JP5250438B2 - Flame retardant aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to a composition containing an aromatic polycarbonate resin. More specifically, it contains an aromatic polycarbonate resin, a styrene resin, a silicone compound having a specific chemical structure, an organic metal salt flame retardant, an inorganic filler, and a fluorine-containing anti-dripping agent, for flame retardancy and moldability. The present invention relates to an excellent resin composition.

Polycarbonate resins have been used for various applications because of their excellent heat resistance, impact resistance, etc., but have drawbacks such as high molding processing temperature and poor fluidity. Thus, attempts have been made to solve these problems by blending polycarbonate resin with ABS resin (Patent Documents 1 to 4).
By the way, PC / ABS alloys are excellent in molding processability, impact resistance, dimensional accuracy, etc., but lack flame retardancy, so various attempts have been made to improve flame retardancy ( Patent Documents 5 and 6). Such PC / ABS alloys are formed into various molded products by a simple and excellent productivity method such as injection molding, and are used in a wide range of industrial fields. In addition, flame retardant resin compositions in which halogen compounds or phosphorus compounds are added to aromatic polycarbonate resins are used in PCs, notebook computers, laser beam printers, ink jet printers, copying machines, fax machines, etc., which have strong demands for flame resistance. It is used for exterior members and internal parts such as office automation equipment and home appliances. However, on the other hand, resin compositions using flame retardants instead of these flame retardants have been developed and are being used in the products listed above. Examples of the purpose of changing the flame retardant include suppression of generation of a corrosive gas at the time of molding or improvement of product recyclability.
Examples of flame retardants that can replace the flame retardants listed above include silicone compounds. In recent years, a flame retardant resin composition in which a silicone compound is blended with an aromatic polycarbonate resin has been intensively studied and various proposals have been made.

  Also, in housing applications for various devices, the trend toward thinning is becoming stronger with the demand for cost reduction and weight reduction. In order to respond to this, a polycarbonate resin composition containing polyorganosiloxane has been reported (Patent Document 7). In addition, a method has been proposed in which an alkali (earth) metal salt of perfluoroalkanesulfonic acid and an organosiloxane having an alkoxy group, a vinyl group, and a phenyl group are blended with a polycarbonate resin (Patent Document 8). In addition, a method is proposed in which an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid and an organopolysiloxane containing an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group are added to a polycarbonate resin. (Patent Document 9). A method of blending a polycarbonate resin with a styrene resin, an aromatic polyester resin, a silicone compound having a specific structure, an organic alkali metal salt, or the like has been proposed (Patent Document 10).

Moreover, a method of blending a specific petroleum heavy oil or pitches and a silicone compound with a resin component has been proposed (Patent Document 11). A non-silicone resin having an aromatic ring having a unit represented by the formula R ₂ SiO _1.0 and a unit represented by RSiO _1.5 , and having a weight average molecular weight of 10,000 or more and 270,000 or less. A method of blending has been proposed (Patent Document 12).
However, the proposed polycarbonate resin composition is not sufficiently flame retardant. For example, in the case of a thin wall, a drip is produced and the UL standard 94 V-0 rank cannot be achieved.

  On the other hand, attempts have been made to improve the fluidity of materials such as reducing the molecular weight of polycarbonate and increasing the ratio of ABS and AS in order to achieve thinning. However, this method has problems such as reduced flame retardancy and difficulty in obtaining desirable heat resistance and impact resistance. In addition, it is easy to obtain a higher fluidity by increasing the molding temperature, but the resin composition by volatilization of the flame retardant in the composition, reduction in flame retardance due to modification, molding at high temperature There are problems of deterioration of the material and insufficient impact resistance.

Japanese Examined Patent Publication No. 38-15225 Japanese Patent Publication No. 48-12170 Japanese Patent Publication No.57-21530 Japanese Examined Patent Publication No. 58-46269 Japanese Patent Publication No.54-30417 Japanese Patent Laid-Open No. 61-62556 JP-A-4-298554 JP-A-6-306265 JP-A-6-336547 JP 2003-147188 A JP-A-9-169914 Japanese Patent Laid-Open No. 10-139964

In view of the above, an object of the present invention is to include an aromatic polycarbonate resin containing a styrene resin, a silicone compound having a specific structure, an organic metal salt flame retardant, a fluorine-containing anti-dripping agent, and flame retardant in an improved thin-walled molded product. It is in providing the resin composition which has heat resistance, heat resistance, and moldability. Moreover, it is providing the molded article and transparent sheet which were formed from this resin composition.
The present inventors have intensively studied to solve the above problems. It has been found that the above-mentioned problems can be solved by blending an aromatic polycarbonate resin and a styrene resin with a silicone compound having a specific structure containing an aromatic group in the molecule, and the present invention has been completed.

According to the present invention, the above-mentioned problem is that 100 parts by weight of a resin component (component A) comprising 100 to 70% by weight of an aromatic polycarbonate resin (component A-1) and 30 to 0% by weight of a styrene resin (component A-2). Against
(i) 0.01 to 5 parts by weight of a silicone compound (component B) represented by the following formula (2) in which the content of the aromatic group represented by the following formula (1) is 20 to 50 % by weight;
(ii) 0.001 to 0.3 parts by weight of an organometallic salt flame retardant (component C), and
(iii) Fluorine-containing anti-dripping agent (component D) 0.01 to 5 parts by weight,
Ru is achieved by a flame retardant resin composition containing.

