JP2009040843A - Polycarbonate-based resin composition and optical molded article comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polycarbonate (PC)-based resin composition that reduces yellowing in high-temperature molding and resultingly provides an excellent optical molded article. <P>SOLUTION: The PC-based resin composition comprises (A) 100 parts by mass of a PC-based resin containing a PC copolymer that is synthesized from polycarbonate precursors such as dihydric phenol, a phenol-modified diol, phosgene etc. and has a viscosity number of 30-71 and (B) 0.001-1 part by mass of a phosphite having a spiro structure and/or a phosphite compound containing two phenyl groups. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition, and more specifically, a polycarbonate resin composition containing a polycarbonate copolymer having a specific repeating constitutional unit and a specific phosphite compound, and a molded product thereof. It relates to optical molded products.

Polycarbonate (hereinafter sometimes abbreviated as PC) resin is produced mainly from bisphenol A and is used in a wide range of applications because of its excellent transparency, heat resistance, mechanical properties, and the like. However, when this PC resin is used for optical parts such as lenses, light guide plates, optical disks, etc., there is a problem that satisfactory molded products cannot be obtained due to low fluidity. An improved PC resin has been proposed.
On the other hand, Patent Document 1 discloses a PC copolymer obtained by copolymerizing polytetramethylene glycol-bis (4-hydroxybenzoate). This PC copolymer has remarkably improved fluidity during molding and excellent thermal stability, so it can cope with a wide range of molding conditions as a molding raw material, and as a result, a good optical molded product can be obtained. It is known.
When a PC copolymer obtained by copolymerizing the polytetramethylene glycol-bis (4-hydroxybenzoate) was continuously produced, there was a problem that yellowing occurred in molding at a high temperature.

JP 2005-247947 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin composition in which yellowing is reduced when molded at a high temperature, and as a result, a good optical molded product is obtained. is there.

As a result of intensive studies, the inventors have found that a specific amount of a PC-based resin containing a PC copolymer having a specific amount of a specific repeating unit and a viscosity number in a specific range and a specific phosphite compound. It has been found that the above-mentioned object is achieved by the PC-based resin composition to be included. That is, it has been found that when this PC-based resin composition is used as a material for an optical molded product, yellowing that occurs when molding at a high temperature is reduced. The present invention has been completed based on such findings.
That is, the present invention provides the following polycarbonate resin composition and an optical molded product comprising the same.
1. (A) It has a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), and the content of the repeating unit represented by the general formula (II) is 1 to 30% by mass. 100 parts by mass of a polycarbonate resin containing a polycarbonate copolymer having a viscosity number of 30 to 71 and (B) a phosphite compound represented by the general formula (III) and / or the general formula (IV) A polycarbonate resin composition comprising 0.001 to 1 part by mass of a phosphite compound.

[Wherein, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms. X is a single bond, 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, -S-, -SO- , —SO ₂ —, —O—, —CO—, or a bond represented by the following formula (V-1) or the following formula (V-2).

R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. a to d are each an integer of 0 to 4, and n is an integer of 2 to 200. R ^{5 to} R ⁷ each independently represents a group selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms. R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ^{10 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Indicates the group to be selected. ]
2. In formula (II), Y _{is, -CH 2 -CH 2 -CH 2 -CH} 2 -, - CH 2 -CH 2 -CH 2 -CH (CH 3) - and -CH ₂ -CH ₂ -CH ₂ 2. The polycarbonate resin composition according to 1 above, which is one or more selected from-.
3. The polycarbonate resin composition according to 1 or 2 above, wherein the viscosity of the polycarbonate copolymer contained in the polycarbonate resin as the component (A) is 37 to 62.
4). The polycarbonate resin according to any one of 1 to 3 above, wherein a flow rate value (Q value) at 280 ° C. of the polycarbonate copolymer contained in the polycarbonate resin as the component (A) is 30 × 10 ⁻² mL / s or more. Composition.
5). (A) The polycarbonate-type resin composition in any one of said 1-4 which the polycarbonate-type resin of a component consists of a polycarbonate copolymer and the polycarbonate which uses bisphenol A as a single monomer.
6). (A) The polycarbonate-type resin composition in any one of said 1-5 containing 0.01-1 mass part of acrylic resins with a molecular weight of 200-100,000 with respect to 100 mass parts of polycarbonate-type resin of a component. object.
7). 7. An optical molded article comprising the polycarbonate resin composition according to any one of 1 to 6 above.

