JP5080054B2 - Method for producing flame retardant resin composition - Google Patents

Description

  The present invention relates to a method for producing a flame-retardant thermoplastic resin composition. More specifically, it has good flame retardancy without substantially containing an organic halogen flame retardant and phosphate ester flame retardant, and also has excellent rigidity, heat resistance, impact resistance, thermal stability, and appearance. The present invention relates to a method for producing a flame retardant thermoplastic resin composition.

  Aromatic polycarbonate resins have excellent mechanical properties, dimensional accuracy, electrical properties, and the like, and are widely used as engineering plastics in various fields such as the electrical / electronic equipment field, automobile field, and OA equipment field. Of these uses, in general, in the OA equipment field and the electronic / electric equipment field, the resin material is required to have flame retardancy.

  In order to meet the demand for flame retardancy, flame retardant aromatic polycarbonate resins containing organic halogen flame retardants and phosphate ester flame retardants are widely used (see Non-Patent Document 1). However, in both organic halogen flame retardants and phosphate ester flame retardants, resin compositions containing such flame retardants should be burned or incinerated (thermal recycling), or disposed of in landfills. In some cases, environmental impacts may be considered a problem. These flame retardants are not easily replaceable because they have characteristics that are difficult to replace except for such environmental concerns. However, even if other characteristics are complemented by product design or the like, there is a growing trend to use flame retardant resin materials that do not substantially use these flame retardants.

  On the other hand, a flame retardant aromatic polycarbonate resin composition using a silicone compound or a metal salt compound as a flame retardant having a small environmental load has been proposed. Furthermore, in recent years, products are becoming thinner and lighter in the OA field and the electronic / electric field, and the flame retardant polycarbonate resin material is also required to have high rigidity and high strength, that is, reinforcement with an inorganic filler is desired. Yes. However, the flame retardant aromatic polycarbonate resin composition containing a silicone compound has a problem that the flame retardancy is greatly reduced when an inorganic filler is further combined.

  As an example using a silicone compound, a resin composition comprising a non-silicone resin containing an aromatic ring and a silicone resin comprising a methyl group and a phenyl group is known (see Patent Document 1). Moreover, a resin composition comprising a synthetic resin containing an aromatic ring in the molecule and a phenyl group and alkoxy group-containing organosiloxane is known (see Patent Document 2).

  As an example in which a silicone compound and a metal salt compound are used in combination, a resin composition comprising a polycarbonate resin, a silicone compound, and a metal salt of an aromatic sulfur compound is known (see Patent Document 3). A resin composition comprising an aromatic polycarbonate resin, an organic alkali metal salt and / or an organic alkaline earth metal salt, and an epoxy group-containing organopolysiloxane is known (see Patent Document 4). A resin composition comprising an aromatic polycarbonate and an alkali (earth) metal salt of perfluoroalkanesulfonic acid, an organosiloxane having an alkoxy group, a vinyl group, and a phenyl group is known (see Patent Document 5).

However, some silicone compounds may solidify when left at room temperature for more than one week, causing problems in handling. No specific method for solving this problem is described in these documents.
On the other hand, as an improvement in the handling and dispersibility of silicone resins, a flame retardant resin composition in which a thermoplastic organic resin and a phenyl group-containing silicone resin are mixed and then pelletized by an extruder and blended with them is known. Yes (see Patent Document 6).

However, the method of using a thermoplastic organic resin and a phenyl group-containing silicone resin as a masterbatch by an extruder has poor masterbatch productivity, and an extra heat history is added. Flame resistance, impact resistance, and thermal stability may be problematic.
Therefore, in order to improve the handling of the silicone compound and sufficiently satisfy all of the flame retardancy, impact resistance, and thermal stability, further improvement is necessary.

"Polycarbonate resin handbook" (page 141, line 6 to page 143, line 5) (Seiichi Honma, published by Nikkan Kogyo Shimbun, 1992) Japanese Patent No. 3240972 JP-A-11-222559 Japanese Patent Laid-Open No. 11-217494 JP-A-8-176425 Japanese Patent No. 2719486 JP 2001-31771 A

  The object of the present invention is to have good flame retardancy without substantially containing an organic halogen flame retardant or a phosphate ester flame retardant, and further, rigidity, heat resistance, impact resistance, thermal stability. Another object of the present invention is to provide a method for producing a flame retardant thermoplastic resin composition having an excellent appearance, which can avoid problems in handling organosiloxane.

