JP6133644B2 - Flame retardant light diffusing polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to a flame retardant light diffusing polycarbonate resin composition excellent in flame retardant properties while maintaining high light diffusibility even in a thin wall, and a molded article comprising the same.

  Disperse organic and inorganic light diffusing agents in transparent resins such as aromatic polycarbonate resin, acrylic resin, and styrene resin for applications that require light diffusibility such as various lighting covers, display covers, automobile meters, and various nameplates. The material used is widely used. Among such transparent resins, aromatic polycarbonate resins are particularly widely used as resins having excellent mechanical properties, heat resistance, weather resistance, and high light transmittance. Examples of the light diffusing agent include organic particles having a crosslinked structure, and more specifically, crosslinked acrylic particles, crosslinked silicone particles, and crosslinked styrene particles. Further, inorganic particles such as inorganic particles such as calcium carbonate, barium sulfate, aluminum hydroxide, silicon dioxide, titanium oxide, and calcium fluoride, or short glass fibers can be used. In particular, organic particles are excellent in surface smoothness of molded products as compared with inorganic particles and can achieve a high appearance of molded products, and thus can be applied to a wide range of applications.

  In these applications, in recent years, flaming at the time of a fire in a resin lighting cover promotes the spread of fire, and light diffusing polycarbonate resin also has flame retardancy of V-0 in UL Standard (US Underwriters Laboratory Standard) -94. Is starting to be requested. A flame retardant polycarbonate resin composition in which an organic metal salt compound and polytetrafluoroethylene having a fibril-forming ability as an anti-drip agent are added to an aromatic polycarbonate resin is known (Patent Document 1). It has also been reported that a light diffusing resin composition imparts flame retardancy with a similar flame retardant composition (Patent Documents 2 and 3). All of them achieve flame retardancy by adding a substantial amount of polytetrafluoroethylene having fibril-forming ability more than the organometallic salt compound.

  However, in the trend of recent miniaturization of optical components and the provision of high designs, lighting covers are also required to be thinner. As a result, higher levels of light diffusibility, thinner flame retardancy, The fluidity at the time of molding is required, and the conventional techniques are insufficient. In general, as the molded product becomes thinner, dripping of the resin at the time of combustion is more likely to occur. Therefore, more antidrip agent such as polytetrafluoroethylene needs to be added. However, when the amount of polytetrafluoroethylene added increases, not only the transmittance decreases but also the appearance deteriorates due to the re-aggregation of polytetrafluoroethylene, and the molding processability also deteriorates. It is not preferable. On the other hand, Patent Document 4 reports a flame retardant light diffusing polycarbonate resin composition comprising an aromatic polycarbonate having a branched structure, a silicone flame retardant having a specific structure, an organometallic salt compound and a light diffusing agent. However, further improvements are required for light diffusibility and flame retardancy.

Japanese Patent No. 4387306 JP 2006-143949 A JP 2010-280846 A JP 2011-116839 A

  An object of the present invention is to provide a flame retardant light diffusing polycarbonate resin composition having excellent flame retardant properties while maintaining high light diffusibility even in a thin wall.

  As a result of intensive research aimed at achieving the above object, the present inventors have made a flame-retardant light-diffusing polycarbonate comprising an aromatic polycarbonate resin, an organometallic salt compound, polytetrafluoroethylene having a fibril-forming ability, and a light diffusing agent. In the resin composition, it was found that by adding more organometallic salt compound than polytetrafluoroethylene, high light diffusibility and flame retardancy can be obtained even in a thin wall, and the present invention has been achieved.

That is, according to the present invention, (1) (A) aromatic polycarbonate resin (component A) 100 parts by weight, (B) organometallic salt compound (component B) 0.05 to 1.0 parts by weight, (C ) Flame retardant light diffusibility containing 0.001 to 0.08 part by weight of polytetrafluoroethylene (component C) having fibril forming ability and 0.005 to 6.0 parts by weight of (D) light diffusing agent (component D) There is provided a flame retardant light diffusing polycarbonate resin composition, which is a polycarbonate resin composition, wherein the B component content is higher than the C component content.
One of the more preferable embodiments of the present invention is as described in the above constitution (1), wherein (2) the A component is an aromatic polycarbonate resin having a branched structure with a branching rate of 0.3 to 1.6 mol%. It is a flame retardant light diffusing polycarbonate resin composition.
One of the more preferred embodiments of the present invention is the above-mentioned constitution (1) or (3) wherein the component (A) is an aromatic polycarbonate resin having a branched structure with a branching rate of 0.7 to 1.6 mol% The flame-retardant light diffusing polycarbonate resin composition according to (2).
One of the more preferable embodiments of the present invention is that (4) the component B is an alkali (earth) metal salt of a perfluoroalkyl sulfonate, an alkali (earth) metal salt of an aromatic sulfonate, and an alkali of an aromatic imide ( The flame retardant light diffusion according to any one of the above constitutions (1) to (3), wherein the flame retardant light diffusion is one or more organic alkali (earth) metal salts selected from the group consisting of (earth) metal salts It is a conductive polycarbonate resin composition.
One of the more preferable embodiments of the present invention is (5) the flame retardant light diffusibility according to any one of the above constitutions (1) to (4), wherein the C component is branched polytetrafluoroethylene. It is a polycarbonate resin composition.
One of the more preferable embodiments of the present invention is (6) the flame-retardant light diffusing polycarbonate resin composition according to any one of the above constitutions (1) to (5), wherein the D component is polymer fine particles. .
One of the more preferable aspects of the present invention is (7) the above-mentioned constitution comprising 0.01 to 3 parts by weight of an ultraviolet absorber (E component) per 100 parts by weight of component A ( It is a flame retardant light diffusing polycarbonate resin composition according to any one of 1) to (6).
One of the more preferable embodiments of the present invention is characterized in that (F) fluorescent whitening agent (F component) is contained in an amount of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of component A. It is a flame retardant light diffusing polycarbonate resin composition in any one of said structure (1)-(7).
One of the more preferable embodiments of the present invention is (9) The difficulty according to any one of the above constitutions (1) to (8), wherein the portion where the thickness of the molded product is 1.2 mm or less is 10% or more of the whole. It is an injection-molded product molded from a flame diffusing polycarbonate resin composition.
One of the more preferable aspects of the present invention is (10) The difficulty according to any one of the above constitutions (1) to (8), wherein the portion where the thickness of the molded product is 1.2 mm or less is 10% or more of the whole. It is an extrusion-molded product molded from a light diffusing polycarbonate resin composition.

Hereinafter, the present invention will be specifically described.
<A component: aromatic polycarbonate resin>
The aromatic polycarbonate resin used as the component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. It is obtained by polymerizing by an exchange method or polymerized by a ring-opening polymerization method of a cyclic carbonate compound. As a dihydroxy component used here, what is normally used as a dihydroxy component of an aromatic polycarbonate should just be used. Bisphenols are preferred as the main component of the dihydroxy component, but aliphatic diols can also be partly used as long as they do not impair the spirit of the present invention. Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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-bis (4-hydroxypheny) ) 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′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-sulfoni Diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyl Diphenyl 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) cyclohexane, 1,3-bis (4-hydro Cyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-Hydroxyphenyl) -5,7-dimethyladamantane etc. and the following general formula [1]

(In the above general formula [1], R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl having 6 to 15 carbon atoms. A substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, and a substituted or unsubstituted aralkyloxy group having 7 to 15 carbon atoms. , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. And a and b are natural numbers of 0 or 1 to 4, c + d is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples include bisphenol compounds It is.

  Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4′-bis (2- Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxy) Ethoxy) -3,3′-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2,2-bis {3-tert-butyl-4- (2-hydroxy) Ethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2 -Hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2- Bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxyethyl) Xyl) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane, 9,9-bis {(2-hydroxy) Ethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis { (2-hydroxyethoxy) phenyl} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether Ter, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D-sorbitol (Isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol Isoidide), and the like.

  Among these, aromatic bisphenols are preferable, and 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'-sulfonyl Diphenol, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, particularly 2,2-bis 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the above general formula [ 2] is preferable. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  The aromatic polycarbonate resin used as the component A of the present invention may be a branched polycarbonate resin using a branching agent in combination with the dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred. The branching ratio of the branched polycarbonate resin is preferably 0.3 to 1.6 mol%, more preferably 0.7 to 1.6 mol%, particularly preferably 0.7 to 1.5 mol%, and most preferably 0.00. 7 to 1.1 mol%.

  These aromatic polycarbonate resins are produced by a reaction means known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight adjustment, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [2] to [4].

[In the formula, A is an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, and r is 0. -5, preferably an integer of 0-1. ]

[Wherein, n is an integer having 1 to 50 carbon atoms. ]

[Wherein, W is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; Represents a valent aliphatic hydrocarbon group, and n is an integer of 1 to 50. ]

  Specific examples of the monofunctional phenols represented by the general formula [2] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [3] to [4] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula [3] preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. Further, as the substituted phenols of the above general formula [4], compounds in which W is —R—CO—O— and R is a single bond are preferable, and those in which n is 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [2] are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. These monofunctional phenolic terminal terminators are desirably introduced at the terminal at least 5 mol%, preferably at least 10 mol%, based on all the terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

The aromatic polycarbonate resin used as the component A of the present invention is a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, within the range not impairing the gist of the present invention. May be.
The viscosity average molecular weight of the aromatic polycarbonate resin used as the component A of the present invention is preferably in the range of 12,000 to 50,000, more preferably 12,000 to 30,000, and 12,000 to 25,000. A range is even more preferred, with a range of 15,000 to 25,000 being most preferred.

If the molecular weight exceeds 50,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 12,000, there may be a problem in mechanical strength. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following formula.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The polycarbonate resin used as the component A of the present invention has a total Cl (chlorine) amount in the resin of preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content in the polycarbonate resin exceeds 200 ppm, the hue and thermal stability deteriorate, which is not preferable.

<B component: organometallic salt compound>
Examples of the organometallic salt compound used as the component B of the present invention include alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) of aromatic imides. ) One or more organic alkali (earth) metal salts selected from the group consisting of metal salts are preferably used. (Here, the notation of alkali (earth) metal salt is used in the meaning including both alkali metal salt and alkaline earth metal salt.)
Content of B component is 0.05-1.0 weight part with respect to 100 weight part of A component, Preferably it is 0.05-0.5 weight part, More preferably, it is 0.1-0.5 weight. Part, more preferably 0.15 to 0.5 part by weight. When the content is less than 0.05, sufficient flame retardancy cannot be obtained, and when it exceeds 1.0 part by weight, not only sufficient flame retardancy is not obtained, but also sufficient mechanical properties cannot be obtained.

  The metal constituting the organic alkali (earth) metal salt is an alkali metal or an alkaline earth metal, and more preferably an alkali metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, and lithium, sodium, and potassium are particularly preferable.

  Preferred examples of the alkali (earth) metal salt of perfluoroalkyl sulfonate include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluoropropane sulfonate, perfluorobutane sulfonate, perfluoromethyl. Examples include butanesulfonate, perfluorohexanesulfonate, perfluoroheptanesulfonate, and perfluorooctanesulfonate, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Of these, the alkali metal salt of perfluoroalkylsulfonic acid is most preferable. Among these alkali metals, rubidium and cesium are suitable when the demand for flame retardancy is higher, but these are not versatile and difficult to purify, resulting in disadvantages in terms of cost. There is. On the other hand, although it is advantageous in terms of cost, lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  Examples of the aromatic sulfonic acid used in the alkali (earth) metal salt of aromatic sulfonate include monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric form. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid And at least one acid selected from the group consisting of aromatic sulfonic acid sulfonic acids and condensates of methylene type bonds of aromatic sulfonic acids. These may be used alone or in combination of two or more. can do.

  Monomer or polymer aromatic sulfite alkali (earth) metal salts of aromatic sulfides are described in JP-A-50-98539, for example, disodium diphenyl sulfide-4,4′-disulfonate. And dipotassium diphenyl sulfide-4,4′-disulfonate.

  Examples of sulfonic acid alkali (earth) metal salts of aromatic carboxylic acids and esters are described in JP-A No. 50-98540, for example, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polyethylene terephthalate. And polysodium acid polysulfonate.

  Monomeric or polymeric aromatic ether sulfonate alkali (earth) metal salts are described in JP-A-50-98542, for example, 1-methoxynaphthalene-4-sulfonate calcium, 4- Disodium dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate, polysodium poly (1,3-phenylene oxide) polysulfonate, polysodium poly (1,4-phenylene oxide) polysulfonate And poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, and the like.

  Examples of alkali (earth) metal sulfonates of aromatic sulfonates are described in JP-A No. 50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

  Monomeric or polymeric aromatic (earth) metal sulfonates are described in JP-A No. 50-98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, Examples include dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, and calcium biphenyl-3,3′-disulfonate.

  Monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts are described in JP-A-52-54746, for example, sodium diphenylsulfone-3-sulfonate, diphenylsulfone-3- Examples include potassium sulfonate, dipotassium diphenyl-3,3′-disulfonate, dipotassium diphenylsulfone-3,4′-disulfonate, and the like.

  Examples of alkali sulfonate alkali (earth) metal salts of aromatic ketones are described in JP-A No. 50-98547, for example, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzophenone-3 , 3'-disulfonic acid dipotassium.

  Heterocyclic sulfonic acid alkali (earth) metal salts are described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate. Thiophene-2,5-disulfonate calcium, sodium benzothiophenesulfonate, and the like.

  Examples of the alkali (earth) metal sulfonate of aromatic sulfoxide are described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate.

  Examples of the condensate obtained by methylene bond of alkali (earth) metal salt of aromatic sulfonate include formalin condensate of sodium naphthalene sulfonate and formalin condensate of sodium anthracene sulfonate.

  Examples of the alkali (earth) metal salt of the aromatic imide include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonamide (in other words, di (p-toluenesulfone) imide), N- (N Examples include '-benzylaminocarbonyl) sulfanilimide, and alkali (earth) metal salts such as N- (phenylcarboxyl) sulfanilimide and bis (diphenylphosphoric acid) imide.