(In the formula, each X independently represents an OH group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. And m represents an integer of 0 to 5. Further, when m is 2 or more, different types of X can be taken.

(In formula (2), R _{1 to} R ₈ are each independently an aliphatic group, an aromatic group or an alicyclic group, and n is an integer of 3 to 20 and represents the average degree of polymerization.)
One of the preferred embodiments of the present invention is (2) In addition, an inorganic filler, preferably mica, talc, wollastonite (E component) is added to the resin composition comprising A, B, C and D components. It is a resin composition containing 0.5 to 50 parts by weight with respect to 100 parts by weight of the component.

  One of the preferred embodiments of the present invention is (3) a molded product and a transparent sheet formed from the resin composition having the above-described configurations (1) and (2).

  The flame retardant resin composition of the present invention is excellent in flame retardancy, heat resistance, recyclability and molding processability in a thin region. Moreover, the molded product and transparent sheet of this invention are excellent in a flame retardance and heat resistance.

Details of the present invention will be described below.
(A-1 component: aromatic polycarbonate resin)
The aromatic polycarbonate resin which is the component A-1 of the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of dihydric phenols include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol) A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '-(P-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) diph 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. The preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and among them, the A-1 component is preferably an aromatic polycarbonate resin derived from bisphenol A from the viewpoint of impact resistance.

  As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  When producing polycarbonate resin by interfacial polymerization method with dihydric phenol and carbonate precursor, use catalyst, terminal terminator, antioxidant to prevent oxidation of dihydric phenol as necessary. May be. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.
When a polyfunctional compound that produces a branched polycarbonate is included, the ratio is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and particularly preferably 0.001 in the total amount of the aromatic polycarbonate. 01 to 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure amount is preferably 0.001-1 mol%, more preferably 0.005-0.9 mol%, particularly preferably 0.01-0.8 mol% in the total amount of the aromatic polycarbonate. is there. Such a ratio can be calculated by ¹ H-NMR measurement.
The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The aromatic polycarbonate resin is a mixture of two or more of the above-mentioned various aromatic polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, various polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. It may be. Furthermore, what mixed 2 or more types can also be used about various types, such as the polycarbonate from which the manufacturing method shown below differs, and the polycarbonate from which a terminal terminator differs.

Reaction formats such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, which are polycarbonate resin production methods, can be found in various documents and patent publications. This is a known method.
The molecular weight of the aromatic polycarbonate resin is not specified, but if the molecular weight is less than 1 × 10 ^4, it is difficult to obtain sufficient strength as a molded product, and if it exceeds 5 × 10 ⁴ , molding processability is deteriorated. Therefore, the viscosity average molecular weight is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 3 × 10 ⁴ , and still more preferably 1.4 × 10 ⁴ to 2. 4 × 10 ⁴ . Also, two or more aromatic polycarbonate resins may be mixed. In this case, it is naturally possible to mix an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

In particular, a mixture with an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ has a high entropy elasticity, and has a feature that appearance defects of a molded product due to rheological behavior represented by jetting hardly occur. When such an appearance defect occurs, it is an appropriate mode. Further, the gas injection amount is stable in gas injection molding and the like, and in the foam molding, the foamed cells are stable, and fine and homogeneous cells are easily formed.
More preferably, it is a mixture with a polycarbonate resin having a viscosity average molecular weight of 8 × 10 ⁴ or more, and further preferably a mixture with a polycarbonate resin having a viscosity average molecular weight of 1 × 10 ⁵ or more. That is, those capable of observing a molecular weight distribution of two or more peaks in a measuring method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of a polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., as calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T0 is the drop time of methylene chloride, t is the drop time of the sample solution]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(A-2 component: styrene resin)
The styrene resin as the component A-2 of the present invention is a resin selected from a polymer or copolymer of an aromatic vinyl compound, or an aromatic vinyl compound and another vinyl monomer and a rubbery polymer. It refers to a resin made of a copolymer obtained by copolymerizing a seed or more. The aromatic vinyl compound preferably contains 10% by weight or more in 100% by weight of the resin.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, Examples thereof include dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.
Preferable examples of the other vinyl monomer copolymerizable with the aromatic vinyl compound include a vinyl cyanide compound and a (meth) acrylic acid ester compound. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.

  Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included. Particularly preferred (meth) acrylic acid ester compounds include methyl methacrylate.

  Other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth) acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide, N-methylmaleimide, Examples include maleimide monomers such as N-phenylmaleimide, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof.

  Examples of the rubber polymer include polybutadiene, polyisoprene, and diene copolymers (for example, random copolymers and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and (meth) acrylic acid alkyl esters. Copolymer of ethylene and α-olefin (eg, ethylene / propylene random copolymer and block copolymer, ethylene / butene random copolymer and block copolymer, etc.) , Copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (for example, ethylene / vinyl acetate) Copolymer), ethylene and propylene Non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymers), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate Etc.), as well as silicone rubber (eg, polyorganosiloxane rubber, IPN type rubber composed of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; that is, the two rubber components are entangled with each other so that they cannot be separated. And rubber having a structure, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component). Of these, polybutadiene, polyisoprene, or diene-based copolymers that are more likely to exhibit the effect are more preferable, and polybutadiene is particularly preferable. These rubbery polymers are preferably 90% by weight or less, more preferably 80% by weight or less, in 100% by weight of the styrene resin.

