved, but a yellowing problem due to the novolak resin occurs.

[Patent Document 1] Patent No. 3198485

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-87337

[Patent Document 3] Japanese Unexamined Patent Publication No. 10-120853

[Patent Document 4] Japanese Patent Application Publication No. 57-1547

[Patent Document 5] Japanese Patent Application Laid-Open No. 61-291642

[Patent Document 6] Japanese Patent Application Laid-Open No. 61-291642

An object of the present invention is to provide a flame retardant resin composition excellent in flame retardancy and impact resistance. Another object of the present invention is to provide a molded article made of the present flame retardant resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, it discovered the flame-retardant resin composition from which the molded article excellent in flame-retardance and impact resistance is obtained by mix | blending boron oxide with ABS resin, and came to complete this invention.

That is, according to one aspect of the present invention, the following component (A) and component (B) are included, and the following component (B) is blended in an amount of 0.5 to 100 parts by mass based on 100 parts by mass of the following component (A). A flame retardant resin composition is provided:

(A) a styrene resin formed by (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; And

(B) boron oxide.

According to the other aspect of this invention, the molded article which consists of said flame-retardant resin composition is provided.

Since the flame-retardant resin composition of this invention mix | blended and comprised a specific amount of boron oxide (B) with styrene resin (A), the molded article excellent in flame retardance and impact resistance can be obtained.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in detail.

The styrene resin as the component (A) of the present invention is a monomer (b) composed of an aromatic vinyl compound or an aromatic vinyl compound and other vinyl monomers copolymerizable with the aromatic vinyl compound in the presence or absence of the rubbery polymer (a). Is formed by (co) polymerization, and may be a mixture of at least one of styrene resins (co) polymerized in the presence of a rubbery polymer and at least one of styrene resins (co) polymerized in the absence of a rubbery polymer. do. From the viewpoint of improving the flame retardancy and impact resistance aimed at by the present invention, the content of the rubbery polymer (a) in the component (A) is in the range of 3 to 80 mass%, with the entire component (A) being 100 mass%. Preferably, it is 5-50 mass%, More preferably, it is 10-30 mass%.

In addition, in this specification, "(co) polymerization" means homopolymerization and / or copolymerization. In addition, "(meth) acryl" means an acryl and / or methacryl.

The rubbery polymer (a) is not particularly limited, but specific examples thereof include polybutadiene, butadiene styrene copolymer, butadiene acrylonitrile copolymer, butadiene (meth) acrylic acid ester copolymer, and styrene butadiene block copolymer. Butadiene-based (co) polymers such as styrene-isoprene-based block copolymers, partial or complete hydrogenated products of these butadiene-based copolymers, ethylene / propylene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / butene- 1 copolymer, an ethylene butene-1 non-conjugated diene copolymer, an acrylic rubber, a silicone rubber, a silicone acrylic IPN rubber, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Among these, polybutadiene, butadiene styrene copolymer, styrene butadiene block copolymers and their hydrogenated substances, ethylene propylene copolymer, ethylene propylene nonconjugated diene copolymer, acrylic rubber and silicone rubber are preferable.

Although the gel content rate of the said rubbery polymer is not specifically limited, When obtaining component (A) by emulsion polymerization, gel content rate becomes like this. Preferably it is 98 mass% or less, More preferably, it is 40-98 mass%, Especially preferably, It is 50-95 mass%. In this range, a flame retardant resin composition can be obtained which provides a molded article 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 added to 100 ml of toluene, and after standing at room temperature for 48 hours, it was filtered through a 100 mesh wire mesh (with a mass of W ₁ gram), and the toluene insolubles and the wire mesh were vacuum dried at 80 ° C. for 6 hours. Thereafter, weighing (mass W ₂ grams) was calculated according to the following formula (1):

Gel content (mass%) = [{W ₂ (g) -W ₁ (g)} / 1 (g)] x 100. (One)

A gel content can be adjusted by setting suitably the kind and quantity of a molecular weight modifier, superposition | polymerization time, superposition | polymerization temperature, superposition | polymerization conversion rate, etc. at the time of manufacture of a rubbery polymer.