  The present inventor has intensively studied to achieve such an object, and in the handling of silicone compounds that have not been sufficiently studied in the inventions of Patent Documents 1 to 5, an organic siloxane having an aromatic group and an inorganic powder, preferably scaly By blending a premixed product obtained by premixing with a glassy inorganic powder at a specific ratio into a thermoplastic resin, preferably an aromatic polycarbonate resin in a specific range, the productivity and storage stability of the organosiloxane are improved and the rigidity is improved. The present inventors have found that a flame retardant thermoplastic resin composition excellent in heat resistance, impact resistance, thermal stability, and appearance can be obtained, and have further studied and completed the present invention.

  The present invention provides a total of 100 weights of (1) thermoplastic resin, preferably aromatic polycarbonate resin (component A) 99 to 50% by weight, and inorganic powder, preferably scaly inorganic powder (component B) 1 to 50% by weight. A method for producing a flame retardant thermoplastic resin composition containing 0.01 to 10 parts by weight of an organosiloxane having an aromatic group per part (C component), wherein the B component and the C component are premixed in advance. The present invention relates to a method for producing a flame retardant thermoplastic resin composition, wherein the obtained premixed product is used.

  One of the preferred embodiments of the present invention is (2) the flame retardant thermoplastic resin composition of the above constitution (1), wherein the component B is at least one kind of flake-like inorganic powder selected from talc and mica. is there.

  One of the preferred embodiments of the present invention is that (3) the premixed product contains (B) inorganic powder (B component) and (C) an organosiloxane having an aromatic group (C component) from 10:80 to 99: 1. It is a manufacturing method of the flame retardant thermoplastic resin composition of either the said structure (1) or (2) which is the premixed product mixed in the ratio.

  One of the preferred embodiments of the present invention is (4) a method for producing a flame retardant thermoplastic resin composition having the above constitutions (1) to (3), wherein the C component has a cohesiveness of 60 or more.

  One of the preferred embodiments comprises (5) 0.001-0.1 part by weight of an alkali (earth) metal salt (component D) sulfonate per 100 parts by weight of the total of the component A and the component B. It is a manufacturing method of the flame-retardant thermoplastic resin composition of said structure (1)-(4).

  One of the preferred embodiments is the above constitution (1) to (6) containing 0.01 to 1 part by weight of a fluorine-containing anti-dripping agent (E component) per 100 parts by weight in total of the A component and the B component. (5) A method for producing a flame-retardant thermoplastic resin composition. According to this structure (5)-(6), the said flame-retardant thermoplastic resin composition which was further excellent in rigidity and a flame retardance is provided.

  One of the more preferable embodiments is (7) a flame retardant thermoplastic resin composition produced by the production method of the above constitutions (1) to (6).

  One of the more preferred embodiments is a preliminary obtained by premixing (8) (B) inorganic powder, preferably scaly inorganic powder (B component) and (C) organosiloxane having an aromatic group (C component). It is a mixed product.

Hereinafter, the details of the present invention will be described.
(Component A: thermoplastic resin)
The thermoplastic resin of component A used in the present invention is not fundamentally limited, and in particular, a thermoplastic resin used for a casing of an electronic device is preferably used. Examples of such thermoplastic resins include polypropylene resins, styrene resins, modified polyphenylene oxide resins, polyamide resins, polycarbonate resins, polyphenylene sulfide resins, and polyester resins. Particularly preferable examples include AS resin, ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and a mixture of two or more thereof. In particular, a polycarbonate resin is preferable.

  The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization 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 the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 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-phenylenediisopropyl Pyridene) diphenol, 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, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

  In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

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

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resins, copolymerized polycarbonate resins copolymerized with bifunctional alcohols (including alicyclics), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and difunctional alcohols are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  Since the branched polycarbonate resin can synergistically improve the anti-drip ability of the aromatic polycarbonate resin composition of the present invention, its use is preferable. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

The ratio of the polyfunctional compound in the branched polycarbonate resin is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, more preferably 0.01 to 0.8 mol in the total amount of the aromatic polycarbonate resin. The mol%, particularly preferably 0.05 to 0.4 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 is also preferably in the above-mentioned range in the total amount of the aromatic polycarbonate resin. Such a branched structure amount 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 reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.
The details of the reaction formats other than those described above are also well known in books and patent publications.

In producing the aromatic polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1 4 × 10 ^{4 to} 3 × 10 ⁴ , and more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ .

Aromatic polycarbonate resins having a viscosity average molecular weight of less than 1 × 10 ⁴ may not provide practically expected impact resistance or the like, and may not provide sufficient drip-preventing ability, so that flame retardancy is not obtained. Inferior. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. ,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
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

Moreover, the calculation method of the said viscosity average molecular weight is applied also to the viscosity average molecular weight measurement of the resin composition of this invention and the molded article shape | molded from this resin composition. That is, in the present invention, these viscosity average molecular weights are obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution obtained by dissolving 0.7 g of a molded product in 100 ml of methylene chloride into the above formula.

