JP2009280725A - Flame-retardant polycarbonate resin composition and light reflection member - Google Patents

Abstract

[PROBLEMS] To provide a high degree of light reflectivity and flame retardancy without using a flame retardant containing halogen or phosphorus, good appearance, light reflectivity, light shielding property, thermal conductivity (heat dissipation), machine Provided are a flame retardant polycarbonate resin composition and a light reflecting member from which a molded product having characteristics (rigidity) and dimensional stability can be obtained.
SOLUTION: (a) Aromatic polycarbonate resin, (b) White pigment and (c) Alkali neutralization treatment and silane coupling surface-treated talc, (a) to (c) total amount of components 100 mass The flame retardant polycarbonate resin composition and the polycarbonate resin, wherein the mass ratio of (a) component: (b) component: (c) component in the part is 91-40: 4-40: 4-20 A light reflecting plate formed by molding the composition and its peripheral members.
[Selection figure] None

Description

  The present invention relates to a polycarbonate resin composition and a light reflecting member. More specifically, a polycarbonate resin composition having excellent heat resistance and flame retardancy, light reflectance, light shielding properties, heat dissipation, mechanical properties (rigidity), dimensional stability and moldability of the molded product and the The present invention relates to a light reflector formed by molding a composition and its peripheral members.

  In recent years, the use of liquid crystal displays (LCDs) has expanded to notebook personal computers, monitors, and televisions, and in particular, development competition for increasing the size, weight, and thickness of liquid crystal televisions has been remarkable recently. At the same time, image quality has improved, and backlights as LCD lighting devices have become larger, thinner, and lighter as well as LED light sources, and mechanical characteristics (rigidity), dimensional stability, There is an increasing demand for heat dissipation, that is, demand for heat-resistant dimensional stability.

Polycarbonate resins having excellent mechanical properties are widely used in these fields by adding a white pigment such as titanium oxide to improve reflection performance and light shielding performance.
On the other hand, the resin materials used in these devices need to be flame retardant, and a number of flame retardant formulations have been developed, especially for the purpose of reducing the corrosion of the mold and the environmental load. In addition, it is required to contain no halogen-based or phosphorus-based flame retardant.
In addition, in order to respond to the development trend of upsizing, thinning, and weight reduction, the requirements of light reflectivity, light shielding, mechanical properties (rigidity), dimensional stability, heat dissipation (thermal conductivity), etc. must be satisfied at the same time. There is a need for polycarbonate resins.

  Polycarbonate resin composition capable of obtaining molded article having high light reflectivity and flame retardancy, good appearance and dimensional accuracy, and light reflecting plate formed by molding the flame retardant polycarbonate resin composition and its periphery As a resin material relating to a member, for example, in Patent Document 1, (a) 3 to 30 parts by weight of titanium oxide and (c) 0.1 to 10 parts by weight of a silicone compound with respect to 100 parts by weight of an aromatic polycarbonate resin. A flame retardant polycarbonate resin composition comprising: (d) 0.1 to 1 part by weight of polytetrafluoroethylene, and (e) 0.5 to 15 parts by weight of a plate-like inorganic filler. ing.

  However, in Patent Document 1, since a silicone-based compound based on silica is used as the component (c), flame retardancy can be ensured without containing a halogen-based compound. ) The talc used in the plate-like inorganic filler has a problem that the polycarbonate resin is hydrolyzed because it exhibits alkalinity, resulting in a decrease in mechanical properties due to molecular weight deterioration, and talc cannot be blended at a high concentration. .

For this reason, in Patent Document 1, (b) 3 to 30 parts by weight of titanium oxide and (e) 0.5 to 15 parts by weight of a plate-like inorganic filler with respect to 100 parts by weight of (a) aromatic polycarbonate resin. Therefore, the light reflectance, the light shielding property, the heat radiation property, the mechanical property (rigidity) and the dimensional stability are not sufficiently satisfied.
JP 2005-15659 A

  The present invention was made under such circumstances, without using a flame retardant containing halogen or phosphorus, has high light reflectivity and flame retardancy, good appearance and light reflectance, Flame-retardant polycarbonate resin composition capable of obtaining molded product having light-shielding property, thermal conductivity (heat dissipation), mechanical property (rigidity), dimensional stability, and light reflector formed by molding the polycarbonate resin composition, and The object is to provide a peripheral member.

  As a result of intensive studies to achieve the above object, the inventors of the present invention used talc that has been subjected to a specific treatment in an aromatic polycarbonate resin, and titanium oxide as a white pigment, so as to be contained at a specific ratio. The present inventors have found that the polycarbonate resin composition meets the above-mentioned purpose, and reached the present invention.

That is, the present invention provides the following aromatic carbonate resin composition and light reflecting member.
1. (A) Aromatic polycarbonate resin, (b) White pigment and (c) Alkali neutralization treatment and silane coupling surface-treated talc are contained, and (a) to (c) components in a total amount of 100 parts by mass (a The flame retardant polycarbonate resin composition is characterized in that the mass ratio of component (b): component (b): component (c) is 91-40: 4-40: 4-20.
2. The flame retardant polycarbonate resin composition according to 1 above, wherein the aromatic polycarbonate resin as the component (a) contains a high-fluidity polycarbonate copolymer and / or a polycarbonate-polyorganosiloxane copolymer.
3. The flame retardant polycarbonate resin composition according to 2 above, wherein the aromatic polycarbonate resin as the component (a) contains a polycarbonate-polydimethylsiloxane copolymer.
4). (C) The difficulty of 1 or 2 above, wherein the silane coupling surface treatment of component talc is at least one silane coupling surface treatment selected from amino-modified silane, carboxy-modified silane, acrylic-modified silane, and epoxy-modified silane. Flammable polycarbonate resin composition.
5. (A) It contains 0.1-3 parts by mass of an organopolysiloxane and (e) 0.1-5 parts by mass of a polyorganosiloxane-containing graft copolymer with respect to 100 parts by mass of the components. The flame-retardant polycarbonate resin composition according to any one of 1 to 4 above.
6). (D) The flame retardant polycarbonate resin composition as described in 5 above, wherein the organopolysiloxane is alkyl hydrogen silicone or alkoxy silicone.
7). 6. The flame retardant polycarbonate resin composition according to 6 above, wherein the alkoxysilicone is an organopolysiloxane having a molecular structure in which an alkoxy group is bonded to the silicone main chain via a methylene group.
8). (E) In the presence of 40 to 90 parts by mass of (X) polyorganosiloxane particles, (Y) polyfunctional monomer (y-1) 100 to 50% by mass and (e) polyorganosiloxane-containing graft copolymer Other copolymerizable monomer (y-2) is polymerized from 0.5 to 10 parts by mass of vinyl monomer composed of 0 to 50% by mass, and (Z) other vinyl monomer 5 to The flame-retardant polycarbonate resin composition according to 5 above, obtained by polymerizing 50 parts by mass (provided that the total amount of (X), (Y) and (Z) is 100 parts by mass).
9. The light reflection member obtained by shape | molding the flame-retardant polycarbonate resin composition in any one of said 1-8.

