JP6513897B2 - Flame retardant polycarbonate resin composition - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition which has a polycarbonate resin and a polycarbonate-polydiorganosiloxane copolymer resin as a base, is excellent in flame retardancy and heat resistance, and has impact strength. More specifically, the present invention relates to a flame retardant polycarbonate resin composition in which a decrease in impact strength and flame retardancy due to light degradation is suppressed, and a decrease in impact strength and flame retardancy due to wet heat degradation is also suppressed.

  Aromatic polycarbonate resins are excellent in mechanical properties, dimensional accuracy, electrical properties, thermal properties and the like, and are widely used as engineering plastics in various fields such as the fields of electricity, electronics, automobiles and OA. In particular, in recent years, plastic housings used outdoors, represented by smart grids, are flame retardant, heat resistant, impact characteristics, and light resistance, from the viewpoint of protecting internal precision equipment from various outdoor environments. A material having excellent moist heat characteristics has been required.

  In Patent Documents 1 to 3, an aromatic compound with improved flame retardancy, hydrolysis resistance and impact strength comprising polycarbonate resin and phosphazene compound, polycarbonate resin, phosphazene compound and rubber-reinforced styrene, polycarbonate resin, phosphazene compound and fluorine compound etc. Polycarbonate resin compositions have been proposed. However, the description on the effect of suppressing the decrease in flame retardancy due to photodegradation and wet heat degradation is insufficient, and the addition of the phosphazene compound alone can reduce the impact strength and flame retardancy due to the required photodegradation and wet heat degradation. It was not sufficient for suppression and was not satisfactory.

Patent Document 4 proposes an aromatic polycarbonate resin composition comprising a polycarbonate resin, a phosphazene compound, a rubber-reinforced styrene and an ultraviolet absorber and having improved light resistance, flame retardancy and mechanical strength. However, although the description about the effect of suppressing the decrease in flame retardancy due to wet heat deterioration is insufficient, and the addition of the ultraviolet absorber shows the effect of suppressing the light deterioration, the hue after the light deterioration due to the influence of rubber reinforced styrene. The change was extremely large, and was not sufficient to suppress the decrease in impact strength and flame retardancy due to the required light deterioration and wet heat deterioration, and was not satisfactory.
On the other hand, it is known to introduce a polycarbonate-polydiorganosiloxane copolymer into an aromatic polycarbonate resin in order to improve the durability, impact strength and flame retardancy.

  In patent documents 5-8, mechanical strength and impact resistance which fall by introducing a polycarbonate polydiorganosiloxane copolymer to aromatic polycarbonate resin, and adding glass fiber and flat section glass fiber were improved. Aromatic polycarbonate resin compositions have been proposed. However, in the compositions described in these patent documents, data showing suppression of decrease in impact strength and flame retardancy due to photodegradation and moist heat degradation due to the addition of phosphazene compounds is not disclosed, but is required due to photodegradation and moist heat degradation It was insufficient to suppress the decrease in impact strength and flame retardancy and was not satisfactory. In addition, data on heat resistance was not disclosed as well, and the heat resistance required was insufficient and unsatisfactory.

  Although the resin composition containing the polycarbonate polydiorganosiloxane copolymer which prescribed | regulated the siloxane domain size was proposed by patent document 9, the data regarding a flame retardance and heat resistance are not disclosed, and it specifies in the literature. The resin composition containing a polycarbonate-polydiorganosiloxane copolymer characterized by the above-mentioned siloxane domain size was not satisfactory for the required flame retardancy and heat resistance, and was not satisfactory.

JP, 2013-001801, A Japanese Patent Application Publication No. 2007-045906 Unexamined-Japanese-Patent No. 07-292233 JP, 2000-351893, A Japanese Patent Application Laid-Open No. 55-160052 Unexamined-Japanese-Patent No. 02-173061 Japanese Patent Application Publication No. 07-026149 JP, 2012-116915, A Japanese Patent Application Publication No. 2006-523243

  The object of the present invention is to provide a flame retardant polycarbonate resin composition which is excellent in flame retardancy, heat resistance and impact strength, and in which the decrease in impact strength and flame retardancy due to light deterioration and wet heat deterioration is suppressed. is there.

  The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, a resin composition comprising a polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, a phosphazene compound, an inorganic filler, and a fluorine-containing antidropping agent. And a resin composition having a siloxane domain size derived from a polycarbonate-polydiorganosiloxane copolymer resin in a specific range is excellent in target rigidity, impact strength, flame retardancy, and further, impact strength due to photodegradation and wet heat degradation. The present invention has been found out to be a flame retardant polycarbonate resin composition in which the decrease in flame retardancy and the change in hue are suppressed.

  According to the present invention, 100 parts by weight of a resin component comprising (A) 90 to 90% by weight of an aromatic polycarbonate resin (component A) and 10 to 100% by weight of a (B) polycarbonate-polydiorganosiloxane copolymer resin (component B) (C) phosphazene compound (C component) 0.1 to 4 parts by weight, (D) inorganic filler (D component) 5 to 44 parts by weight, (E) fluorine-containing anti-dropping agent (E component) 0. A flame retardant reinforced polycarbonate resin composition is provided, which contains 01 to 1 part by weight, and the size of the siloxane domain derived from the component B is 8 to 19 nm.

Hereinafter, the details of the present invention will be described.
(A component: polycarbonate resin)
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting dihydric phenol with a carbonate precursor. As an example of the reaction method, an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, a ring opening polymerization method of a cyclic carbonate compound, and the like can be mentioned.

  Representative examples of dihydric phenols used herein are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Propane (generally 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) Fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like can be mentioned. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes. Among them, bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present invention, it is possible to use, as the component A, special polycarbonates produced using other dihydric phenols in addition to polycarbonates of bisphenol A type which is a general-purpose polycarbonate.
For example, as a part or all of a 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 change and morphological stability requirements 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 all dihydric phenol components constituting the polycarbonate.

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used with the bisphenol A type polycarbonate generally used. The production methods and properties of these special polycarbonates are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. ing.

  Among the various polycarbonates described above, those having the coefficient of water absorption and Tg (glass transition temperature) within the following ranges by adjusting the copolymerization composition etc. have good hydrolysis resistance of the polymer itself, and Since it is extremely excellent also in low curvature after molding, it is particularly suitable in the field where form stability is required. (1) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180 ° C., or (3) a Tg of 160 to 250 ° C. Polycarbonate preferably having a temperature of 170 to 230 ° C. and 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 rate of polycarbonate is a value obtained by measuring the moisture content after immersion for 24 hours in water at 23 ° C. according to ISO 62-1980 using a disk-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, diester of carbonic acid or haloformate, etc. are used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, etc. may be mentioned.

