WO2000046299A1

WO2000046299A1 - Aromatic polycarbonate resin composition

Info

Publication number: WO2000046299A1
Application number: PCT/JP2000/000681
Authority: WO
Inventors: Hajime Nishihara
Original assignee: Asahi Kasei Kogyo Kabushiki Kaisha
Priority date: 1999-02-08
Filing date: 2000-02-08
Publication date: 2000-08-10
Also published as: DE10080144T1

Abstract

An aromatic polycarbonate resin composition, characterized by comprising (A) a resin component selected from among aromatic polycarbonates and mixtures thereof with other organic polymer resins which have aromatic polycarbonate contents of 50 wt. % or above, and (B) a linear or cyclic aromatic silicone component which contains a monomer or polymer represented by general formula (1) or a mixture of both and whose aromatic group content is 5 to 100 % by mole based on the total amount of R1 to R4.

Description

Description Aromatic polycarbonate resin composition Technical field

The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention provides (A) a resin mixture of an aromatic polycarbonate or an aromatic polycarbonate and at least one other organic polymer resin; Or a cyclic aromatic group-containing silicone compound, wherein the component (B) contains a specific amount of an aromatic group. The polycarbonate resin composition of the present invention not only has excellent flame retardancy, but also has excellent melt fluidity and stability during melt molding (quality stability of molded articles). Furthermore, when the polycarbonate resin composition of the present invention is molded, a molded article having excellent mechanical properties, light resistance, and appearance can be obtained. Conventional technology

Polycarbonate is used in a wide range of fields, including automobile parts, home appliances parts, and 〇A equipment parts, because of its light weight and excellent impact resistance. Its use is limited. : As a method of making a resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to the resin, thereby achieving a certain degree of flame retardancy. . However, in recent years, the demand for fire safety has been greatly increased, and advanced flame retardant technology has been developed. In addition, environmental problems and mechanical properties of resin molded products have also been increased. There is a strong demand for technological development that does not lead to a decline.

It is also known to use an organic silicon compound as a flame retardant for a resin. For example, Japanese Unexamined Patent Publication No. 63-41565 discloses a smoke suppressant comprising hydrocarbon, silicon and zinc borate, and is disclosed in U.S. Pat. No. 7,925,5 and U.S. Pat. Nos. 4,387,176 disclose a flame-retardant resin composition containing dimethyl silicone. The silicones described in the above publications have a very low aromatic group content (less than 5 mol%). When a flame retardant containing silicone having a low aromatic group content is blended with an aromatic group-containing resin to form a resin composition, the silicone has low compatibility with the resin. The resin composition is phase-separated, and therefore, when the resin composition is molded, there are problems such as a decrease in mechanical properties such as impact resistance of the resulting molded article, and there is room for improvement in practical use. Was.

Japanese Patent Application Laid-Open No. 63-1662756 discloses a resin composition for the purpose of improving abrasion, comprising aromatic poly-carbonate, polyolefin and silicone fluid. I have. In this gazette The silicones described also have very low aromatics content. The resin compositions disclosed in this publication are also disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 63-41565, and the above-mentioned U.S. Pat. Nos. 4,497,925 and U.S. Pat. There was a problem similar to that of Japanese Patent Publication No. 87,176.

In addition, Japanese Patent Application Laid-Open Nos. H10-139964 and H11-140294 describe flame retardant compositions containing branched and Z- or cross-linked methylphenylsilicone. Aromatic polycarbonate] :; A resin composition is disclosed. However, the above methylphenylsilicone has a branched structure and / or a crosslinked structure, so that it has low compatibility with aromatic polycarbonate-based resins, and thus has poor dispersibility in the resin composition. was there. In addition, the aromatic polycarbonate resin composition disclosed in this publication has another problem such as inferior flame retardancy.

Also known is methylphenylsilicone, which has no branched or cross-linked structure, used as oil for diffusion pumps or oils for high-temperature oil baths. Until now, the above-mentioned silicones have been combined with aromatic polycarbonates to excel. There is no report that a polycarbonate composition having both the above-mentioned flame retardancy and mechanical properties was obtained.

On the other hand, as a combination with a resin other than polycarbonate, a composition of polyphenylene ether and phenylsiloxane (JP-A-5-76080) is known. . The above composition The product flame retardant is a linear aromatic group-containing polyorganosiloxane, which uses polyphenylene ether as the power resin, and is inferior in impact strength and light resistance, and solves the problem of polycarbonate. It does not disclose any technology that does. Summary of the Invention

Under such circumstances, the present inventor has not only the above-mentioned problems, but also excellent flame retardancy, excellent melt fluidity and stability during melt molding (quality of molded products). The present inventors have conducted intensive studies to develop a poly-carbonate-based resin composition which can be advantageously used in the production of molded articles having excellent mechanical properties, light resistance and appearance. The result is a straight-chain or cyclic aromatic group-containing silicone compound having a specific structure, which has a specific amount of aromatic group. It has been found that not only the flame retardancy can be dramatically improved, but also the physical properties other than the flame retardancy can be improved. The present invention has been completed based on this finding.

Therefore, the main object of the present invention is not only to have excellent flame retardancy, but also to have excellent melt fluidity and stability during melt molding (quality stability of molded articles) and mechanical properties, An object of the present invention is to provide an aromatic polycarbonate resin composition which can be advantageously used for producing a molded article having excellent light resistance and appearance.

The above and other objects, features and benefits of the present invention are: It will become apparent from the following detailed description and claims. Detailed description of the invention

According to the present invention, (A) an aromatic polycarbonate and a resin mixture of an aromatic polycarbonate and at least one other organic polymer resin are selected, and the aromatic polycarbonate of the resin mixture is selected from the group consisting of: 100 parts by weight of a resin component having a bone content of 50% by weight or more and (B) 0.1 to 100 parts by weight of a linear or cyclic aromatic group-containing silicone compound;

And

The aromatic group-containing silicone compound (B) is represented by the following formula (1) ′:

R ¹

R 〇 + S i—〇 R C l)

R n

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent C i —C sa hydrocarbon group;

R ³ and R ⁴ are each independently a hydrogen atom or monovalent or divalent C ₂ . Wherein R ³ and R ⁴ are each independently divalent —C ₂ . R ³ and R ⁴ are divalent at the same time and are bonded to each other Forming a ring;

At least ^{one of} R ¹ , R ² , R ³ and R ⁴ is C ₆ —C ₂ . Wherein the aromatic group has a valency as defined above for RR ² , R ³ or R ⁴ ; and

n is 1 or more, expressed as a number average n value. The above polymer as the component (B) includes a monomer, a polymer or a mixture thereof represented by the following formula (2):

(2)

(Wherein ¹ and 1 and ² respectively represent the formula (1)

As defined above. )

And the repeating unit may be the same or different. Therefore, the above-mentioned polymer as the component (B) is a homopolymer or a copolymer, and In this case, the copolymer is a random copolymer, a block copolymer or an alternating copolymer,

The amount of the aromatic group in the component (B) is 5 to 100 mol% based on the total molar amount of R ¹ R ² , R ³ and R ⁴ ;

Provided is an aromatic polycarbonate resin composition characterized by the following features: Is done.

Next, in order to facilitate understanding of the present invention, first, basic features and preferred embodiments of the present invention will be listed.

1. (A) A resin selected from aromatic polycarbonate and a resin mixture of aromatic polycarbonate and at least one other organic polymer resin, wherein the aromatic polycarbonate content of the resin mixture is 5 100 parts by weight of a resin component which is 0% by weight or more,

(B) Linear or cyclic aromatic group-containing silicone compound J3.

1 0 0 i∑I7

And

The aromatic group-containing silicone compound (B) has the following formula (1)

R ³ —〇 (1

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent C i —C _2. Hydrocarbon group;

R ³ and R ⁴ are each independently a hydrogen atom or monovalent or divalent mono C ₂ . Wherein R ³ and R ⁴ are each independently a divalent C 1 -C 1. When representing a hydrocarbon group of R ³ and And R ⁴ are simultaneously divalent and are linked to each other

Forming a ring;

RR ^2, one at least of the R ³ and R ⁴ are C ₆

Represents a C _{2 Q} aromatic group, said aromatic group having the valency of RR ² , R ³ or R ⁴ as defined above;

n is 1 or more, expressed as a number average n value. )

Including monomers, polymers or mixtures thereof represented by

The polymer as the component (B) is represented by the following formula (2):

(2)

(Wherein ェ, 及び and 尺)

As defined above. )

And the repeating unit may be the same or different. Therefore, the above-mentioned polymer as the component (B) is a homopolymer or a copolymer. The copolymer is a random copolymer, a block copolymer or an alternating copolymer,

The amount of the aromatic group in the component (B) is 5 to 100 mol% based on the total molar amount of R ¹ , R ² , R ³ and R ⁴ ; An aromatic polycarbonate-based resin composition, comprising:

2. The resin composition according to item 1, wherein the component (B) exhibits a kinematic viscosity of 100 centistokes or more when measured at 25 ° C. in accordance with JIS—K2410.