  Specific examples of the styrene resin include styrene polymers such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and SMA resin. And a styrene-based thermoplastic elastomer (for example, (hydrogenated) styrene-butadiene-styrene copolymer, (hydrogenated) styrene-isoprene-styrene copolymer, etc.). Is meant to include both non-hydrogenated copolymers and hydrogenated copolymers, which are readily available, of which HIPS resins, ABS resins, AS resins are more preferred. Such as AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and styrenic thermoplastic elastomer A reinforced styrene resin.

  Among these, HIPS resin, ABS resin, and AS resin are particularly preferable. ABS resin has excellent moldability for thin-walled molded products, and also has good impact resistance. In particular, favorable characteristics are exhibited in combination with an aromatic polycarbonate resin. Here, MS resin is a copolymer resin mainly composed of methyl methacrylate and styrene, AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber and styrene, and ASA resin is mainly composed of acrylonitrile, styrene and acrylic rubber. MABS resin is a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene and styrene, MAS resin is a copolymer resin mainly composed of methyl methacrylate, acrylic rubber and styrene, SMA resin is styrene and anhydrous male A copolymer resin mainly composed of an acid (MA) is shown.

Styrenic resins can be used alone or in combination of two or more. For example, in an ABS resin, a mixture of an AS polymer (a copolymer of acrylonitrile and styrene) and an ABS copolymer (a copolymer obtained by graft copolymerization of acrylonitrile and styrene on a polybutadiene rubber) is generally used. Is also preferably used in the present invention.
Furthermore, the styrenic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during the production thereof. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution obtained by methods such as anion living polymerization and radical living polymerization, block copolymers, and polymers and copolymers having high stereoregularity Also good.

  In the ABS resin used in the present invention, the proportion of the diene rubber component is preferably 5 to 80% by weight in 100% by weight of the ABS resin component (that is, in the total of 100% by weight of the ABS polymer and the AS polymer). Preferably it is 8-50 weight%, Most preferably, it is 10-30 weight%.

Examples of the vinyl cyanide compound used in the ABS resin include those described above, and acrylonitrile is particularly preferable. As the aromatic vinyl compound, those described above can be used as well, and styrene and α-methylstyrene are particularly preferable. The proportion of the component grafted to the diene rubber component is preferably 95 to 20% by weight, more preferably 92 to 50% by weight in 100% by weight of the ABS resin component. Further, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for a part of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, chain transfer agent, emulsifier, etc. which are used by reaction as needed.
In the ABS resin, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The rubber particle diameter distribution can be either a single distribution or a rubber particle having a plurality of peaks of two or more, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  Further, it is well known that an ABS resin contains a copolymer of a vinyl cyanide compound and an aromatic vinyl compound that is not grafted to a diene rubber component. In the present invention, the ABS resin may contain a free polymer component generated during such polymerization as described above, and a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. A blended blend may be used. The reduced viscosity (30 ° C.) determined by the method described below is preferably 0.2 to 1 for the reduced viscosity of the copolymer (AS copolymer) comprising such free vinyl cyanide compound and aromatic vinyl compound. 0.0 dl / g, more preferably 0.3 to 0.7 dl / g.

The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS copolymer and measuring a solution dissolved in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. A viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined from the following formula from the solvent flow down seconds (t ₀ ) and the solution flow down seconds (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) −1} /0.5
The ratio of the free AS copolymer can be obtained by dissolving the ABS resin in a good solvent for the AS copolymer such as acetone and collecting the soluble resin. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.

The ratio of the vinyl cyanide compound and aromatic vinyl compound grafted to the diene rubber component in the ABS copolymer (the ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (% by weight) is 20 -200% is preferable, More preferably, it is 20-80%.
Such ABS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. From the viewpoint of hydrolysis resistance, an ABS resin produced by a bulk polymerization method and a suspension bulk polymerization method is more preferable. Further, the copolymerization may be carried out in one step or in multiple steps.

In the present invention, the AS resin is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Examples of such vinyl cyanide compounds include those described above, and acrylonitrile is particularly preferred. Examples of the aromatic vinyl compound include those described above, and styrene and α-methylstyrene are preferable. The proportion of each component in the AS resin is preferably 5 to 50% by weight of vinyl cyanide compound, more preferably 15 to 35% by weight, and preferably 95% of aromatic vinyl compound when the total is 100% by weight. -50% by weight, more preferably 85-65% by weight. Further, those vinyl compounds may be copolymerized with the above-mentioned other copolymerizable vinyl compounds. These contents are preferably 15% by weight or less in the AS resin component. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed.
Such an AS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably based on bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. The reduced viscosity of the AS resin is preferably 0.2 to 1.0 dl / g, more preferably 0.4 to 0.7 dl / g (the method for measuring the reduced viscosity is the same as described above).
Such an AS resin has a range of 15 to 35% by weight of acrylonitrile and 85 to 65% by weight of styrene in 100% by weight of the whole AS resin, and is produced by bulk polymerization, and its reduced viscosity is 0.4 to 0.7 dl. / G can be preferably used. In the ABS resin, when the ABS copolymer and the AS copolymer are blended, the ratios of the aromatic vinyl compound and the vinyl cyanide compound in the copolymer may be the same or different. Preferably they are almost the same.