As an aromatic vinyl compound which comprises the said monomer (b), styrene, (alpha) -methylstyrene, hydroxy styrene, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Among these, styrene and α-methylstyrene are preferable.

Other monomers copolymerizable with the aromatic vinyl compound include vinyl cyan compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, and acid anhydride groups. A containing unsaturated compound, a substituted or unsubstituted amino group containing unsaturated compound, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types, respectively.

Acrylonitrile, methacrylonitrile, etc. are mentioned as a vinyl cyanide compound used here, These can be used individually by 1 type or in combination of 2 or more types.

Methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate etc. are mentioned as a (meth) acrylic acid ester compound, These can be used individually by 1 type or in combination of 2 or more types. Can be.

As a maleimide compound, maleimide, N-phenylmaleimide, N-cyclohexyl maleimide, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Moreover, this maleimide unit can also be introduce | transduced by the method of imidating, after copolymerizing maleic anhydride.

The unsaturated acid compound may be acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like, and these may be used alone or in combination of two or more thereof.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like. These may be used alone or in combination of two or more thereof.

The hydroxyl group-containing unsaturated compound is 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy Hydroxy-2-methyl-1-propene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide, and the like, and these may be used alone or in combination. It can be used in combination of 2 or more type.

Vinyl oxazoline etc. are mentioned as an oxazoline group containing unsaturated compound, These can be used individually by 1 type or in combination of 2 or more type.

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like, and these may be used alone or in combination of two or more thereof.

Substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethyl aminoethyl methacrylate, aminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, acrylamine and methacryl Amine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-amino styrene, and the like, and these may be used alone or in combination of two or more thereof.

When the said other vinyl monomer copolymerizable with an aromatic vinyl compound makes the whole monomer (b) 100 mass%, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less. Preferred combinations of monomers are 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 may be used alone or in combination of two or more thereof. Can be used.

The component (A) of this invention can be manufactured by a well-known polymerization method, for example, emulsion polymerization, block polymerization, solution polymerization, suspension polymerization, and the polymerization method which combined these.

In the case of preparing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier and the like are used, but all of them can be used.

Examples of the polymerization initiator include cumene hydroperoxide, p-mentane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butylhydro peroxide, potassium persulfate, azobisisobutyronitrile and the like. Can be mentioned. In addition, it is preferable to use a red-ox system such as various reducing agents, sugar-containing iron pyrrolate prescription formulations, sulfoxylate formulations, and the like as the polymerization initiation assistant.

Octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, tapinylene, etc. are mentioned as a chain transfer agent.

As emulsifiers, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, potassium salts of sodium fatty acids having 10 to 20 carbon atoms, sodium salts, potassium salts of rosin acid, and sodium salts can be used. have.

In addition, the method of using a rubbery polymer (a) and a monomer (b) in emulsion polymerization can superpose | polymerize by adding all the monomer (b) in presence of the whole amount of rubbery polymer (a), or superposing | polymerizing by dividing or continuous addition. It may be. In addition, a part of the rubbery polymer (a) may be added during the polymerization.

After emulsion polymerization, the latex obtained is usually made into a powder of the component (A) of the present invention by solidifying with a coagulant, washing with water and drying. At this time, after mixing the latex of 2 or more types of component (A) obtained by emulsion polymerization suitably, it can also coagulate | solidify. As the coagulant used herein, 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 manufacturing component (A) by solution polymerization, the solvent which can be used is an inert polymerization solvent used by normal radical polymerization, For example, aromatic hydrocarbons, such as ethylbenzene and toluene, methyl ethyl ketone, acetone, etc. Ketones, acetonitrile, dimethylformamide, N-methylpyrrolidone, etc. are mentioned. Polymerization temperature becomes like this. Preferably it is the range of 80-140 degreeC, More preferably, it is the range of 85-120 degreeC.