  In the production of an aromatic polycarbonate resin by interfacial polymerization of the dihydric phenol and the carbonate precursor, a catalyst, an end terminator, an antioxidant for preventing oxidation of dihydric phenol, etc., as necessary You may use The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid A carbonate resin, a copolymerized polycarbonate resin copolymerized with a difunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with such a difunctional carboxylic acid and a difunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used for the branched polycarbonate resin include phloroglucin, phloroglucide, 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- [4 Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-amino) Droxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and the like And the like, and among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and in particular 1,1 1,1-tris (4-hydroxyphenyl) ethane is preferred.

  The constituent unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably in a total of 100 mol% of the constituent unit derived from dihydric phenol and the constituent unit derived from such polyfunctional aromatic compound. 0.01 to 2 mol%, more preferably 0.05 to 1.2 mol%, particularly preferably 0.05 to 1.0 mol%.

In particular, in the case of the melt transesterification method, branched structural units may occur as a side reaction, and the amount of such branched structural units is also preferably 100% by total with the structural units derived from dihydric phenol. It is preferable that it is 0.001 to 2 mol%, more preferably 0.005 to 1.2 mol%, and particularly preferably 0.01 to 1.0 mol%. The proportion of such branched structures can be calculated by ¹ H-NMR measurement.

  The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Aliphatic difunctional carboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid Aliphatic dicarboxylic acids such as are preferably mentioned. An alicyclic diol is more preferable as the difunctional alcohol, and examples thereof include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.

Reaction methods such as an interfacial polymerization method, a melt transesterification method, a carbonate prepolymer solid phase transesterification method, and a ring opening polymerization method of a cyclic carbonate compound, which are methods for producing a polycarbonate resin of the present invention, include various literatures and patent publications Is a well-known method.
The viscosity average molecular weight (Mv) of the aromatic polycarbonate resin which is the component A is not particularly limited, but is preferably 1.0 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 3 × It is 10 ⁴ , more preferably 1.2 × 10 ^{4 to} 2.4 × 10 ⁴ .
An aromatic polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ can not obtain good mechanical properties. 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 because it is inferior in fluidity at the time of injection molding.

The viscosity-average molecular weight in the present invention, first, determined using an Ostwald viscometer specific viscosity is calculated by the following equation (eta _SP) from a solution prepared by dissolving polycarbonate resin 0.7g methylene chloride 100ml at 20 ° C.,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the second drop of methylene chloride, t is the second drop of the sample solution]
The viscosity average molecular weight Mv is calculated by the following formula from the determined specific viscosity (( _SP ).
η _SP /c=[η]+0.45×[η] ² c (where []] is the limiting viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  In addition, calculation of the viscosity average molecular weight of the resin component which consists of an aromatic polycarbonate resin of this invention, and a polycarbonate polydiorganosiloxane copolymer resin is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve solubles in the composition. The solubles are collected by celite filtration. The solvent in the resulting solution is then removed. The solid after removal of the solvent is sufficiently dried to obtain a solid of a component which is dissolved in methylene chloride. From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is determined in the same manner as above, and the viscosity average molecular weight Mv is calculated from the specific viscosity in the same manner as above.

(Component B: polycarbonate-polydiorganosiloxane copolymer resin)
The polycarbonate-polydiorganosiloxane copolymer resin used as component B in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and is a dihydric phenol represented by the following general formula (1) It is preferable that it is a copolymer resin prepared by copolymerizing a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[In the above general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and when there are plural groups, they may be the same or different And e and f each represent an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2) .

(In the above general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 18 selected from the group consisting of an aryl group of 3 to 14 atoms and an aralkyl group of 7 to ²⁰ carbon atoms. Alkyl group, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 3 carbon atoms To 14 aryl groups, aryloxy groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of groups, they may be the same or different, and g is an integer of 1 to 10 and h is an integer of 4 to 7)]

(In the above general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms And R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 110. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

  Examples of the dihydric phenol represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1. -Bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis ( 4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane , 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-biphenyl (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis ( 3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxy Diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyl diphenyl Ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) Phenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,1 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis { 2- (4-hydroxyphenyl) propyl} benzene is preferred, in particular 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4) Hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane (generally called bisphenol A) which is excellent in strength and has good durability is most preferable.

  As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the following compounds are suitably used.

  The hydroxyaryl-terminated polydiorganosiloxane (3) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of the polysiloxane chain having a polymerization degree of Among them, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferable, and in particular (2-allylphenol) -terminated polydimethylsiloxane, (2-methoxy-4) -Allylphenol) -terminated polydimethylsiloxanes are preferred. Moreover, in order to make a flame retardance and a wet heat characteristic compatible, the diorganosiloxane polymerization degree (p + q) of the hydroxyaryl terminal polydiorganosiloxane (3) is preferably less than 110. The diorganosiloxane polymerization degree (p + q) is more preferably 10 to 100, still more preferably 20 to 95, and particularly preferably 30 to 90. Below the lower limit of this preferred range, flame retardancy and impact resistance decrease due to photodegradation and wet heat degradation occur, and above the upper limit of such preferred range, the flame retardancy after photodegradation and wet heat degradation occurs It can not be exhibited stably.

It is preferable that polydiorganosiloxane content derived from B component in a resin composition is 0.3 to 8.0 weight%. The polydiorganosiloxane content is more preferably 0.7 to 7.0% by weight, still more preferably 1.0 to 4.0% by weight. If it is less than the lower limit of such a suitable range, flame retardancy may not be exhibited sufficiently, and if it exceeds the upper limit of such a suitable range, flame retardancy and weld strength may not be exhibited stably. The diorganosiloxane polymerization degree and the polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

In the method of the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (3) may be used, or two or more types may be used.
In addition, other comonomers other than the above-mentioned dihydric phenol (1) and hydroxyaryl-terminated polydiorganosiloxane (3) are contained in an amount of 10% by weight or less based on the total weight of the copolymer within the range not interfering with the method of the present invention. It can also be used together in the range.

In the method of the present invention, a mixed solution containing an oligomer having a terminal chloroformate group by the reaction of a dihydric phenol (1) and a carbonate-forming compound in a mixture of an organic solvent insoluble in water and an aqueous alkaline solution in advance. Prepare.
In order to form an oligomer of dihydric phenol (1), the entire amount of dihydric phenol (1) used in the method of the present invention may be oligomerized at once, or a part thereof may be used as a post addition monomer in the subsequent interface. You may add to polycondensation reaction as a reaction raw material. The post-addition monomer is added to accelerate the subsequent polycondensation reaction, and it is not necessary to add it if not necessary.

Although the system of this oligomer formation reaction is not specifically limited, Usually, the system performed in a solvent in the presence of an acid binder is preferable.
The use ratio of the carbonate ester forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonic acid ester forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ | adopted suitably.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures of these. Similarly to the above, the use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of an acid binder based on the number of moles of dihydric phenol (1) used for forming the oligomer (usually 1 mole is equivalent to 2 equivalents). .