3. A silicone compound in which the component (B) contains the aromatic group in an amount of 5 mol% to less than 50 mol% based on the total molar amount of R ¹ , R ² , R ³ and R ⁴ ; ^3. The resin composition according to the above item 1 or 2, which is a mixture with a silicon compound containing 50 mol% or more based on the total molar amount of R ¹ , R ² , R ³ and R ⁴ .

4. The resin composition according to any one of items 1 to 0.3, further comprising (C) a flame retardant in an amount of 0.01 to 100 parts by weight.

5. The flame retardant (C) is at least one flame retardant selected from metal salt flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, inorganic flame retardants, and fluorine flame retardants. 5. The resin composition according to the above item 4, wherein

6. The resin composition according to the above item 5, wherein the metal salt-based flame retardant is a metal salt of an organic sulfur compound. 7. The resin composition according to the above item 6, wherein the metal salt of the organic sulfur compound is a metal salt of an organic sulfonic acid.

8. The resin composition according to the above item 5, wherein the metal salt-based flame retardant is an aromatic organic polymer containing a metal sulfonic acid salt.

9. The nitrogen-based flame retardant is at least one member selected from the group consisting of triazine-based compounds, triazole-based compounds, tetrazole-based compounds, phosphazene-based compounds, and diazo-based compounds. A certain resin composition according to the preceding item 5.

10. The resin component (A) is composed of an aromatic polycarbonate, an aromatic vinyl polymer, an olefin polymer, a polyester polymer, a polyamide polymer, and a polyphenylene ether. 10. The resin composition according to any one of the above items 1 to 9, which is a resin mixture with at least one kind of organic polymer resin selected from the group consisting of a polymer and an epoxy polymer. Hereinafter, the present invention will be described in detail.

The aromatic polycarbonate resin composition of the present invention is selected from the group consisting of (A) a aromatic polycarbonate and a resin mixture of an aromatic polycarbonate and at least one other organic polymer resin. The aromatic polycarbonate content of the resin mixture is 50% by weight or more (B) a linear or cyclic aromatic group-containing silicone compound containing a specific amount of an aromatic group, in an amount of 0.1 to 100 parts by weight. It becomes.

The component (B) not only acts as a flame retardant for the resin component (A), but also provides the resin composition with excellent melt fluidity and stability during melt molding (quality stability of molded articles). And an effect of improving the mechanical properties, light resistance and appearance of a molded article of the resin composition.

Regarding the action as a flame retardant, the component (B) forms a silica coating on the surface of the molded product as soon as the composition of the present invention, in particular, the molded product starts burning, and the resin component (A) Improve the flame retardancy of

The component (B) can dramatically improve the flame retardancy of the resin component (A). The reasons for the improvement in flame retardancy are considered as follows. .

Since the component (B) contains an aromatic group, the compatibility with the resin component (A) is improved, and as a result of the component (B) being finely dispersed in the resin component (A), the resin is dramatically improved. The flame retardancy of the composition is improved. Furthermore, since the component (B) is a linear or cyclic aromatic group-containing silicone compound having no branched structure and no cross-linked structure, the molded product obtained from the resin composition of the present invention can be obtained. When the gas begins to burn, the molecular motion of the component (B) is activated, and the compatibility between the component (B) and the resin component (A) is improved. Therefore, the siloxane group and the resin component ( The reaction with the carbonate group of A) is promoted. to this Thus, the combustion of the resin component (A) is suppressed.

In addition, since the silicon atom contained in the component (B) is an element having a low surface energy, the component (B) segregates on the surface of a molded article obtained from the resin composition of the present invention. In addition, when the component (B) is a linear or cyclic compound having no branched structure and no crosslinked structure, the mobility of the component (B) to the surface of the molded article is promoted. As a result, when the molded article obtained from the resin composition of the present invention starts burning, a high concentration of the component (B) is present on the surface, and excellent flame retardancy is exhibited. 5 O A (Angstrom) especially from the surface of the compact

The average concentration C ¹ (%) of silicon atoms determined by X-ray photoelectron spectroscopy up to a depth of (5 nm) and the average concentration C ² determined by fluorescent X-rays of silicon atoms in the entire molded body When the ratio of CZC ² to (%) is 2 to 100, the molded product becomes an excellent flame retardant material.

In the present invention, the aromatic polycarbonate (hereinafter often referred to as “PC:”) used for the resin component (A) may be one or more different types of bifunctional phenolic compounds contained therein. Any of aromatic homopolycarbonate and aromatic copolycarbonate obtained by the above method may be used.

As a method for producing PC, a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of caustic alkali and a solvent, or, for example, transesterification of a bifunctional phenolic compound with getyl carbonate in the presence of a catalyst Transesterification method It can be.

Examples of the above-mentioned bifunctional phenolic compounds include 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis ( 4—Hydroxyphenyl) methane, 1,1′-bis (4—hydroxyphenyl) ethane, 2,2′-bis (4—hydroxyphenyl) butane, 2,2′-bis (4—hydroxy-3 , 5 —diphenyl) butane, 2,2'-bis (4-hydroxy35-dipropylpyrphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1, 1'-bis (4-hydroxyphenyl) ethane and the like, and 2,2'-bis (4-hydroxyphenyl) propane, which is known as bisphenol A, is particularly preferable.In the present invention, as described above, the bifunctional phenolic compound may be used alone or in combination.

The PC preferably has a viscosity-average molecular weight in the range of 10,000 to 100,000. <The viscosity-average molecular weight of PC can be measured by gel permeation chromatography (GPC).

When the above resin mixture is used as the resin component (A), the PC content of the resin mixture is 50% by weight or more, preferably 70% by weight or more.

Examples of organic polymer resins other than PC include thermoplastic resins other than PC, rubbery polymers, and thermosetting resins. Among them, thermoplastic resins other than PC and rubbery polymers are preferred, and thermoplastic resins other than PC are particularly preferred.

The thermoplastic resin other than the above-mentioned PC is not particularly limited as long as it can be dispersed uniformly with the PC. For example, aromatic vinyl polymer, polyphenylene ether polymer, olefin polymer, polyvinyl chloride polymer, polyamide polymer, polyester polymer, polyphenylene sulfide Polymers, polymethacrylate polymers, epoxy polymers, etc., or a mixture of two or more of them can be used. Of these, at least one selected from the group consisting of an aromatic vinyl polymer, an olefin polymer, a polyester polymer, a polyamide polymer, a polyphenylene ether polymer, and an epoxy polymer. With

It is preferable to use one kind.

The aromatic vinyl resin which can be used in the resin mixture as the component (A.) is a rubber-modified aromatic vinyl resin and a Z- or non-rubber-modified aromatic vinyl resin, particularly a rubber-modified aromatic resin. It is preferable that the resin be composed of a vinyl-based resin alone or a rubber-modified aromatic vinyl-based resin and a non-rubber-modified aromatic vinyl-based resin, and is not particularly limited as long as it can be uniformly dispersed with PC. Further, the rubber-modified aromatic pinyl-based polymer refers to a polymer in which a rubber component for modification is dispersed in a matrix composed of an aromatic vinyl-based polymer in the form of particles. Below, obtained by adding an aromatic vinyl monomer and, if desired, a vinyl monomer copolymerizable therewith, It can be obtained by subjecting a monomer mixture capable of undergoing graft polymerization to the modifying rubber component to be subjected to graph polymerization to the modifying rubber component by a known method such as bulk polymerization, emulsion polymerization, or suspension polymerization.

Examples of such polymers include impact-resistant polystyrene (HIPS), ABS polymer (acrylonitrile-butadiene-styrene copolymer), AAS polymer (Acrylonitrile). Examples include an acrylic rubber-styrene copolymer) and an AES polymer (acrylonitrile ethylene propylene rubber-styrene copolymer).

Here, the modifying rubber component preferably has a glass transition temperature (T g) of −30 ° C. or lower, and if it exceeds 130 ° C., a molded article obtained from the composition of the present invention The impact resistance tends to decrease. The glass transition temperature should be measured by the differential scanning calorimetry (DSC) described in the "Polymer Handbook" (edited by J. Brandrup, A Wiley-Interscience Publication, John Wiley S Sons, New York (1975)). Can be.

Examples of such rubber components for modification include gen-based rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile butadiene); saturated rubber obtained by hydrogenating the gen rubber; and isoprene rubber. , Chloroprene rubber, acrylic rubbers such as polybutyl acrylate, ethylene-propylene copolymer rubber, ethylene-propylene-monomer terpolymer rubber (EPDM), ethylene-octene copolymer Rubber etc. Gen-based rubbers are particularly preferred.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the above-mentioned rubber component for modification is, for example, styrene, α-methylstyrene, paramethylstyrene, etc. Yes, styrene is most preferred, but the above-mentioned other aromatic vinyl monomers may be copolymerized mainly with styrene.