The component A-2 is preferably at least one styrenic resin selected from the group consisting of ABS resin and AS resin.
The blending amount of the styrene resin (component A-2) is 0 to 30% by weight, preferably 1 to 30% by weight, based on the total of 100% by weight of the component A-1 and the component A-2. Therefore, it is preferable that A component consists of 99-70 weight% of aromatic polycarbonate resin (A-1 component) and 30-1 weight% of styrene resin (A-2 component).
The blending amount of the styrenic resin (component A-2) is more preferably 1 to 20% by weight, further preferably 3 to 15% by weight, and most preferably 5 to 15% by weight. The effect (for example, moldability) expected by blending the styrene resin is exhibited as the preferable range is reached. On the other hand, when it is more than the above range, flame retardancy is impaired.

(B component: silicone compound)
The silicone compound (component B) used in the present invention has an aromatic group content of 20 to 60% by weight, an average degree of polymerization of 3 to 20, and substantially no Si—H bond in the molecular structure. It is a silicone compound.
A silicone compound (B component) improves a flame retardance by the chemical reaction at the time of combustion. The silicone compound (component B) binds itself during combustion or binds to a component derived from the resin to form a structure, or by a reduction reaction during the formation of the structure, a flame retardant effect is exerted on the polycarbonate resin. It is considered to grant.

The silicone compound (component B) used in the present invention is represented by the following formula (2).

(In the formula _(2), independently R 1 to R ₈ are each an aliphatic group, an aromatic group, or a cycloaliphatic radical, n is to display the average polymerization degree by an integer from 3 to 20.)

Engaging number n in the above above formula (2) represents an average polymerization degree of the siloxane units. The average degree of polymerization of this is in the range of 3 to 20, preferably in the range of 4 to 17, more preferably from 4 to 15. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.

It is preferred organic radicals attached to a divorced atom is an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

Furthermore, the silicone compound used in the present invention contains an aromatic group represented by the following general formula (1), and its content is 20 to 50 % by weight, preferably 30 to 50 % by weight, more preferably 35 to 50% by weight. When the content of the aromatic group is within this range, the dispersibility of the silicone compound present in the composition is improved, so that the flame retardancy performance is improved and a favorable result is obtained.

(In the formula, each X independently represents an OH group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. And m represents an integer of 0 to 5. Further, when m is 2 or more, different types of X can be taken.
The silicone compound blended in the present invention may contain other reactive groups other than Si-H groups. Examples of such reactive groups include amino groups, carboxyl groups, epoxy groups, vinyl groups, mercapto groups. And a methacryloxy group.
The compounding quantity of a silicone compound is 0.01-5 weight part on the basis of 100 weight part of resin components (A component), Preferably it is 0.01-4 weight part, More preferably, it is 0.05-3.5 weight part. Parts, more preferably 0.1 to 3 parts by weight.

(C component: organometallic salt flame retardant)
The organometallic salt flame retardant which is the component C of the present invention is preferably a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids and metal salts of fluorine-substituted organic sulfates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among these, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant (component C) is preferably an alkali metal or an alkaline earth metal. These are sometimes called alkali (earth) metals. Alkali metals include lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant (component C) is an alkali (earth) metal salt of perfluoroalkyl sulfonic acid. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and the like. These can be used alone or in combination of two or more. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organometallic salt preferably has a fluoride ion content as measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect.

  Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  The compounding amount of the fluorine-containing organometallic salt compound is 0.001 to 0.3 parts by weight, preferably 0.005 to 0.3 parts by weight, more preferably 0.005 to 0.3 parts by weight based on 100 parts by weight of component A. 2 parts by weight, more preferably 0.008 to 0.15 parts by weight. The effect (for example, flame retardancy) expected by blending the fluorine-containing organic metal salt is exhibited as the preferable range is reached.

  In addition, as an organic metal salt flame retardant (component C) other than the fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof -2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.
Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable.

  When blending such an alkali (earth) sulfonate metal salt, the content is 0.001 to 0.3 parts by weight, preferably 0.005 to 0.005 parts, based on 100 parts by weight of component A. 2 parts by weight, more preferably 0.008 to 0.15 parts by weight.

(D component: fluorine-containing anti-drip agent)
The fluorine-containing anti-dripping agent which is the component D of the present invention is for preventing melt dripping during combustion and further improving flame retardancy, and polytetrafluoroethylene having a fibril forming ability is preferably used. Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.
Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 from Daikin Chemical Industries, and F-201L. . Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.
The content of the fluorine-containing anti-dripping agent (component D) is 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of component A. More preferably, it is 0.1 to 0.6 parts by weight.