(B component: inorganic powder)
The inorganic powder used as the component B is usually used for the purpose of improving the rigidity of the molded resin, reducing warpage, and / or improving the surface appearance, and is generally produced naturally. It is an inorganic mineral. Among them, scale-like or plate-like ground powder such as mica such as talc, muscovite and phlogopite, glass flakes, kaolinite and sericite are preferable. Of these, talc and mica are particularly preferable.

(I) Talc The talc in the present invention is hydrous magnesium silicate in terms of chemical composition, and is generally represented by the chemical formula 4SiO ₂ · 3MgO · 2H ₂ O, and is usually a scaly particle having a layered structure. There also compositionally the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less. The composition of more preferred _talc, SiO 2: 62-63.5 wt%, MgO: from 31 to 32.5 _{wt%, Fe} 2 O 3: _{0.03~0.15 wt%,} Al _{2 O} 3: 0.05-0.25 weight% and CaO: 0.05-0.25 weight% are preferable. Further, the loss on ignition is preferably 2 to 5.5% by weight. With such a suitable composition, a resin composition having good thermal stability and hue can be obtained, and a good molded product can be produced by further increasing the molding processing temperature. As a result, the composition of the present invention can be further fluidized, and can be used for thin molded products having larger or complex shapes.

The average particle size of talc is in the range of 0.1 to 50 μm (more preferably 0.1 to 10 μm, still more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm). Is preferred. Therefore, a more preferable talc of the present invention is a talc having the above-mentioned preferable composition and having an average particle diameter of 0.2 to 5 μm. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. As an example of talc that satisfies such conditions, “Upn HS-T0.8” manufactured by Hayashi Kasei Kogyo Co., Ltd. is exemplified. The average particle size of talc refers to D50 (median diameter of particle size 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.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

(Ii) Mica Mica having an average particle size of 5 to 250 μm can be used. Preferably it is 5-50 micrometers mica. If the average particle diameter of mica is less than 5 μm, it is difficult to obtain the effect of improving rigidity. On the other hand, a resin composition containing mica having an average particle size exceeding 250 μm is inferior in appearance and flame retardancy while its mechanical properties tend to be saturated. The average particle diameter of mica is measured by a laser diffraction / scattering method or a vibration sieving method. In the laser diffraction / scattering method, it is preferable that a 325 mesh (aperture 45 μm) pass is performed on 95% or more of mica by vibration sieving. For mica having a larger particle size, the vibration sieving method is generally used. In the vibration sieving method of the present invention, first, sieving is carried out for 10 minutes using a JIS standard standard sieve in which 100 g of mica powder to be used is stacked in the order of openings using a vibration sieve device. This is a method of obtaining the particle size distribution by measuring the weight of the powder remaining on each sieve.

  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 0.3 μm. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a better level. Accordingly, more preferred mica of the present invention is a mascobite having an average particle size of 5 to 250 μm, more preferably 5 to 50 μm. As such a suitable mica, for example, “A-41” manufactured by Yamaguchi Mica Industry Co., Ltd. is exemplified. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more general, but the wet pulverization method is more effective for pulverizing mica thinner and finer (the rigidity improvement effect of the resin composition becomes higher). In the present invention, the wet pulverized mica is more preferable.

(C component: organosiloxane)
The organic siloxane having an aromatic group (component C) used in the present invention is an organic siloxane having a phenyl group, a biphenyl group, a naphthalene group, or a derivative thereof as an aromatic group, and in particular, an organic siloxane having a phenyl group. Is preferred. The content of the aromatic group is preferably 20 mol% or more, more preferably 40 mol% or more and 80 mol% or less of the organic groups bonded to the silicon atoms contained in the organosiloxane. . Examples of the organic group other than the aromatic group include a methyl group, an alkoxy group, an epoxy group, a carboxyl group, and a vinyl group. Among them, a methyl group is preferable. When the aromatic group of the organic siloxane is less than 20 mol%, the compatibility with the aromatic polycarbonate resin is lowered and the flame retardancy is lowered. On the other hand, if the phenyl group exceeds 80 mol%, the compatibility with the aromatic polycarbonate resin becomes too high, the surface migration of the organic siloxane during combustion is lowered, and the flame retardancy is lowered.

In general, the structure of organosiloxane is constituted by arbitrarily combining the following four types of siloxane units. That is,
M unit: monofunctional siloxane unit of R ¹ R ² R ³ SiO _1/2
D unit: R ⁴ R ⁵ SiO bifunctional siloxane unit,
T unit: trifunctional siloxane unit of R ⁶ SiO _3/2 ,
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group, an aryl group having 6 to 12 carbon atoms, and 1 to 7 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a vinyl group, a propenyl group, and a phenyl group. Particularly preferred are a phenyl group and a methyl group.