In addition, as a component of the rubber-modified aromatic vinyl polymer, one or more other monomer components as described below, which can be copolymerized with an aromatic vinyl monomer, can be introduced as desired. When it is necessary to increase the oil resistance, an unsaturated nitrile monomer such as acrylonitrile and methacrylonitrile can be used. When it is necessary to lower the melt viscosity at the time of blending with the aromatic vinyl monomer, an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to further increase the heat resistance of the resin composition of the present invention, a monomer such as acrylic acid, methacrylic acid, maleic anhydride, or Ν-substituted maleimide is copolymerized. May be. The heat resistance can also be increased by using α-methylstyrene as at least a part of the aromatic vinyl monomer.

The content of the other monomer copolymerizable with the aromatic vinyl monomer in the polymerizable monomer mixture which is polymerized in the presence of the rubber component for modification described above is 0 to 40. % By weight.

The rubber component for modification in the rubber-modified aromatic vinyl polymer, Preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight, the graft-polymerizable monomer mixture is preferably from 95 to 20% by weight, more preferably from 90 to 90% by weight. It is in the range of 50% by weight. Within this range, the balance between impact resistance and rigidity of a molded article obtained from the composition of the present invention is improved. Further, the rubber-modified aromatic vinyl-based polymer has a rubber average particle diameter of preferably from 0.1 to 5.0 μm, and particularly preferably from 0.2 to 3.0 m. Within the above range, the impact resistance of a molded article obtained from the composition of the present invention is particularly improved.

Reduced viscosity of the polymer part, which is a measure of the molecular weight of the rubber-modified aromatic vinyl polymer 7] _sp / _c (0.5 gd1, 30 ° C measurement: toluene when the matrix resin is polystyrene When the solution or the matrix resin is an unsaturated ditolyl-aromatic vinyl copolymer, use methylethyl ketone), preferably in the range of 0.30 to 0.80 dlZg. More preferably, it is in the range of 0.40 to 0.60 dl / g. Reduced viscosity of rubber-modified aromatic vinyl resin 7] Means for satisfying the above requirements for sp / _c include adjustment of polymerization initiator amount, polymerization temperature, chain transfer agent amount, and the like. .

Among the above aromatic vinyl polymers, when heat resistance and oil resistance are particularly required, a syndiotactic styrene polymer which is a crystalline styrene polymer is preferable. Syndiotactic styrene-based polymers have superior heat and chemical resistance characteristics compared to ordinary amorphous, atactic polystyrene. However, it is brittle and has poor impact resistance. Syndiotactic structure means that the stereochemical structure is a syndiotactic structure, that is, a steric structure in which phenyl groups, which are side chains, are alternately located in the opposite direction to the polymer main chain formed from carbon-carbon bonds. Ri Contact means, the tacticity one is quantified Ri by the nuclear magnetic resonance method according to carbon isotope ^{(1 3} C-NMR method). Such styrenic polymers include polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (vinyl benzoic acid), and mixtures thereof, or a mixture thereof. Means a copolymer represented by the formula: Examples of poly (alkylstyrene) include poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), and poly (Yuichi-Shearylstyrene), and poly (halogenated styrene). Examples include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Examples of the poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferred are polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-short-butylstyrene), poly (p-chlorostyrene), and poly (m —Chlorosperene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.

Among the above aromatic vinyl resins, impact-resistant polystyrene (H IPS) and ABS polymer (acrylonitrile-butadiene-styrene copolymer) are preferred. When the above HIPS is used, it is preferable to use a styrene-based copolymer as a compatibilizer from the viewpoint of compatibility with PC. For example, it is preferable to use a styrene-based copolymer described in WO95-353346 as a compatibilizer.

The polyphenylene ether resin (hereinafter often referred to as “PPE”) which can be used in the resin mixture as the component (A) includes poly (2,6-dimethyl-1,4-phenylene). Ter), a copolymer of 2,6—dimethylphenol and 2,3,6—trimethylphenol, and the like are preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferred. The method for producing such PPE is not particularly limited, and examples thereof include a method for preparing a mixture of a cuprous salt and an amine by the method described in US Patent No. 3,306,874. It can be easily produced by oxidative polymerization of 2,6-xylenol using a plex as a catalyst. In addition, U.S. Pat. No. 3,306,875 and U.S. Pat. No. 7, 357, U.S. Pat. No. 3,257, 358, Japanese Patent Publication No. 52-17880, and Japanese Patent Publication No. 50-511197. It can be easily manufactured by the method described. The reduced viscosity of the above PPE is 7 _sp / c (0.5 g / d 1, close-form solution, measured at 30 ° C). It should be in the range of 0.20 to 0.70 d 1 Zg. And preferably in the range of 0.30 to 0.60 dl Z g Is more preferred. Means for adjusting the reduced viscosity of PPE to 77 sp / c; in the above-mentioned preferred range include means for adjusting the amount of catalyst in the production of PPE.

As the above-mentioned olefin-based polymer which can be used as an organic polymer resin other than PC in the resin mixture as the component (A), a propylene-based resin is preferable, and a homo-isotactic polypropylene and propylene are preferred. And other α-olefins such as ethylene, butene-11, pentene-11, hexene-11, etc. (including block and random).

Particularly preferred as the above-mentioned olefin polymer is a mixture obtained by mixing a crosslinkable rubber component and an olefin polymer and a polymer, for example, by melt-kneading in the presence of a crosslinking agent and a crosslinking assistant. A partially or completely crosslinked thermoplastic polymer that can be produced by dynamically crosslinking.

As the crosslinkable rubber component, an ethylene 'α-olefin copolymer or a hydrogenated gen-based rubber is preferable. Among ethylene-α one-year-old olefin copolymers, ethylene and α-olefins having 3 to 20 carbon atoms are more preferable, and particularly ethylene and α-olefin having 6 to 1 carbon atoms produced using a meta-open catalyst. The α-olefin copolymer of No. 2 is preferred because of its narrow molecular weight distribution. Further, among hydrogenated gen-based rubbers, random hydrogenated gen-based rubbers in which 50% or more of the total double bonds of the gen-based rubber are hydrogenated are preferable. Of the gen-based rubber is hydrogenated with 90% or more of the total double bonds, and 1,2—vinyl bonds after hydrogenation are 5% or less, and 1,4-bonds after hydrogenation are 5% or less. Certain random hydrogenated gen rubbers are more preferred. Here, an aromatic vinyl unit can be contained in the gen-based rubber.

In the present invention, when a rubber-like polymer is used as the organic polymer resin other than PC in the above resin mixture as the resin component (A), the glass transition temperature (T g) of the rubber-like polymer is −30 °. ς It is preferable that the following is satisfied. If the Tg of the rubber-like polymer exceeds −30 ° C., the impact resistance of the molded article obtained from the composition of the present invention tends to decrease.

Examples of such rubbery polymers include gen-based rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); saturated rubbers obtained by hydrogenating the gen rubber; Acrylic rubbers such as isoprene rubber, chloroprene rubber, and polybutyl acrylate; ethylene-propylene copolymer rubber; ethylene-propylene-gen monomer terpolymer rubber (EPDM); Examples thereof include crosslinked rubber or non-crosslinked rubber such as butene copolymer rubber, and a thermoplastic elastomer containing the above rubber component.

Among the above-mentioned thermoplastic elastomers, an aromatic vinyl-based thermoplastic elastomer is particularly preferable, and a block copolymer comprising an aromatic vinyl unit and a conjugated gen unit, or the conjugated gen unit portion A partially hydrogenated or epoxy-modified block copolymer or the like can be used. By blending the above-mentioned thermoplastic elastomer into PC, it is possible to solve the problem that the impact strength is reduced when PC is formed into a thick molded body. At that time, by further blending the styrene-based copolymer as a compatibilizer, excellent impact strength is exhibited.

Examples of the aromatic vinyl monomer used to form the aromatic vinyl unit constituting the block copolymer include styrene, α-methylstyrene, paramethylstyrene, ρ-chlorostyrene, ρ-bromostyrene, 4, 5-tribromostyrene, etc., of which styrene is most preferred, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized. Examples of the conjugated diene monomer used to form the conjugated diene unit constituting the copolymer include 1,3-butanediene and isoprene.

For the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated gen and / or a partially hydrogenated unit thereof is represented by S. When displayed as Β, the linear block of SB, S (BS) n (where n is an integer of 1 to 3), and S (BSB) n (where n is an integer of 1 to 2) A polymer or (SB) n X (where n is an integer of 3 to 6; X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, polyepoxy compound, etc.) X part is the connection center It is preferably a star (star) blog copolymer. Among them, a linear one block copolymer of SB type 2, SBS type 3, and SBSB type 4 is preferable.