In the case of superposition | polymerization, a polymerization initiator may be used and it may superpose | polymerize 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 and benzoyl peroxide are preferably used.

In addition, when using a chain transfer agent, mercaptans, (alpha) -methylstyrene dimer, tapinylene, etc. can be used, for example.

In addition, when manufacturing by block polymerization or suspension polymerization, the polymerization initiator, chain transfer agent, etc. which were demonstrated by solution polymerization can be used.

In addition, the polymer component obtained by polymerizing the monomer (b) in the presence of the rubbery polymer (a) is usually a copolymer in which the monomer (b) is graft copolymerized to the rubbery polymer (a) and the rubbery polymer (a). Ungrafted components ((co) polymers of the monomers (b)) are included.

The amount of the monomer amount remaining in the component (A) obtained by each polymerization method is preferably 10,000 ppm or less, and more preferably 5,000 ppm or less.

The graft ratio of the above-mentioned component (A) becomes like this. Preferably it is 20-200 mass%, More preferably, it is 30-150 mass%, Especially preferably, it is 40-120 mass%. This graft rate (%) is calculated | required by following formula (2):

Graft ratio (mass%) = {(T-S) / S} x 100. (2)

In Formula (2), T is added 1 g of component (A) to 20 ml of acetone, stirred for 2 hours with a shaker, and then centrifuged for 60 minutes with a centrifuge (rotation speed; 23,000 rpm), insoluble content and soluble It is the mass (g) of the insoluble content obtained by isolate | separating powder, and S is the mass (g) of the rubbery polymer contained in 1 g of component (A).

The intrinsic viscosity [η] of the acetone soluble component of the 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 0.2-1 dl / g, Especially preferably, it is 0.3-0.8 dl / g.

The average particle diameter of the grafted rubbery polymer particles dispersed in component (A) according to the present invention is preferably 500 to 30,000 mm 3, more preferably 1,000 to 20,000 mm 3, particularly preferably 1,500 to 8,000 mm 3. 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 calculated from natural minerals and preferably contains at least 80% by mass of the B ₂ O ₃ component. As impurities, silicon oxide, iron oxide, aluminum oxide, calcium oxide, magnesium oxide, and the like may be included, but each content is preferably 5% by mass or less. Moreover, it is preferable for the surface appearance of a final molded article that the said boron oxide grind | pulverized to the average particle diameter of 1,000 micrometers or less.

Moreover, what processed the surface of boron oxide can also be used. Although the processing method is not specifically limited, (1) The method of melt | dissolving a processing agent in a solvent, apply | coating to a boron oxide, and drying, (2) The method of carrying out the extraction and drying after immersing a boron oxide in the organic solvent solution which melt | dissolved the processing agent, (3) a method of mixing boron oxide and a treatment agent with a mixer, attaching the treatment agent to the surface of boron oxide, (4) coating the treatment agent on the surface of boron oxide particles by impact striking means, and the like (5) thermosetting resins Coating on the surface of boron oxide, curing on the surface, and coating. The method by the impact-type hitting means of (4) can be performed using commercially available apparatuses, such as the (heterogeneous) crossing system of Nara Kikai Sesaku Co., Ltd., for example.

As the surface treating agent, for example, a silane coupling agent, a titanate coupling agent, a coupling agent such as aluminum coupling, a silicone oil such as hydrodiene silicone oil, a salt consisting of triazine derivative and cyanuric acid or isocyanuric acid Fluorine-containing polymers such as polytetrafluoroethylene, epoxy resins, urea resins, unsaturated polyester resins, phenol resins, melamine resins, ketone resins, polymers such as alkyd resins, metal hydroxides such as magnesium hydroxide, silica, and the like. These surface treating agents can be used individually by 1 type or in combination of 2 or more type.

The usage-amount of the said component (B) in the flame-retardant resin composition of this invention is 0.5-100 mass parts with respect to 100 mass parts of components (A) of this invention, Preferably it is 1-80 mass parts, More preferably, it is 3-70 Mass part, Especially preferably, it is 5-50 mass parts, and when it is less than 0.5 mass part, a flame retardance does not improve and when it exceeds 100 mass parts, impact resistance falls large.