In the present invention, by using specific talc based on the unique titanium oxide stabilization technology, hydrolysis degradation of polycarbonate resin by conventional talc is suppressed, so a high concentration of talc and titanium oxide can be blended. It becomes possible.
As a result, in the polycarbonate resin composition, flame retardance is ensured without containing halogen flame retardants and metal salt flame retardants, and furthermore, a high level of light reflectivity, light shielding properties, thermal conductivity. (Heat dissipation), mechanical characteristics (rigidity), and dimensional stability, structural parts that require high light reflection performance and rigidity, and reflective base materials and reflective members that use light-emitting LEDs as a light source It can be widely used in fields that require heat-resistant dimensional stability.

[(A) Aromatic polycarbonate resin]
The aromatic polycarbonate resin (a) in the flame retardant polycarbonate resin composition of the present invention is composed of a high-fluidity polycarbonate copolymer (a-1: also called high-fluidity copolymerization PC), a polycarbonate-polyorganosiloxane copolymer (a -2: Polyorganosiloxane copolymerized PC) and general aromatic polycarbonate resin (a-3: also referred to as general PC) polycarbonate resin in any combination, the shape of the molded product, molding method It can be adjusted to any molding fluidity, mechanical properties, and heat resistance.
By containing (a) the aromatic polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention, a high-flow copolymerization PC (a-1) and / or a polyorganosiloxane copolymer PC (a-2), (B) Since the influence of the fall of the mechanical characteristic (impact resistance) by a talc compound of a component is reduced, it can utilize suitably.
Among them, polydimethylsiloxane copolymer polycarbonate resin (also referred to as PC-PDMS) as polyorganosiloxane copolymer PC (a-2) improves the deterioration of mechanical properties (impact resistance) due to the incorporation of component (b) talc. Can be suitably used.

  (A) The high flow copolymerization PC (a-1) used for the aromatic polycarbonate resin is a phenol-modified diol copolymer polycarbonate and can be produced by a conventional production method called an interfacial polymerization method. That is, it can be produced by a method of reacting carbonate precursors such as dihydric phenol, phenol-modified diol and phosgene. Specifically, for example, in an inert solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, a catalyst or a branching agent is added as necessary, and dihydric phenol, phenol-modified diol and phosgene are added. A carbonate precursor such as is reacted.

で表される繰り返し単位を有する。
一般式（Ｉ）中、Ｒ¹、Ｒ²、ａ、ｂ及びＸについては、下記一般式（Ｉａ）と併せて説明する。また、一般式（ＩＩ）中、Ｒ³、Ｒ⁴、ｃ、ｄ、ｎ及びＹについては、後述する一般式（ＩＩａ）と併せて説明する。 High fluidity copolymerization PC (a-1) has the following general formulas (I) and (II)

It has the repeating unit represented by these.
In the general formula (I), R ¹ , R ² , a, b and X will be described together with the following general formula (Ia). In general formula (II), R ³ , R ⁴ , c, d, n, and Y will be described together with general formula (IIa) described later.

で表される化合物を挙げることができる。 The dihydric phenol used in the production of the highly fluid copolymerized PC includes the following general formula (Ia)

The compound represented by these can be mentioned.

In the general formula (Ia), R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, and an isohexyl group. , Cyclopentyl group, cyclohexyl group and the like. a and b each represent the number of substitutions of R ¹ and R ² and are integers of 0 to 4. In addition, when there are a plurality of R ^{1 s} , they may be the same as or different from each other. When there are a plurality of R ^{2 s} , they may be the same as or different from each other.

で表される基を示す。 X is a single bond, an alkylene group having 1 to 8 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylylene group, or a hexylene group), an alkylidene group having 2 to 8 carbon atoms (for example, an ethylidene group, Isopropylidene group, etc.), C5-C15 cycloalkylene group (for example, cyclopentylene group, cyclohexylene group, etc.), C5-C15 cycloalkylidene group (for example, cyclopentylidene group, cyclohexylidene group) etc.), - S -, - SO -, - SO 2 -, - O -, - CO- bond or the following formula (III) or formula (IV)

The group represented by these is shown.

  There are various dihydric phenols represented by the general formula (Ia), and 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is particularly preferable. Examples of bisphenols other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) butane; (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-1-methylphenyl) propane; bis (4-hydroxyphenyl) naphthylmethane; 1 1,2-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) ) Propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydro) Bis-3,5-tetrachlorophenyl) propane; bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) propane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 4'-dihydroxyphenyl ether; dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxy-3,3'- Dihydroxydiaryl sulfides such as dimethyldiphenyl sulfide, 4,4 ′ Dihydroxydiphenyl sulfoxide; dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone; 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone Dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl, 9,9-bis (4-hydroxyphenyl) fluorene; 9,9-bis (4-hydroxy-3-methylphenyl) fluorene Dihydroxydiarylfluorenes such as 1,3-bis (4-hydroxyphenyl) adamantane; 2,2-bis (4-hydroxyphenyl) adamantane; 1,3-bis (4-hydroxyphenyl) -5,7-dimethyl Jihi, such as adamantane Roxydiaryladamantanes, bis (4-hydroxyphenyl) diphenylmethane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene and the like. These dihydric phenols may be used alone or in admixture of two or more.

  Various molecular weight regulators can be used as long as they are usually used for polymerization of polycarbonate resin. Specifically, as monohydric phenol, for example, phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot -Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol M-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tribromo Phenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 in the ortho position, meta position or para position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl); Le) fluorene; 4- (1-adamantyl) phenol, and the like. Among these monohydric phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used.

  As the catalyst, a phase transfer catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, or a quaternary phosphonium salt can be preferably used. Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like. Examples of the tertiary amine salt include hydrochlorides and bromates of these tertiary amines. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, etc. , Tetrabutylphosphonium chloride, tetrabutylphosphonium bromide and the like. These catalysts may be used alone or in combination of two or more. Among the above catalysts, tertiary amines are preferable, and triethylamine is particularly preferable.

  There are various kinds of inert organic solvents. For example, dichloromethane (methylene chloride); trichloromethane; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane; -Tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene, toluene, acetophenone, and the like. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred.

  Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; 4,4 ′-[1- [4- [1 -(4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol; a compound having three or more functional groups such as phloroglysin, trimellitic acid, isatin bis (o-cresol); phloroglycin, trimellitic acid, isatin bis ( A compound having three or more functional groups such as (o-cresol) can also be used.

で表されるフェノール変性ジオールである。 The phenol-modified diol used in the production of the high-flow copolymerization PC has the following general formula (IIa)

It is a phenol modified diol represented by these.

In the general formula (IIa), R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. When there are a plurality of R ^{3 s} , they may be the same as or different from each other. When there are a plurality of R ^{4 s} , they may be the same as or different from each other. Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. As the alkylene group, an alkylene group such as an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group and an isopentylene group, an ethylidene group, Examples include alkylidene groups such as propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, and isopentylidene group. c and d are integers of 0 to 4, and n is an integer of 2 to 200. n is preferably 6 to 70.