  As the solvent, solvents inert to various reactions such as those used for producing a known polycarbonate may be used alone or as a mixed solvent. Representative examples include, for example, hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene, and the like. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

  The reaction pressure of the oligomer formation is not particularly limited and may be normal pressure, elevated pressure or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, it is desirable to be cooled with water or ice because it generates heat during the polymerization. The reaction time depends on other conditions and can not be generally defined, but is usually 0.2 to 10 hours. The pH range of the oligomerization reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

  In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (1) having a terminal chloroformate group in this way, the hydroxyaryl represented by the general formula (3) is stirred while the mixed solution is stirred. The terminal polydiorganosiloxane (3) is added at a rate of 0.01 molar equivalent / min or less based on the charged amount of dihydric phenol (1) to interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (3) and the oligomer. Polycarbonate-polydiorganosiloxane copolymer resin is obtained. Although the present invention is not limited by any theory, in the conventional method, in order to react phosgene to a mixture of BPA and hydroxyaryl-terminated polydiorganosiloxane monomer, reaction of BPA with hydroxyaryl-terminated polydiorganosiloxane monomer A long chain copolymer consisting of only one monomer is likely to be formed due to the sex difference. Furthermore, a structure in which hydroxyaryl-terminated polydiorganosiloxane monomers are linked via short-chain BPA oligomers is likely to be formed. On the other hand, since the process of the present invention can reduce the concentration of the hydroxyaryl-terminated polydiorganosiloxane monomer, it is considered that a structure in which the hydroxyaryl-terminated polydiorganosiloxane monomer is linked via short-chain BPA oligomers is difficult to form Be It is presumed that this results in a copolymer in which the dispersion of the polydiorganosiloxane domain size forms a small aggregation structure. When the addition rate of the hydroxyaryl-terminated polydiorganosiloxane (3) is faster than 0.01 molar equivalent / min, specifications of the size of the polydiorganosiloxane domain dispersed inside in the resulting molded article of polycarbonate-polydiorganosiloxane copolymer resin obtained Is not preferable because the dispersion exceeds 40% and the transparency is deteriorated. When the addition rate of the hydroxyaryl-terminated polydiorganosiloxane (3) is slower than 0.0001 molar equivalent / min, the content of the polydiorganosiloxane component of the resulting copolymer resin is reduced, and the molecular weight tends to vary, which is not preferable. . Accordingly, the lower limit of the addition rate of the hydroxyaryl-terminated polydiorganosiloxane (3) is substantially 0.0001 molar equivalent / min. Moreover, in order to improve uniform dispersibility, it is desirable to add the hydroxyaryl-terminated polydiorganosiloxane (3) in the form of a solution. It is desirable that the concentration of the solution be as thin as not to inhibit the reaction.

  In carrying out the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (3) to be used or a part of the dihydric phenol (1) as described above is added to this reaction step as a post-addition monomer, It is preferable to use 2 equivalents or more of the alkali relative to the total number of moles (generally 1 mole is equivalent to 2 equivalents) of the phenol (1) and the hydroxyaryl-terminated polydiorganosiloxane (3).

  The polycondensation by the interfacial polycondensation reaction of the dihydric phenol (1) oligomer with the hydroxyaryl-terminated polydiorganosiloxane (3) is carried out by vigorously stirring the above mixture. In such polymerization reactions, terminal terminators or molecular weight regulators are usually used. Examples of end terminators include compounds having a monovalent phenolic hydroxyl group, and in addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long chain alkylphenols and aliphatic carboxylic acids Chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like are exemplified. The amount thereof is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all the dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination is there. A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction. The reaction time of such polymerization reaction needs to be relatively long in order to improve the transparency. Preferably it is 30 minutes or more, More preferably, it is 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the above-mentioned dihydric phenol compound to give a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used for the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucide, 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- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and the like Trisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone Examples thereof include tetracarboxylic acids and their acid chlorides, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are exemplified. Particularly preferred is 1,1,1-tris (4-hydroxyphenyl) ethane. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. It is preferably 9 mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. The branched structure amount can be calculated by ¹ H-NMR measurement.

  The reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but it can usually be suitably carried out under normal pressure or about the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, it is desirable to be cooled with water or ice because it generates heat during the polymerization. The reaction time varies depending on other conditions such as the reaction temperature and can not be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of viscosity [η _SP / c].
The obtained reaction product (crude product) can be subjected to various post treatments such as known separation and purification methods, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purification degree).

The viscosity average molecular weight (Mv) of the polycarbonate-polydiorganosiloxane copolymer resin which is the component B is not particularly limited, but is preferably 1.0 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.1 × 10 4 ^{It is 4 to} 3 × 10 ⁴ , more preferably 1.2 × 10 ^{4 to} 2.4 × 10 ⁴ . A polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of less than 1 × 10 ⁴ can not obtain good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of more than 5 × 10 ⁴ is inferior in versatility because it is inferior in fluidity at the time of injection molding.

  The siloxane domain size derived from the polycarbonate-polydiorganosiloxane copolymer resin in the resin composition is 8 to 19 nm, preferably 8 to 18 nm, and more preferably 8 to 17 nm. Below the lower limit of this preferable range, impact resistance is not sufficiently exhibited, and above the upper limit, flame retardancy is not sufficiently exhibited.

The siloxane domain size can be measured by using transmission electron microscopy (TEM) to identify the siloxane domains in the resin composition. The siloxane domain in the TEM micrograph is clear, and analysis software can calculate the size of the siloxane domain in the resin component. The domain size in the present invention is an average domain size which means the number average of individual domain sizes.
The content of the component B is 10 to 100% by weight, preferably 15 to 90% by weight, and more preferably 20 to 80% by weight in 100% by weight of the resin component. If the content of the component B is less than 10% by weight, flame retardancy, moist heat characteristics and light resistance are not sufficiently exhibited.

(C ingredient: phosphazene compound)
The flame retardant reinforced polycarbonate resin composition of the present invention contains a phosphazene compound as component C. The phosphazene compound contains a phosphorus atom and a nitrogen atom in its molecule, whereby the flame retardant glass fiber reinforced polycarbonate resin composition is reduced in flame retardancy, impact strength due to light degradation and wet heat degradation, and reduced in flame retardancy, The effect of suppressing the deterioration of the hue can be provided. When a compound other than a phosphazene compound, for example, a phosphoric acid ester, a condensed phosphoric acid ester, or the like is used as the phosphorus-based flame retardant, the polycarbonate resin is plasticized to reduce heat resistance, and photodegradation and wet heat degradation The impact strength also deteriorates due to Moreover, the flame retardant effect can not be obtained with the additive amount described in the claims. The phosphazene compound is not particularly limited as long as it is a compound which does not contain a halogen atom and has a phosphazene structure in the molecule. The phosphazene structure referred to here represents a structure represented by the formula: -P (R2) = N- (wherein R2 is an organic group). The phosphazene compounds are represented by the general formulas (4) and (5).