The silicone compound which is the component (C) of this invention makes the structural unit represented by general formula (I) and the repeating structural unit represented by general formula (II) an essential component, and is a repeating structure represented by general formula (III) It is preferable to contain 80 mol% or less of the repeating structural unit represented by a unit or general formula (IV), and the shape can use an oil type, a rubbery type, a varnish type, a powder type, a rubber type, and a pellet type:

Wherein 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 substitution and / or an alkylene group substitution aryl group, hydrogen, and ( It is at least 1 type independently selected from the group which consists of a meta) acryl group. Typically, R ₁ ~R least 5mol% of ₆ is less than 10mol% ~80mol% preferred, and it is an aryl group such as phenyl group is an aryl group is more preferred, and less than 30mol% ~80mol% if this aryl group is particularly preferred. In case, R ₁ ~R ₆ is a (meth) acrylic group, is preferable in the flame-retardant surface.

Silicon compounds of the present invention the above-mentioned formula (I), (II) and (III) composed of a ground minutes polyorganosiloxane are preferred, R ₁ ~R ₆ under 20~80mol% of the carbon atoms of 6 to 12 aryl group is more preferred, and an aryl group is a phenyl group, are particularly preferred R ₁ ~R ₆ other than the phenyl group in phenyl methyl polysiloxane.

Moreover, what modified | denatured the side chain, both terminal, one terminal, and side chain terminal of a polyorganosiloxane by the amino group, an epoxy group, a carboxy group, a phenol group, etc. can also be used, It is especially preferable to modify | denature the amino group.

Moreover, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned as an alkyl group, A trifluoropropyl group etc. are mentioned as a substituted alkyl group. As an alkoxyl group, a methoxy group, an ethoxy group, etc. are mentioned, As an aryl group, a phenyl group, a tril group, a naphthyl group, etc. are mentioned.

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

Although the silicone compound of this invention is manufactured by a general manufacturing method, when a manufacturing method is illustrated, the unit which comprises the said General formula (III) or the unit which comprises General formula (II), General formula (III) and / or After the co-hydrolysis of the organohalosilane in water at a ratio corresponding to the ratio of the units constituting the general formula (IV), the resulting hydrolysis product is condensed, followed by dehydration by equilibration with an alkali metal hydroxide catalyst. It can manufacture, For example, it can manufacture by the method etc. which are described in Unexamined-Japanese-Patent No. 5-247212.

Component (C) of this invention is 0.1-50 mass parts with respect to 100 mass parts of component (A), 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 It is a part and when it is less than 0.1 mass part, the flame resistance of a component (A) + component (B) cannot be improved, and when it exceeds 50 mass parts, impact resistance will fall.

As a nitrogen containing compound which is the component (D) of this invention, what is illustrated by following (1)-(3) can be used preferably.

(1) Triazine Derivatives: Specific examples thereof include melamine, melamine: formaldehyde = 1: 1 to 1: 6, metholol melamine containing 1 to 6 metholol groups obtained by reacting both, and the above-mentioned metyrolmelamine. Melamine resin obtained by heat-hardening in an acidic solution, modified melamine resin heat-hardened by simultaneously adding urea, phenol, or alcohol when resinizing the methirolmelamine, melamine sulfate obtained by neutralization reaction of sulfuric acid and melamine, benzoguanamine And aceto, a dendritic substance obtained by heating and curing a methirolized benzoguanamine obtained by reacting both at a molar ratio of benzoguanamine: formaldehyde = 1: 1 to 1: 4 and the methirolized benzoguanamine in an acidic solution. Guanamine, methirolized acetoguanamine and the phase obtained by reacting the protons in a ratio of acetoguanamine: formaldehyde = 1: 1 to 1: 4. The dendritic substance etc. which are obtained by heat-hardening group methirolized acetoguanamine in an acidic solution are mentioned.