  As C component of this invention, it is preferable that the molar ratio of T unit is 20 mol% or more of all the siloxane units, More preferably, it is 40 mol% or more and 95 mol% or less. If the T unit is less than 20 mol%, there may be an effect such as deterioration of moldability due to a decrease in the viscosity of silicone and deterioration of flame retardancy due to a decrease in heat resistance. However, if it exceeds 95 mol%, moldability and flame retardancy due to increased viscosity may be reduced.

  Furthermore, as C component of this invention, the thing of the weight average molecular weights measured by GPC (gel permeation chromatography) method shown below of 5,000-200,000 is preferable, More preferably, the weight average molecular weight is 8, 000 to 150,000, more preferably 10,000 to 100,000. The GPC method used for measuring the C component of the present invention is as follows: apparatus: Gulliver series (manufactured by JASCO), column: MIXED-C (manufactured by PL), mobile phase: chloroform, standard substance: easy cal (PS -2) Detector: Using a differential refractometer, 100 μl of a sample having a concentration of 0.1 mg / ml was injected at a flow rate of 1 ml / min and measured at a column temperature of 35 ° C. Such molecular weight has a great influence on the uniformity of dispersion of the C component in the polycarbonate resin. The non-uniform dispersion may cause defects in the local flame retardant performance of the resin and may not exhibit good flame retardant performance as a whole.

  These can be used alone or in combination of two or more. Moreover, not only when each compound is synthesize | combined separately, but mixing according to the objective, it may produce | generate by mixing various compounds with the raw material at the time of a synthesis | combination.

  In addition, the organic siloxane which is the component C has a remarkable effect when it is an organic siloxane having a cohesiveness of 60 or more. In the present invention, “aggregability” means that the powder (a) passing through a 16-mesh sieve in organosiloxane is allowed to stand for 24 hours in an atmosphere of 0 ° C. × 30% RH and then 3 kg of nitrogen is added under a nitrogen atmosphere. Expressed as a weight percentage (b / a × 100) based on the total solid content (b) remaining on the sieve when fractionated with a 16-mesh sieve after 72 hours at 40 ° C. × 90% RH under load. It is a numerical value. In the present invention, the effect becomes more remarkable when the cohesiveness is 70 or more, preferably 80 or more.

(D component: alkali sulfonate (earth) metal salt)
Examples of the alkali (earth) metal sulfonate in the present invention include a metal salt of perfluoroalkylsulfonic acid and an alkali metal or alkaline earth metal, or a metal of aromatic sulfonic acid and an alkali metal or alkaline earth metal salt. Salts are exemplified.

  Examples of the alkali metal constituting the metal salt of the present invention include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium having larger ionic radii are suitable when the requirement for transparency is higher, but these are not general-purpose and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium, which are advantageous in terms of cost and flame retardancy, may be disadvantageous in terms of transparency. Considering these, the alkali metal in the sulfonic acid alkali metal salt can be properly used. In any respect, the sulfonic acid potassium salt having an excellent balance of properties is most preferable. Such potassium salts and sulfonic acid alkali metal salts comprising other alkali metals can be used in combination.

  In the perfluoroalkylsulfonic acid alkali metal salt, the alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms. Specific examples thereof include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, perfluorooctane. Sodium sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctanesulfonate, cesium perfluorohexanesulfonate , Rubidium perfluorobutane sulfonate, and rubidium perfluorohexane sulfonate Is, it may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The aromatic sulfonate alkali (earth) metal salt has 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms. Specific examples thereof include diphenyl sulfide-4,4′-disulfonic acid disodium salt and diphenyl sulfide-4. , 4'-disulfonic acid dipotassium, 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, poly (ethylene terephthalic acid polysulfonic acid polysodium), 1-methoxynaphthalene-4-sulfonic acid calcium salt, 4-dodecylphenyl ether disulfonic acid disodium acid Poly (2,6-dimethylphenylene oxide) polysodium sulfonate, poly (1,3-phenylene oxide) polysodium sulfonate, poly (1,4-phenylene oxide) polysodium sulfonate, poly (2,6- Gif Nylphenylene oxide) polypotassium polysulfonate, lithium poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, p-benzene Dipotassium disulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3′-disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, diphenylsulfone-3,3 ′ -Dipotassium disulfonate, dipotassium sulfone-3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzofe -3,3'-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid disodium salt, thiophene-2,5-disulfonic acid dipotassium salt, thiophene-2,5-disulfonic acid calcium salt, benzothiophene sulfonic acid sodium salt, diphenylsulfone Examples include potassium xylene-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, and formalin condensate of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonate alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3′-disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