（式中、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４は、水素、水酸基、アミノ基、またはハロゲン原子を含まない有機基を表す。また、ｎは３〜１０の整数を表す）。

(In the formula, X ₁ , X ₂ , X ₃ and X _{4 each} represent a hydrogen, a hydroxyl group, an amino group or an organic group not containing a halogen atom. N represents an integer of 3 to 10).

The formula (4), _(5), as the organic group containing no halogen atom represented by _{X 1, X 2, X 3} , X 4, for example, an alkoxy group, a phenyl group, an amino group, an allyl group Can be mentioned.
Among them, the phosphazene compound is preferably a cyclic phenoxy phosphazene represented by the general formula (6).

〔式中ｎは３〜２５の整数を示す。Ｐｈはフェニル基を示す。〕

Wherein n represents an integer of 3 to 25. Ph represents a phenyl group. ]

Commercially available phosphazene compounds include SPS-100, SPE-100, SPR-100, SA-100, SPB-100, SPB-100L (all from Otsuka Chemical Co., Ltd.), FP-100, FP And -110 (manufactured by Fushimi Pharmaceutical Co., Ltd.). In the present invention, it is acceptable to contain other components as long as the function of the phosphazene compound is not impaired.
The content of the component C is 0.1 to 4 parts by weight, preferably 0.5 to 2.9 parts by weight, and more preferably 1 to 2.0 parts by weight with respect to 100 parts by weight of the resin component. If the content of the component C is less than 0.1 parts by weight, the effect of flame retardancy can not be obtained, and if it exceeds 4 parts by weight, the heat resistance decreases.

(D ingredient: inorganic filler)
The resin composition of the present invention contains an inorganic filler as component D. As the inorganic filler, reinforcing fillers to be blended for the purpose of improving the rigidity and strength of the flame retardant resin composition, inorganic pigments to be blended for the purpose of coloring of the thermoplastic resin composition, and the like are typically exemplified. Be done. As a reinforcing filler, various glass fibers (chopped strands, milled fibers, flat cross section glass fibers, etc.), glass flakes, glass beads, glass balloons, carbon fibers, carbon flakes, carbon beads, talc, clay, kaolin, wollastonite, Mica, calcium carbonate, various inorganic whiskers, metal fibers, metal flakes, metal coated glass fibers, metal coated glass flakes, metal coated carbon fibers and the like can be mentioned. Among them, at least one selected from mica, talc, kaolin, wollastonite, glass fiber, carbon fiber, carbon flake, metal fiber, metal flake, metal coated glass fiber, metal coated glass flake, metal coated carbon fiber and glass flake At least one selected from glass fibers, carbon fibers, carbon flakes, metal fibers, metal flakes, metal coated glass fibers, metal coated glass flakes, metal coated carbon fibers and glass flakes from the viewpoint of moist heat properties . Glass fibers, carbon fibers and glass flakes are furthermore particularly preferred. On the other hand, titanium dioxide, zinc oxide, zinc sulfide, iron oxide and the like are exemplified as typical examples of the inorganic filler blended as a colorant, and titanium dioxide is most preferably used.

  The content of the component D is 5 to 44 parts by weight, preferably 8 to 40 parts by weight, and more preferably 10 to 35 parts by weight, per 100 parts by weight of the resin component. If the content of the component D is less than the lower limit, the mechanical strength and dimensional accuracy required as a mechanical component can not be obtained, and good heat resistance can not be obtained. If the upper limit is exceeded, the flame retardancy is deteriorated and the moldability is significantly impaired, which is not suitable for practical use.

(Component E: Fluorine-containing anti-dripping agent)
Examples of the fluorine-containing anti-dripping agent which is the component E of the present invention include fluorine-containing polymers having fibril-forming ability, and such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene-based copolymers). And ethylene / hexafluoropropylene copolymer, etc., partially fluorinated polymers as shown in U.S. 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.

  The molecular weight of the fibril-forming PTFE has an extremely high molecular weight, and tends to bond the PTFE to form a fiber by an external action such as shear force. The molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in number average molecular weight determined from the standard specific gravity. Such PTFE may be used in the form of an aqueous dispersion in addition to the solid form. It is also possible to use a PTFE mixture in the form of a mixture with other resins in order to improve the dispersibility in the resin and to obtain good flame retardancy and mechanical properties, as well as such fibril-forming PTFE. is there.

  As a commercial item of PTFE which has such fibril formation ability, Teflon (registered trademark) 6J of Mitsui-Dupont Fluorochemicals Co., Ltd., polyflon MPA FA500 and F-201L of Daikin Industries, Ltd., etc. can be mentioned. Commercially available products of the aqueous dispersion of PTFE include Fluon AD-1 and AD-936 manufactured by Asahi IC Eye Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui Dupont Floro Representative examples thereof include Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. and the like.

  As a mixed form of PTFE, (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and performing co-precipitation to obtain a co-agglomerated mixture (JP-A-60-258263, Method described in JP-A-63-154744, etc.), (2) Method of mixing aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957) (3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution, and simultaneously removing the respective media from the mixture (see, for example, JP-A 06-220210 and JP-A 08-188653). Method described), (4) Method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5 A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion, and thereafter obtaining a mixture (described in JP-A-11-29679 and the like) Method) can be used. As commercial products of these mixed forms of PTFE, "Metabrene A3750" (trade name) of Mitsubishi Rayon Co., Ltd., "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals, and "SN3307" manufactured by ShinePolymer And the like.

The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the PTFE mixture. If the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. The proportion of the component D indicates the net amount of the fluorine-containing anti-dropping agent, and in the case of the mixed form of PTFE, the net amount of PTFE.
The content of component E is 0.01 to 1 part by weight, preferably 0.05 to 0.8 parts by weight, and more preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of the resin component. . When the content of the component E is less than 0.01 parts by weight, a sufficient flame retarding auxiliary effect is not exhibited, and when it is more than 1 part by weight, it falls out of the category of non-halogen and has poor moist heat properties.

(F component: an olefin wax having a carboxyl group and / or an acid anhydride group thereof)
The resin composition of the present invention can contain, as component F, an olefin wax having a carboxyl group and / or an acid anhydride group thereof. Examples of olefin waxes include paraffin waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymers. Examples of polyethylene wax include polyethylene having a molecular weight of about 1,000 to 15,000. A polypropylene etc. are illustrated. The molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography).

  As a method of bonding a carboxyl group and / or an acid anhydride group to such an olefin wax, for example, (a) a monomer having a carboxyl group and / or an acid anhydride group and an α-olefin monomer And (b) a method of bonding or copolymerizing a compound or monomer having a carboxyl group and / or an acid anhydride group thereof to the above-mentioned olefin wax, or the like.