(2) (iso) cyanuric acid derivatives: specific examples include cyanuric acid melamine, isocyanuric acid melamine, triallyl cyanurate, triallyl isocyanurate and trimeta which are obtained by the neutralization reaction of (iso) cyanuric acid and melamine. And allyl isocyanurate.

(3) Imidazolidinone derivatives: Specific examples include a resinous phase obtained by heat condensation of a methirolized substance obtained by reacting both in an ethylene urea or ethylenethiourea: formaldehyde ratio of 1: 1: 1: 2 in an acidic solution. A substance is mentioned.

The said component (D) of this invention is 0.5-50 mass parts with respect to 100 mass parts of components (A) of this invention, Preferably it is 1-40 mass parts, More preferably, it is 2-30 mass parts, Especially preferably, It is 3-20 mass parts, and when it is less than 0.5 mass part, the effect which improves the flame retardance of a component (A) + component (B) or a component (A) + component (B) + component (C) is not obtained, 50 mass parts If it exceeds, impact resistance will fall.

Moreover, a fluorine resin powder and / or a metal oxide can be mix | blended with the flame-retardant resin composition of this invention for the purpose of further improving flame retardance. Fluorine resin powders used herein include fluorinated ethylene resins (polymers of monomers substituted with fluorine atoms having one or more hydrogen atoms of ethylene), and specific examples thereof include polyfluoroethylene, polydifluoroethylene, and polytrifluoroethylene. , Polytetrafluoroethylene, polytetrafluoroethylene / fluoropropylene copolymer, polyvinylidene fluoride, and the like, and the preferred weight average molecular weight is usually 500,000 or more, more preferably 1 million or more. As for an average particle diameter, 10-600 micrometers is preferable. In addition, the fluorine resin powder used in the present invention can also be used to improve dispersibility with polyethylene wax, organic acid, organic acid metal salt and the like. It is preferable to use the said fluororesin powder in the range of 0.01-5 mass parts with respect to 100 mass parts of components (A) of this invention.

Examples of the metal oxides include magnesium oxide, aluminum oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, zinc oxide, and tin oxide, which are 100 parts by mass of the component (A) of the present invention. It is preferable to use in the range of 0.001-5 mass parts with respect to.

The flame-retardant resin composition of this invention can be prepared by kneading each component by the method using various extruders, a Banbury mixer, a stirrer, a continuous stirrer, etc., or a combination thereof. Preferable manufacturing method is a method using an extruder, and particularly preferably a method using a multi-screw extruder, a method using a Banbury mixer or a continuous stirrer, and a combination thereof.

In addition, in kneading each component, these components may be kneaded collectively, or may be kneaded by being divided and blended in multiple stages.

A well-known inorganic filler can be mix | blended with the flame-retardant resin composition of this invention. Inorganic fillers used herein include glass fibers, glass flakes, ground glass, glass beads, hollow glass, carbon fibers, ground fibers of carbon fiber, talc, calcium carbonate, calcium carbonate whiskers, wallastonite, Mica, kaolin, montmorillonite, hectorite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, plate alumina, silica, plate silica, and organic treated smectite, which are used alone or in combination of two or more. It can be used in combination. Moreover, what surface-treated with the well-known coupling agent can be used for the purpose of improving the dispersibility of the said inorganic filler. Known coupling agents include silane coupling agents, aluminum coupling agents, titanate coupling agents and the like.

Moreover, organic fillers, such as an aramide fiber, a phenol fiber, and a polyester fiber, can also be mix | blended.

These fillers are normally used in 1-100 mass parts with respect to 100 mass parts of flame retardant resin compositions of this invention.

In the flame-retardant resin composition of the present invention, known light-resistant (after) agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, dyes, antibacterial agents, antifungal agents, and foaming agents can be blended.

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 and polyphenylene. A sulfide, an epoxy resin, a phenol resin, an LCP, a polyurethane, a phenoxy resin, urea resin, etc. can be mix | blended suitably.