  The phenol-modified diol represented by the general formula (IIa) is, for example, a compound derived from hydroxybenzoic acid or an alkyl ester thereof, an acid chloride and a polyether diol. This phenol-modified diol can be synthesized by the methods proposed in JP-A-62-79222, JP-A-60-79072, JP-A-2002-173465, and the like. It is desirable to appropriately purify the phenol-modified diol obtained by the above. As a purification method, for example, the system is depressurized in the latter stage of the reaction, and excess raw material (for example, parahydroxybenzoic acid) is distilled off, phenol-modified diol is removed with water or an aqueous alkaline solution (for example, an aqueous sodium bicarbonate solution), etc. The method of washing with is desirable.

  Representative examples of the hydroxybenzoic acid alkyl ester include hydroxybenzoic acid methyl ester and hydroxybenzoic acid ethyl ester. The polyether diol is represented by HO— (Y—O) n—H (Y and n are the same as described above), and is a repeating group consisting of a linear or branched oxyalkylene group having 2 to 15 carbon atoms. It has a unit. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polytetramethylene glycol is particularly preferable from the viewpoints of availability and hydrophobicity. The repeating number n of the oxyalkylene group of the polyether diol is 2 to 200, preferably 6 to 70. When n is 2 or more, the efficiency when copolymerizing the phenol-modified diol is high, and when n is 200 or less, there is an advantage that the heat resistance of the (a-1) polycarbonate copolymer is small.

  Representative examples of acid chlorides are those obtained from hydroxybenzoic acid and phosgene. More specifically, it can be obtained by the method described in Japanese Patent No. 2652707. Hydroxybenzoic acid or an alkyl ester thereof may be any of a para isomer, a meta isomer, and an ortho isomer, but the para isomer is preferable from the viewpoint of the copolymerization reaction. Ortho forms may be inferior in copolymerization reactivity due to steric hindrance to hydroxyl groups.

In the production process of the high fluidization copolymerized PC, the phenol-modified diol is preferably used as a methylene chloride solution as much as possible in order to prevent its alteration and the like. When it cannot be used as a methylene chloride solution, it can be used as an alkaline aqueous solution such as sodium hydroxide.
In the production process of the highly fluid copolymerized PC, increasing the copolymerization amount of the phenol-modified diol improves the fluidity but decreases the heat resistance. Therefore, the copolymerization amount of the phenol-modified diol is preferably selected according to the desired balance between fluidity and heat resistance. When the amount of the phenol-modified diol copolymerized is too large, as shown in JP-A-62-79222, it becomes elastomeric and may not be applicable to the same use as a general polycarbonate resin. In order to maintain heat resistance of 100 ° C. or higher, the amount of the phenol-modified diol residue contained in the high-flow copolymerized PC (a-1) polycarbonate copolymer is 1 to 30% by mass, preferably 1 -20% by mass, more preferably 1-15% by mass.

The high flow copolymerization PC has a viscosity number of 30 to 71 [equivalent to Mv (viscosity average molecular weight) = 10,000 to 28,100], preferably 34 to 62 (Mv = 12,000 to 24,100). Equivalent). When the viscosity number is 30 or more, the mechanical properties are good, and when the viscosity number is 71 or less, the copolymerization effect of the phenol-modified diol (comonomer) is exhibited well.
In addition, a large amount of comonomer is required to exhibit high fluidity, but when the viscosity number is 71 or less, the heat resistance does not greatly decrease with respect to the amount of comonomer used. The viscosity number is a value measured according to ISO 1628-4 (1999).

［式中、Ｒ⁵及びＲ⁶は、それぞれハロゲン原子（例えば、塩素、臭素、フッ素、沃素）又は炭素数１〜８のアルキル基であり、ｅ及びｆは、それぞれ０〜４の整数である。Ｒ⁵が複数ある場合、互いに同一でも異なっていてもよく、Ｒ⁶が複数ある場合、互いに同一でも異なっていてもよい。そして、Ｚは、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基又は−ＳＯ₂−、−ＳＯ−、−Ｓ−、−Ｏ−、−ＣＯ−結合、単結合もしくは下記一般式（ＶＩ） (A) The polyorganosiloxane copolymer PC (a-2) used for the aromatic polycarbonate resin includes various types, and preferably the following general formula (V)

[Wherein, R ⁵ and R ⁶ are each a halogen atom (eg, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, and e and f are each an integer of 0 to 4] . When there are a plurality of R ^{5 s} , they may be the same as or different from each other. When there are a plurality of R ^{6 s} , they may be the same as or different from each other. Z is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or —SO ₂ —, —SO. -, -S-, -O-, -CO- bond, single bond or the following general formula (VI)

で表される基を示す。］
で表される構造を有する繰り返し単位を有するポリカーボネート部と、下記一般式（ＶＩＩ）

The group represented by these is shown. ]
A polycarbonate part having a repeating unit having a structure represented by the following general formula (VII)

［式中、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ水素原子、炭素数１〜６のアルキル基又はフェニル基であり、それぞれ同一でも異なっていてもよい。また、ｇ及びｈは、それぞれ０又は１以上の整数である。］
で表わされる繰返し単位を有するポリオルガノシロキサン部とからなるものである。
このポリオルガノシロキサン部の重合度は、５〜１０００が好ましく、より好ましくは２０〜３００であるものが、難燃性、成形品の外観の点から好ましい。ポリオルガノシロキサン共重合ＰＣは、上記一般式（Ｖ）で表わされる繰返し単位を有するポリカーボネート部と、上記一般式(ＶＩＩ)で表わされる繰返し単位を有するポリオルガノシロキサン部とからなるブロック共重合体であって、粘度平均分子量１０,０００〜５０,０００、好ましくは１５,０００〜３５,０００のものである。また、ポリカーボネート−ポリオルガノシロキサン共重合体のｎ−ヘキサン可溶分が１.０質量％以下であることが好ましい。
このポリオルガノシロキサン共重合ＰＣは、難燃性の観点からポリオルガノシロキサン部の含有量は好ましくは０．１〜１０質量％であり、更に好ましくは０．５〜５質量％である。

[In formula, R < ⁷ >, R < ⁸ > and R < ⁹ > are respectively a hydrogen atom, a C1-C6 alkyl group, or a phenyl group, and may be same or different, respectively. G and h are each 0 or an integer of 1 or more. ]
The polyorganosiloxane part which has a repeating unit represented by these.
The degree of polymerization of the polyorganosiloxane part is preferably 5 to 1000, more preferably 20 to 300, from the viewpoint of flame retardancy and the appearance of the molded product. The polyorganosiloxane copolymer PC is a block copolymer comprising a polycarbonate part having a repeating unit represented by the general formula (V) and a polyorganosiloxane part having a repeating unit represented by the general formula (VII). The viscosity average molecular weight is 10,000 to 50,000, preferably 15,000 to 35,000. Moreover, it is preferable that the n-hexane soluble part of a polycarbonate polyorganosiloxane copolymer is 1.0 mass% or less.
In the polyorganosiloxane copolymerized PC, the content of the polyorganosiloxane part is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass from the viewpoint of flame retardancy.

  This polyorganosiloxane copolymerized PC includes, for example, a previously produced polycarbonate oligomer (PC oligomer) constituting a polycarbonate part and a polyorganosiloxane having a reactive group at the terminal constituting a polyorganosiloxane part [for example, poly Dimethylsiloxane (PDMS), polydialkylsiloxane such as polydiethylsiloxane or polymethylphenylsiloxane] is dissolved in a solvent such as methylene chloride, chlorobenzene, chloroform, etc., and an aqueous sodium hydroxide solution of bisphenol is added, and triethylamine or It can be produced by interfacial reaction using trimethylbenzylammonium chloride or the like. Also, a polycarbonate-polyorganosiloxane copolymer produced by the method described in Japanese Patent Publication No. 44-30108 and Japanese Patent Publication No. 45-20510 can be used.