(E component: inorganic filler)
The resin composition of the present invention may contain an inorganic filler (E component). The inorganic filler which is the E component of the present invention includes, for example, talc, wollastonite, mica, clay, montmon-lilonite, smectite, kaolin, calcium carbonate, carbon fiber, carbon flake, carbon bead, carbon milled fiber, metal flake. , Metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, ceramic balloon, aramid particle, aramid fiber, polyarylate fiber, graphite, potassium titanate whisker, aluminum borate Examples include whiskers and various whiskers such as basic magnesium sulfate. Of these, silicate-based fillers such as talc, wollastonite and mica are preferably used. These inorganic fillers may be used alone or in combination of two or more.
The E component is preferably at least one inorganic filler selected from mica (E-1 component), talc (E-2 component), and wollastonite (E-3 component).
Content of an inorganic filler (E component) is 0.5-50 weight part on the basis of 100 weight part of A component, Preferably it is 0.5-40 weight part, More preferably, it is 1-30 weight part.

(E-1 component: mica)
Examples of the mica (E-1 component) used in the present invention include powders having an average particle diameter of 1 to 80 μm. More preferably, an average particle diameter of 2-50 micrometers can be mentioned. The average particle diameter is a value measured by a laser diffraction / scattering method. When the average particle size is 1 to 80 μm, the flame retardancy is better and the fine dispersion condition in the resin is satisfied. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 3 μm. Further, such mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder such as epoxy, urethane or acrylic, and may be granulated.

(E-2 component: talc)
Examples of the talc (E-2 component) used in the present invention include those having an average particle diameter of 5 μm or less. More preferred are those having an average particle size of 3 μm or less, particularly preferably 2 μm or less. An example of the lower limit is 0.05 μm. Here, the average particle diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.
Talc is preferably used in a granulated form. As a granulation method, there are a case where a binder is used and a case where it is not substantially used. What does not use a binder is more suitable. As a granulation method when a binder is not used, a deaeration compression method (for example, a roller compression with a briquetting machine while deaeration in a vacuum state), a rolling granulation method or an agglomeration granulation method Etc.

(E-3 component: wollastonite)
The wollastonite (E-3 component) used in the present invention preferably has a number average fiber diameter of 0.5 to 5 μm. The number average fiber diameter is obtained by measuring a total of 1000 fiber diameters randomly extracted from an image observed with an electron micrograph and calculating the number average value. Moreover, the aspect ratio L / D (L: number average fiber length, D: number average fiber diameter) is preferably 5 or more, and more preferably 6 or more. The number average fiber length is calculated by observing wollastonite with an optical microscope or an electron microscope at a magnification at which the entire image of wollastonite can be observed almost completely, and inputting the image into an image analyzer. be able to. Examples of the image analysis apparatus include PIAS-III system manufactured by Pierce. As wollastonite used in the present invention, the loss on ignition at 1000 ° C. is preferably 2% by weight or less, more preferably 1.5% by weight or less, and further preferably 1% by weight or less.

  The flame retardant resin composition of the present invention can contain a fold inhibitor for suppressing the breakage of the reinforcing filler. The breakage suppressor inhibits adhesion between the matrix resin and the reinforcing filler, reduces stress acting on the reinforcing filler during melt kneading, and suppresses breakage of the reinforcing filler. As an effect of a crease suppressant, rigidity is improved (the aspect ratio of the reinforcing filler is increased), toughness is improved (effective when the main component is an aromatic polycarbonate resin, which is easy to exhibit the toughness of the matrix resin, particularly good toughness), Examples thereof include an improvement in conductivity (in the case of a conductive filler). Specifically, the breakage suppressor includes (i) a compound having a low affinity with the resin and the filler surface directly coated with the compound, and (ii) a structure having a low affinity with the resin, and a reinforcing filler. A compound having a functional group capable of reacting with the surface.

Representative examples of the compound having a low affinity for the resin include various lubricants. Examples of the lubricant include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefinic wax (paraffin wax, polyolefin wax, etc.), polyalkylene glycol, fluorinated fatty acid. Fluorine oils such as esters, trifluorochloroethylene, polyhexafluoropropylene glycol, etc.
As a method of directly coating the surface of the reinforcing filler with a compound having a low affinity with the resin, (1) a method of immersing the compound directly or a solution or emulsion of the compound in the reinforcing filler; Examples include a method of passing a reinforcing filler in steam or powder, (3) a method of irradiating the reinforcing filler with powder of the compound at high speed, and (4) a mechanochemical method of rubbing the reinforcing filler and the compound. be able to.
Examples of the compound having a structure having a low affinity with the resin and having a functional group capable of reacting with the surface of the reinforcing filler include the above-described lubricants modified with various functional groups. Examples of such functional groups include a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, and an alkoxysilyl group.

More preferred as a folding inhibitor is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 15,000 in terms of weight average molecular weight. In such a polyolefin wax, the amount of carboxyl group and carboxylic anhydride group is in the range of 0.05 to 10 meq / g per gram of lubricant having at least one functional group selected from carboxyl group and carboxylic anhydride group. Is preferable, more preferably 0.1 to 6 meq / g, and still more preferably 0.5 to 4 meq / g. In the case of other functional groups, it is preferable that they are contained to the same extent as carboxyl groups.
A particularly preferred example of the folding inhibitor is a copolymer of an α-olefin and maleic anhydride. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable α-olefins include those having an average carbon number of 16 to 60, and more preferably 25 to 55. The folding inhibitor is preferably 0.01 to 2% by weight, more preferably 0.05 to 1.5% by weight in 100% by weight of the flame retardant aromatic polycarbonate resin composition of the present invention, and 0.1 to 0. 8% by weight is more preferred.