(E component: fluorine-containing anti-dripping agent)
Examples of the fluorine-containing anti-dripping agent as the E component include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexa Fluoropropylene copolymer, etc.), partially fluorinated polymers as disclosed in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

  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 and F-201L from Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Asahi IC Fluoropolymers' full-on AD-1, AD-936, Daikin Kogyo's full-on D-1 and D-2, 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 a vinyl monomer is further polymerized in the mixture dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3000” (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. In addition, the ratio of the said F component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

(About the composition ratio of each component)
The present invention relates to an organic compound having an aromatic group per 100 parts by weight in total of thermoplastic resin, preferably 99 to 50% by weight of aromatic polycarbonate resin (component A) and 1 to 50% by weight of inorganic powder (component B). A method for producing a flame-retardant thermoplastic resin composition containing 0.01 to 10 parts by weight of siloxane (C component), wherein a premixed product obtained by premixing B component and C component in advance is used. It is a manufacturing method of the flame-retardant thermoplastic resin composition characterized. Further, 0.00100 to 0.1 parts by weight of an alkali (earth) metal salt (component D) sulfonated anti-dripping agent (component E) 0. It is a manufacturing method of the flame-retardant thermoplastic resin composition formed by containing 01-1 weight part.

  The content rate of B component is 1 to 50 weight%, 5 to 30 weight% is preferable and 8 to 25 weight% is more preferable. When the component B is less than 1% by weight, the effect of improving the rigidity is not sufficiently exhibited, and when it exceeds 50% by weight, the thermal stability during high temperature molding tends to be lowered. In the preferred range of the B component, both good rigidity and thermal stability during high temperature molding can be achieved at a high level.

  The content of component C is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 1 part by weight per 100 parts by weight of the total of component A and component B. If it is less than 0.01 part by weight, good flame retardancy cannot be obtained, and if it exceeds 10 parts by weight, the appearance of the molded product tends to be inferior.

  The content of component D is preferably 0.001 to 0.1 parts by weight, more preferably 0.005 to 0.05 parts by weight per 100 parts by weight of the total of components A and B. More preferred is 0.01 to 0.1 parts by weight. If it is less than 0.001 part by weight, good flame retardancy cannot be obtained, and if it exceeds 0.1 part by weight, the heat and moisture resistance tends to be inferior.

  The content of the E component is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight per 100 parts by weight of the total of the A component and the B component, -0.6 parts by weight is more preferred. If it is less than 0.01 part by weight, a good melt dripping preventing effect cannot be obtained and the flame retardancy is poor. If it exceeds 1 part by weight, the appearance of the molded product tends to be inferior.

(Other additives)
(Phosphorus stabilizer)
In the present invention, a phosphorus stabilizer may be optionally contained in order to obtain a flame retardant aromatic polycarbonate resin composition having a better hue and stable fluidity.
Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.

  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, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl 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, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  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- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl 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.
The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, a phosphate compound typified by trimethyl phosphate is preferably blended.

(Hindered phenol stabilizer)
When the resin composition of the present invention further contains a hindered phenol-based stabilizer, effects such as hue deterioration during molding and hue deterioration during long-term use are further exhibited. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (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) -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-thiodiethyl Nbis- [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 Anurate, 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-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.

  The compounding amount of the phosphorus stabilizer and the hindered phenol stabilizer is 0.0001 to 1 part by weight, preferably 0 with respect to 100 parts by weight in total of the thermoplastic resin (component A) and the inorganic powder (component B). 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

(UV absorber)
Since the flame-retardant thermoplastic resin composition of the present invention is excellent in hue and appearance, it may be used without coating. In such a case, good light resistance may be required, and in such a case, it is effective to add an ultraviolet absorber.

  Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 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 Methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (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) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 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 co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-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) ) -5-butyloxyphenol and the like. 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.

  Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet 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) acrylic acid ester. The

  The compounding quantity of a ultraviolet absorber is 0.01-2 weight part with respect to a total of 100 weight part of a thermoplastic resin (A component) and inorganic powder (B component), Preferably it is 0.03-2 weight part. Preferably it is 0.02-1 weight part, More preferably, it is 0.05-0.5 weight part.

(Light stabilizer)
In the resin composition of this invention, the said ultraviolet absorber and a light stabilizer can be used together. Examples of such light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2 , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- (2,2,6,6- Tetrame Le) piperidinyl] hindered amine light stabilizer typified by a siloxane is exemplified. The above light stabilizers may be used alone or in a mixture of two or more. The blending amount of the light stabilizer is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight based on 100 parts by weight of the total of the thermoplastic resin (component A) and the inorganic powder (component B). 0.02 to 1 part by weight is more preferable.