Examples of thermoplastic resins which are preferably blended with PC when particularly high melt fluidity is required for the composition of the present invention include polybutylene terephthalate, polyethylene terephthalate, and thermoplastic epoxy resin. Coalescence, polyamide and the like.

Examples of the above-mentioned thermosetting resins that can be used as an organic fluoropolymer resin other than PC in the resin mixture as the component (A) include phenol resins, amino resins, melamine resins, and imido resins. And epoxy polymers.

The weight average molecular weight of the organic polymer resin other than PC is preferably 50,000 to 1,000,000, and 100,000 to 500,000. More preferably, it is 0 0.

In the present invention, a particularly preferred example of the resin mixture as the resin component (A) is a mixture of PC and the above-mentioned aromatic vinyl polymer.

The aromatic group-containing silicone compound (B) has the following formula (1):

R

R 0 -H S i〇 + R (1)

R ² n (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent —C _2. Hydrocarbon group;

R ³ and R ⁴ are each independently a hydrogen atom or monovalent or divalent —C ₂ . Wherein R ³ and R ⁴ are each independently a divalent mono-C ₂ . R ³ and R ⁴ are divalent at the same time, and combine with each other to form a ring;

RR ^2, one at least of the R ³ and R ⁴ are C ₆ one C _2. Wherein the aromatic group has a valency as defined above for RR ² , R ³ or R ⁴ ; and

(In the formula, R ¹ and R ² are each as defined in the formula (1).) And the repeating unit may be the same or different. Therefore, the above-mentioned polymer as the component (B) is a homopolymer or a copolymer, and In this case, the copolymer is a random copolymer, a block copolymer or an alternating copolymer,

The amount of the aromatic group in the component (B) is from 5 to 100 mol% based on the total molar amount of RR ² , R ³ and R ⁴ .

As the non-aromatic hydrocarbon group that can be contained in the component (B), a methyl group, an ethyl group, and a butyl group are preferable, and a methyl group is more preferable.

The aromatic group in the component (B) is preferably a phenyl group. The component (B) is a bifunctional D unit represented by the following formula (3) described in "Silicon Handbook" (edited by Nikkan Kogyo Shimbun, Kunio Ito (1990), Japan). Is a silicone compound having a linear or cyclic structure.

R

1〇1 S i — 0— (3)

R

The silicone compound used as the component (B) in the present invention does not contain a structural unit that forms a branched structure or a crosslinked structure. When the component (B) has a branched structure or a crosslinked structure, the flame retardancy of the resin component (A) cannot be sufficiently improved. Branched or bridged structures Examples of the structural unit that forms the structure include a trifunctional T unit represented by the following formula (4) described in the above “Silicon Handbook”.

〇 (4)

RSOII

The amount of the component (B) in the resin composition of the present invention

-1

One

Fat component (A) 0.1 to 100 parts by weight, preferably 0.10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of component (B). The amount of the aromatic group in R ¹ R ² , R ³ and

Ri Ah is necessary for the total moles of R ⁴ is a 5-1 0 0 mol%, preferably 1 0-9 0 mol%, further preferred properly 2 0-9 0 mol%, and most preferably 3 0 ~ 90 mol%. N in the above formula (1) is preferably at least 10 and more preferably at least 100. The aromatic group-containing silicone compound used as the component (B) preferably has a kinematic viscosity measured at 25 ° C. of 100 centistokes or more in accordance with JIS-K240, more preferably It is at least 300 centistokes, most preferably at least 1000 centistokes. The kinematic viscosity is 100 centi-cents. When full, component (B) becomes volatile and may not be desirable.

The upper limit of the kinematic viscosity of the component (B) is not particularly limited, and may be a gum that exceeds the measurement limit (1, 000, 000 centistokes).

Further, as the component (B), a mixture of a plurality of different aromatic group-containing silicone compounds satisfying the requirements of the present invention can be used. In this case, the component (B) is a silicone compound containing the aromatic group in an amount of 5 mol% to less than 50 mol% based on the total molar amount of R ¹ , R ² , R ³ and R ⁴ ; It is preferably a mixture with a silicone compound containing 50% by mole or more of the aromatic group based on the total moles of RR ² , R ³ and R ⁴ . The above-mentioned silicone compound containing an aromatic group in an amount of 50 mol% or more is extremely advantageous for obtaining the excellent effects of the present invention, but is relatively expensive. Therefore, from the viewpoint of economy, the above-mentioned silicone compound containing an aromatic group in an amount of 5 mol% to less than 50 mol% and the above-mentioned silicone compound containing an aromatic group in an amount of 50 mol% or more are mixed. It is preferred to use as component (B).

The composition of the present invention may further contain (C) 0.001 to 100 parts by weight of a flame retardant.

Flame retardants (C) include silicon-based flame retardants, metal-salt-based flame retardants, halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, inorganic flame retardants, fibrous flame retardants, and char forming. At least one flame retardant selected from agents can be used. Of the above flame retardants (C), Silicone flame retardants, metal salt flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants are particularly preferred.

As the silicon-based flame retardant, polyorganosiloxane (silicon, organic silicate, etc.) other than the silicone-based compound used as the component (B), silica, and the like can be used.

Polyorganosiloxane is classified into oil, resin, and rubber according to their properties. The polyorganosiloxane that can be used as the silicon-based flame retardant (C) in the present invention is a structural unit described in the above-mentioned “Silicon Had Book”, that is, M represented by monofunctional R 3 Si 2. units, the above difunctional D units, the above trifunctional T units, R (R 0) which contained 4 S i 0 ₂ represented by Q units, and alkoxy groups or § Li bite alkoxy group functional S at least one selected from the group consisting of an X unit represented by i O 2.0 and a Y unit represented by (RO) 2 Si 0 3.0 (R is a hydrocarbon having 1 to 20 carbon atoms) A polyorganosiloxane containing one type of structural unit, but when it is composed of only D units, is a polyorganosiloxane in which the amount of the aromatic group is less than 5 mol% based on the total molar amount of the R group. Such a polyorganosiloxane is a polyorganosiloxane having an oily branched structure or a silicone resin having a three-dimensional network structure. The rubbery polyorganosiloxane is a vulcanized product of a high molecular weight gum-like linear polydiorganosiloxane.

Further, as the flame retardant (C), a modified form of the above-mentioned polyorganosiloxane or a complex with another substance may be used. Above denaturation Examples of the body include a modified polyorganosiloxane modified with an epoxy, amino, mercapto, methyl group or the like. Examples of the above-mentioned composite include a polycarbonate (PC) -silicon copolymer, an acrylic rubber-silicon composite, and the like. R in the polyorganosiloxane that can be used as the flame retardant (C) is a hydrocarbon group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a butyl group, a phenyl group, or a benzyl group. Groups are preferred, and a methyl group and a phenyl group are particularly preferred. In the case of a polyorganosiloxane containing the above-mentioned constitutional unit having three or more functional groups, it is preferable that the phenyl group is contained in an amount of 5 to 100 mol% based on the total molar amount of R. Such a polyorganosiloxane not only has excellent compatibility with aromatic resins such as PC, but also improves the water resistance and thermal stability of the composition of the present invention.

Silica, one of the silicon-based flame retardants, is amorphous silicon dioxide. In the present invention, in particular, a hydrocarbon-based compound-coated silica obtained by treating the silica surface with a hydrocarbon-based silane-capping agent is preferable, and a vinyl-containing hydrocarbon-based compound-coated silica is more preferable. .

Examples of the above silane coupling agents include p-styrilyltrimethoxysilane, vinyltrichlorosilane, vinyltris (jSmethoxylethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, Ryoichi Vinyl group-containing silanes such as methacryloxyprovir trimethoxyxylane, β- (3,4 epoxy Epoxysilanes such as (cyclohexyl) ethyl trimethoxysilane, aglycidoxypropyl trimethoxysilane, and aglycidoxypropyl triethoxysilane; and N—β (aminoethyl) aminopropyl Aminosilanes such as built-in trimethoxysilane, Ν-3 (aminoethyl) aminopropylmethyldimethoxysilane, amiaminopropyl triethoxysilane, and phenylaminopropyl built-in rimethoxysilane. Here, a silane coupling agent having a unit similar in structure to the thermoplastic resin is particularly preferable. For example, for a styrene-based polymer, styrene-trimethoxysilane is preferable.

The treatment of the silane coupling agent on the silica surface is roughly classified into a wet method and a dry method. The wet method is a method in which silica is treated in a silane coupling agent solution and then dried. The dry method is a method in which silica is charged into a device capable of high-speed stirring such as a Henschel mixer, and the silane-based printing agent solution is slowly dropped while stirring, followed by heat treatment. .