  The PC-based resin composition of the present invention containing a PC-based resin containing a specific PC copolymer and a specific phosphite compound that is an antioxidant is yellowed when the resin composition is molded at a high temperature. Therefore, a molded product obtained by molding the resin composition is suitable as an optical molded product.

In the PC resin composition of the present invention, the PC copolymer contained in the PC resin as the component (A) is a phenol-modified diol copolymer polycarbonate and can be manufactured by a conventional manufacturing method called an interfacial polymerization method. it can. 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 further added as necessary, so that dihydric phenol, phenol-modified diol and phosgene are added. A carbonate precursor such as is reacted.
The PC copolymer contained in the (A) component PC-based resin can be obtained by copolymerizing a dihydric phenol and a phenol-modified diol, which will be described later, by an interfacial polymerization method. The following general formulas (I) and ( II)

(In the formula, R ^{1 to} R ⁴ , X, Y, ad, and n will be described later.)
It has the repeating unit represented by these. As the dihydric phenol, 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. Incidentally, when R ¹ are a plurality of multiple R ¹ may be the same or different, when R ² are a plurality, the plurality of R ² may be the same or different from each other.
X is a single bond, an alkylene group having 1 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylylene group, hexylene group, etc.), an alkylidene group having 2 to 8 carbon atoms (for example, ethylidene group, isopropylidene group). Group), a cycloalkylene group having 5 to 15 carbon atoms (eg, cyclopentylene group, cyclohexylene group, etc.), a cycloalkylidene group having 5 to 15 carbon atoms (eg, cyclopentylidene group, cyclohexylidene group, etc.),- S—, —SO—, —SO ₂ —, —O—, —CO— bond or the following formula (V-1) or the following formula (V-2)

The bond represented by 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-3-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; 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; 2,2′-bis (4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes such as norbornene, 4,4′-dihydroxyphenyl ether; dihydroxyaryl ethers such as 4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxy Diphenyl sulfide; 4,4′-dihydroxy-3,3′-dimethyldiphenyls Dihydroxy diaryl sulfides such as fido; 4,4′-dihydroxydiphenyl sulfoxide; dihydroxy diaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone; Dihydroxydiaryl sulfones such as 4′-dihydroxy-3,3′-dimethyldiphenylsulfone; dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl; 9,9-bis (4-hydroxyphenyl) fluorene; Dihydroxydiarylfluorenes such as bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane; 2,2-bis (4- Hide Xylphenyl) adamantane; dihydroxydiaryladamantanes such as 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 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, α, ω -Bishydroxyphenyl polydimethylsiloxane compound etc. are mentioned. These dihydric phenols may be used alone or in combination of two or more.

  As the molecular weight regulator, various types can be used as long as they are usually used for polymerization of PC 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, and examples of the tertiary amine salt include hydrochlorides and bromates of these tertiary amines. Etc. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide. Examples thereof include butylphosphonium chloride and tetrabutylphosphonium bromide. 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 branching agents include 1,1,1-tris (4-hydroxyphenyl) ethane; 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene Bisphenol; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- A compound having three or more functional groups such as [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglucin, trimellitic acid, and isatin bis (o-cresol) can also be used.
The phenol-modified diol used in the present invention has the following general formula (IIa)