  Among these, potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, sulfonate of diphenylsulfone represented by the formula [5], potassium salt of di (p-toluenesulfone) imide, and di (p-toluene) More preferred are one or more compounds selected from the group consisting of sodium salts of sulfone) imides. Most preferred is potassium perfluorobutane sulfonate.

[Wherein, m represents 0 to 3, and M represents K or Na. ]

<C component: polytetrafluoroethylene having fibril-forming ability>
The polytetrafluoroethylene having fibril-forming ability used as the C component of the present invention may be a fibrillated polytetrafluoroethylene or a fibrillated polytetrafluoroethylene particle in a mixed form, even if it is a fibrillated polytetrafluoroethylene alone. It may be a polytetrafluoroethylene-based mixture made of an organic polymer. Fibrilized polytetrafluoroethylene has an extremely high molecular weight and tends to be bonded to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE of the component B has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. . Such PTFE can be used in solid form or in the form of an aqueous dispersion. Such fibrillated PTFE can also be used in the form of a PTFE mixture with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used. Examples of such commercially available fibrillated polytetrafluoroethylene include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. As the mixed form of fibrillated polytetrafluoroethylene, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and subjected to coprecipitation to obtain a coaggregated mixture (Methods described in JP-A-60-258263, JP-A-63-154744, etc.), (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (JP-A-4-272957). (3) A method in which an aqueous dispersion of fibrillated polytetrafluoroethylene and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open No. 06-2006). 220210, JP-A-08-188653, etc.), (4) fibrillated polytetrafluoroethylene A method of polymerizing a monomer forming an organic polymer in an aqueous dispersion (method described in JP-A-9-95583), and (5) an aqueous dispersion of polytetrafluoroethylene and an organic polymer dispersion The solution obtained by uniformly mixing the liquid, further polymerizing the vinyl monomer in the mixed dispersion, and then obtaining the mixture (method described in JP-A-11-29679 etc.) is used. it can. Commercially available products of these mixed forms of fibrillated polytetrafluoroethylene are represented by Mitsubishi Rayon Co., Ltd.'s "Metablene A3000" (trade name), "Metablene A3700" (trade name), and "Metablene A3800" (trade name). Metabrene A series, “SN3307” (trade name) manufactured by Shine Polymer, and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals are exemplified.

  The polytetrafluoroethylene having fibril forming ability used as the C component of the present invention is preferably branched polytetrafluoroethylene. When the polytetrafluoroethylene contained is a branched polytetrafluoroethylene, a sufficient anti-dripping effect can be obtained even if the addition of polytetrafluoroethylene is reduced. Examples of commercially available polytetrafluoroethylene having a fibril-forming ability using branched polytetrafluoroethylene include “SN3306” (trade name) and “SN3300B7” (trade name) manufactured by Shine Polymer.

  Content of C component is 0.001-0.08 weight part with respect to 100 weight part of A component, Preferably it is 0.01-0.08 weight part, More preferably, it is 0.01-0.05 weight. Part, most preferably 0.01 to 0.022. When the content of component C is less than 0.001 part by weight, sufficient optical properties and flame retardancy cannot be obtained, and when it exceeds 0.08 part by weight, the light transmittance is lowered.

  Furthermore, in the flame retardant light diffusing polycarbonate resin composition of the present invention, it is necessary that the content of the B component is larger than the content of the C component. Specifically, the ratio of the content of B component to the content of C component (content of B component / content of C component) is preferably in the range of 2.2 to 50, more preferably 2.5. It is -45, More preferably, it is the range of 5-45. When the content of the B component is less than or equal to the content of the C component, unevenness in light diffusibility occurs due to the difference in the thickness of the molded product.

<D component: Light diffusing agent>
Examples of the light diffusing agent used as the D component of the present invention include inorganic fine particles typified by glass fine particles, organic fine particles that are polymer fine particles such as polystyrene resin, (meth) acrylic resin, and silicone resin. However, organic fine particles are preferable. Such organic fine particles are preferably cross-linked organic fine particles, which are at least partially cross-linked in the production process, are not practically deformed in the processing process of the aromatic polycarbonate resin, and maintain the fine particle state. is there. As a particularly preferred specific example, partially crosslinked styrene-methyl methacrylate copolymer fine particles [for example, product name MSX405KN manufactured by Sekisui Plastics Co., Ltd.], a core / shell monoform containing a rubbery vinyl polymer core and shell Examples thereof include polymers having a gee (for example, trade name Paraloid EXL-5136 manufactured by Rohm and Haas Company) and silicone resins having a crosslinked siloxane bond [for example, Tospearl 120 manufactured by Toshiba Silicone Co., Ltd.].
Content of D component is 0.005-6.0 weight part with respect to 100 weight part of A component, Preferably it is 0.05-4.0 weight part, More preferably, it is 0.05-2.0 weight. Part. When the content of component D is less than 0.005 parts by weight, sufficient light diffusibility cannot be obtained, and when it exceeds 6.0 parts by weight, the light transmittance becomes insufficient.

<E component: UV absorber>
The flame retardant light diffusing polycarbonate resin composition of the present invention can be blended with an ultraviolet absorber in the sense of imparting weather resistance. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2- Hydroxy-4-benzyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2, 2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-Benzoyl-4-hydroxy-2 May be mentioned benzophenone-based ultraviolet absorbers typified methoxyphenyl) methane.

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, and 2- (2′-hydroxy). -5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'- Di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α'-dimethylbenzyl) phenylbenzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetraphthal Ruimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ' , 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2- Yl) phenol], methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-benzotriazole ultraviolet rays typified by condensation products with polyethylene glycol An absorbent can be mentioned.

Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol, 2- (4,6-bis- (2,4 There may be mentioned hydroxyphenyltriazine compounds such as -dimethylphenyl-1,3,5-triazin-2-yl) -5-hexyloxy-phenol.
The content of component E is preferably 0.01 to 3.0 parts by weight, preferably 0.02 to 1.0 parts by weight, and more preferably 0.05 to 0. 0 parts by weight with respect to 100 parts by weight of component A. 3 parts by weight. When the content of the E component is less than 0.01 parts by weight, it is difficult to obtain desired weather resistance, and when it exceeds 3.0 parts by weight, bleeding of the ultraviolet absorber and a decrease in hue occur.

<F component: fluorescent whitening agent>
The fluorescent whitening agent that is the F component used in the flame retardant light diffusing polycarbonate resin composition of the present invention is not particularly limited as long as it is used to improve the color tone of the resin to white or bluish white, Examples include stilbene, benzimidazole, benzoxazole, naphthalimide, rhodamine, coumarin, and oxazine compounds. Specifically, CI Fluorescent Brightener 219: 1, Eastman Chemical OB-1 manufactured by Eastman Chemical Co., etc. can be used. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part.
The content of the component F is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the component A. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

<Other ingredients>
The flame retardant light diffusing polycarbonate resin composition of the present invention may contain a small amount of additives known per se for imparting various functions and improving properties. These additives are used in usual amounts as long as the object of the present invention is not impaired.
Examples of such additives include flame retardants other than organic metal salt compounds, heat stabilizers, light stabilizers, mold release agents, lubricants, sliding agents (PTFE particles, etc.), and colorants (carbon black, pigments such as titanium oxide). , Dyes), phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.) and graft rubber Impact modifiers, infrared absorbers or photochromic agents.