(About the content of each component)
In the flame-retardant resin composition of the present invention, the A-2 component is 0 to 30% by weight, preferably 1 to 30% by weight, more preferably 100% by weight of the total of the A-1 component and the A-2 component. 1 to 20% by weight, more preferably 3 to 15% by weight, and most preferably 5 to 15% by weight. If it is less than 1% by weight, the improvement of formability is insufficient, and if it exceeds 20% by weight, the flame retardancy and heat resistance are lowered, which is not suitable.
Content of B component is 0.01-5 weight part with respect to 100 weight part of A component, Preferably it is 0.01-4 weight part, More preferably, it is 0.05-3.5 weight part, More preferably 0.1 to 3 parts by weight. If it is less than 0.01 part by weight, the flame retardancy is insufficient, and if it exceeds 10 parts by weight, the flame retardancy is lowered and is not suitable.
Content of C component is 0.001-0.3 weight part with respect to 100 weight part of A component, Preferably it is 0.005-0.3 weight part, More preferably, it is 0.005-0.2 weight part. More preferably, it is 0.008 to 0.15 parts by weight. If it is less than 0.001 part by weight, the flame retardancy is insufficient, and if it exceeds 0.3 part by weight, the flame retardancy is lowered and is unsuitable.
Content of D component is 0.01-5 weight part with respect to 100 weight part of A component, Preferably it is 0.01-3 weight part, More preferably, it is 0.05-1 weight part, More preferably, it is 0. 0.1 to 0.6 parts by weight. When the content of the D component exceeds 5 parts by weight, the impact strength is lowered, which is not preferable.
Content of E component is 0.5-50 weight part with respect to 100 weight part of A component, Preferably it is 0.5-40 weight part, More preferably, it is 1-30 weight part. If the amount of component E exceeds 50 parts by weight, fluidity and impact strength are significantly reduced, which is not suitable.

(Other additives)
Various stabilizers and coloring materials can be used in the resin composition of the present invention in order to stabilize the molecular weight and hue at the time of molding. Examples of such stabilizers include phosphorus stabilizers, hindered phenol stabilizers, mold release agents, ultraviolet absorbers, dyes and pigments, and light stabilizers.
(I) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following formula (3) are preferable.

(In Formula (3), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (3), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.
Either of the phosphorus stabilizer and the hindered phenol antioxidant is preferably blended, and the combination of these is more preferred. More preferably, 0.01 to 0.3 parts by weight of a phosphorus stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol antioxidant are blended based on 100 parts by weight of component A. .

(Iii) Release agent It is preferable to add a release agent to the resin composition of the present invention for the purpose of improving productivity at the time of molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. The release agent is preferably 0.005 to 2 parts by weight based on 100 parts by weight of component A.
Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30.
Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  In the present invention, the fatty acid ester may be a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value of the fatty acid ester is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0.5 parts by weight based on 100 parts by weight of the component A. It is. In such a range, the resin composition has good release properties and roll release properties. In particular, such an amount of fatty acid ester provides a resin composition having good release properties and roll release properties without impairing good hue.

(Iv) Ultraviolet Absorber The resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention is excellent in transparency, it is very suitable for use in transmitting light.
Specific examples of the ultraviolet absorber of the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzen in benzophenone series. Roxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ' , 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5 -Benzoyl-4-hydroxy-2-methoxy Phenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like.

  Specific examples of the UV absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, and benzotriazole. -(2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazo 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- 2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) ) Benzotriazol, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis ( 1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2 '-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and copolymerizable with the monomer 2-hydroxy such as a copolymer with a nyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer Examples thereof include a polymer having a phenyl-2H-benzotriazole skeleton.

Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6) in the hydroxyphenyltriazine series. -Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) Examples include -5-butyloxyphenol. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.
As the ultraviolet absorber, specifically, in the cyclic imino ester system, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) Examples thereof include bis (3,1-benzoxazin-4-one) and 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one).
As the ultraviolet absorber, specifically, in the cyanoacrylate series, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano Examples include -3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet-absorbing monomer and / or a light-stable monomer having a hindered amine structure, an alkyl (meth) acrylate, etc. It may be a polymer type UV absorber obtained by copolymerization with the above monomer. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The
Of these, benzotriazoles and hydroxyphenyltriazines are preferred in terms of ultraviolet absorption, and cyclic iminoesters and cyanoacrylates are preferred in terms of heat resistance and hue (transparency). You may use a ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.02 to 1 part by weight, more preferably 0, based on 100 parts by weight of the component A. 0.05 to 0.5 parts by weight.

(V) Dye / pigment The resin composition of the present invention can further contain various dyes / pigments and can provide molded products that exhibit various design properties. Since the resin composition of the present invention is excellent in transparency, it is very suitable for use in transmitting light. Therefore, for example, by adding a fluorescent brightening agent, the resin composition of the present invention is given higher light transmittance and natural transparency, and a fluorescent brightening agent or other fluorescent dye that emits light is added. By doing so, the further better design effect which utilized the luminescent color can be provided. In addition, a resin composition which is finely colored with a very small amount of dye and pigment and has high transparency can also be provided.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the component A.

(Vi) Other Heat Stabilizers The resin composition of the present invention may contain other heat stabilizers other than the above phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the component A.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of component A.

(Vii) White pigment for high light reflection The resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on 100 parts by weight of the component A. Two or more kinds of white pigments for high light reflection can be used in combination.