(Fluorescent brightener)
In the resin composition of the present invention, it may be necessary to adjust the hue. In such a case, the blending of the optical brightener is effective. Examples of the fluorescent whitening agent include coumarin-based, naphthalimide-based, and benzoxazolyl-based fluorescent whitening agents. Among them, a coumarin-based fluorescent whitening agent is preferable. ) Hakkol PSR is preferably exemplified. The compounding amount of the optical brightener is 0.0001 to 3 parts by weight, preferably 0.0005 to 1 part by weight, based on 100 parts by weight of the total of the thermoplastic resin (component A) and the inorganic powder (component B). Preferably it is 0.0005-0.5 weight part, More preferably, it is 0.001-0.5 weight part, Most preferably, it is 0.001-0.1 weight part.

(Other flame retardants)
The resin composition of the present invention achieves good flame retardancy without substantially containing an organic halogen flame retardant or a phosphate ester flame retardant. It does not hinder the flame retardant effect. However, in order to make the most of the features of the present invention, it is preferable that the flame retardant thermoplastic resin composition of the present invention does not substantially contain an organic halogen flame retardant or a phosphate ester flame retardant. On the other hand, for example, various organic alkali (earth) metal salts can be further blended in order to further improve the flame retardancy utilizing the features of the present invention.

  Similarly, various organic alkali (earth) metal salts can be further blended in the flame-retardant thermoplastic resin composition of the present invention. For example, an alkali (earth) metal salt of a sulfate ester can be mentioned, and in particular, an alkali (earth) metal salt of a monovalent and / or polyhydric alcohol sulfate ester can be mentioned. Sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, lauric acid monoglyceride sulfate, palmitic acid monoglyceride sulfuric acid Examples thereof include esters and sulfates of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other organic alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, Examples thereof include N- (N′-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide. The blending ratio of these organic alkali (earth) metal salts is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight per 100 parts by weight in total of the component A and the component B. Part.

(Filler)
In the flame-retardant thermoplastic resin composition of the present invention, various fillers other than the component B can be blended as reinforcing fillers within the range where the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, vapor grown ultrafine carbon fiber (fiber diameter is 0.1 μm Carbon nanotubes (fiber diameter is less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more.

(Other resins and elastomers)
In the resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range in which the effects of the present invention are exhibited.
Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  In addition, the flame retardant thermoplastic resin composition of the present invention may contain a small amount of additives known per se for imparting various functions to the molded article and improving properties. These additives are used in usual amounts as long as the object of the present invention is not impaired.

  Examples of such additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black and titanium oxide), light diffusing agents (for example, acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, carbonic acid Calcium particles), fluorescent dyes, inorganic phosphors (for example, phosphors containing aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine particle titanium oxide) , Fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

(Manufacture of resin composition)
(I) Preparation of premixed product In the method for producing a flame retardant thermoplastic resin composition of the present invention, an inorganic powder (B component) and an organic siloxane having an aromatic group (C component) are preliminarily mixed. Use a pre-mixed product. This premixed product is a premixed product in which the B component and the C component are premixed at a ratio of 20:80 to 99: 1, preferably 30:70 to 95: 5, more preferably 50:50 to 90:10. .

This premixed product can be produced by the following method.
The super mixer is rotated at a peripheral speed of 200 to 700 rpm, the inorganic powder is charged first, then the organosiloxane is charged, and after 1 minute, stirring is stopped to obtain a premixed product. The peripheral speed of the mixer is 200 to 700 rpm, preferably 300 to 600 rpm, more preferably 400 to 500 rpm. When the peripheral speed is less than 200 rpm, the mixed state of the inorganic powder and the organosiloxane is not sufficient, and when it exceeds 700 rpm, the heat generation becomes large and the powder aggregates.
The order of charging is most suitable first with inorganic powder and then with organic siloxane. When the organic siloxane is first introduced, partial aggregation of the organic siloxane is observed even after the inorganic powder is introduced.

  By using this pre-mixed product, it will aggregate or contain an agglomerated part after a long period of time, so it is necessary to grind when adding organosiloxane to the thermoplastic resin composition. The problem can be avoided. Moreover, compared with the master batch of thermoplastic organic resin and organosiloxane, the premixed product has good productivity and improves workability.

(Ii) Manufacture of resin composition Arbitrary methods are employ | adopted in order to manufacture the flame-retardant thermoplastic resin composition of this invention. For example, the above premixed product, A component, B component, optionally D component, E component, and optionally other components are respectively used as premixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. And sufficiently mixing, and then melt-kneading with a melt-kneader typified by a vent type biaxial rudder and pelletizing with a device such as a pelletizer.