[Wherein, R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. c and d are integers of 0 to 4, and n is an integer of 2 to 200. ]
It is a compound represented by these. Examples of the alkyl group represented by R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. If there are a plurality of R ^3, a plurality of R ³ may be the same or different from each other, if R ⁴ is plural, R ⁴ may be the same or different from each other. Examples of the linear or branched alkylene group having 2 to 15 carbon atoms represented by Y include alkylene groups such as ethylene group, propylene group, butylene group, isobutylene group, pentylene group and isopentylene group, ethylidene group, propylidene group, isopropylene group. Examples include alkylidene residues such as a lidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. The _{Y, -CH 2 -CH 2 -CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -CH (CH 3) - and -CH ₂ -CH ₂ -CH ₂ - of one or more selected It is preferable that n is preferably 2 to 200, more preferably 6 to 70.
The phenol-modified diol represented by the general formula (IIa) is a compound derived from hydroxybenzoic acid or an alkyl ester thereof, an acid chloride and a polyether diol. The phenol-modified diol can be synthesized by methods proposed in JP-A-62-279222, JP-A-60-79072, JP-A-2002-173465, and the like. It is desirable to appropriately purify the resulting phenol-modified diol. As the purification method, for example, the system is depressurized after the reaction, and excess raw material (for example, parahydroxybenzoic acid) is distilled off. The phenol-modified diol is washed with water or an aqueous alkaline solution (for example, sodium bicarbonate aqueous solution). The method of doing 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, and is composed of repeating linear or branched alkyl ethers having 2 to 15 carbon atoms. 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 ether part of the polyether diol is 2 to 200, preferably 6 to 70. When n is 2 or more, the efficiency at the time of copolymerizing the phenol-modified diol is good, and when n is 70 or less, there is an advantage that the decrease in heat resistance of the PC copolymer is small.
Typical examples of acid chlorides include 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 PC copolymer, 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 PC copolymer, if the amount of the phenol-modified diol is increased, the fluidity is improved, but the heat resistance is lowered. Therefore, the copolymerization amount of the phenol-modified diol is preferably selected according to the desired balance between fluidity and heat resistance. If the amount of phenol-modified diol copolymerization exceeds 40% by mass, as shown in JP-A-62-79222, it becomes elastomeric and may not be applicable to the same applications as general PC resins. In order to maintain heat resistance of 100 ° C. or higher, the amount of the repeating unit represented by the general formula (II) contained in the PC copolymer is required to be 1 to 30% by mass in the present invention. The amount is preferably 1 to 20% by mass, more preferably 1 to 15% by mass.

The PC copolymer contained in the component (A) requires a viscosity number of 30 to 71 (equivalent to Mv (viscosity average molecular weight) = 10,000 to 28,100), preferably 37 to 62 ( Mv = 13, 100 to 24, 100). 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 comonomer is exhibited well. In addition, a large amount of comonomer is required to exhibit high fluidity. However, when the viscosity number is 71 or less, the heat resistance is not greatly reduced when the comonomer is used. The viscosity number is a value measured according to ISO 1628-4 (1999).
The PC copolymer preferably has a flow value (Q value) at 280 ° C. of 30 × 10 ⁻² mL / s or more, and more preferably 40 × 10 ⁻² mL / s or more. The flow value (Q value) is a melt viscosity measured with an elevated flow tester in accordance with JIS K7210, and the flow value (Q value) is 30 × 10 ⁻² mL / s or more. The melt viscosity of the coalescence does not become too high. The same applies to the PC resin composition of the present invention.

  In the PC resin composition of the present invention, the phosphite compound of component (B) is a phosphite compound represented by the following general formula (III) and / or a phosphite compound represented by the general formula (IV). .

[Wherein, R ^{5 to} R ⁷ each independently represents a group selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms. R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ^{10 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Indicates the group to be selected. ]
The alkyl group having 1 to 20 carbon atoms represented by R ^{5 to} R ⁷ or R ^{10 to} R ¹³ may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, various heptyl groups Groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, and various octadecyl groups. Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R ^{5 to} R ⁷ or R ^{10 to} R ¹³ include a cyclopentyl group and a cyclohexyl group. Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁸ and R ^9, may be mentioned those having 1 to 8 carbon atoms of the alkyl group having the carbon number of 1 to 20. Examples of the aryl group having 6 to 30 carbon atoms represented by R ^{10 to} R ¹³ include a phenyl group, a tolyl group, and xylyl. Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ^{10 to} R ¹³ include a benzyl group and a phenethyl group.
As R < ⁵ > -R < ⁷ >, a C1-C20 alkyl group is preferable, More preferably, it is an octyl group. R ⁸ and R ⁹ are preferably a hydrogen atom. As R < ¹⁰ > -R < ¹³ >, a C1-C10 alkyl group is preferable, More preferably, it is a t-butyl group.