  In the method (a), a living polymerization method can also be employed in addition to radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible. The form of the copolymer can be used as a copolymer of various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer, in addition to the random copolymer. In the method (b), a radical generating agent such as peroxide or 2,3-dimethyl-2,3 diphenylbutane (generally called "dicumyl") is added to the olefin wax, if necessary, and the reaction is conducted at high temperature Alternatively, a method of copolymerizing can be employed. Such a method is to thermally generate reactive sites in an olefin wax, and to react compounds or monomers that react to such active points. As another method of generating an active point required for the reaction, irradiation of a radiation or an electron beam or application of an external force by a mechanochemical method may be mentioned. Furthermore, there may also be mentioned a method in which a monomer which generates an active point required for the reaction is copolymerized in advance in the olefin wax. The active site for the reaction includes unsaturated bond and peroxide bond, etc. Further, as a method of obtaining the active site, nitroxide-mediated radical polymerization represented by TEMPO can be mentioned.

Examples of the compound or monomer having a carboxyl group and / or an acid anhydride group thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, etc. Maleic acid is preferred.
More preferably, the carboxyl group and / or the acid anhydride group is preferably 0.05 to 10 meq / g of the olefin wax having the carboxyl group and / or the acid anhydride group as the F component of the present invention. It is an olefin wax having a carboxyl group and / or an acid anhydride group contained in the range of g, more preferably in the range of 0.1 to 6 meq / g, further preferably in the range of 0.5 to 4 meq / g. Furthermore, as for the molecular weight of the olefin wax which has a carboxyl group and / or its acid anhydride group, 1,000-10,000 are preferable.

A preferred embodiment of the F component includes a copolymer of an α-olefin and maleic anhydride, and the content ratio of the above-mentioned carboxyl group and / or acid anhydride group of the copolymer. And those satisfying the molecular weight are particularly preferred. 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 an alpha-olefin, the thing whose carbon number is 10-60 as an average value can be mentioned preferably. As the α-olefin, one having an average carbon number of 16 to 60, more preferably 25 to 55 can be mentioned more preferably.
The content of the F component is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 parts by weight, and still more preferably 0.1 to 0.6 per 100 parts by weight of the resin component. It is a weight part. If the content of the F component is less than 0.01 parts by weight, a resin composition having excellent impact strength may not be obtained, and if it exceeds 1 part by weight, flame retardancy may be impaired.

(G component: phosphorus stabilizer)
It is preferable to contain the phosphorus stabilizer which is G component of this invention, in order to obtain the flame-retardant resin composition which has a further favorable impact strength and thermal stability. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof.

  As a 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) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) 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, phenyl bisphenol A pentaerythritol diphosphite, And bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like.

  Furthermore, as another phosphite compound, one having a cyclic structure by reacting with a dihydric phenol 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 And 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

  As a phosphate compound, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monooroxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, preferably triphenyl phosphate and trimethyl phosphate.

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

As the phosphonate compound, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned.
The above-mentioned phosphorus stabilizers can be used alone or in combination of two or more.
The content of the G component is preferably 0.001 to 0.1 parts by weight, more preferably 0.002 to 0.07 parts by weight, and still more preferably 0.005 to 0.05 with respect to 100 parts by weight of the resin component. It is a weight part. If the amount of the phosphorus-based stabilizer is less than the above range, a good stabilization effect may not be obtained. If the amount is more than the above range, the physical properties of the composition may be deteriorated.

(H ingredient: UV absorber)
The resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention also has a good hue, such a hue can be maintained for a long time even in outdoor use by the incorporation of a UV absorber. In the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy -4-n-dodecyloxy bensophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone and the like.

  In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,3) 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-chlorobenzotriazole, 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- (2-hydroxy-5-tert-butylphenyl) benzotriazole) 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4) -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomers copolymerizable with the monomer 2-hydroxyphenyl-2H-benzotriazole skeleton such as copolyester of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomer copolymerizable with said monomer And the like.

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-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 It is illustrated. Furthermore, the phenyl group of the above exemplified compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl The compound which became a phenyl group is illustrated.

  In cyclic imino ester systems, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -4-one), and 2,2 '-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, in the case of cyanoacrylate type, 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 above-mentioned ultraviolet absorber takes such a structure of a monomer compound capable of radical polymerization, whereby such a UV-absorbing monomer and / or a light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate The ultraviolet absorber of the polymer type which copolymerized with monomers, such as, may be sufficient. 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.

Among the above, benzotriazole-based and hydroxyphenyltriazine-based ones are preferable in view of the ultraviolet light absorbing ability, and cyclic imino ester-based ones and cyanoacrylate-based ones are preferable in terms of heat resistance and hue. The UV absorbers may be used alone or in combination of two or more.
The content of the H component is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.8 parts by weight, and most preferably 0.05 to 0.6 based on 100 parts by weight of the resin component. It is a weight part.

(About other additives)
In the resin composition of the present invention, various stabilizers, mold release agents, and colorants for stabilizing molecular weight reduction and hue during molding can be used.

(I) Stabilizer Various well-known stabilizers other than G component can be mix | blended with the resin composition of this invention. As a stabilizer, a hindered phenol type stabilizer etc. are mentioned.

(I-1) Hindered Phenol-Based Stabilizer The resin composition of the present invention further contains a hindered phenol-based stabilizer such as, for example, the hue deterioration during molding and processing, and the hue deterioration during long-term use, etc. The effect is further exhibited. Examples of hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl 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-hydroxybenzyl phosphonate 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'-butylidene bis (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 Bis- [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′-hexamethylene bis- (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-tris2 [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 above hindered phenolic stabilizers can be used alone or in combination of two or more.

  The content of the hindered phenol-based stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, still more preferably 0.005 to 0 with respect to 100 parts by weight of the resin component. .3 parts by weight. If the amount of hindered phenol-based stabilizer is less than the above range, it is difficult to obtain a good stabilization effect. If the amount is more than the above range, the physical properties of the composition may be lowered.

(I-2) Other Thermal Stabilizers In the resin composition of the present invention, other thermal stabilizers other than phosphorus stabilizers and hindered phenol stabilizers can be blended. Such other heat stabilizers are preferably used in combination with any of these stabilizers, particularly preferably 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 The details of are preferably exemplified in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Furthermore, stabilizers obtained by mixing the compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. Such premixed stabilizers can also be utilized in the present invention. The content 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 resin component.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. It is illustrated. Such stabilizers are particularly effective when the resin composition is applied to rotomolding. The amount of the sulfur-containing stabilizer blended 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 the resin component.

(Ii) Release Agent The resin composition of the present invention can contain a release agent. As the releasing agent, for example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax other than F component (polyethylene wax, 1-alkene polymer, etc.), silicone compound, fluorine compound (polyfluoroalkyl ether, etc.) Fluorine oil etc.), paraffin wax, beeswax etc. are illustrated.