  In addition, the premixed product, a method of supplying each of the other components independently to a melt-kneader represented by a vent type twin screw extruder, or a part of each component other than the premixed product was premixed. Thereafter, a method of supplying the melt kneader independently of the remaining components may also be mentioned. As a method of premixing a part of each component other than the premixed product, for example, a method of premixing components other than components A and C in advance and then mixing the thermoplastic resin of component A or supplying it directly to an extruder Is mentioned.

  As a method of premixing other than the above premixed product, for example, when a component having a powder form is included as the component A, a master of an additive diluted with powder by blending a part of the powder and an additive to be blended The method of manufacturing a batch and using such a master batch is mentioned. 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. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. 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.

(Molding)
A molded product comprising the flame retardant thermoplastic resin composition of the present invention can be usually obtained by injection molding the pellet. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, according to this invention, a flame-retardant thermoplastic resin composition can be extrusion-molded and it can also be made into shapes, such as various profile extrusion molded articles, a sheet | seat, a film. 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. Further, the flame-retardant thermoplastic resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

(surface treatment)
Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.

  The method for producing the thermoplastic resin composition of the present invention uses a premixed product obtained by premixing an inorganic powder and an organic siloxane having an aromatic group in advance, so that the productivity and storage stability of the organosiloxane are obtained. It is a method that can achieve both the rigidity and heat resistance of the product, and further, a flame retardant thermoplastic resin composition having excellent flame resistance by combining an alkali (earth) sulfonate metal salt and a fluorine-containing anti-dripping agent. It is a manufacturing method.

  In addition, the flame-retardant thermoplastic resin composition produced by the production method of the present invention is extremely useful for various industrial uses such as the OA equipment field and the electrical and electronic equipment field, and has particularly good characteristics corresponding to the OA equipment. Satisfied. In particular, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.), display devices (CRT, liquid crystal, plasma, projector, organic EL, etc.), printers, copiers, It is suitable for scanners and fax machines (including these multifunction machines).

The flame-retardant thermoplastic resin composition produced by the production method of the present invention is useful for a wide variety of other applications, such as a portable information terminal (so-called PDA), a cellular phone, a portable book (dictionaries, etc.), and a portable TV. , Drives for recording media (CD, MD, DVD, next-generation high-density discs, hard disks, etc.), readers for recording media (IC cards, smart media, memory sticks, etc.), optical cameras, digital cameras, parabolic antennas, electric tools, VTRs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, air purifiers, negative ion generators, typewriters, etc. Resin products formed from a flammable thermoplastic resin composition can be used. Other resin products include lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, auto mobile computer parts, and other vehicle parts. it can.
The industrial effect produced by the production method of the present invention capable of efficiently producing such a resin composition is extremely large.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.
(I) Rigidity (flexural modulus)
The flexural modulus (MPa) was measured according to ISO178. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.
(Ii) Flame retardancy A vertical combustion test of UL standard 94 was performed on a test piece of length 130 mm × width 13 mm × thickness 1.5 mm, and the grade was evaluated.
(Iii) Heat resistance (deflection temperature under load)
The deflection temperature under load (° C.) was measured at a load of 1.80 MPa in accordance with ISO75. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.
(Iv) Impact resistance Charpy impact strength with a notch was measured according to ISO179. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.
(V) Productivity (organosiloxane premixed product)
In the preparation of the organic siloxane premixed product, after mixing with the mixer, the case where a film-like welded material was seen on the bottom surface of the mixer was rated as x, and the case where the welded material was not seen was marked as ◯.
(Vi) Preservability (organosiloxane or organosiloxane premixed product)
1 kg of organic siloxane or organic siloxane pre-mixed product was put in a bag, left under a nitrogen atmosphere at 40 ° C. × 90% RH for 72 hours under a nitrogen atmosphere, sieved with a 16 mesh sieve, and the aggregation state was confirmed. The evaluation was performed according to the following criteria.
○: Solid content remaining on 16-mesh sieve is less than 60% by weight of the whole X: Solid content remaining on 16-mesh sieve is 60% by weight or more of the whole

The following were used as raw materials.
(A component)
PC-1: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A, p-tert-butylphenol as a terminal terminator, and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX, viscosity) Average molecular weight 19,700)
PC-2: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene (manufactured by Teijin Chemicals Ltd .: CM-1000, viscosity average molecular weight) 16,000)

(B component)
Talc: XD-25 manufactured by Katsumiyama Mining Co., Ltd.
Mica: A-41 manufactured by Yamaguchi Mica Industry Co., Ltd.