In order to improve the thermal stability, antioxidant property, mold release and weather resistance of the flame retardant light diffusing polycarbonate resin composition of the present invention, additives used for these improvements in aromatic polycarbonate resin Advantageously used. Hereinafter, these additives will be specifically described.
The flame retardant light diffusing polycarbonate resin composition of the present invention can contain a phosphorus-containing stabilizer as a heat stabilizer. As the phosphorus-containing stabilizer, any of phosphite compounds, phosphonite compounds, and phosphate compounds can be used.

  Various phosphite compounds can be used. Specific examples include phosphite compounds represented by the following general formula [6], phosphite compounds represented by the following general formula [7], and phosphite compounds represented by the following general formula [8].

[Wherein R ⁹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio thereof (an alkyl group) Represents 1 to 30 carbon atoms) or a hydroxy substituent, and three R ⁸ can be selected from the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. ]

[Wherein R ¹⁰ and R ¹¹ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group or those substituted with an alkyl group. ]

[In formula, R < ¹² >, R < ¹³ > is a C12-C15 alkyl group. Note that R ¹² and R ¹³ can be selected to be the same or different from each other. The phosphite compound represented by this can be mentioned.

  Examples of the phosphonite compound include a phosphonite compound represented by the following general formula [9] and a phosphonite compound represented by the following general formula [10].

[In the ^formula, Ar 1, Ar ² represents a 2- (4-oxyphenyl) propyl-substituted aryl group of the aryl group or alkyl aryl group having 6 to 20 carbon atoms, or 15-25 carbon atoms, the four Ar ¹ Either the same or different from each other can be selected. Alternatively, ^two Ar ² can be selected to be the same or different from each other. ]

  Preferable specific examples of the phosphite compound represented by the above general formula [6] include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenylmono (Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite are mentioned.

  Preferred specific examples of the phosphite compound represented by the general formula [7] include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc., preferably distearyl pentaerythritol diphosphite, Examples thereof include bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

  Preferable specific examples of the phosphite compound represented by the general formula [8] include 4,4'-isopropylidenediphenol tetratridecyl phosphite.

  Preferable specific examples of the phosphonite compound represented by the general formula [9] include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di -N-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert) -Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propyl) Phenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4′-biphe Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylene diphospho And nitrite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, and the like. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis (2 , 4-Di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylenediphosphonite (E-1 component), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite (E-2 component) and tetrakis (2,4- One kind or two or more kinds of di-tert-butylphenyl) -3,3′-biphenylenediphosphonite (component E-3) can be used in combination, but a mixture of the three kinds is preferred. Further, in the case of three kinds of mixtures, the mixing ratio is preferably in the range of 100: 37 to 64: 4 to 14 by weight ratio of E-1 component, E-2 component and E-3 component, and 100: 40 to 60 : The range of 5-11 is more preferable.

  Preferable specific examples of the phosphonite compound represented by the general formula [10] include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n -Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3 -Phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, Bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butyl) Benzyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, bis (2,4-di-tert-butylphenyl) -phenyl-phenyl Phosphonite is more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- One or two of phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite can be used in combination. It is a mixture. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.

  On the other hand, as phosphate compounds, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate, and trimethyl phosphate is preferable.

  Among the above phosphorus-containing heat stabilizers, more preferred compounds include compounds represented by the following general formulas [11] and [12].

[Wherein, R ¹⁴ and R ¹⁵ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. ]

Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl. R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²¹ represents a hydrogen atom or a methyl group.)

In the formula [11], R ¹⁴ and R ¹⁵ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula [11] include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl). Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) Examples thereof include phosphite, and tris (2,6-di-tert-butylphenyl) phosphite is particularly preferable.

  Specifically, the compound represented by the formula [12] is a phosphite derived from 2,2′-methylenebis (4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2 2,2'-methylenebis (4,6-di-tert-butylphenol) and phosphites derived from phenol, especially from 2,2'-methylenebis (4,6-di-tert-butylphenol) and phenol. Derived phosphites are preferred.

  The flame retardant light diffusing polycarbonate resin composition of the present invention can contain a phenolic antioxidant as an antioxidant. The phenolic antioxidant can suppress discoloration when exposed to heat and exhibits a certain degree of effect on improving flame retardancy. Various types of such phenolic antioxidants can be used.

  Specific examples of such phenolic antioxidants include, for example, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3 , 5-Di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert- Butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-me Renbis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-tert- Butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3 -(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [ 2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) fe Ru] 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), 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N , N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-) Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3 -(3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane can be mentioned and can be preferably used.

  More preferably, 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, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Further, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate is preferable.

  Also, a sulfur-containing antioxidant can be used as the antioxidant. It is particularly suitable when the resin composition is used for rotational molding or compression molding. Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4 -(3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. be able to. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

  The phosphorus-containing heat stabilizer, phenolic antioxidant, and sulfur-containing antioxidant listed above can be used alone or in combination of two or more. The proportion of these stabilizers in the composition is 0.0001 to 1 part by weight of the phosphorus-containing stabilizer, phenol-based antioxidant, or sulfur-containing antioxidant per 100 parts by weight of component A, respectively. preferable. More preferably, it is 0.0005-0.5 weight part, More preferably, it is 0.001-0.2 weight part.

  The flame retardant light diffusing polycarbonate resin composition of the present invention can be blended with a release agent as required. As such a release agent, those known per se can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-alkene polymer may be used. These may be modified with a functional group-containing compound such as acid modification), silicone compounds And fluorine compounds (fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and fluorine oil can be mentioned. Preferable mold release agents include saturated fatty acid esters. For example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, and lower fatty acid esters such as stearic acid stearate. , Higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The content of the release agent is preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of component A.

  The flame retardant light diffusing polycarbonate resin composition of the present invention can be blended with a bluing agent to counteract the yellowish taste based on an ultraviolet absorber or the like. As such a bluing agent, if it is normally used for polycarbonate resin, it can be used without any problem. In general, anthraquinone dyes are preferred because they are readily available. Specific examples of the bluing agent include the general name Solvent Violet 13 [CA. No. (Color Index No.) 60725; Trade names “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Violet 31 [CA. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No. 60725; trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Blue 94 [CA. No. 61500; trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation, generic name Solvent Violet 36 [CA. No. 68210; Trade name: “Macrolex Violet 3R” manufactured by Bayer, Inc., generic name: Solvent Blue 97 [trade name: “Macrolex Blue RR” manufactured by Bayer, Inc.], and generic name: Solvent Blue 45 [CA. No. 61110; trade name “Terrazol Blue RLS” manufactured by Sand Corp.] and the like, and Macrolex Blue RR, Macrolex Violet B and Terrazol Blue RLS are particularly preferable. The content of the bluing agent is preferably 0.000005 to 0.0010 parts by weight, more preferably 0.00001 to 0.0001 parts by weight per 100 parts by weight of component A.

  Although the flame retardant light diffusing polycarbonate resin composition of the present invention has sufficient flame retardancy per se, a flame retardant other than an organometallic salt compound can be blended as necessary. Specifically, an organophosphorus flame retardant and a silicone flame retardant are mentioned. These flame retardants will be specifically described below.