(Viii) Other additives The resin composition of the present invention includes thermoplastic resins other than component A and component B, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, A heat ray absorbent, a photochromic agent, etc. can be mix | blended.

  As thermoplastic resins other than A component and B component, aromatic polyester resin (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G resin) Polyethylene naphthalate resin, polybutylene naphthalate resin, etc.), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, thermoplastic fluororesin (eg, polyvinylidene fluoride resin) ), And polyolefin resins (polyethylene resin, polypropylene resin, etc.).

(Manufacture of resin composition)
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, components A to E and optionally other additives are sufficiently mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then extruded as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method of premixing components other than the component A-1 in advance, and then mixing or feeding directly to the polycarbonate resin of the component A-1.
As a premixing method, for example, when an A-1 component having a powder form is included, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with powder. And a method using such a master batch. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver.

  Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

Moreover, the master pellet which melt-kneaded and pelletized A-1 component and D component with the melt-kneader beforehand so that it may contain D component of the high density | concentration of this invention is manufactured, and this master pellet is the remaining A-1 component. And a method of mixing with other additives and pelletizing with a melt kneader.
The resin composition of the present invention achieves the flame resistance level V-0 of UL94 standard in a molded product having a thickness of 1.4 mm.

(Molding)
This invention includes the molded article formed from the said resin composition. The resin composition in the present invention can be usually produced by injection molding pellets obtained by the above-described method. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

Moreover, the resin composition of this invention can also be used in the form of various profile extrusion molded products, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. In addition, the resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like. Specific examples of the molded product in which the resin composition of the present invention is used include internal parts of OA equipment and home appliances. It is suitable for application to a housing or the like. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, etc. Resin products formed from the flame-retardant resin composition of the present invention can be used for various parts such as these cases. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

(Flame retardants)
The present invention relates to a silicone compound having a content of an aromatic group represented by the following formula (1) of 20 to 60% by weight, an average degree of polymerization of 3 to 20, and substantially no Si—H bond in the molecular structure. It comprises a flame retardant comprising (B component) and an organometallic salt flame retardant (C component) and having a mixing weight ratio of B component: C component = 95: 50 to 5:50.

(In the formula, each X independently represents an OH group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. And m represents an integer of 0 to 5. Further, when m is 2 or more, different types of X can be taken.

The following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.
(Evaluation of resin composition)
(I) Flame Retardancy Measured according to the test method shown in Bulletin 94 “Flame Test for Material Classification” (UL94) of Underwriters Laboratories, Inc. The test was performed using five test pieces having a thickness of 1.4 mm. For one test piece, the operation of measuring the burning time (time to extinguish) after flame contact for 10 seconds was repeated twice. Flame retardancy was classified into V-0, V-1, and V-2. The classification criteria for each V for UL94 are outlined below.
(1) V-0: Combustion time after flame contact for 10 seconds is 10 seconds or less, total combustion time for 5 tubes is 50 seconds or less, and all test specimens do not drop fine flames that ignite absorbent cotton .
(2) V-1: Combustion time after flame contact for 10 seconds is 30 seconds or less, total combustion time for 5 tubes is 250 seconds or less, and all test specimens do not drop fine flames that ignite absorbent cotton .
(3) V-2: Combustion time after flame contact for 10 seconds is 30 seconds or less, the total combustion time of 5 tubes is 250 seconds or less, and the absorbent cotton is ignited from the particulate flame dropped from these test pieces.
(4) NG: When the combustion does not correspond to any of the above combustion times and the combustion continues.
The flame retardance rank is preferably V-0 class.
(Ii) Heat resistance The deflection temperature under load was measured according to ISO 75-1 and 75-2. The measurement load was 1.80 MPa.
(Iii) Molding processability An Archimedes-type spiral flow mold having a channel thickness of 2 mm and a channel width of 8 mm was used to measure the spiral flow length in the case of injection molding, and the molding processability was evaluated. The evaluation conditions were a cylinder temperature of 280 ° C., a mold temperature of 70 ° C., an injection pressure of 98.1 MPa, and SG150U manufactured by Sumitomo Heavy Industries, Ltd. was used as the injection molding machine.

[Examples 1 to 16, Comparative Examples 1 to 10]
A mixture having the composition shown in Table 1 and excluding other components (only in the case of the phosphate ester of FR-2) was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing the following premix (i) with other components using a V-type blender.
That is, (i) A mixture of D component (fluorine-containing anti-dripping agent) and A-1 component aromatic polycarbonate, and shake the entire bag in a polyethylene bag so that E component is 2.5% by weight. It is a mixture uniformly mixed by moving. Furthermore, FR-2 of other components is heated to 80 ° C., and is supplied to a second supply port (first supply port and middle) using a liquid injection device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.). From the position between the vent exhaust port), each was supplied to the extruder at a predetermined ratio. The liquid injection device was set to supply a constant amount, and the supply amounts of other raw materials were precisely measured with a measuring instrument [CWF manufactured by Kubota Corporation]. Extrusion is performed using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ, melt kneading at a screw rotation speed of 180 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 280 degreeC from the 1st supply port to the die part.
A part of the obtained pellets was dried in a hot air circulation dryer at 100 to 110 ° C. for 6 hours, and then compliant with each regulation (UL94, ISO75-1 and 75-2) using an injection molding machine. A test piece for evaluation was molded.