The flame-retardant resin composition of this invention prepared in this way can obtain a molded article by well-known shaping | molding methods, such as injection molding, press molding, sheet extrusion molding, vacuum molding, mold release extrusion molding, and foam extrusion molding. Examples of molded articles molded by these molding methods include the followings:

-Gears, Cases, Sensors, LEP Lamps, Connectors, Sockets, Resistors, Relay Cases, Switches, Coil Bobbins, Capacitors, Variable Capacitor Cases, Optical Pickup Components, Oscillators, Various Terminal Boards, Transformers, Plugs, Printed Wiring Boards, Tuners, Electrical and electronic components represented by speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related components.

-Home and office electrical appliance parts such as VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio machine parts such as audio / laser discs and compact discs, lighting parts, refrigerator parts, etc. .

-Parts for office computers, parts for telephone machines, parts for fax machines, parts for copiers, parts for cleaning fixtures.

-Sanitary parts, such as toilet seats, tank covers, casings, parts around the kitchen, vanity parts and bathroom parts.

-Parts related to housing and housing facilities such as window frames, furniture, flooring and wall materials.

-Parts related to optical instruments and precision instruments represented by microscopes, binoculars, cameras, watches, etc.

-Valves such as alternator terminals, alternator connectors, IC regulators, exhaust gas valves, and valves for fuel, exhaust, and intake systems.

-Intake nozzle snorkel, suction branch pipe, fuel pump, engine coolant joint, carburetor body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake putting 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, wind washer nozzle, Air conditioner panel switch boards, coil bobbins for fuel-related solenoid valves, connectors for fuses, horn terminals, electrical components insulators, stepper rollers, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition case .

-Housings, chassis, relays, switches, case members, transformer members, coil bobbins of storage devices such as personal computers, printers, displays, CRT displays, notebook personal computers, mobile phones, PHS, DVD drives, PD drives, flexible disk drives, etc. Electric and electronic device parts, and other various applications.

Example

Although an Example is given to the following and this invention is demonstrated in detail, this invention is not limited to these Examples, unless the meaning of this invention is exceeded. In addition, in an Example, a part and% are mass references | standards unless there is particular notice. In addition, the various measurements in an Example and a comparative example were based on the following method.

[1] evaluation methods

(1) gel content of the rubbery polymer; The method described above was followed.

(2) Average particle diameter of rubbery polymer latex:

The average particle diameter of the rubbery polymer latex used for formation of component (A) was measured by the light scattering method. The measuring machine used the LPA-3100 type | mold by Otsuka Denshisha, and used the methane-landing method by 70 times integration. In addition, it was confirmed by electron microscopy that the particle diameter of the dispersed grafted rubbery polymer particles in component (A) was approximately the same as the latex particle diameter.

(3) Graft ratio of component (A): The above method was followed.

(4) Intrinsic viscosity [eta] of the acetone soluble content of component (A): It followed the said method.

(5) flame retardant

(Flammability-1) limit oxygen index (LOI)

LOI was measured based on ASTMD-2863. The higher the value, the more the flame retardant material was used.

(Flammability-2) self-extinguishing

Self-extinguishing property was confirmed at the oxygen concentration of 25% using the limit oxygen index measuring device and the test piece. Automatically extinguishing fire after self ignition (self-extinguishing) is highly flame retardant. Evaluation was made according to the following criteria:

(Double-circle): Fire extinguishes within 5 second after ignition.

(Circle): It burns for 5 second or more but self-extinguishing.

X: No self-extinguishing.

(6) impact resistance

In accordance with ISO test method 179, the notched Charpy impact strength (KJ / m ² ) was measured.