<Organic phosphorus flame retardant>
As the organophosphorus flame retardant, an aryl phosphate compound is suitable. This is because such phosphate compounds are generally excellent in hue. Moreover, since the phosphate compound has a plasticizing effect, it is advantageous in that the moldability of the resin composition of the present invention can be improved. As the phosphate compound, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula [13] can be mentioned.

(In the formula, M represents a divalent organic group derived from a dihydric phenol, and R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ each represents a monovalent organic group derived from a monohydric phenol. , E, f, g and h are each independently 0 or 1, k is an integer of 0 to 5, and k represents an average value in the case of a mixture of phosphate esters having different degrees of polymerization k. 0 to 5)

  The phosphate compound of the above formula may be a mixture of compounds having different k numbers, in which case the average n number is preferably 0.5-1.5, more preferably 0.8-1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.

Preferable specific examples of the dihydric phenol for deriving M include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 A divalent group obtained by removing two hydroxyl groups of a dihydroxy compound selected from the group consisting of -hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide. Specific examples of R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ include phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumyl each independently substituted with one or more halogen atoms. Examples thereof include monovalent groups obtained by removing one hydroxyl group of a monohydroxy compound selected from the group consisting of phenol.

Preferable specific examples of the monohydric phenol for deriving R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.
The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that it may contain a small amount of other components having different degrees of polymerization, more preferably the component of k = 1 in the formula [17] is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Shown the door.).
The content of the organophosphorus flame retardant is preferably 0.01 to 20 parts by weight, more preferably 2 to 15 parts by weight, and further preferably 2 to 10 parts by weight per 100 parts by weight of the component A.

<Silicone flame retardant>
The silicone flame retardant is not particularly limited as long as it can obtain the flame retardancy and good optical properties which are the object of the present invention, but in order to obtain good optical properties, a silicone flame retardant having an aromatic group. Is preferred. Furthermore, in order to exhibit the flame retardant effect efficiently, the dispersed state in the combustion process is important. Viscosity is an important factor that determines the dispersion state. This is because when the silicone flame retardant tends to volatilize too easily in the combustion process, that is, in the case of a silicone flame retardant having a viscosity that is too low, the silicone remaining in the system at the time of combustion is dilute. It is considered that it is difficult to form a uniform silicone structure. Moreover, when the viscosity of a silicone type flame retardant is too high, the dispersibility of a silicone type flame retardant will deteriorate and it will have a bad influence on a flame retardance and an optical characteristic. From this viewpoint, the viscosity at 25 ° C. is more preferably 10 to 300 cSt, still more preferably 15 to 200 cSt, and most preferably 20 to 170 cSt.

The silicone flame retardant that can be blended in the flame retardant light diffusing polycarbonate resin composition of the present invention is preferably a silicone flame retardant containing Si-H groups. In particular, a silicone-based flame retardant containing Si—H groups and aromatic groups in the molecule,
(1) The amount of Si—H group contained (Si—H amount) is 0.1 to 1.2 mol / 100 g.
(2) The ratio (aromatic group amount) of the aromatic group represented by the following general formula [14] is 10 to 70% by weight, and
[In formula, B shows a C1-C20 hydrocarbon group which may have OH group and a hetero atom containing functional group each independently. j represents an integer of 0 to 5; Further, when j is 2 or more in the formula, different types of B can be taken. ]
(3) Average polymerization degree is 3 to 150
It is preferable that it is at least 1 type of silicone flame retardant selected from the silicone flame retardant which is.

  More preferably, the Si—H group-containing unit is selected from silicone-based flame retardants containing at least one structural unit represented by the formula among the structural units represented by the following general formulas [15] and [16]. At least one silicone flame retardant.

[In Formula [15] and Formula [16], Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group, or the following general formula [ 17]. α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more. Furthermore, in the formula [15], when m1 is 2 or more, the repeating unit can take a plurality of different repeating units. ]

[Wherein, Z ^{4 to} Z ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom-containing functional group. α4 to α8 each independently represents 0 or 1. m2 represents 0 or an integer of 1 or more. Further, in the formula, when m2 is 2 or more, the repeating unit can take a plurality of different repeating units. ]

  More preferably, when M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit, it is a silicone flame retardant composed of MD units or MDT units.

Z ^{1 to} Z ^{8 of} the structural units represented by the above general formulas [15], [16] and [17], and 1 to 1 carbon atoms which may have a hetero atom-containing functional group in B of the general formula [14] Examples of the hydrocarbon group 20 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a decyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group and an allyl group, and a phenyl group. , Aryl groups such as tolyl groups, and aralkyl groups, and these groups may include various functional groups such as epoxy groups, carboxyl groups, carboxylic anhydride groups, amino groups, and mercapto groups. Good. More preferably, it is a C1-C8 alkyl group, an alkenyl group, or an aryl group, and especially a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a propyl group, a vinyl group, or a phenyl group is preferable.

  Of the structural units represented by the general formulas [15] and [16], in the silicone-based flame retardant containing at least one structural unit represented by the formula, when having a plurality of repeating units of siloxane bonds, Any of random copolymerization, block copolymerization, and tapered copolymerization may be employed.

  About the preferable silicone-type flame retardant containing Si-H group, it is preferable to make the amount of Si-H in a silicone-type flame retardant into the range of 0.1-1.2 mol / 100g. When the Si—H amount is in the range of 0.1 to 1.2 mol / 100 g, formation of a silicone structure is facilitated during combustion. More preferably, it is a silicone flame retardant having a Si-H amount in the range of 0.1 to 1.0 mol / 100 g, and most preferably in the range of 0.2 to 0.6 mol / 100 g. When the amount of Si—H is small, it is difficult to form a silicone structure, and when the amount of Si—H is large, the thermal stability of the composition is lowered. Here, the silicone structure refers to a network structure formed by a reaction between silicone flame retardants or a reaction between a resin and silicone.

In addition, the Si-H group amount mentioned here refers to the number of moles of the Si-H structure contained per 100 g of the silicone flame retardant, and this is generated per unit weight of the silicone flame retardant by the alkali decomposition method. It can be determined by measuring the volume of hydrogen gas. For example, when 122 ml of hydrogen gas is generated per 1 g of the silicone flame retardant at 25 ° C., the Si—H amount is 0.5 mol / 100 g according to the following calculation formula.
122 × 273 / (273 + 25) ÷ 22400 × 100≈0.5

  On the other hand, in a resin composition in which a silicone-based flame retardant is blended with an aromatic polycarbonate resin (component A), the molded product made of the flame-retardant light diffusing polycarbonate resin composition of the present invention becomes cloudy or changes in optical properties due to wet heat treatment. In order to suppress this, as described above, the dispersion state of the silicone-based flame retardant is important. When the silicone flame retardant is unevenly distributed, the resin composition itself becomes cloudy, and further, peeling occurs on the surface of the molded article made of the flame retardant light diffusing polycarbonate resin composition of the present invention. This is because it becomes difficult to obtain a molded product with good optical characteristics, for example, the system flame retardant migrates and is unevenly distributed to change the optical characteristics. Important factors that determine the dispersion state include the amount of aromatic group and average degree of polymerization of the silicone flame retardant. In particular, the average degree of polymerization is important in a resin composition capable of maintaining good optical properties.