  Among such release agents, saturated fatty acid esters, in particular, partial esters and / or full esters of higher fatty acids and polyhydric alcohols are preferred. Particularly preferred is full ester. Here, the higher fatty acids refer to aliphatic carboxylic acids having 10 to 32 carbon atoms, and specific examples thereof include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid) ), Saturated aliphatic carboxylic acids such as heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, hexacosanoic acid, and palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenic acid, eicosapentaene Mention may be made of unsaturated aliphatic carboxylic acids such as acids and cetoleic acid. Among these, as an aliphatic carboxylic acid, a C10-C22 thing is preferable and a C14-C20 thing is more preferable. In particular, saturated aliphatic carboxylic acids having 14 to 20 carbon atoms, particularly stearic acid and palmitic acid, are preferred. Aliphatic carboxylic acids, such as stearic acid, are often mixtures containing other carboxylic acid components which usually have different numbers of carbon atoms. Also in the saturated fatty acid ester, an ester compound obtained from stearic acid or palmitic acid which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components is preferably used.

  On the other hand, as a polyhydric alcohol which is a structural unit of a saturated fatty acid ester, a C3-C32 thing is more preferable. Specific examples of such polyhydric alcohols include glycerin, diglycerin, polyglycerin (such as decaglycerin etc.), pentaerythritol, dipentaerythritol, diethylene glycol and propylene glycol.

The acid value of the saturated fatty acid ester of the present invention is preferably 20 or less (can be substantially 0), and the hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Furthermore, the iodine value is preferably 10 or less (can be substantially 0). These properties can be determined by the method defined in JIS K 0070.
The content of the releasing agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 parts by weight, still more preferably 0.05 to 0.5 based on 100 parts by weight of the resin component. It is a weight part. In such a range, the resin composition has both good flame retardancy and impact characteristics.

(Iii) Dyeing and Pigmenting The resin composition of the present invention can further provide a molded article which contains various dyeings and pigments other than the D component and expresses various design properties. Dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Dioxazine dyes, isoindolinone dyes, phthalocyanine dyes and the like can be mentioned. Furthermore, the resin composition of this invention can also mix | blend a metallic pigment and can also obtain a better metallic color. Further, by blending a fluorescent whitening agent and a fluorescent dye that emits light other than that, it is possible to impart a better design effect utilizing the luminescent color.

Examples of the fluorescent dye (including a fluorescent whitening agent) used in the present invention include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, xanthene fluorescent dyes And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among them, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes which are excellent in heat resistance and which cause little deterioration during molding of a resin are preferable.
The content of the dye and pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the resin component.

(Iv) Compound having heat ray absorbing ability The resin composition of the present invention can contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, ATO, ITO, iridium oxide and ruthenium oxide, metal oxide-based near-infrared absorbers such as immonium oxide, metal borides such as lanthanum boride, cerium boride and tungsten boride Preferred examples thereof include various metal compounds excellent in near-infrared absorptivity, such as tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene and the like, with preference given to carbon black and graphite. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and more preferably 0.001 to 0. 100 parts by weight of the resin component. 07 parts by weight is more preferred. The content of the metal oxide near infrared absorber, the metal boride near infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention, 0.5 The range of -100 ppm is more preferable.

(V) Light Diffusing Agent A light diffusing agent can be blended into the resin composition of the present invention to impart a light diffusing effect. Examples of such light diffusing agents include polymer particles, inorganic particles having a low refractive index such as calcium carbonate, and composites of these. Such polymer particles are particles already known as a light diffusing agent for thermoplastic resins. More preferably, acrylic crosslinked particles having a particle diameter of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane are exemplified. Examples of the shape of the light diffusing agent include a sphere, a disc, a pillar, and an amorphous. Such spheres need not be perfect spheres, but include those that are deformed, and such pillars include cubes. The preferred light diffusing agent is spherical, and its particle size is preferably as uniform as possible. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the resin component. . In addition, 2 or more types of light diffusing agents can be used together.

(Vi) White pigment for high light reflection The resin composition of the present invention can be blended with a white pigment for high light reflection to give a light reflection effect. As such a white pigment, titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferable. The content of the white light reflecting pigment is preferably 3 to 30 parts by weight, and more preferably 8 to 25 parts by weight, based on 100 parts by weight of the resin component. Incidentally, two or more kinds of white pigments for high light reflection can be used in combination.

(Vii) Antistatic Agent The resin composition of the present invention may be required to have further antistatic performance, and in such a case, it is preferable to include an antistatic agent. Such antistatic agents include, for example, (1) arylsulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and phosphonium tetrafluoroborate salts And boric acid phosphonium salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, still more preferably 1 based on 100 parts by weight of the resin component. The range is from 5 to 3 parts by weight.

  Examples of the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonic acid alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably 0 based on 100 parts by weight of the resin component. .005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium and rubidium are preferred.

  Examples of the antistatic agent include (3) ammonium ammonium sulfonates and organic sulfonic acid ammonium salts such as ammonium arylsulfonic acid salts. The appropriate amount of the ammonium salt is 0.05 parts by weight or less based on 100 parts by weight of the components A, B and C in total. Examples of the antistatic agent include polymers containing a poly (oxyalkylene) glycol component such as (4) polyether ester amide as its component. The amount of the polymer is 5 parts by weight or less based on 100 parts by weight of the resin component.

(Viii) Other Additives In the resin composition of the present invention, thermoplastic resins other than Component A, Component B, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and A photochromic agent etc. can be mix | blended. Such other resins include, for example, polyamide resin, polyimide resin, polyether imide resin, polystyrene resin, MS resin (copolymer resin composed mainly of methyl methacrylate and styrene), polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene Sulfide resin, Polysulfone resin, Polyolefin resin such as polyethylene and polypropylene, Polystyrene resin, Acrylonitrile / Styrene copolymer (AS resin), Polymethacrylate resin, Phenolic resin, Epoxy resin, Cyclic polyolefin resin, Polylactic acid resin, Polycaprolactone resin, And resins such as thermoplastic fluoroplastics (for example, represented by polyvinylidene fluoride resin).

(Production of resin composition)
Any method is adopted to produce the resin composition of the present invention.
For example, the components A, B, C, D, E and optionally F, G, H, and other additives may be added to the V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. After sufficient mixing using a mixing means, such a pre-mixture is granulated by an extrusion granulator or briquetting machine, if necessary, and then a melt kneader represented by a vented twin-screw extruder. The method of melt-kneading and then pelletizing with a pelletizer is mentioned.
Besides, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or after pre-mixing a part of each component, supply it to a melt kneader independently of the remaining components. And the like. As a method of pre-mixing a part of each component, for example, there is a method of pre-mixing components other than the component A in advance, and then mixing or directly feeding the component A to the extruder.