  The polycarbonate oligomer having a repeating unit represented by the general formula (V) used as the polyorganosiloxane copolymer PC is a solvent method, that is, in the presence of a known acid acceptor or molecular weight regulator in a solvent such as methylene chloride. General formula (VIII)

［式中、Ｒ⁵、Ｒ⁶、Ｚ、ｅ及びｆは、前記と同じである。］
で表わされる二価フェノールとホスゲンのようなカーボネート前駆体との反応又は二価フェノールとジフェニルカーボネートのようなカーボネート前駆体とのエステル交換反応によって製造することができる。上記一般式(ＶＩＩＩ)で表わされる二価フェノールとしては様々なものがあるが、特に２，２−ビス（４−ヒドロキシフェニル）プロパン〔所謂ビスフェノールＡ〕が好ましい。また、ビスフェノールＡの一部又は全部を他の二価フェノールで置換したものであってもよい。ビスフェノールＡ以外の二価フェノールとしては、ビス（４−ヒドロキシフェニル）アルカン、ハイドロキノン；４，４’−ジヒドロキシジフェニル；ビス（４−ヒドロキシフェニル）シクロアルカン；ビス（４−ヒドロキシフェニル）スルフィド；ビス（４−ヒドロキシフェニル）スルホン；ビス（４−ヒドロキシフェニル）スルホキシド；ビス（４−ヒドロキシフェニル）エーテル；ビス（４−ヒドロキシフェニル）ケトンのような化合物又はビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン；ビス（３，５−ジクロロ−４−ヒドロキシフェニル）プロパンのようなハロゲン化ビスフェノール類等を挙げることができる。

[Wherein, R ⁵ , R ⁶ , Z, e and f are the same as described above. ]
It can be produced by a reaction of a dihydric phenol represented by the formula (1) with a carbonate precursor such as phosgene or a transesterification reaction of a dihydric phenol with a carbonate precursor such as diphenyl carbonate. There are various dihydric phenols represented by the above general formula (VIII), and 2,2-bis (4-hydroxyphenyl) propane [so-called bisphenol A] is particularly preferable. Further, a part or all of bisphenol A may be substituted with another dihydric phenol. Examples of dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) alkane and hydroquinone; 4,4′-dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; 4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; a compound such as bis (4-hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) ) Propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane.

The polycarbonate oligomer used for the production of the polyorganosiloxane copolymerized PC may be a homopolymer using one of these dihydric phenols, or may be a copolymer using two or more. Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient. In order to produce a polycarbonate-polyorganosiloxane copolymer having an n-hexane soluble content of 1.0% by mass or less, for example, the polyorganosiloxane content in the copolymer is made 10% by mass or less. In addition, the number of repeating units represented by the general formula (VII) is 5 or more, and a catalyst such as a tertiary amine is used at 5.3 × 10 ⁻³ mol / (kg oligomer) or more. Polymerization is preferably performed.

  (A) General PC (a-3) used for aromatic polycarbonate resin is produced by a conventional production method, that is, usually by reacting a dihydric phenol with a polycarbonate precursor such as phosgene or a carbonate compound. Can be mentioned. Specifically, for example, in a solvent such as methylene chloride, a branching agent is added as necessary in the presence of a known acid acceptor or molecular weight regulator, and a dihydric phenol and a carbonate precursor such as phosgene are added. It is produced by a reaction or by a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate.

  There are various dihydric phenols used for the production of general PC, and 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is particularly preferable. As the bisphenol other than bisphenol A, for example, those exemplified for the aforementioned polycarbonate copolymer can be used.

  Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Various kinds of molecular weight regulators can be used as long as they are usually used for polymerization of polycarbonate. Specifically, what was illustrated by the above-mentioned polycarbonate copolymer, such as a phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, is used as monohydric phenol, for example. Among monohydric phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used.

  In addition, as the branching agent, for example, 1,1,1-tris (4-hydroxyphenyl) ethane; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3 , 5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglysin, A compound having three or more functional groups such as trimellitic acid and isatin bis (o-cresol) can also be used.

In general, the general PC used in the present invention preferably has a viscosity average molecular weight of 10,000 to 100,000, more preferably 13,000 to 40,000. As the general PC, those described above or commercially available products can be used.
(A) Mixing ratio (a-1) of high flow PC (a-1), polyorganosiloxane copolymerized PC (a-2) and general PC (a-3) contained in the aromatic polycarbonate resin: (a -2): (a-3) is preferably 1 to 100: 99 to 0:99 to 0, more preferably 10 to 90:90 to 10:80 to 0, and still more preferably 20 to 20 by mass ratio. 60: 80-10: 70-10.

[(B) White pigment]
(B) Various pigments can be used as the white pigment. Specific examples include titanium oxide, zinc oxide, lithopone, zinc sulfide, and lead white. In these, the titanium oxide which is excellent in coloring power is preferable. Titanium oxide may be either a rutile type or an anatase type, but it is preferable to use a rutile type that is excellent in thermal stability and weather resistance. It is effective to treat titanium oxide with various surface treatment agents and coat the surface. As the treating agent, hydrated aluminum, silica, zinc or the like is usually used. In addition, in order to improve the dispersibility of the titanium oxide in the resin, silicone oil, polyol, or the like can be used.

[(C) Talc]
In the present invention, talc subjected to alkali neutralization treatment and silane coupling surface treatment is used as the inorganic filler.
As described above, ordinary talc is alkaline and hydrolyzes the polycarbonate resin. For this reason, the mechanical characteristic accompanying the molecular weight deterioration of polycarbonate-type resin is brought about. In the present invention, this problem is solved by applying talc that has been subjected to an alkali neutralization treatment with an acid in advance. Further, by suppressing the molecular weight deterioration due to this neutralization treatment, the inorganic particles of (b) white pigment and (c) talc can be blended at a high concentration in the present invention.
Moreover, the talc used for this invention uses what gave the silane coupling surface treatment after the alkali neutralization process. This silane coupling surface treatment is effective in improving the mechanical properties by improving the adhesion strength with the resin interface and suppressing the elution of alkali metal ions remaining in a trace amount.
Examples of the coupling agent used for the silane coupling surface treatment include amino-modified silane, carboxy-modified silane, acrylic-modified silane, and epoxy-modified silane, and any of them can be suitably used.

In the flame-retardant polycarbonate resin composition of the present invention, the mass ratio of (a) component: (b): (c) component in 100 parts by mass of the total amount of components (a) to (c) is 91-40: 4— It is 40: 4-20, Preferably it is 80-50: 10-30: 30-10.
By setting the mass ratio of the component (a) to 91 or less, the content of titanium oxide and talc is ensured, and sufficient light reflectivity, light shielding properties, thermal conductivity (heat dissipation), mechanical properties (rigidity), dimensions Stability can be expressed, and by setting it to 40 or more, sufficient molding fluidity can be ensured.
By setting the mass ratio of the component (b) to 4 or more, the light reflectivity and the light shielding property are improved, and by setting it to 40 or less, it is difficult to mix at the time of melt-kneading and mechanical properties (impact resistance). Decrease is reduced.
By setting the mass ratio of the component (c) to 4 or more, mechanical properties (rigidity) and dimensional stability are improved, and by setting it to 40 or less, the decrease in mechanical properties (impact resistance) is reduced.