[2] fire retardant resin composition components

(1) Component (A)

(1-1) Preparation Example A1; ABS resin

In a 7-liter glass flask equipped with a stirrer, 75 parts of ion-exchanged water, 0.5 parts of potassium rosinate, 0.1 parts of t-dodecyl mercaptan, polybutadiene latex (average particle diameter: 3500 kPa, gel content: 85%) in a nitrogen stream The temperature was raised while adding 40 parts (solid content), 15 parts of styrene, and 5 parts of acrylonitrile, stirring. When internal temperature reached 45 degreeC, the solution which melt | dissolved 0.2 part of sodium pyrrolate, 0.01 part of ferrous sulfate heptahydrate, and 0.2 part of glucose in 20 parts of ion-exchange water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After the polymerization for 1 hour, additional 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 parts of t-dodecyl mercaptan and 0.01 part of cumene hydroperoxide were continuously added for 3 hours. After the polymerization was continued for another 1 hour, 0.2 part of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) was added to complete the polymerization. The latex of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and 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) Preparation Example A2; AS resin

Two jacketed polymerization reaction vessels having a volume of 30 L ribbon wings were connected and 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel after nitrogen substitution. A solution of 0.12 parts of t-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution of 0.1 parts of 1,1'-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene were continuously supplied as a polymerization initiator. The polymerization temperature of the first reaction vessel was controlled to 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion rate was 57%. The obtained polymer solution was continuously taken out of the supply amount and the same amount of styrene, acrylonitrile, toluene, a molecular weight regulator, and a polymerization initiator by a pump provided outside the first reaction vessel, and supplied to the second 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 2nd reaction container directly deodorized and removed the unreacted monomer and solvent using the twin screw 3-stage vent extruder, and obtained styrene resin A2 of intrinsic viscosity [(eta)] 0.48.

(2) Component (B)

B1: As the boron oxide, a product having an average particle diameter of 250 µm manufactured by Nippon Denko Co., Ltd. was used.

B2: The surface treatment of boron oxide B1 with methylhydrodiene silicon oil KF99 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

(3) Component (C)

As a silicone compound, the following polyorganosiloxane by Shin-Etsu Chemical Co., Ltd. was used.

C1: X-40-9805 (brand name of methylphenyl type silicone resin)

C2: X-40-9805-64 (brand name of methylphenyl type silicone resin)

C3: KR-511 (brand name of methylphenyl silicone oligomer)

(4) Component (D)

As melamine cyanurate, MC-640 (brand name) by Nissan Chemical Industries, Ltd. was used.

(5) Other ingredients (E)

E1: Hostaflon TF1620 (trade name) manufactured by Sumitomo 3M was used as polytetrafluoroethylene.

E2: Fine particle titanium oxide TTO-51 (C) (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used.

Examples 1-14, Comparative Examples 1 and 2

After mixing by Henschel mixer in the mixing | blending ratio of Table 1, it melt-kneaded and pelletized using the twin screw extruder (cylinder setting temperature 220 degreeC). After drying the obtained pellet sufficiently, the test piece for evaluation was produced with the injection molding machine (cylinder setting temperature 210 degreeC). This test piece was used to evaluate flame retardancy and impact resistance by the above method.

TABLE 1

The following is clear from the result shown in Table 1.

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, the comparative example 1 is an example in which the usage-amount of the component (B) of this invention is few outside the scope of the invention, and it is inferior to flame retardance. Comparative Example 2 is an example in which the amount of the component (B) of the present invention is many outside the scope of the present invention, and the impact resistance is largely inferior.

The flame-retardant resin composition of the present invention has excellent flame retardancy and impact resistance, and is useful as various parts such as the vehicle field, the electric / electronic field, the communication field, and the OA / home appliance field where high performance is required.

Claims (4)

(A) a styrene resin formed by (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; And (B) boron oxide Flame retardant resin composition containing the said (A) in 0.5-100 mass parts with respect to 100 mass parts of said components (A). The method of claim 1, The flame-retardant resin composition in which (C) silicone compound is further mix | blended with 0.1-50 mass parts with respect to 100 mass parts of said components (A). The method according to claim 1 or 2, The flame-retardant resin composition in which (D) nitrogen-containing compound is further mix | blended at 0.5-50 mass parts with respect to 100 mass parts of said components (A). The molded article which consists of a flame-retardant resin composition of any one of Claims 1-3.