  From this point of view, the amount of aromatic group in the silicone flame retardant is preferably 10 to 70% by weight as the silicone flame retardant used in the flame retardant light diffusing polycarbonate resin composition of the present invention. More preferred is a silicone flame retardant having an aromatic group content in the range of 15 to 60% by weight, most preferably in the range of 25 to 55% by weight. If the amount of aromatic group in the silicone flame retardant is less than 10% by weight, the silicone flame retardant is unevenly distributed, resulting in poor dispersion, and it may be difficult to obtain a molded article having good optical characteristics. If the amount of the aromatic group is more than 70% by weight, the molecular rigidity of the silicone-based flame retardant itself is increased, so that it is also unevenly distributed and poorly dispersed, and it may be difficult to obtain a molded product with good optical characteristics. .

Here, the amount of the aromatic group means the ratio of the aromatic group represented by the general formula [14] described above in the silicone-based flame retardant, and can be obtained by the following calculation formula.
Aromatic group amount = [A / M] x 100 (wt%)
Here, A and M in the above formula represent the following numerical values, respectively.
A = Total molecular weight of the aromatic group moiety represented by the general formula [14] contained in one molecule of the silicone flame retardant M = Molecular weight of the silicone flame retardant

  Furthermore, the silicone flame retardant desirably has a refractive index in the range of 1.40 to 1.60 at 25 ° C. More preferred is a silicone flame retardant having a refractive index in the range of 1.42 to 1.59, and most preferred in the range of 1.44 to 1.59. When the refractive index is within the above range, the silicone flame retardant is finely dispersed in the aromatic polycarbonate, thereby providing a resin composition with less white turbidity and good dyeability.

  Further, it is preferable that the silicone flame retardant has a volatilization amount of 18% or less by a heat loss method at 105 ° C./3 hours. More preferably, it is a silicone-based flame retardant having a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, there is a problem that the amount of the volatile matter from the resin increases when the resin composition of the present invention is extruded and pelletized, and further, the flame-retardant light diffusing polycarbonate resin of the present invention. There is a problem that air bubbles generated in the composition tend to increase.

  The silicone-based flame retardant that may be blended in the flame retardant light diffusing polycarbonate resin composition of the present invention may be linear or have a branched structure as long as the above conditions are satisfied. It is possible to use various compounds having a Si—H group at any of a side chain, a terminal, a branch point, or a plurality of sites in the molecular structure.

In general, the structure of a silicone-based flame retardant containing a Si—H group in a molecule is configured by arbitrarily combining the following four types of siloxane units.
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _{1/2 and} other monofunctional siloxane units D units: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. Unit T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 trifunctional siloxane units Q units etc: tetrafunctional siloxane represented by SiO ₂ Place

Specifically, the structure of the silicone-based flame retardant that may be blended in the flame retardant light diffusing polycarbonate resin composition of the present invention is specifically expressed as Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq. , MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferable structures of the silicone-based flame retardant are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferable structure is MmDn or MmDnTp.
(The coefficients m, n, p, q in the above formula are integers representing the degree of polymerization of each siloxane unit. Also, if any of m, n, p, q is a numerical value of 2 or more, the coefficient The siloxane units with can be two or more siloxane units having different hydrocarbon groups having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom-containing functional group.

Here, the sum of the coefficients in each characteristic formula is the average degree of polymerization of the silicone flame retardant. In this invention, it is preferable to make this average degree of polymerization into the range of 3-150, More preferably, it is the range of 4-80, More preferably, it is the range of 5-60. When the degree of polymerization is less than 3, the volatility of the silicone flame retardant itself is increased, and there is a problem that the volatile content from the resin tends to increase during the processing of the resin composition containing the silicone flame retardant. When the degree of polymerization is greater than 150, the flame retardancy and optical properties of the resin composition containing the silicone flame retardant are likely to be insufficient.
In addition, said silicone flame retardant may be used independently, respectively and may be used in combination of 2 or more type.

  Such a silicone-based flame retardant having a Si—H bond can be produced by a conventionally known method. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone flame retardant and removing by-product hydrochloric acid and low-boiling components. In addition, a silicone oil having a C1-C20 hydrocarbon group that may have an Si-H bond, an aromatic group represented by the general formula [19], or other heteroatom-containing functional group in the molecule, cyclic When using siloxane or alkoxysilane as a starting material, use an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc., and optionally add water for hydrolysis to advance the polymerization reaction, By removing the used acid catalyst and low boiling point in the same manner, the intended silicone flame retardant can be obtained.

Further, the silicone-based flame retardant containing a Si—H group is a siloxane unit M, MH, D, DH, Dφ ₂ , T, Tφ (where M: (CH ₃ ) ₃ SiO _1/2 ) represented by the following structural formula: MH: H (CH ₃ ) ₂ SiO _1/2 D: (CH ₃ ) ₂ SiODH: H (CH ₃ ) SiODφ ₂ : (C ₆ H ₅ ) ₂ SiT: (CH ₃ ) SiO _3/2 Tφ: (C ₆ H ₅ ) SiO _3/2 ), and the average number of each siloxane unit per molecule is m, mh, d, dh, dp2, t, tp, Is preferably satisfied.
2 ≦ m + mh ≦ 40
0.35 ≦ d + dh + dp2 ≦ 148
0 ≦ t + tp ≦ 38
0.35 ≦ mh + dh ≦ 110

  Outside this range, it becomes difficult to simultaneously achieve good flame retardancy and excellent optical properties in the resin composition of the present invention, and in some cases, it is difficult to produce a silicone-based flame retardant containing Si-H groups. Become.

  The amount of the silicone flame retardant that may be blended in the flame retardant light diffusing polycarbonate resin composition of the present invention is preferably 0.05 to 7 parts by weight, more preferably 100 parts by weight of component A. 0.1-4 weight part More preferably, it is 0.3-2 weight part, Most preferably, it is 0.3-1 weight part. If the content is too large, there is a problem that the heat resistance of the resin is lowered or gas is easily generated during processing, and if it is too small, there is a problem that flame retardancy is not exhibited.

<About production of resin composition>
In order to produce the flame retardant light diffusing polycarbonate resin composition of the present invention, any method is adopted. For example, after thoroughly mixing A component, B component, C component and D component, and other components using premixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Accordingly, there is a method in which granulation is performed by an extrusion granulator or a briquetting machine, followed by melt kneading with a melt kneader represented by a vent type biaxial ruder, and pelletization with an apparatus such as a pelletizer. Alternatively, the A component and optionally the B component, the C component, the D component, and other components are independently fed to a melt kneader represented by a vented twin screw rudder, the A component and the other components. Examples include a method in which a part is premixed and then supplied to the melt-kneader independently of the remaining components. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

<Manufacture of injection molded products>
The injection-molded article comprising the flame-retardant light diffusing polycarbonate resin composition of the present invention can be obtained by injection molding the flame-retardant light diffusing polycarbonate resin composition of the present invention. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, blow molding, foaming Molding (including those using supercritical fluid), rapid heating / cooling mold molding, heat insulation mold molding and in-mold remelt molding, and molding methods composed of these combinations can be used.