[(D) Organopolysiloxane]
(D) Organopolysiloxane can be mix | blended with the flame-retardant polycarbonate resin composition of this invention.
(D) As organopolysiloxane, alkyl hydrogen silicone and alkoxy silicone are preferably used. Can be mentioned.
(D) As the organopolysiloxane, an alkoxypolysiloxane having a molecular structure in which an alkoxysilicone is bonded to an alkoxy group via a methylene group with respect to the silicone main chain (BY16-161) is particularly preferably used. .
The content of the component (d) is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (a) to (c). More preferably, it is 0.1-2 mass parts, Especially preferably, it is 0.4-2 mass parts.
(D) By blending 0.01 part by mass or more of organopolysiloxane, (a) the polycarbonate resin can be prevented from deteriorating and the molecular weight can be suppressed, and the molded article can be made to be 3 parts by mass or less. There is no risk that silver will be generated on the surface and the appearance of the product will be reduced.

[(E) Flame retardant]
(E) A flame retardant can be mix | blended with the flame-retardant polycarbonate resin composition of this invention. There is no restriction | limiting in particular in (e) component, Although flame retardants, such as a phosphorus type | system | group, a metal salt type, and a silicone type, can be used, A polyorganosiloxane containing graft copolymer is used suitably.
Preferable specific examples of the polyorganosiloxane-containing graft copolymer include (Y) polyfunctional monomer (y-1) 100 to 50 mass in the presence of (X) 40 to 90 mass parts of polyorganosiloxane particles. % And other copolymerizable monomer (y-2) 0.5 to 10 parts by weight of vinyl monomer consisting of 0 to 50% by weight, and (Z) other vinyl monomer The thing obtained by superposing | polymerizing 5-50 mass parts is mentioned. [However, the total amount of (X), (Y) and (Z) is 100 parts by mass]

(X) The polyorganosiloxane particles have a number average particle diameter determined by light scattering or electron microscope observation, preferably 0.008 to 0.6 μm, more preferably 0.01 to 0.2 μm, and particularly preferably 0. 0.01 to 0.15 μm. When the number average particle diameter is less than 0.008 μm, it tends to be difficult, and when it exceeds 0.6 μm, the flame retardancy tends to deteriorate.
Further, (X) the amount of insoluble toluene in the polyorganosiloxane particles (the amount of insoluble toluene when 0.5 g of the particles are immersed in 80 ml of toluene at room temperature for 24 hours) is 95% or less, more preferably 50% or less, particularly 20%. The following are preferable from the viewpoint of flame retardancy and impact resistance.

  The polyfunctional monomer (y-1) is a compound containing two or more polymerizable unsaturated bonds in the molecule. Specific examples include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, Examples include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. These may be used alone or in combination of two or more. In these, use of allyl methacrylate is preferable from the point of economical efficiency and an effect.

  Specific examples of the other copolymerizable monomer (y-2) include aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, and parabutylstyrene, acrylonitrile, and methacrylo. Vinyl cyanide monomers such as nitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methacrylic acid (Meth) acrylate monomers such as methyl, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, etc. Carboxyl group-containing vinyl monomers And the like. These may be used alone or in combination of two or more.

(Z) The other vinyl-based monomer is a component used to obtain a polyorganosiloxane-containing graft copolymer. Further, the graft copolymer is blended with an aromatic polycarbonate resin to provide flame retardancy and When improving impact resistance, it is also a component used to ensure the compatibility of the graft copolymer and the aromatic polycarbonate resin and to uniformly disperse the graft copolymer in the aromatic polycarbonate resin.
Therefore, as the other vinyl monomer (Z), the solubility parameter of the polymer of the vinyl monomer is preferably 9.15 to 10.15 [(cal / cm ³ ) ^1/2 ]. More preferably, it is 9.17 to 10.10 [(cal / cm ³ ) ^1/2 ], and particularly preferably 9.20 to 10.05 [(cal / cm ³ ) ^1/2 ]. When the solubility parameter is within the above range, the flame retardancy is improved. Details of the solubility parameter are described in JP-A No. 2003-238639.

(E) It is preferable that the average particle diameter of a component can be disperse | distributed by 0.1-1 micrometer by the value calculated | required from electron microscope observation. When the average particle diameter is larger than 1 μm, sufficient flame retardancy, rigidity and impact strength cannot be obtained, and when it is smaller than 0.1 μm, the impact strength is not sufficiently improved.
(E) The compounding quantity of a component is about 0.1-5 mass parts normally with respect to 100 mass parts of total amounts of (a)-(c) component, Preferably it is 0.2-4 mass parts, More preferably 0.4 to 3 parts by mass. By setting it as 0.1 mass part or more, a flame retardance and impact strength are obtained, and a flame retardance and rigidity do not fall by setting it as 5 mass parts or less.
However, the component (e) can be blended in accordance with the demand for flame retardancy level. (E) Even if the component is not blended, if the blending amount of (c) talc exceeds about 10 parts by mass, the flame retardancy specified in UL standards should be ensured depending on the thickness of the test piece. Can do.

[Others]
Moreover, a phosphorus stabilizer, polytetrafluoroethylene, and various additives can be mix | blended with the flame-retardant polycarbonate resin composition of this invention as needed.
Phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of such phosphorus stabilizers include phosphoric acid compounds and / or aromatic phosphine compounds.

  Examples of phosphoric acid compounds include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-Di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert- Tilphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxylenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-tert-butylphenyl), benzenephosphone Examples thereof include dimethyl acid, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the following compounds 1 to 10.

  Among these, the compound 1, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by ADEKA, trade name: PEP-36) and tris (2,4- Di-tert-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, trade name: Irg168) is preferred.

As an aromatic phosphine compound, for example, the following general formula (IX)
P- (W) ₃ (IX)
[Wherein W is a hydrocarbon group, at least one of which is an aryl group having 6 to 18 carbon atoms which may have a substituent. ]
The aryl phosphine compound represented by these is mentioned.

Examples of the arylphosphine compound of the general formula (IX) include triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris- (p-tolyl) phosphine, tris- (p-nonylphenyl) phosphine, and tris- (naphthyl). ) Phosphine, diphenyl- (hydroxymethyl) -phosphine, diphenyl- (acetoxymethyl) -phosphine, diphenyl- (β-ethylcarboxyethyl) -phosphine, tris- (p-chlorophenyl) phosphine, tris- (p-fluorophenyl) Phosphine, diphenylbenzylphosphine, diphenyl-β-cyanoethylphosphine, diphenyl- (p-hydroxyphenyl) -phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine And phenylnaphthylbenzylphosphine. Among these, triphenylphosphine can be particularly preferably used.
A phosphorus stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compounding quantity of the phosphorus stabilizer used by this invention is 0.001-1 mass part normally with respect to 100 mass parts of aromatic polycarbonate resin of (a) component, Preferably it is 0.005-0.5 mass part. More preferably, it is 0.01-0.1 mass part. When the blending amount of the phosphorus stabilizer is within the above range, the thermal stability during molding is improved.