The metal salt-based flame retardant as the flame retardant (C) is preferably an organic sulfur compound metal salt. Examples of metal salts of organic sulfur compounds include potassium tribenzene sulfonic acid, potassium perfluorobutanesulfonic acid, potassium disulfonic acid-3-sulfonic acid, and the like. Organic sulfonic acid metal salts are exemplified.

In addition, as metal salt-based flame retardants, aromatic sulfonimide metal salts, Alternatively, a metal salt in which a metal sulfonate, a metal sulfate, a metal phosphate, or a metal borate is bonded to an aromatic ring of an aromatic group-containing polymer such as an aromatic vinyl polymer or a polyphenylene ether. A contained aromatic organic polymer can be used. Alkali metals and alkaline earth metals can be used as the metals of the above metal salts. Such a metal salt-based flame retardant promotes a decarboxylation reaction at the time of burning a molded article obtained from the composition of the present invention, and improves flame retardancy. As the above-mentioned metal salt-containing aromatic organic polymer, a metal sulfonate-containing aromatic organic polymer is particularly preferred. When the aromatic organic polymer containing a metal sulfonic acid salt is used as the flame retardant (C), the metal sulfonic acid salt becomes a cross-linking point and forms a carbonized film when the molded product obtained from the composition of the present invention is burned. Greatly contributes to

Examples of the halogen-based flame retardants as the flame retardant (C) include bisphenol phenol, aromatic halogen compounds, halogenated polycarbonate, halogenated aromatic vinyl polymer, and halogenated halogenated flame retardant. Examples include cyanurate resin and halogenated polyphenylene ether. Specifically, decabromodiphenyloxyside, tetrabromobisphenol A, an oligomer of tetrabromobisphenol A, bisphenol bromide phenolic resin, bisphenol bromide polycarbonate, bromide Polystyrene, brominated cross-linked polystyrene, polyphenylene bromide, polydibromophenylene oxide, condensate of decabromdiphenyloxide with bisphenol, halogenated phosphoric acid ester It is preferable to use a fluorine resin or the like.

Examples of the phosphorus-based flame retardant as the flame retardant (C) include organic phosphorus compounds, red phosphorus, and inorganic phosphorus salts.

Examples of the organic phosphorus compound include phosphine, phosphoxide, biphosphine, phosphonium salt, phosphinate, phosphinate, phosphite and the like. More specific examples include triphenyl phosphate, methyl neopentyl phosphite, henyl erythritol getyl diphosphite methyl neopentyl phosphonate, phenyl neopentyl phosphite Erythritol phenyldiphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite, phenylpyrophosphate phosphite, ethylpyrocatechol phosphate, zipiro Catechol hypothetic phosphate is an example.

Here, as the organic phosphorus compound, an aromatic phosphate ester monomer or an aromatic phosphate ester condensate is particularly preferred.

Among the above aromatic phosphate ester monomers, among the aromatic phosphate ester monomers, those described in U.S. Pat. Phosphoric acid ester monomers or aromatic phosphoric acid ester monomers containing one or two or more phenolic hydroxyl groups in cresyl phosphate, triphenyl phosphate and the like are preferred. Or a long-chain alkyl such as tris (nonylphenyl) phosphate described in WO96-27736 Preferred is an aromatic phosphate ester monomer containing a hydroxyl group.

Among the above aromatic phosphoric acid ester condensates, bisphenol A bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) and the like are preferable.

Further, an aromatic phosphoric acid ester condensate produced by a method disclosed in Japanese Patent Application Laid-Open No. 5-17979 or the like is also preferable as the organic phosphorus compound. For example, a monofunctional phenol substituted at the 2- and 6-positions is reacted with oxyhalogenated phosphorus in the presence of a Lewis acid catalyst to obtain diaryl phosphorohalide, and then to obtain the resulting diaryl phosphorohalide. The aromatic phosphate condensate obtained by reacting the compound with a bifunctional phenol in the presence of a Lewis acid catalyst can be suitably used as a phosphorus-based flame retardant.

Red phosphorus, one of the phosphorus-based flame retardants mentioned above, is selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide in advance, in addition to ordinary red phosphorus. Coated with a coating of a metal hydroxide to be coated, coated with a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide, and a thermosetting resin Or a double-coated thermosetting resin film on a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. is there.

As an example of the inorganic phosphate used as the above phosphorus flame retardant, For example, ammonium phosphate is used.

The nitrogen-based flame retardant includes at least one selected from the group consisting of triazine-based compounds, triazole-based compounds, tetrazole-based compounds, phosphazene-based compounds, and diazo-based compounds. Seeds can be used.

Specific examples of the above triazine-based compounds include melamine, melamine, melem, melon (a product of deammonification of three molecules from three molecules of melem at 600 ° C. or higher), melamine cyanide Melamine phosphate, succinoguanamine, adipoguanamine, methylglutalogamine, melamine resin, BT resin, and the like, and melamine cyanurate are particularly preferred from the viewpoint of low volatility.

Specific examples of the above triazole-based compound include triazole, methyltriazole, and phenyltriazole. The phosphazene compound as a nitrogen-based flame retardant is not particularly limited as long as it has a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond, and examples thereof include cyclic phosphazene and linear phosphazene. Can be Among phosphazenes, phosphazenes containing an aromatic group as a substituent are preferred from the viewpoint of compatibility with aromatic polycarbonate. In terms of structure, linear phosphazene is preferred.

Specific examples of the cyclic phosphazene include propoxyphosphazene, phenoxyphosphazene, aminophosphazene, and full Specific examples of linear phosphazenes include polyarylphosphazenes such as polyphenylphenylphosphazene, polyaryloxyphosphazenes such as polydiphenoxyphosphazene, polydiaminophosphazenes, and the like. And polydifluoroalkylphosphazene. These phosphazene compounds are produced by substituting the clog phosphazene with alcohols or phenols.

Te Torazo Ichiru compounds as nitrogen-based flame retardant, 5 - full _÷ two ruthenate Torazo Ichiru, 5, 5 '- Bisute Torazoru 2 Anmoniumu salt 5, 5' - Bisute Torazo Ichiru 2 amino Nogua two gin salt, 5, 5 '— bisestrazole piperazine salt, azoviste torazole 2 guanidine salt, azoviste tolazole 2 amino guanidine salt and the like.

Examples of the diazo compounds include azodicarbonamide, azobisisobutyronitrile, diazoaminobenzene, and polyvinylazodicarboxylate.

Examples of inorganic flame retardants as the flame retardant (C) include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and basic magnesium carbonate. Hydrates of inorganic metal compounds such as hydrates of zirconium hydroxide, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, Bismuth oxide, acid Metal oxides such as chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper , Tungsten, tin, antimony and other metal powders, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have particularly good flame retardant effects and are economically advantageous.

Fibrous flame retardant as flame retardant (C) is a flame retardant used to prevent dripping of fire, and becomes fibrous when added or processed. Specific examples thereof include aramide fiber, polyacrylonitrile fiber, and fluororesin.

The above-mentioned aramide fiber preferably has an average diameter of 1 to 500 m and an average fiber length of 0.1 to 10 mm, and is preferably made of isophthalamide or polyparaphenylene terephthalamide. It can be produced by dissolving in a basic solvent or sulfuric acid and spinning the solution by a wet or dry method.

The polyacrylonitrile fiber as the fibrous flame retardant preferably has an average diameter of 1 to 500 m, an average fiber length of 0.1 to 10 mm, and dimethylformamide. Dry spinning, in which the polymer is dissolved in a solvent such as Is produced by a wet spinning method in which a polymer is dissolved in a solvent such as nitric acid and wet-spun in water.

The fluororesin as the fibrous flame retardant is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene Z-hexafluoropropylene copolymer, and the like. . Further, the fluorine-based resin may be obtained by copolymerizing a fluorine-containing monomer with a monomer which can be combined with the fluorine-containing monomer.

Methods for producing fluororesins are disclosed in U.S. Pat. No. 2,393,697 and U.S. Pat. No. 2,534,058. For example, Te trough Ruo Russia ethylene in an aqueous medium persulfate Anmoniumu, using a radical open. Initiator such as persulfate mosquito Li um, a pressure of _{7~ 7 0 kg / cm 2,} 0~ 2 0 0 ° Polytetrafluoroethylene powder can be produced by polymerization at a temperature of C, followed by coagulation or precipitation from a suspension, dispersion or emulsion.