  As a method of pre-mixing, for example, in the case of including one having a form of powder as component A, a masterbatch of additives diluted with powder is manufactured by blending a part of the powder and an additive to be compounded, There is a method of using a master batch. As a method of pre-mixing, for example, in the case of including one having a form of powder as component A, a masterbatch of additives diluted with powder is manufactured by blending a part of the powder and an additive to be compounded, There is a method of using a master batch. Furthermore, the method of supplying C component, D component, and arbitrary components independently from the middle of a melt extruder, etc. are mentioned. In addition, when there is a liquid thing as a component to mix | blend, what is called a liquid pouring apparatus or a liquid addition apparatus can be used for the supply to a melting extruder.

As the extruder, one having a vent capable of degassing the water in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed to efficiently discharge generated water and volatile gases out of the extruder from the vent. It is also possible to remove foreign matter from the resin composition by installing a screen for removing foreign matter mixed in the extruded material in the zone in front of the extruder die. Such screens may include wire mesh, screen changers, sintered metal plates (such as disc filters) and the like.
As the melt-kneader, in addition to a twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, a multi-screw extruder having three or more shafts, etc. can be mentioned.

  The resin extruded as described above is directly cut and pelletized or, after forming the strands, such strands are cut and pelletized with a pelletizer. When it is necessary to reduce the influence of external dust and the like at the time of pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, narrowing of the shape distribution of pellets, reduction of miscut substances, and reduction of fine powder generated during transportation or transportation are carried out using various methods already proposed in polycarbonate resins for optical disks. And air bubbles (vacuum air bubbles) generated inside the strands and pellets can be appropriately reduced. These formulations make it possible to achieve high cycle of molding and reduction of the rate of occurrence of defects such as silver. Moreover, the shape of a pellet can take a general shape, such as a cylinder, a prism, and a spherical shape, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, 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.

  The flame retardant polycarbonate resin composition of the present invention can be manufactured into various products by injection molding of the pellets produced as described above to obtain molded articles. In such injection molding, in addition to the usual molding method, 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 Mold molding, rapid heating cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding can be mentioned. In addition, either cold runner method or hot runner method can be selected.

  The flame retardant polycarbonate resin composition of the present invention can also be used in the form of various profile extrusions, sheets, films and the like by extrusion molding. Further, an inflation method, a calendar method, a casting method and the like can be used to form a sheet and a film. Furthermore, it is also possible to shape it as a heat-shrinkable tube by subjecting it to a specific drawing operation. Further, the flame retardant reinforced polycarbonate resin composition of the present invention can be formed into a molded article by rotational molding, blow molding or the like.

  As a result, a flame retardant reinforced polycarbonate resin composition and a molded article are provided which are excellent in flame retardancy, impact strength, heat resistance, and further, are reduced in impact strength due to light deterioration and wet heat deterioration, and in flame retardancy. That is, according to the present invention, a resin component 100 comprising (A) 90 to 90% by weight of an aromatic polycarbonate resin (component A) and 10 to 100% by weight of a (B) polycarbonate-polydiorganosiloxane copolymer resin (component B) 0.1 to 4 parts by weight of (C) phosphazene compound (C component), 5 to 44 parts by weight of (D) inorganic filler (D component) with respect to parts by weight, (E) fluorine-containing anti-dropping agent (E component) A molded article obtained by melt-molding a flame retardant reinforced polycarbonate resin composition comprising 0.01 to 1 part by weight and having a siloxane domain size derived from component B of 8 to 19 nm is provided.

  Molded articles made of the resin composition of the present invention include various electronic / electrical device parts, camera parts, OA equipment parts, precision machine parts, mechanical parts, vehicle parts, other agricultural materials, transport containers, play equipment and sundries. It is useful for applications, particularly housings for computers, notebooks, ultrabooks, tablets, and mobile phones, and its industrial effects are outstanding. Furthermore, it is possible to perform various surface treatments on a molded article made of the resin composition of the present invention. With surface treatment here, a new layer is formed on the surface layer of resin moldings such as deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. It is formed, and the method used for normal polycarbonate resin can be applied. Specific examples of the surface treatment include various surface treatments such as a hard coat, a water and oil repellent coat, an ultraviolet ray absorbing coat, an infrared ray absorbing coat, and metalizing (e.g. vapor deposition). Hard coat is a particularly preferred and required surface treatment. In addition, since the resin composition of the present invention has improved metal adhesion, deposition and plating applications are also preferred. Thus, the molded article provided with the metal layer can be used for electromagnetic wave shielding parts, conductive parts, antenna parts and the like. Such parts are particularly preferably in the form of sheets and films.

  The flame retardant reinforced polycarbonate resin composition of the present invention is excellent in flame retardancy, impact strength and heat resistance, and further, the reduction in impact strength and flame retardancy due to light deterioration and wet heat deterioration is suppressed, so As described above, the present invention is useful in a wide range of fields such as buildings, building materials, agricultural materials, marine materials, vehicles, electric and electronic devices, machines, and various other fields, and particularly useful for resin casings for outdoor installation. Therefore, the industrial effects exerted by the present invention are extremely large.

  The form of the present invention which the present inventor considers to be the best is an aggregation of the preferred ranges of the above-mentioned respective requirements, and for example, representative examples thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

(1) Evaluation of flame retardant reinforced polycarbonate resin composition (i) Heat resistance (deflection temperature under load)
It measured based on ISO75-1 and 2 of ISO standard. The test piece was molded at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). The deflection temperature under load was measured at a load of 1.80 MPa using the prepared 4 mm thick test piece. The deflection temperature under load needs to be 120 ° C. or more.

(Ii) Flexural modulus Measured in accordance with ISO 178 (measurement condition 23 ° C.). The test piece was molded at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). The flexural modulus needs to be 3 GPa or more.

(Iii) Dupont Impact Strength A weight was dropped from the upper part to a firing core placed on a plate-like molded product, impact was applied to the plate-like molded product, and a fracture state was visually observed. The thickness of the plate-like molded product is 3 mm, the tip shape of the striker is hemispherical with a radius of 12.7 mm, and the striker is movable to such an extent that its core axis is not deviated, and vertically. The product was placed on a plate-like molded product while being restrained by a jig to an extent. The weight was 2,000 g and the drop height was 1 m. The case where the hole was not opened in the molded product was evaluated as ○, the case where the micro crack occurred was evaluated as Δ, and the case where the hole was completely opened was evaluated as x. The plate-like molded article was molded at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.).

(Iv) Flame retardancy In accordance with the UL94 standard, the UL94 rank was evaluated at a thickness of 0.8 mm. The test piece was molded at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). In addition, when judgment can not satisfy | fill any reference | standard of V-0, V-1, and V-2, suppose that it shows as "not." It is important not to drip during the combustion test, and in the UL94 rank, V-1 or V-0 is desirable.