(C component)
Si-1: Organosiloxane having a phenyl group content of 65 mol% of the whole organic group and a weight average molecular weight of 61,200 measured by the GPC method defined in the text (manufactured by GE Toshiba Silicone Co., Ltd.) XC99-B5664)
Si-2: an organic siloxane having a phenyl group content of 75 mol% of the whole organic group and a weight average molecular weight of 12,500 measured by the GPC method defined in the text (manufactured by Shin-Etsu Chemical Co., Ltd.) X-40-9805)

(D component)
F114: Perfluorobutanesulfonic acid potassium salt (Megafac F-114P, manufactured by Dainippon Ink and Chemicals, Inc.)
KSS: 2: 8 mixture of diphenylsulfone-3,3′-disulfonic acid dipotassium salt and diphenylsulfone-3-monosulfonic acid dipotassium salt (KSS manufactured by UCB Japan)

(E component)
PTFE: Polytetrafluoroethylene having a fibril forming ability (Polyflon MPA FA500, manufactured by Daikin Industries, Ltd.)
B449: A mixture of polytetrafluoroethylene particles having fibril-forming ability and styrene-acrylonitrile copolymer particles (polytetrafluoroethylene content 50% by weight) (BLENDEX B449 manufactured by GE Specialty Chemicals)

(Other)
AY: Isobutyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-048)
DC: Acid-modified olefin wax which is a copolymer of maleic anhydride and α-olefin (manufactured by Mitsubishi Chemical Corporation: Diacarna 30M)
Ti: Titanium dioxide (Resino Color Industry Co., Ltd .: White DCF-T-17007)

[Examples 1 to 5, Comparative Examples 1 to 4]
<Preparation of premixed product>
A mixed product was obtained by mixing A component, B component and C component in a mixing ratio shown in Table 1 using a super mixer (capacity: 300 liters) manufactured by Kawata Co., Ltd. and a stirring blade rotating speed of 425 rpm for 1 minute. Next, an aromatic polycarbonate resin, an inorganic powder, an organic siloxane having an aromatic group, a sulfonic acid alkali metal salt, a fluorine-containing dripping inhibitor, a premixed product described in Table 1, and other components having the composition shown in Table 2 Using a tumbler, the mixture was uniformly mixed to prepare a mixture. This mixture is supplied to the first supply port located at the screw base of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, and the cylinder temperature is 280 ° C., the screw rotation speed is 150 rpm, and the discharge amount is 20 kg / h, and melt-extruded at a reduced pressure of 3 kPa and pelletized.

  The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours. After drying, test pieces for evaluation were molded by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: SG-150U) at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and evaluated.

  As is apparent from the above table, the method for producing the flame-retardant thermoplastic resin composition of the present invention produces organic siloxane by using a premixed inorganic powder and an organic siloxane having an aromatic group. It can be seen that the property and storage stability are improved, and the production of the resin composition is facilitated.

Claims (8)

(C) Organosiloxane having aromatic group (C) per 100 parts by weight in total of (A) thermoplastic resin (component A) 99 to 50% by weight and (B) inorganic powder (component B) 1 to 50% by weight Component) A method for producing a flame-retardant thermoplastic resin composition containing 0.01 to 10 parts by weight, wherein a premixed product obtained by premixing B component and C component in advance using a super mixer A method for producing a flame retardant thermoplastic resin composition, comprising using   The method for producing a flame retardant thermoplastic resin composition according to claim 1, wherein the component A is an aromatic polycarbonate resin.   The method for producing a flame-retardant thermoplastic resin composition according to claim 1 or 2, wherein the component B is a scaly inorganic powder.   The method for producing a flame-retardant thermoplastic resin composition according to claim 3, wherein the component B is at least one scale-like inorganic powder selected from talc and mica.   The premixed product is a premixed product in which (B) inorganic powder (component B) and (C) an organic siloxane having an aromatic group (component C) are mixed in a ratio of 20:80 to 99: 1. 5. The method for producing a flame retardant thermoplastic resin composition according to any one of 4 above.   The method for producing a flame-retardant thermoplastic resin composition according to any one of claims 1 to 5, wherein the C component has a cohesiveness of 60 or more.   In any one of Claims 1-6 formed by containing 0.001-0.1 weight part of sulfonate alkali (earth) metal salt (D component) per 100 weight part of total of A component and B component. The manufacturing method of the flame-retardant thermoplastic resin composition of description.   The flame-retardant heat according to any one of claims 1 to 7, comprising 0.01 to 1 part by weight of a fluorine-containing anti-dripping agent (component E) per 100 parts by weight of the total of the A component and the B component. A method for producing a plastic resin composition.