The polytetrafluoroethylene blended in the flame retardant polycarbonate resin composition is not particularly limited as long as it has fibril forming ability. Here, the fibril forming ability refers to a tendency of the resins to be bonded and become fibrous due to an external action such as shearing force.
The polytetrafluoroethylene having fibril-forming ability imparts the effect of preventing melt dripping to the resin composition of the present invention and exhibits excellent flame retardancy. Specific examples include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers) and the like. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as “PTFE”) is preferable.

  PTFE having fibril-forming ability has a very high molecular weight and is a number average molecular weight determined from the standard specific gravity, and is usually 500,000 or more, preferably 500,000 to 15 million, more preferably 1,000,000 to 10 million. Such PTFE, for example, polymerizes tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide at a pressure of 7 to 700 kPa at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. Can be obtained. Such PTFE can be used in solid form or in the form of an aqueous dispersion.

As PTFE having such fibril forming ability, for example, those classified into type 3 according to the ASTM standard can be used. Examples of commercially available products classified as Type 3 include Teflon (registered trademark) 6-J (trade name, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1 and Polyflon F-103 (trade name, Daikin). Kogyo Co., Ltd.). Other than Type 3, Algoflon F5 (trade name, manufactured by Montefluos) and Polyflon MPA FA-100 (trade name, manufactured by Daikin Industries, Ltd.) can be used.
Polytetrafluoroethylene can be used alone or in combination of two or more.
The compounding quantity of polytetrafluoroethylene is about 0.1-0.5 mass part with respect to a total of 100 mass parts of (a) component and (b) component, Preferably it is 0.2-0.4. Part by mass.

  Examples of various additives blended in the flame retardant polycarbonate resin composition include hindered phenol-based and ester-based antioxidants, hindered amine-based light stabilizers, commonly used release agents, and antistatic agents. , Fluorescent whitening agents and the like, and these can be appropriately contained.

[Flame-retardant polycarbonate resin composition and light reflecting member]
The flame-retardant polycarbonate resin composition of the present invention is applied to various known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, etc. It can be. Moreover, it can extrude using the flame-retardant polycarbonate resin composition of this invention, can be heat-molded or press-molded, and can obtain a favorable molded object.
Specific examples of the heat molding method include a method in which the preform is heated and molded with vacuum and / or compressed air pressure. Here, the heating may be performed from one side or both sides of the preform, and may be performed by directly contacting the heat source. At this time, when the heating temperature is less than 150 ° C., uniform molding may not be possible, and when it exceeds 200 ° C., foaming tends to occur, which is not preferable.
The method of thermoforming is not particularly limited, for example, simple vacuum forming method, drape homing method, matched die method, pressure bubble plug assist vacuum forming method, plug assist method, vacuum snapback method, pressure bubble vacuum snapback method, Examples thereof include air slip homing, trapped sheet contact heating-pressure homing, and a simple pressure forming method.
The pressure at the time of molding is preferably 0.1 MPa or less in the case of the vacuum forming method and 0.3 to 0.8 MPa in the case of the pressure forming method, and the vacuum forming method and the pressure forming method can be performed in combination. By this thermoforming, a shape corresponding to the type and number of light sources and a shape capable of uniform surface reflection can be obtained.
This molded body has excellent mechanical properties (rigidity), heat dissipation (thermal conductivity), heat resistance (dimensional stability), and flame retardancy, as well as high light reflectivity and light shielding properties. It can be suitably used for producing molded products such as light reflectors or molded products and parts in the field of optical elements and the like.

Moreover, it is also possible to produce a molded body having both a reflector and a chassis function by subjecting the flame-retardant polycarbonate resin composition of the present invention to extrusion molding.
Further, the flame retardant polycarbonate resin composition of the present invention thus obtained is molded into a flat plate or a curved plate using a normal molding method, for example, an injection molding method or a compression molding method. The light reflecting member of the present invention is obtained.
This light reflecting member is preferably used, for example, for an illumination device or a liquid crystal display backlight, and is particularly suitable as a reflector for a liquid crystal display backlight. Since the light reflecting member of the present invention does not contain a bromine compound in the material, it has excellent light resistance, little decrease in reflectance even when used for a long period of time, and exhibits excellent characteristics such as excellent characteristics. It is equipped with. Furthermore, since the light reflecting member of the present invention does not contain a bromine compound in the material, the light reflecting member is excellent in light resistance, has little decrease in reflectance even when used for a long period of time, and exhibits excellent characteristics such as excellent characteristics. It has the special characteristics.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, performance evaluation in each Example and a comparative example was performed in accordance with the following measuring method.

(1) Mechanical properties Flexural modulus (rigidity); conformed to ASTM D790 (measurement condition 23 ° C.).
Izod impact strength (impact resistance); conformed to ASTM D790 (measurement condition 23 ° C.).
(2) Light reflectance Y
The pellets obtained in each Example and Comparative Example were each hot-air dried at 120 ° C. for 5 hours, and then using a molding machine [Sumitomo Heavy Industries, Ltd., Sumitomo Nestal N515 / 150], a molding temperature of 300 ° C., A flat plate for reflectance measurement of 140 mm × 140 mm × 3.2 mm was produced at a mold temperature of 80 ° C.
The light reflectance was evaluated by the Y value using an LCM spectrophotometer MS2020 plus (manufactured by Macbeth).

(3) Light shielding property: total light transmittance (%)
A flat plate for measuring total light transmittance of 80 mm × 80 mm × 1.0 mm at a molding temperature of 300 ° C. and a mold temperature of 80 ° C. using a molding machine (Sumitomo Heavy Industries, Ltd., Sumitomo Nestal N515 / 150). Was made. Based on JIS K7105, the parallel light transmittance was measured with a testing machine manufactured by Nippon Denshoku Industries Co., Ltd.
(4) Heat dissipation (thermal conductivity)
Using an IS80EPN (80t) injection molding machine, molding a square plate molded product of 60 mm × 60 mm × thickness 2 mm made of pellets obtained in each example and comparative example at the resin temperature and mold temperature shown in the table, The thermal conductivity coefficient was measured in the hot disk method slab mode using a thermal conductivity measuring device TPA-501 (manufactured by Kyoto Electronics Co., Ltd.).

(5) Heat resistance (heat-resistant dimensional stability)
Using a 1.6 mm thick UL standard test piece, the dimensional change in the longitudinal direction of the test piece after being held at 90 ° C. for 480 hours was measured, and the rate of change (%) with respect to the initial dimension was calculated.
(6) Flame retardancy evaluation test The pellets obtained in each of the examples and comparative examples were each hot-air dried at 120 ° C for 5 hours, and then a molding temperature of 300 using Nestal N515 / 150 manufactured by Sumitomo Heavy Industries, Ltd. A test piece for a combustion test having a thickness of 127 mm × 12 mm × 1 mm was prepared at a mold temperature of 80 ° C. and a mold temperature of 80 ° C. The produced test piece was evaluated by a flame resistance test in accordance with UL94 [Flame retardance: UL94V-0 (thickness 1.6 mmt) compliance test].
UL94 is a method for evaluating flame retardancy from the after-flame time after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, and passed the V-0 test. , And the case of failing the V-0 test was evaluated as x.