  Furthermore, various surface treatments can be performed on the molded article made of the flame retardant light diffusing polycarbonate resin composition of the present invention. Surface treatment includes decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, UV absorbing coat, infrared absorbing coat, electromagnetic wave absorbing coat, heat generating coat, antistatic coat, antistatic coating, conductive coating, and meta coating. Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed. In particular, a transparent sheet coated with a transparent conductive layer is preferred.

  The flame retardant light diffusing polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin (component A), an organometallic salt compound (component B), polytetrafluoroethylene (component C) having fibril-forming ability, and a light diffusing agent ( By making D component) into a specific compounding ratio, it has succeeded in achieving both good flame retardancy and high light diffusibility. In addition, a molded product comprising the flame-retardant light diffusing polycarbonate resin composition of the present invention is a molded product having good light diffusibility, specifically, light diffusion unevenness due to the thickness of the molded product. It is not in the technology of the light diffusing polycarbonate resin composition, and is extremely useful for various lighting applications, and its industrial effect is extremely great.

It is the schematic which shows the measuring method of the dispersion degree in this invention. It is the schematic of the injection molded product shape | molded in the Example. It is the schematic of the extrusion molded product shape | molded in the Example.

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

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
The following items were evaluated.

(I) Viscosity average molecular weight An Ostwald viscometer was obtained from a solution in which 0.7 g of pellets obtained from the respective compositions of Examples were dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. Using
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7
In addition, when the pellet obtained from each composition of an Example contains an insoluble component, calculation of the viscosity average molecular weight was performed in the following way. That is, the pellet is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, methylene chloride in the obtained solution is removed, and the solid after the methylene chloride is removed is sufficiently dried to obtain a solid of a component that dissolves in methylene chloride. The specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight Mv is calculated from the specific viscosity in the same manner as described above.

(Ii) Flame retardance The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours in a hot air circulation dryer, and the cylinder temperature was measured by an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. Test pieces having thicknesses of 1.0 mm, 1, 5 mm, 1.8 mm, and 2.4 mm for flame retardance evaluation were molded and evaluated at 310 ° C. and a mold temperature of 90 ° C. according to UL standard 94. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated. The flame retardancy is preferably V-1 or higher.

(Iii) Optical characteristics (1) Total light transmittance The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours in a hot air circulating dryer, and then an injection molding machine [Toshiba Machine Co., Ltd. IS150EN- 5Y], a plate-shaped test piece having a cylinder temperature of 310 ° C., a mold temperature of 90 ° C. and a side of 150 mm and a thickness of 2 mm was formed, and the thickness was measured using a haze meter HR-100 manufactured by Murakami Color Research Laboratory Co., Ltd. Directional transmittance was measured according to JIS-K7136.

(2) Diffusion degree Pellets obtained from the compositions of the examples were dried at 120 ° C. for 6 hours in a hot air circulating dryer, and the cylinder temperature was 310 ° C. using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. The diffusivity of a flat specimen having a side of 150 mm, a thickness of 1 mm and a thickness of 2 mm at a mold temperature of 90 ° C. was measured by the method shown in FIG. 1 using a variable angle photometer manufactured by Nippon Color Technology Laboratory Co., Ltd. did. Note that the diffusivity is the angle of γ when the amount of transmitted light is 50 when the amount of transmitted light is 100 when γ = 0 degrees when a light beam is vertically applied to the specimen surface in FIG. .

(3) Diffusion unevenness
The diffusion unevenness (D) of the pellets obtained from each composition of the examples was calculated from the following formula [1]. In the formula, D1 represents the diffusivity at a thickness of 1 mm, and D2 represents the diffusivity at a thickness of 2 mm. The larger the value of the diffusion unevenness (D), the larger the diffusion unevenness due to the difference in thickness.
D = (D2-D1) / D2 [1]

(4) Surface impact property Evaluation was performed using a high-speed surface impact tester Hydroshot HTM-1 (manufactured by Shimadzu Corp.) using a flat plate test piece having a side of 150 mm and a thickness of 2 mm.
The test conditions were an impact speed of 7 m / s, a semi-circular tip with a radius of 6.35 mm, and a cradle hole diameter of 25.4 mm. The determination was made according to the following criteria.
○ The state of destruction is ductile destruction.
X The state of fracture is brittle fracture.

(5) Evaluation of injection-molded product The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours with a hot-air circulating drier, and cylinders with an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A hemispherical lighting cover having a diameter of 50 mm shown in FIG. 2 was prepared at a temperature of 310 ° C. and a mold temperature of 90 ° C. The lighting cover attached to the commercially available light bulb type LED lighting (equivalent to 40 W) was replaced with the lighting cover of this example, the light diffusivity was evaluated by visual observation, and the determination was made according to the following criteria.
○ There is no unevenness in diffusibility.
X Unevenness occurs in diffusibility.

(6) Evaluation of Extruded Product The pellets obtained from each composition of the examples were dried at 120 ° C. for 6 hours in a hot air circulating dryer, and extruded with an extruder to obtain the thickness shown in FIG. A 1-mm semi-cylindrical lighting cover was prepared. The lighting cover attached to the commercially available fluorescent tube type LED lighting (equivalent to 40 W) was replaced with the lighting cover of this example, the light diffusivity was evaluated by visual observation, and the determination was made according to the following criteria.
○ There is no unevenness in diffusibility.
X Unevenness occurs in diffusibility.

[Examples 1 to 12 and Comparative Examples 1 to 8]
The resin composition which consists of a mixture ratio of Table 1 was created in the following ways. The description will be made according to the symbols in the following table. Each component of the ratio of the table | surface was measured, it mixed uniformly using the tumbler, this mixture was thrown into the extruder, and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. The strand was extruded under the conditions of cylinder temperature and die temperature of 290 ° C. and vent suction of 3000 Pa, cooled in a water bath, then strand-cut with a pelletizer and pelletized. Using the obtained pellets, a test piece for evaluating flame retardancy and optical properties and a lighting cover were molded. In addition, the used raw material etc. of Table 1 are as follows.

(A component)
PC-1: Aromatic polycarbonate comprising 4,4′-dihydroxy-2,2′-diphenylpropane (PC-1 production method)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution and 0.7 parts of hydrosulfite, and 2,2-bis (4-hydroxyphenyl) under stirring. ) After dissolving 710 parts of propane (hereinafter sometimes referred to as “bisphenol A”) (bisphenol A solution), 2299 parts of methylene chloride and 112 parts of 48.5% aqueous sodium hydroxide solution were added, and the temperature was 15-25 ° C. The phosgenation reaction was performed by blowing 354 parts of phosgene over about 90 minutes.
After completion of the phosgenation, 125 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added to stop stirring. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) for 3 hours at 35 ° C. under non-stirring conditions to complete the polymerization. After completion of the reaction, 5728 parts of methylene chloride was added for dilution, the methylene chloride phase was separated from the reaction mixture, 5000 parts of ion-exchanged water was added to the separated methylene chloride phase and mixed with stirring, and the stirring was stopped. The phase and the organic phase were separated. Next, water washing was repeated until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water to obtain a purified polycarbonate resin solution. Next, this resin solution was put into a kneader filled with warm water, and methylene chloride was evaporated while stirring to obtain a polycarbonate resin granule. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer. This polycarbonate had a viscosity average molecular weight of 22,400.