In addition to the above, other methods for producing a fluororesin include melt-kneading a fluororesin, a thermoplastic resin, and a dispersant, if desired, to prepare a masterbatch, and then prepare a thermoplastic resin. Using a two-stage process in which a fuel is melt-kneaded, or an extruder consisting of a side-feedable nizon, melts and kneads a thermoplastic resin, a fluorine-based resin, and a dispersant as required in the first stage, and the second stage. Difficult to lower melting temperature „ _Λ , ~„ PCT / JP00 / 00

00/46299 A one-stage process method in which 3 _{g of the} fuel is fed and melt-kneaded, or a one-stage process method in which all components including the fluororesin are fed to the main feeder and melt-kneaded. Here, from the viewpoint of flame retardancy, a two-step process for producing a master batch is preferable.

The novolak resin as a char forming agent, one of the flame retardants (C), is an acid catalyst such as sulfuric acid or hydrochloric acid for phenols and aldehydes. Is a phenolic novolak resin obtained by condensation in the presence of water.

5 “Polycondensation and polyaddition” p. 433-7455 (Kyoritsu Shuppan Co., Ltd.) ”.

The phenols used in the production of novolak resins include phenol, 0—cresol, m—cresol, p—cresol, 2,5—dimethyl, 3,5—dimethyl, and 2 , 3, 5 — trimethylol, 3, 4, 5 — trimethyl-1, p-t — butyl, p — n — octyl, p — stearyl, ρ — fenuru, p — (2 — Phenylethyl), o—isopropyl—, p—isopropyl, m—isopropyl, p—methoxy, and p—phenoxyphenol, pyrocatechol, resorcinol, nose Quinone, salicylaldehyde, salicylic acid, p—hydroxybenzoic acid, methyl p—hydroxybenzoate, p—cyano—, and 0—cyanophenol, p—hydroxybenzenesulfonic acid, p — Hydroxy Emissions Zen sulfonamidyl de, hexyl consequent b P - hydroxycarboxylic benzene scan Rehone one preparative, 4-arsenide Dorokishifue two Ruphenylphosphinic acid, methyl 4-hydroxyphenylphenylphosphine, 4-heptahydroxyphenylphosphonic acid, ethyl 4—hydroxyphenylphosphonate, diphenyl4—hydroxyphenylphosphonate And so on.

The aldehydes used in the production of novolak resins include formaldehyde, acetate aldehyde, n-propanal, n-butane nar, isopropanal, isobutyl aldehyde, 3-methylene n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylphenylaldehyde, etc.

The amount of the flame retardant (C) in the composition of the present invention is preferably 0.01 to 100 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the resin component (A). To 50 parts by weight, more preferably 3 to 20 parts by weight, and most preferably 5 to 15 parts by weight.

The composition of the present invention may further contain (D) a processing aid, if desired. Processing aids (D) include aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty alcohols, metal stones, organosiloxane-based waxes, polyolefin waxes, and polyproprolactones. At least one kind of mold release agent or melt flowability improver selected from the following can be used. The amount of the processing aid (D) is preferably from 0.01 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component (A). Most preferably, it is 1 to 5 parts by weight.

The molded article obtained from the composition of the present invention has high light resistance. If required, (E) a lightfastness improver can be added to the composition of the present invention, if desired. The lightfastness improver (E) is at least one selected from ultraviolet absorbers, hindered amine light stabilizers, antioxidants, active species scavengers, light-blocking agents, metal deactivators, and quenchers. Seeds can be used. The amount of the light fastness improver (E) is preferably from 0.05 to 20 parts by weight, more preferably from 0 ::! To 100 parts by weight of the resin component (A). It is 10 parts by weight, most preferably 1 to 5 parts by weight.

Examples of the method for producing the resin composition of the present invention include a method in which the resin components (A) and (B) are mixed and melt-kneaded with an extruder. The resin component (A) is first melted, and then (B) Ingredients are added and melt-kneaded in the same extruder. Alternatively, after preparing a masterbatch in which the (B) component is blended with the resin component (A), the masterbatch and the remaining resin component (A) or There is a method of kneading the remaining component (B) or another flame retardant.

As an extruder used in the method for producing the resin composition of the present invention, a twin-screw extruder is preferable, and the ratio L ZD of the screw length L to the cylinder inner diameter D is 20 to 50. It has two or more supply openings, namely a main feed opening and a side feed opening which differ in the distance from the tip of the twin-screw extruder. A knee portion between the end portions and between the tip portion and the supply opening at a distance close to the tip portion, and the length of the two-sided portion is 3D to 10D, respectively. But preferable.

As a preferable example of the resin composition of the present invention, as the resin component (A), 100 parts by weight of an aromatic polycarbonate alone or a mixture of an aromatic polycarbonate and an aromatic vinyl-based resin; 0.1 to 100 parts by weight of methylphenylsilicone oil which satisfies the requirements of the present invention described above, and an organic metal sulfonate such as potassium diphenylsulfon-3-sulfonic acid as a flame retardant (C). Examples thereof include a resin composition containing 0.001 to 10 parts by weight of a salt and a phosphazene compound, and 0.0001 to 10 parts by weight of polytetrafluoroethylene. This resin composition has particularly excellent balance properties of flame retardancy, continuous moldability, moldability (melt fluidity), impact resistance, and heat resistance.

The resin composition of the present invention may be, for example, a force obtained by melt-blending each of the above components with a commercially available single-screw extruder, twin-screw extruder, or the like. Agents, lubricants, fillers, reinforcing agents such as glass fibers, coloring agents such as dyes and pigments, and the like can be added.

The composition of the present invention thus obtained can be continuously molded for a long period of time using an injection molding machine or an extrusion molding machine, and the obtained molded article has flame retardancy, heat resistance and heat resistance. The impact resistance is excellent. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited thereto. In Examples and Comparative Examples, various measurements were performed using the following measuring methods or measuring instruments.

(1) Flame retardant

Self-extinguishing properties were evaluated by the VB (Vertica1Burning) method based on UL-94 (18-inch test specimens). The evaluation criteria are as follows.

◎ Self-extinguishing within 20 seconds

自己 Self-extinguishing within 20 to 40 seconds

X Burnt

(2) Iz 0 d impact strength

It was measured by a method according to ASTM-D255. (23 ° C V-notched 1Z4 inch test piece: unit kg'cm / cm)

(3) Thickness dependence of Iz o ci impact strength

The Izocl impact strength of a 1/8 inch test piece and a 1Z4 inch test piece was measured by the measurement method described in the above section (2), and the ratio was used as an index of thickness dependence. The closer the ratio is to 1, the less the thickness dependence, and the more stable the impact strength is.

(4) Melt molding stability <Molded product quality stability> Using a melt extruder, the resin composition was continuously melt-extruded for 10 hours, and the Izod impact strength of the molded product obtained every hour was measured, and the change rate (%) from the average strength was continuously measured. We evaluated melt molding stability (stability of molded product quality), which is an indicator of productivity.

(5) Melire tofu mouth rate (MFR)

The melt fluidity index was measured by a method in accordance with ASTM-D1238. It was determined from the extrusion rate (g / 10 minutes) per 10 minutes under the conditions of a load of 10 kg and a melting temperature of 260.

(6) SP value (<5) [Solubility Parameter] and average SP value

The SP value was calculated from the Fedors equation described in Polymer Engineering and Science, 14, (2), 147 (1974), and the data of Δe 1 and △ V 1 summarized in the literature.

.δ = [∑ (Δ e 1) / ∑ (Δ v 1)] ^1/2

[Where, Δe 1 is the cohesive energy per unit functional group, ΔV 1 is the molecular volume per unit functional group, and the unit of δ is

(c a 1 / c m3) 1/2. ]

The SP value of the copolymer or blend is assumed to satisfy the addition rule.For copolymers, the SP value of the monomer unit is used, or for blends, the SP value of each component is used. Calculated by proportional distribution of weight ratio, and this was used as the average SP value.

(7) Surface appearance

Yellowness Δ Υ I value by a method based on JIS-Z-8 7 2 2 Was evaluated, and the surface appearance of the molded body was evaluated (the smaller the ΔYI value, the lower the yellowness and the better the appearance).

(8) Light fastness

The light resistance test was performed by a method based on JISK 7102 using an ATLAS CI35W Weatherometer manufactured by ATLAS Electric Devices Co., USA as a light resistance tester. Irradiation conditions were as follows: internal temperature of the test machine was 55 ° (: 55% humidity, no rain, xenon light (wavelength: 340 nm, energy: 0.3 OW / m ² ), 300 hours, Japan Using the SM Color Computer Model SM-3 manufactured by Koku Suga Test Instruments Co., Ltd., the color difference ΔE of the molded body before and after the test was determined by the L. a. B. Method, and the color tone change was evaluated. The smaller the is, the higher the light resistance.The components used in Examples and Comparative Examples are as follows.

(A) Silicone flame retardant as aromatic compound-containing silicone compound (B) and flame retardant (C)

It has the above D units and / or T units shown in Tables 1 to 7 in accordance with Chapter 17 of "Silicon Handbook" [edited by Kunio Ito, Nikkan Kogyo Shimbun (1990), Japan] A silicon compound was produced.