<Production example>
<Production Example 1 of Copolymerized Comonomer>
[Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate): average molecular weight of PTMG chain = 2000]
Under nitrogen, 100 parts by mass of polytetramethylene glycol (PTMG, Mn = 2000) and 16.7 parts by mass of methyl p-hydroxybenzoate were heated at 210 ° C. in the presence of 0.05 part by mass of dibutyltin oxide, and methanol was added. Distilled off.
The reaction system was depressurized, and excess methyl p-hydroxybenzoate was distilled off. After the reaction product was dissolved in methylene chloride, 8% by mass aqueous sodium hydrogen carbonate solution was added to the methylene chloride solution, vigorously mixed for 20 minutes, and the methylene chloride phase was collected by centrifugation. The methylene chloride phase was concentrated under reduced pressure to obtain polytetramethylene glycol-bis (4-hydroxybenzoate). As a result of quantifying p-hydroxybenzoic acid and methyl p-hydroxybenzoate by high performance liquid chromatography (HPLC), p-hydroxybenzoic acid was less than 10 ppm by mass, and methyl p-hydroxybenzoate was 0.2% by mass. It was.
The HPLC measurement method was performed using an ODS-3 column manufactured by GL Science Co., under a column temperature of 40 ° C., a 1: 2 mixed solvent of 0.5% phosphoric acid aqueous solution and acetonitrile, and a flow rate of 1.0 mL / min. . The quantification was calculated based on a calibration curve with a standard.

<Production Example 2 of Copolymerized Comonomer>
[Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate): average molecular weight of PTMG chain = 1000]
The same procedure as in Production Example 1 was performed except that 100 parts by mass of polytetramethylene glycol (PTMG, Mn = 1000) and 33.4 parts by mass of methyl p-hydroxybenzoate were used.
The amount of p-hydroxybenzoic acid was less than 10 ppm by mass, and the amount of methyl p-hydroxybenzoate was 0.3% by mass.

<Production Example 3 of Copolymerized Comonomer>
[Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate): average molecular weight of PTMG chain = 600]
The same procedure as in Production Example 1 was conducted except that 100 parts by mass of polytetramethylene glycol (PTMG, Mn = 600) and 50 parts by mass of methyl p-hydroxybenzoate were used.
The amount of p-hydroxybenzoic acid was less than 10 ppm by mass, and the content of methyl p-hydroxybenzoate was 0.2% by mass.

<Production Example 4 of Copolymerized Comonomer>
[Synthesis of polytetraethylene glycol-bis (4-hydroxybenzoate): average molecular weight of PTEG chain = 1000]
The same procedure as in Production Example 1 was conducted except that 100 parts by mass of polytetraethylene glycol (PTEG, Mn = 1000) and 33.4 parts by mass of methyl p-hydroxybenzoate were used.
The amount of p-hydroxybenzoic acid was less than 10 ppm by mass, and the amount of methyl p-hydroxybenzoate was 0.3% by mass.

<Production of polycarbonate oligomer solution>
Add 2,000 ppm sodium dithionite to 5.6 mass% sodium hydroxide aqueous solution to bisphenol A (BPA) that is dissolved later, and dissolve BPA to a BPA concentration of 13.5 mass%. Then, an aqueous sodium hydroxide solution of BPA was prepared. Phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hr at a flow rate of 40 L / hr of sodium hydroxide aqueous solution of BPA and 15 L / hr of methylene chloride. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket. The reaction solution exiting the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and further 2.8 L / hr of sodium hydroxide aqueous solution of BPA, 25% by mass. Sodium hydroxide aqueous solution 0.07L / hr, water 17L / hr, 1 mass% triethylamine aqueous solution was added at 0.64L / hr, and reaction was performed. The reaction liquid overflowing from the tank reactor was continuously extracted and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
The polycarbonate oligomer thus obtained had a concentration of 329 g / L and a chloroformate group concentration of 0.74 mol / L.

<Manufacture of high flow copolymerization PC: PCC1>
Polycarbonate methylene chloride 15L prepared above, 8.9 L methylene chloride, polytetramethylene glycol bis (4-hydroxybenzoate) prepared above in a 50 L tank reactor equipped with baffle plate, paddle type stirring blade and cooling jacket ) 325 g (average molecular weight of PTMG chain = 2000) and 8.7 mL of triethylamine were added, and under stirring, 1710 g of a 6.4 mass% aqueous sodium hydroxide solution was added thereto for 10 minutes, and the polycarbonate oligomer and polytetramethylene glycol-bis (4 -Hydroxybenzoate) reaction.
In this polymerization solution, methylene chloride solution of pt-butylphenol (PTBP) (225 g of PTBP dissolved in 2.0 L of methylene chloride), sodium hydroxide aqueous solution of BPA (617 g of NaOH and 1.9 g of sodium dithionite in water) A solution obtained by dissolving 930 g of BPA in an aqueous solution dissolved in 9.0 L) was added, and a polymerization reaction was carried out for 50 minutes.
For dilution, 15 L of methylene chloride was added and stirred for 10 minutes. Then, the organic phase was separated into an organic phase containing polycarbonate and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.

The polycarbonate methylene chloride solution thus obtained was sequentially washed with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid, and then the electric conductivity in the aqueous phase after washing. Washing with pure water was repeated until the value became 0.01 μS / m or less.
The methylene chloride solution of polycarbonate obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 100 ° C. under reduced pressure.
The amount of polytetramethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 4.0% by mass.
The viscosity number was 38.1 (Mv = 13500) measured according to ISO 1628-4 (1999) (hereinafter, the viscosity number was measured in the same manner).

<Production of Highly Fluidized Copolymer PC: PCC2>
Except for changing 325 g of polytetramethylene glycol-bis (4-hydroxybenzoate) (average molecular weight of PTMG chain = 2000) to 163 g of polytetraethylene glycol-bis (4-hydroxybenzoate) (average molecular weight of PTEG chain = 1000) It carried out similarly to manufacture of PCC1.
The amount of polytetraethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 2.0% by mass.
The viscosity number was 38.0 (Mv = 13500).

<Manufacture of high flow copolymerization PC: PCC3>
PCC1 except that polytetramethylene glycol-bis (4-hydroxybenzoate) (average molecular weight of PTMG chain = 2000) was added to 813 g, PTBP usage was changed to 246 g, and the drying temperature was changed from 100 ° C. to 80 ° C. It carried out similarly to manufacture of.
The amount of polytetramethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 10.7% by mass.
The viscosity number was 35.6 (Mv = 12400).

<Manufacture of high flow copolymerization PC: PCC4>
325 g of polytetramethylene glycol-bis (4-hydroxybenzoate) (average molecular weight of PTMG chain = 2000) was converted into 813 g of polytetramethylene glycol-bis (4-hydroxybenzoate) (average molecular weight of PTMG chain = 600) of PTBP. The same procedure as in the production of PCC1 was carried out except that the amount used was changed to 213 g and the drying temperature was changed to 80 ° C.
The amount of polytetramethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 9.9% by mass.
The viscosity number was 39.6 (Mv = 14200).