PC-2: Aromatic polycarbonate having a branched structure composed of 4,4′-dihydroxy-2,2′-diphenylpropane (PC-2 production method)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution and 0.7 parts of hydrosulfite, and 2,2-bis (4-hydroxyphenyl) under stirring. ) After dissolving 710 parts of propane (hereinafter sometimes referred to as “bisphenol A”) (bisphenol A solution), 2299 parts of methylene chloride, 112 parts of 48.5% aqueous sodium hydroxide solution, 14% strength aqueous sodium hydroxide solution 38.1 parts (1.00 mol%) of an aqueous solution in which 1,1,1-tris (4-hydroxyphenyl) ethane was dissolved at a concentration of 25% was added to the mixture, and 354 parts of phosgene was added at 15 to 25 ° C. over about 90 minutes. And phosgenation reaction was performed. After completion of phosgenation, 119 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added, stirring was stopped, and the mixture was allowed to stand for 10 minutes and then stirred. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) for 3 hours at 35 ° C. under non-stirring conditions to complete the polymerization. After completion of the reaction, 5728 parts of methylene chloride was added for dilution, the methylene chloride phase was separated from the reaction mixture, 5000 parts of ion-exchanged water was added to the separated methylene chloride phase and mixed with stirring, and the stirring was stopped. The phase and the organic phase were separated. Next, water washing was repeated until the conductivity of the aqueous phase was almost the same as that of ion-exchanged water to obtain a purified polycarbonate resin solution. Next, methylene chloride was evaporated at a liquid temperature of 75 ° C. with a 1000 L kneader in which 100 L of ion-exchanged water was added to the purified polycarbonate resin solution to obtain a granular material. 25 parts of the granular material and 75 parts of water were put into a hot water treatment tank equipped with a stirrer and stirred and mixed at a water temperature of 95 ° C. for 30 minutes. Subsequently, the mixture of the granular material and water was separated by a centrifugal separator to obtain a granular material containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously supplied at 50 kg / hr (in terms of polycarbonate resin) to a SUS316L conductive heat receiving groove type biaxial stirring continuous dryer controlled at 140 ° C., and the condition of an average drying time of 3 hours And dried to obtain a polycarbonate resin particle having a branched structure. The polycarbonate resin having a branched structure thus obtained had a viscosity average molecular weight of 23,000 and a branching rate of 0.96 mol%.

PC-3: A polycarbonate-polydimethylsiloxane copolymer comprising 4,4′-dihydroxy-2,2′-diphenylpropane and a bisphenol compound containing a polydimethylsiloxane structure represented by the following formula [23].
(Method for producing PC-3)
In the method for producing PC-1, after completion of the phosgenation, 125 parts of a 11% strength p-tert-butylphenol methylene chloride solution and 88 parts of a 48.5% aqueous sodium hydroxide solution were added, and the following formula [18 ] A polydiorganosiloxane compound (X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure represented by the following formula: It was made into the highly emulsified state by stirring at 8000 rpm for 2 minutes, and then kept at 35 ± 1 ° C. for 2 hours in a stationary state without stirring. A granule of a polycarbonate-polydimethylsiloxane copolymer was obtained. This polycarbonate had a viscosity average molecular weight of 22,800.

(B component)
B-1: Perfluorobutanesulfonic acid potassium salt (Megafac F-114P manufactured by Dainippon Ink, Inc.)
(C component)
C-1: SN3300B7 (trade name) (manufactured by Shine Polymer, the polytetrafluoroethylene-based mixture is a mixture of branched polytetrafluoroethylene particles and styrene-acrylonitrile copolymer particles produced by suspension polymerization. (Polytetrafluoroethylene content 50% by weight))
C-2: SN3307 (trade name) (manufactured by Shine Polymer, the polytetrafluoroethylene-based mixture is composed of linear polytetrafluoroethylene particles and styrene-acrylonitrile copolymer particles produced by suspension polymerization. Mixture (polytetrafluoroethylene content 50% by weight))
(D component)
D-1: Bead-like crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: MBX-5 (trade name), average particle diameter 5 μm)
D-2: Beaded crosslinked silicone (Momentive Performance Materials Japan GK Co., Ltd .: Tospearl 120 (trade name), average particle size 2 μm)
(E component)
E-1: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Kogyo Co., Ltd .: Chemisorb 79 (trade name))
(F component)
F-1: Fluorescent whitening agent (manufactured by Hakkor Chemical Co., Ltd .: Hakkor PSR (trade name))
(Other ingredients)
IRX: Hindered phenol-based antioxidant (manufactured by Ciba Specialty Chemicals: Irganox 1076 (trade name))

A Test piece (flat plate)
B Light source γ Diffuse light angle

Claims (10)

(A) 0.05 to 1.0 part by weight of (B) organometallic salt compound (component B) with respect to 100 parts by weight of aromatic polycarbonate resin (component A), (C) polytetrafluoro having fibril-forming ability A flame retardant light diffusing polycarbonate resin composition comprising 0.001 to 0.08 parts by weight of ethylene (C component) and 0.5 to 6.0 parts by weight of (D) light diffusing agent (D component), Flame retardant light diffusivity, characterized in that the ratio of component content to C component content (B component content / C component content) is 5 or more and does not contain an aryl group-containing polysilane compound Polycarbonate resin composition.   The flame retardant light diffusing polycarbonate resin composition according to claim 1, wherein the component A is an aromatic polycarbonate resin having a branched structure with a branching ratio of 0.3 to 1.6 mol%. Claim 1 or hardly retardant optical diffusing polycarbonate resin composition according to 2, characterized in that component A is an aromatic polycarbonate resin having a branched structure min 岐率 0.7~1.6mol%.   B component is selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides The flame retardant light diffusing polycarbonate resin composition according to claim 1, wherein the flame retardant light diffusing polycarbonate resin composition is an organic alkali (earth) metal salt.   The flame retardant light diffusing polycarbonate resin composition according to claim 1, wherein the component C is branched polytetrafluoroethylene.   The flame retardant light diffusing polycarbonate resin composition according to any one of claims 1 to 5, wherein the D component is polymer fine particles.   The flame-retardant light diffusing polycarbonate according to any one of claims 1 to 6, comprising 0.01 to 3 parts by weight of (E) ultraviolet absorber (E component) with respect to 100 parts by weight of component A. Resin composition.   The flame retardant light according to any one of claims 1 to 7, comprising 0.001 to 0.1 parts by weight of (F) a fluorescent whitening agent (F component) with respect to 100 parts by weight of the A component. A diffusible polycarbonate resin composition.   The injection molded product molded from the flame retardant light diffusing polycarbonate resin composition according to any one of claims 1 to 8, wherein the thickness of the molded product is 1.2% or less.   The extrusion molded product molded from the flame retardant light diffusing polycarbonate resin composition according to any one of claims 1 to 8, wherein a portion of the molded product having a thickness of 1.2 mm or less is 10% or more of the whole.