Some of the components (B) used in the comparative examples do not satisfy the requirements for the component (B) of the aromatic polycarbonate resin composition of the present invention. For convenience, these components are also used as the components (B). component Classified into

(Mouth) Polymer

(1) Aromatic polycarbonate

A commercially available bisphenol A type polycarbonate (manufactured by Sumitomo Dow, Japan; trade name: Caliber 13) (hereinafter referred to as PC) was used.

(2) Rubber modified polystyrene (HIPS)

A commercially available rubber-modified polystyrene (polybutadiene Z-postylene weight ratio: 10Z90) (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: Styron) (hereinafter referred to as HIPS) was used.

(3) ABS resin (ABS)

Commercially available A'BS resin (acrylonitrile polybutadiene styrene weight ratio: 24Z20Z56) (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: SUIRAC ABS) ( Hereinafter, it is called ABS).

(4) Styrene-ethylenebutylene-styrene copolymer (SEBS)

A commercially available styrene-ethylene-butylene-styrene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: Tuftec) (hereinafter referred to as SEBS) was used.

(5) Maleic anhydride-modified styrene-ethylene-butylene-styrene copolymer (hereafter, m-SEBS)

Commercially available maleic anhydride-modified styrene-ethylene-petit A styrene-styrene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: Tuftec) (hereinafter referred to as m-SEBS) was used.

(6) Styrene-butadiene copolymer (SB)

A commercially available styrene-butadiene copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., Japan; trade name: tufprene) (hereinafter referred to as SB) was used.

(7) Epoxy-modified styrene-butadiene copolymer (E

S B)

A commercially available epoxy-modified styrene-butadiene copolymer (manufactured by Daicel Chemical Industries, Ltd., Japan; trade name: Epofrend) (hereinafter referred to as ESB) was used.

(8) Syndiotactic styrenic polymer

Syndiotactic polystyrene (SPS) having a melting point of 270 ° C and a weight average molecular weight of 320,000 was used.

(9) Poly fu, dilen ether (PPE)

A commercially available polyphenylene ether (manufactured by Asahi Kasei Kogyo Co., Ltd .; trade name: Xylon) (hereinafter referred to as PPE) was used.

(10) Polypropylene (PP)

A commercially available polypropylene (manufactured by Japan Polychem Co., Ltd., Japan) (hereinafter referred to as PP) was used.

(11) Ethylene-octene copolymer (E〇) was used. Commercially available ethylene-octene copolymer (Dupont, USA Dowelas Toma One; product name: Engage) (hereinafter referred to as EII).

(12) Acrylonitrile-styrene copolymer (AS)

A) Styrene copolymer having copolymer composition distribution (A

S-1)

The styrene copolymer produced by the following method was used as a compatibilizer.

3.4 parts by weight of acrylonitrile, 81.6 parts by weight of styrene, 15 parts by weight of ethylbenzene, and 1,1,1-bis (t-butylperoxy) -1,3,3,5-trimethylsilicic acid as an initiator Hexane 0.03 parts by weight of the mixture was continuously fed at a rate of 0.7 liter Z-hour to a three-stage in-line plug-flow reactor equipped with a stirrer. The polymerization was carried out at a stirring speed of 100 rpm and 126 ° C., in the second stage at 20 rpm and 135, and in the third stage at 10]: 111 at 147 ° C. Subsequently, the polymerization liquid was led to a devolatilizer at 230 ° C. to remove unreacted monomers and a solvent to obtain a random copolymer (hereinafter referred to as AS-1). The obtained copolymer was analyzed by the method described in W95-35-346. As a result, the ratio of the monomer components of the copolymer was 6% by weight of acrylonitrile unit and 94% by weight of styrene unit, and the average SP value was 10.75 (single amount). The ratio of body components is determined by infrared absorption spectroscopy). Further, the distribution of the ratio of the monomer components of the copolymer was measured by liquid chromatography analysis to find that the acrylonitrile unit was 0 to 12% by weight. The maximum SP value of the copolymer molecule was 11.0, the minimum SP value was 10.5, and the ΔSP value was 0.5.

B) Copolymer having relatively uniform copolymer composition (A S — 2) A copolymer produced by the following method was used as a compatibilizer. The same experiment was repeated except that the reactor was changed to a completely mixed reactor in the production of AS-1. As a result of analyzing the obtained copolymer, the ratio of the monomer components of the copolymer was 6% by weight of acrylonitrile unit and 94% by weight of styrene unit (infrared absorption spectrum). By law). Further, the distribution of the ratio of the monomer components of the copolymer was measured by liquid chromatography analysis, and the maximum SP value of the copolymer molecule was 11.0 and the minimum SP value was The value was 10.8 and the ASP value was 0.2.

(13) E〇—PP crosslinked product (TPV)

Mixture of E〇 and PP (weight ratio: 50 Z50) Add 100 parts by weight of organic peroxide and 0.5 parts by weight of divinylbenzene to 100 parts by weight and extrude with a twin screw extruder A dynamically cross-linked thermoplastic polypropylene (hereinafter referred to as TPV) manufactured by the Company was used.

(14) Polybutylene terephthalate (PBT) A commercially available polybutylene terephthalate (manufactured by Toray Industries, Inc., Japan) (hereinafter referred to as PBT) was used.

(15) Epoxy polymer (EP) A commercially available thermoplastic non-halogen-substituted epoxy polymer (manufactured by Asahi Chiba Co., Ltd., Japan (hereinafter referred to as EP)) was used.

(16) Polyamide polymer

A commercially available polyamide resin (manufactured by Toray Industries, Inc .; trade name: Polyamide 6) (hereinafter referred to as PA) was used.

(8) Non-carbon flame retardants

(1) Metal salt of organic sulfonic acid

A) Commercially available diphenyl sulfone 3-sulfonic acid (manufactured by UCB Japan Ltd. in Japan) (hereinafter referred to as KSS) was used.

B) Commercially available potassium perfluorobutanesulfonate (manufactured by Dainippon Ink Industries, Ltd. in Japan) (hereinafter referred to as FBK) was used.

(2) 1,3-phenylene bis (diphenylphosphophosphate) (FP)

A commercially available resorcinol-derived aromatic condensed phosphoric acid ester (manufactured by Daihachi Chemical Industry Co., Ltd., Japan; trade name: CR733S) (hereinafter referred to as FP) was used.

(3) Polytetrafluoroethylene (PTFE) Commercially available Polytetrafluoroethylene (weight average molecular weight: 1,000,000) (manufactured by Daikin Industries, Ltd., Japan) ) Was used.

(4) Melamine cyanurate (MC) A commercially available melamine cyanate (manufactured by Nissan Chemical Co., Ltd., Japan) (hereinafter referred to as MC) was used.

(5) Phosphazen

A) Linear phosphazene

Polydiphenoxyphosphazene (melting point: 110 ° C.) (hereinafter referred to as PPP) was used.

B) Cyclic phosphazene

Hexakis (acryloyl ethoxy) phosphine (hereinafter referred to as HAP) was used.

(6) Tetrazole

A commercially available 5,5′-viste tolazole piperazine salt (manufactured by Toyo Kasei Kogyo Co., Ltd., Japan) (hereinafter referred to as BPP) was used. Example 9, Comparative Examples 1 to 11

Using a Henschel mixer, each component of the composition was mixed with the composition shown in Table 1, followed by a twin-screw extruder (40 mm <i) having an inlet at the center of the barrel, L / D = 47 ) Was used for continuous melt extrusion at 280 ° C for 10 hours. As a screw, a two-section screw having a kneading part before and after the inlet was used.

From the composition thus obtained, a molded body was produced by injection molding at a cylinder set temperature of 270 ° C. and a mold temperature of 60 ° C. under the following conditions, and was evaluated. The results are shown in Tables 1 and 2. According to Tables 1 and 2, in the resin composition of the aromatic polycarbonate and the silicon-based compound, even in the silicon-based compound silicone, the D-unit was more than the branched or cross-linked silicone resin having the T unit. The resin composition according to the present invention, which comprises a linear silicone having only 5 units and containing an aromatic group in an amount of 5 mol% or more, as the component (B), has not only excellent flame retardancy but also excellent melting properties. It can be seen that it can be used for manufacturing molded products that have fluidity and stability during melt molding (quality stability of molded products) and are excellent in mechanical properties, light resistance and appearance. On the other hand, it was found that even if polyphenylene ether was used in place of the aromatic polycarbonate, the effect of improving the flame retardancy and light resistance exhibited in the composition of the present invention was not confirmed. Example.10 to 5 7

A composition was prepared and evaluated in the same manner as in Example 1 except that the resin composition was changed as shown in Tables 3 to 6. The results are shown in Tables 3-6.