<Polyorganosiloxane Copolymerized PC (PC-PDMS): Production of PCC5>
Allylphenol end-modified with 15L polycarbonate oligomer solution prepared above, 8.9L methylene chloride, 90 repeats of dimethylsilanooxy units in a 50L tank reactor equipped with baffle plate, paddle type stirring blade and cooling jacket 625 g of PDMS and 8.7 mL of triethylamine were charged, and 1390 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto with stirring, and the reaction between the polycarbonate oligomer and allylphenol terminal-modified PDMS was performed for 10 minutes.
In this polymerization solution, a solution of PTBP in methylene chloride (in which 172 g of PTBP was dissolved in 2.0 L of methylene chloride), an aqueous solution of sodium hydroxide in BPA (an aqueous solution in which 566 g of NaOH and 2.2 g of sodium dithionite were dissolved in 8.3 L of water) 1) of BPA (1116 g) was added and the polymerization reaction was carried out for 50 minutes.
For dilution, 15 L of methylene chloride was added and stirred for 10 minutes. Then, the organic phase was separated into an organic phase containing polycarbonate and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.

The polycarbonate methylene chloride solution thus obtained was sequentially washed with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid, and then the electric conductivity in the aqueous phase after washing. Washing with pure water was repeated until the value became 0.01 μS / m or less.
The methylene chloride solution of polycarbonate obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
The amount of PDMS residue determined by NMR was 10.0% by mass.
The viscosity number was 41.5 (Mv = 15000).

Examples 1-16 and Comparative Examples 1-6
The following raw materials are blended in parts by mass shown in Tables 1 to 3, and kneaded at a temperature of 280 ° C. by a twin-screw extruder with a vent (Toshiba Machine Co., Ltd., model name: TEM35) to form a pellet. did. The performance of the obtained pellets was evaluated by the above method, and the results are shown in Tables 1 to 3. In Comparative Example 6, kneading was impossible and performance evaluation could not be performed.

(A) Component: Aromatic polycarbonate resin (a-1) Component: High fluidity copolymerized PC, PCC1-4 (produced according to production examples)
(A-2) Component: Polyorganosiloxane copolymerized PC (PC-PDMS)
Toughlon FC1700
(Idemitsu Kosan Co., Ltd., Mv = 17500, PDMS content 3.5 mass%)
PCC5 (produced according to production example)
(A-3) Component: Polycarbonate resin (general PC)
Toughlon FN1700 (made by Idemitsu Kosan Co., Ltd., Mv = 17500)
(B) Component: Titanium oxide powder PF726 (Ishihara Sangyo Co., Ltd., trade name: PF726, average particle size 0.21 μm)
PC3 (Ishihara Sangyo Co., Ltd., trade name: PC3, average particle size 0.21 μm)
(C) Component: Talc 13T (B); Amino-modified silane coupling agent surface-treated product 13T (C); Vinyl-modified silane coupling agent surface-treated product 13T (D); Epoxy-modified silane coupling agent surface-treated product (above All are manufactured by Asada Flour Milling Co., Ltd .: alkali neutralized product)
TP-A25 [Fujitalc Co., Ltd., for comparison]
(D) Component: Organopolysiloxane BY-16-161 (trade name, manufactured by Toray Dow Corning Co., Ltd.)
(E) Component: Flame retardant: Polyorganosiloxane-containing graft copolymer MR-01 (trade name, manufactured by Kaneka Corporation)
KFBS (organometallic flame retardant)
Flame retardant aid: Polytetrafluoroethylene (PTFE)
PTFE (Asahi Glass Co., Ltd., trade name: CD076)

From the above Tables 1 to 3, the following was found.
(1) As shown in each example, according to the present invention, by blending specific talc and titanium oxide with polycarbonate resin, it has excellent light reflectivity, light shielding property, heat dissipation property, and heat-resistant dimensional stability. Thus, a polycarbonate resin composition having excellent flame retardancy can be obtained.
(2) In the present invention, by using specific talc, hydrolysis degradation of the polycarbonate-based resin due to conventional talc is suppressed, so that high concentrations of talc and titanium oxide can be blended. As shown in 6 to 8, it is possible to obtain a light reflecting member having further excellent light reflectivity and light blocking property and excellent in heat-resistant dimensional stability.

  The polycarbonate resin composition of the present invention has excellent heat resistance and flame retardancy, and also has excellent light reflectivity, light shielding properties, heat dissipation, mechanical properties (rigidity), and dimensional stability of the molded product. Parts such as backlights (reflectors, frames, lamp supports, chassis-integrated reflectors), parts for general lighting devices (housings, reflectors, frames, etc.), LED reflector cases, operation panels for automobiles, etc. It is suitably used for products that require reflection, light shielding and flame retardancy at the same time.

Claims (9)

  (A) Aromatic polycarbonate resin, (b) White pigment and (c) Alkali neutralization treatment and silane coupling surface-treated talc are contained, and (a) to (c) components in a total amount of 100 parts by mass (a The flame retardant polycarbonate resin composition is characterized in that the mass ratio of component (b): component (b): component (c) is 91-40: 4-40: 4-20.   The flame-retardant polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin as component (a) contains a high-fluidity polycarbonate copolymer and / or a polycarbonate-polyorganosiloxane copolymer.   The flame retardant polycarbonate resin composition according to claim 2, wherein the aromatic polycarbonate resin of component (a) contains a polycarbonate-polydimethylsiloxane copolymer.   The silane coupling surface treatment of component (c) talc is at least one silane coupling surface treatment selected from amino-modified silane, carboxy-modified silane, acrylic-modified silane, and epoxy-modified silane. The flame-retardant polycarbonate resin composition according to any one of the above.   (A) It contains 0.1-3 parts by mass of an organopolysiloxane and (e) 0.1-5 parts by mass of a polyorganosiloxane-containing graft copolymer with respect to 100 parts by mass of the components. The flame-retardant polycarbonate resin composition according to any one of claims 1 to 4.   (D) The flame retardant polycarbonate resin composition according to claim 5, wherein the organopolysiloxane is an alkyl hydrogen silicone or an alkoxy silicone.   The flame-retardant polycarbonate resin composition according to claim 6, wherein the alkoxysilicone is an organopolysiloxane having a molecular structure bonded to an alkoxy group via a methylene group with respect to the silicone main chain.   (E) In the presence of 40 to 90 parts by mass of (X) polyorganosiloxane particles, (Y) polyfunctional monomer (y-1) 100 to 50% by mass and (e) polyorganosiloxane-containing graft copolymer Other copolymerizable monomer (y-2) is polymerized from 0.5 to 10 parts by mass of vinyl monomer composed of 0 to 50% by mass, and (Z) other vinyl monomer 5 to The flame-retardant polycarbonate resin composition according to claim 5, wherein the flame-retardant polycarbonate resin composition is obtained by polymerizing 50 parts by mass (provided that the total amount of (X), (Y) and (Z) is 100 parts by mass). .   The light reflection member obtained by shape | molding the flame-retardant polycarbonate resin composition in any one of Claims 1-8.