Each component indicated by symbols in Table 1 is as follows.
(A-1 component)
A-1: Aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX manufactured by Teijin Chemicals Ltd.]
(A-2 component)
A-2: Styrene-butadiene-acrylonitrile copolymer (Clarastic GA-704 (trade name) manufactured by Nippon A & L Co., Ltd.)
A-3: Styrene-acrylonitrile copolymer (HF5670 (trade name) Mw = 95,000 manufactured by Daiichi Woolen)
(B component)
B-1: A silicone compound containing only a methyl group and an aromatic group and having an aromatic group amount of 43% by weight and an average polymerization degree n of 14.
B-2: A silicone compound containing only a methyl group and an aromatic group and having an aromatic group amount of 32% by weight and an average polymerization degree n of 5.
B-3: A silicone compound containing only a methyl group and an aromatic group and having an aromatic group amount of 43% by weight and an average polymerization degree n of 22.
B-4: A silicone compound containing only a methyl group and an aromatic group and having an aromatic group amount of 17% by weight and an average polymerization degree n of 9.
B-5: A silicone compound containing only a methyl group and an aromatic group and having an aromatic group amount of 62% by weight and an average polymerization degree n of 30.
(C component)
C: Perfluorobutanesulfonic acid potassium salt (Dainippon Ink Chemical Co., Ltd. MegaFuck F-114P (trade name))
(D component)
D-1: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Polyflon MP FA500 (trade name))
D-2: Mixture of PMMA and polytetrafluoroethylene (Mitsubrene A3800 (trade name) manufactured by Mitsubishi Rayon Co., Ltd., containing 70% by weight of polytetrafluoroethylene)
(E component)
E-1: Mascobite (manufactured by Yamaguchi Mica Industry Co., Ltd .; A-41 (trade name))
E-2: Talc (Made by Hayashi Kasei Co., Ltd .; HST0.8 (trade name))
E-3: Wollastonite (manufactured by Shimizu Kogyo; H-1250F (trade name))
(Other ingredients)
FR-1: an organosiloxane flame retardant containing Si-H group, methyl group and phenyl group (X-40-2600J (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)
FR-2: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
DC30M: Olefin wax by copolymerization of α-olefin and maleic anhydride (Mitsubishi Chemical Co., Ltd .; Diacarna 30M (trade name))
SL900: Fatty acid ester release agent (Riken Vitamin Co., Ltd .; Riquemar SL900 (trade name))
TMP: Phosphate heat stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .; TMP (trade name))

  From the above table, it can be seen that by adding a specific amount of the silicone compound having the specific structure of the present invention, excellent molding processability can be obtained without reducing heat resistance and flame retardancy.

  The flame-retardant resin composition of the present invention is excellent in flame retardancy, heat resistance, recyclability and molding processability in a thin-walled region, and is widely useful in OA applications and other various fields.

Claims (12)

With respect to 100 parts by weight of a resin component (component A) consisting of 100 to 70% by weight of an aromatic polycarbonate resin (component A-1) and 30 to 0% by weight of a styrene resin (component A-2),
(i) 0.01 to 5 parts by weight of a silicone compound (component B) represented by the following formula (2) in which the content of the aromatic group represented by the following formula (1) is 20 to 50% by weight;
(ii) 0.001 to 0.3 parts by weight of an organometallic salt flame retardant (component C), and
(iii) Fluorine-containing anti-dripping agent (component D) 0.01 to 5 parts by weight,
Containing flame retardant resin composition.

(In the formula, each X independently represents an OH group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. And m represents an integer of 0 to 5. Further, when m is 2 or more, different types of X can be taken.

(In formula (2), R _{1 to} R ₈ are each independently an aliphatic group, an aromatic group or an alicyclic group, and n is an integer of 3 to 20 and represents the average degree of polymerization.) The resin composition according to claim 1, wherein the component A-1 is an aromatic polycarbonate resin derived from bisphenol A. The resin composition according to claim 1 or 2, wherein the A component comprises 99 to 70% by weight of an aromatic polycarbonate resin (A-1 component) and 30 to 1% by weight of a styrene resin (A-2 component). The resin composition according to any one of claims 1 to 3, wherein the component A-2 is at least one styrenic resin selected from the group consisting of an ABS resin and an AS resin. C component is a fluorine-containing organometallic salt compound, The resin composition of any one of Claims 1-4. 6. The resin composition according to claim 5, wherein the component C is an alkali (earth) metal salt of perfluoroalkylsulfonic acid. The resin composition according to any one of claims 1 to 6, wherein the component D is polytetrafluoroethylene. The resin composition according to any one of claims 1 to 7, comprising 0.5 to 50 parts by weight of an inorganic filler (E component) with respect to 100 parts by weight of the A component. The resin composition according to claim 8, wherein the E component is at least one inorganic filler selected from mica (E-1 component), talc (E-2 component), and wollastonite (E-3 component). object. The resin composition according to any one of claims 1 to 9, wherein a flame retardant level V-0 of UL94 standard is achieved in a molded article having a thickness of 1.4 mm. The molded product formed from the resin composition of any one of Claims 1-10. The sheet | seat formed from the resin composition of any one of Claims 1-11.