As shown in Table 1, flame retardants selected from metal salts, phosphorus-based, silicon-based, silicon-based, inorganic-based, and fluorine-based flame retardants as the flame retardant (C) are added to the composition of the present invention. It can be seen that the properties are further improved.

Also, by blending a rubber-like polymer with PC, the impact strength is dramatically improved, while by blending a polyester such as PBT or a thermoplastic epoxy polymer or a polyamide. It can be seen that the melt fluidity is dramatically improved. Example 5 8-6 9

A composition was prepared and evaluated in the same manner as in Example 1, except that the composition of the composition was changed as shown in Table 7. Table 7 shows the results. According to Table 7, as long as the requirement of the component (B) of the composition of the present invention is satisfied, the silicone compound containing an aromatic group in an amount of 5 mol% to less than 50 mol% and the aromatic group in an amount of 50 mol% It can be seen that various excellent effects of the present invention are exhibited even when mixtures having various ratios with a silicon compound containing at least mol% are used as the component (B). The meanings of the abbreviations in Tables 1 to 7 are as follows.

PC: aromatic polycarbonate;

PPE: polyphenylene ether;

HIPS: rubber-modified polystyrene;

ABS: ABS resin;

SEBS: Styrene-ethylene-butylene-styrene copolymer;

m-SEBS: maleic anhydride-modified styrene-ethylene-butylene-styrene copolymer;

S B: Styrene-butadiene copolymer;

ESB: Epoxy-modified styrene-butadiene copolymer;

SPS: syndiotactic styrene polymer; PP: polypropylene;

E〇: ethylene-octene copolymer;

AS-1 and AS-2: Acrylonitrile-styrene copolymer

T P V: E 0 -PP cross-linked product;

PBT: polybutylene terephthalate;

E P: epoxy resin;

KSS: diphenylsulfone-3-potassium sulfonate;

FBK: potassium perfluorinated sulfonate;

F P: 1,3—phenylene bis (diphenyl phosphate)

PTF: Polytetrafluoroethylene;

M C: Melamine cyanulate;

PPPP: polydiphenoxyphosphazene;

HAP: Hexakis (acylethoxy) phosphazene ';

BPP: 5,5'-biste tolazolpiperazine salt

Example Example Comparative Example

1 2 1 2 3 4 5 6 pairs (A) PC 9 2 1 0 0 9 2 0 0 Composition (B) Amount 8 0 8 0 '8 8 Objects D unit ZT unit (ratio) 1) 100/0 100/0 50/50 100/0 50/50 phenyl chill (molar ratio) 25/75 5/95 3/97 25/75 25/75 25/75

Methoxy ist from R ³ and R ⁴

Presence

Ratio P PE 100 9 2 Flame retardance ²⁾ ◎ ◎ XXX 〇〇〇 Izod impact strength (kg · cm / cm) 1 5 1 2 1 5 7 5 7 5 3 3 Appearance: Yellowness ΔΥ Ι 2 2 2 3 3 3 4 3 44 4 5 Light fastness Color difference ΔΕ 2 2 3 3 5 2 0 2 2 2 5 Extrusion stability: Change rate of eye '/ ^ (%) 5 7 5 2 9 3 3 9 1 8 40

1) D unit: R T unit: R

I

— 0— S i—0— — 0— S i— 0—

I I

R 0—

2) Flame retardant: ◎ Self-extinguishing within 20 seconds

自己 Self extinguishing within 20 to 40 seconds

X Burnt

The above 1) and 2) are the same for Tables 2 to 7.

Table 2 Comparative examples

3 4 5 6 7 8 9 7 8 9 1 0 1 1 pair (A) PC 9 0

Composition (B) amount-1 0

Product D unit / T unit (molar ratio) 1) 100/0 100/0 0/100 10/90 50/50 80/20 phenyl / methyl (molar ratio) 10/90 40/60 60/40 70 / 30 90/10 100/0 60/40 0/100 60/40

Methoxy derived from R ³ and R ⁴

Presence or absence of base

Ratio

Flame retardance ²⁾ 〇 ◎ ◎ ◎ 〇 ◎ ◎ XXXXX Izod impact strength (kg · cm / cm) 1 0 1 2 1 3 1 4 1 6 1 8 1 2 2 3 4 6 8 Appearance: Yellowness ΔΥ Ι 2 2 2 3 3 3 2 2 3 3 3 5 Lightfastness Color difference ΔΕ 2 2 2 3 3 3 2 2 4 4 5 6 Extrusion stability: change rate of eye-note (%) 7 5 5 5 4 4 4 5 5 6 3 4 3 3 5 3 1

Table 3

Table 4

Table 5

* The closer the ratio of the Izod impact strength of the molded product to the Izod impact strength of 1/8 "inch and that of 1/4" is closer to 1, the less the thickness dependency, the more stable impact strength is exhibited.

Table 6

Table 7

Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, it not only has outstanding flame retardancy, but also has excellent melt fluidity and stability at the time of melt molding (quality stability of molded products), and has excellent mechanical properties, light resistance and appearance. An aromatic polycarbonate-based resin composition that can be advantageously used for producing excellent molded articles is obtained. Therefore, the flame-retardant materials obtained by using the resin composition of the present invention include VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, and the like. Home appliances such as air conditioners, humidifiers, electric warm air machines, chassis or parts, CD-ROM mainframe (mechanical chassis), printers, fax machines, PPC (plain paper copier), CRT, Warp-copier, electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR (electronic cash register), calculator, toner cartridge機器 A equipment housing, chassis or parts, connectors, coil pobins, switches, relays, relays Socket, LED (1 ight-emi 11 ing diode), Norikon, AC (alternating current) adapter, FBT high-voltage bobbin, FBT case, IFT coil bobbin, jack, battery shaft, motor Electronic and electrical materials such as components, instrument panels, grilles, loudspeakers, clusters, and speakers — grills, louvers, console boxes, and defrosters It is extremely suitable for automobile materials such as nish, ornament, fuse box, relay case, connector shift tape, etc. Therefore, the role of the present invention in these industrial fields is great.

Claims

Range of request

(B) a linear or cyclic aromatic group-containing silicone compound 0.1 to 100 parts by weight,

And

R ³ —〇 (1)

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a monovalent C i -C _2. Hydrocarbon group;

R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent or divalent C i -C _{2 Q} hydrocarbon group, provided that R ³ and R ⁴ are each independently a divalent mono-C ₂ . R ³ and R ⁴ are divalent at the same time and are bonded to each other Forming a ring;

RR ^2, one at least of the R ³ and R ⁴ are C ₆

One C _2. Wherein the aromatic group has a valency as defined above for RR ² , R ³ or R ⁴ ; and

(Wherein, R ¹ and R ² each represent the formula (1)

As defined above. )

The amount of the aromatic group in the component (B) is 5 to 100 mol% based on the total molar amount of R ¹ , R ² , R ³ and R ⁴ ;

An aromatic polycarbonate-based resin composition, comprising:

2. The resin composition according to claim 1, wherein the component (B) exhibits a kinematic viscosity of 100 centistokes or more when measured at 25 ° C in accordance with JIS-K224.

3. A (silicon) compound in which the component (B) contains the aromatic group in an amount of 5 to less than 50 mol% based on the total molar amount of RR ² , R ³ and R ⁴ ; ^3. The resin composition according to claim 1, which is a mixture with a silicone compound containing a group in an amount of 50 mol% or more based on the total molar amount of R ^1_ , R ² , R ³ and R ⁴ .

4. The resin composition according to any one of claims 1 to 3, further comprising (C) 0.01 to 100 parts by weight of a flame retardant.

5. Flame retardant (C) is at least one flame retardant selected from metal salt flame retardant, phosphorus flame retardant, nitrogen flame retardant, silicon flame retardant, inorganic flame retardant and fluorine flame retardant The resin composition according to claim 4, which is:

6. The resin composition according to claim 5, wherein the metal salt-based flame retardant is a metal salt of an organic sulfur compound.

7. The organic sulfur compound metal salt is an organic sulfonic acid metal salt. 7. The resin composition according to claim 6.

8. The resin composition according to claim 5, wherein the metal salt-based flame retardant is an aromatic organic polymer containing a metal sulfonic acid salt.

9. The nitrogen-based flame retardant is at least one selected from the group consisting of a triazine-based compound, a triazole-based compound, a tetrazole-based compound, a phosphazene-based compound, and a diazo-based compound. 6. The resin composition according to 5.

10. The resin component (A) is composed of an aromatic polycarbonate, an aromatic vinyl polymer, an olefin polymer, a polyester polymer, a polyamide polymer, a polyphenylene ether polymer and The resin composition according to any one of claims 1 to 9, which is a resin mixture with at least one organic polymer resin selected from the group consisting of epoxy polymers.