(V) Light resistance Dupont impact strength and flame retardancy after implementation of ultraviolet irradiation under the following conditions were measured in the same manner as in (iii) and (iv) above.
(Xenon arc irradiation condition)
Equipment used: Atlas Ci 4000 (made by Toyo Seiki Seisakusho)
Irradiance: 0.35 W / m ² (at 340 nm)
Black panel temperature: 63 ° C
Humidity: 50% RH
Test time: 500 hours Filter: (Outer) Boro Silicate, (Inner) Boro Silicate

(Vi) Moisture-and-moisture resistance Dupont impact strength and flame retardancy after carrying out the moist heat treatment under the following conditions were measured by the same methods as the above (iii) and (iv).
(Wet heat treatment condition)
Equipment used: PR-3KP (manufactured by ESPEC)
Temperature: 75 ° C
Humidity: 85% RH
Test time: 1,000 hours

(Vii) Siloxane domain size Three-step plate (total size is 90 mm × 50 mm, thickness up to 20 mm in the longitudinal direction is 3 mm, thickness of 20 to 65 mm is 2 mm, thickness of 65 to 90 mm The flow of resin with a microtome (EMCA UC6 manufactured by Leica Microsystems) at a cross point of 0.5 mm at the intersection of 5 mm from the end and 5 mm from the side in a 1.0 mm thick portion of a 1 mm stepped plate) Ultra-thin sections were prepared by cutting perpendicular to the direction, and photographed with a transmission electron microscope (TENAI G2 manufactured by FEI, acceleration voltage 120 kv). Next, the average siloxane domain size was calculated from 200 siloxane domains in the photographed image using image processing software (Nexus New Qube). The three-stage plate was molded at a cylinder temperature of 280 ° C. and a mold temperature of 70 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.).

[Examples 1 to 16, Comparative Examples 1 to 10]
An aromatic polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, a phosphazene compound, an inorganic filler, a fluorine-containing antidropping agent and various additives are mixed in respective blend amounts described in Tables 1 and 2 in a blender, and then bent. The mixture was melt-kneaded using a twin screw extruder to obtain pellets. The various additives to be used were preliminarily mixed with a polycarbonate resin in advance with a concentration of 10 to 100 times that of the compounding amount as a standard, and then overall mixing was performed by a blender. The vent type twin-screw extruder manufactured by Japan Steel Works, Ltd .: TEX-30XSST (full mesh, co-rotation, double thread screw) was used. The extrusion conditions are: discharge amount 20 kg / h, screw rotation speed 150 rpm, vent vacuum 3 kPa, and extrusion temperature 280 ° C. from the first supply port to the second supply port and 290 ° C. from the second supply port to the die portion did. The reinforcing filler was fed from the second feed port using the side feeder of the extruder, and the remaining polycarbonate resin and additives were fed to the extruder from the first feed port. Here, the first supply port is the supply port farthest from the die, and the second supply port is the supply port located between the die of the extruder and the first supply port. The obtained pellets were dried at 120 ° C. for 5 hours in a hot air circulating drier, and then an injection molding machine was used to form a test piece for evaluation. The evaluation results are shown in Tables 1 and 2.

Each component of the symbol notation in Tables 1 and 2 is as follows.
(A component)
A-1: aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 19,800 prepared from bisphenol A and phosgene according to a conventional method, manufactured by Teijin Limited Panlite L-1225WX]
(B component)
B-1: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 37)
B-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 8.4%, PDMS polymerization degree 37)
B-3: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 90)
B-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 8)
B-5: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS amount 4.2%, PDMS polymerization degree 150)
(C ingredient)
C-1: Cyclic phenoxy phosphazene (manufactured by Fushimi Pharmaceutical Co., Ltd .: FP-110 (trade name))
C-2: Crosslinked phenoxy phosphazene (Otsuka Chemical Co., Ltd. SPS-100 (trade name))
(D component)
D-1: Circular cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CS-3PE-455FB, long diameter 13 μm, cut length 3 mm, aminosilane surface treatment and urethane type sizing agent)
D-2: Flat cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG 3PA-830, long diameter 28 μm, short diameter 7 μm, cut length 3 mm, epoxy based sizing agent)
D-3: Carbon fiber (manufactured by Toho Tenax Co., Ltd .: HT C422 6 mm, cut length 6 mm, urethane type sizing agent)
D-4: Glass flakes (manufactured by Nippon Sheet Glass Co., Ltd .: Freca REFG-301, median average particle diameter 140 μm, thickness 5 μm, epoxy-based sizing agent by standard sieving method)
(E ingredient)
E-1: polytetrafluoroethylene having a fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA 500)
(F ingredient)
F-1: Acid-modified olefin wax which is a copolymer of maleic anhydride and α-olefin (Mitsubishi Chemical Corporation: Diacarna DC 30 M)
(G component)
G-1: Phosphorus stabilizer (made by Daihachi Chemical Industry Co., Ltd .: TMP trimethyl phosphate)
(H component)
H-1: Benzotriazole-based ultraviolet absorber (manufactured by Chemi-Pol Chemical Industries, Ltd .: Chemisorb 79)
(Other ingredients; phosphorus flame retardants)
I-1: resorcinol bis (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.):
PX-200 (trade name))

Claims (9)

  (C) 100 parts by weight of a resin component consisting of (A) 90 to 90% by weight of the aromatic polycarbonate resin (component A) and 10 to 100% by weight of the (B) polycarbonate-polydiorganosiloxane copolymer resin (component B) 0.1 to 4 parts by weight of phosphazene compound (component C), 5 to 44 parts by weight of (D) inorganic filler (component D), 0.01 to 1 parts by weight of (E) fluorine-containing antidrop agent (component E) A flame retardant reinforced polycarbonate resin composition comprising the B component-derived siloxane domain size of 8 to 19 nm.   The flame retardant reinforced polycarbonate resin composition according to claim 1, wherein the polydiorganosiloxane content derived from the component B in the resin composition is 0.3 to 8.0% by weight. The flame retardant reinforced polycarbonate resin composition according to claim 1 or 2 , wherein the content of the component C is 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the resin component. The flame retardant reinforced polycarbonate resin composition according to any one of claims 1 to 3 , wherein the D component is at least one selected from the group consisting of glass fibers, glass flakes and carbon fibers. The resin composition according to any one of claims 1 to 4 , comprising 0.01 to 1 part by weight of an olefin wax (component F) having (F) a carboxyl group and / or an acid anhydride group thereof per 100 parts by weight of the resin component. The flame retardant reinforced polycarbonate resin composition as described in 4. The flame retardant reinforced polycarbonate resin according to any one of claims 1 to 5 , wherein the (G) phosphorus-based stabilizer (G component) is contained in an amount of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the resin component. Composition. The flame retardant reinforced polycarbonate resin composition according to any one of claims 1 to 6 , which comprises 0.01 to 1 part by weight of (H) an ultraviolet absorber (H component) with respect to 100 parts by weight of the resin component. A molded article comprising the flame retardant reinforced polycarbonate resin composition according to any one of claims 1 to 7 . A resin case for outdoor installation comprising the flame retardant reinforced polycarbonate resin composition according to any one of claims 1 to 7 .