The phosphite compound represented by the general formula (III) or (IV) has an effect of reducing yellowing that occurs when a PC resin composition is molded at a high temperature.
Specific examples of the phosphite compound represented by the general formula (III) include distearyl pentaerythritol diphosphite (ADK STAB PEP-8, manufactured by ADEKA Corporation), bis (2,4-di-tert-butyl). Phenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite and the like. . Among them, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol Diphosphite is preferred.
As the phosphite compound represented by the general formula (IV), for example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-ethylhexyl) phosphite (Adeka Stub HP-10, Co., Ltd.) ADEKA) and the like.
(B) The compounding quantity of the phosphite compound of a component is 0.01-1 mass part with respect to 100 mass parts of PC-type resin of (A) component, Preferably it is 0.02-0.5 mass part, and more. Preferably it is 0.03-0.3 mass part. When the blending amount of the component (B) exceeds 1 part by mass, the heat and humidity resistance is lowered, which is not preferable. When the amount is less than 0.01 part by mass, yellowing tends to occur when molded at a high temperature.

  When the PC resin composition of the present invention is used for a light guide plate or an optical lens, it is preferable to blend (C) an acrylic resin having a molecular weight of 200 to 100,000 for the purpose of increasing the light transmittance. In addition to the component (C), it is more preferable to use a PC resin composition containing (D) an alicyclic epoxy compound or (E) a polysiloxane compound having at least one selected from an alkoxy group, a vinyl group and a phenyl group. preferable.

The component (C) acrylic resin refers to a polymer having a repeating unit of at least one selected from monomer units of acrylic acid, acrylic ester, acrylonitrile and derivatives thereof, and is a homopolymer or styrene, butadiene, α- A copolymer with olefin, vinyl chloride or the like. Specifically, polyacrylic acid, polymethyl methacrylate (PMMA), polyacrylonitrile, ethyl acrylate-acrylic acid-vinyl chloride copolymer, acrylic acid-n-butene-acrylonitrile copolymer, acrylonitrile-styrene copolymer , Acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like. Among these, polymethyl methacrylate (PMMA) can be particularly preferably used.
The (C) component acrylic resin preferably has a molecular weight of 200 to 100,000, more preferably 20,000 to 60,000. When the molecular weight is 200,000 to 100,000, the phase separation between the PC copolymer and other PC resin and the acrylic resin does not become too fast during molding, so that sufficient transparency can be obtained in the molded product. . As polymethyl methacrylate (PMMA), known ones can be used. Usually, those produced by bulk polymerization of methyl methacrylate monomer in the presence of a peroxide or an azo polymerization initiator are used. preferable.
The compounding quantity of acrylic resin is about 0.01-1 mass part normally with respect to 100 mass parts of PC-type resin of (A) component, Preferably it is 0.05-0.5 mass part, More preferably, it is 0. 0.1 to 0.3 parts by mass. When the blending amount of the acrylic resin is 0.01 parts by mass or more, the transparency of the molded product is improved, and when it is 1 part by mass or less, the transparency can be maintained without impairing other desired physical properties. .

  The alicyclic epoxy compound as the component (D) refers to an alicyclic epoxy group, that is, a cycloaliphatic compound having an epoxy group in which one oxygen atom is added to an ethylene bond in the aliphatic ring. Specifically, Those represented by the following formulas (1) to (10) disclosed in JP-A-11-158364 are preferably used.

（Ｒ：Ｈ又はＣＨ₃）

(R: H or CH ₃ )

（Ｒ：Ｈ又はＣＨ₃）

(R: H or CH ₃ )

（ａ＋ｂ＝１又は２）

(A + b = 1 or 2)

（ａ＋ｂ＋ｃ＋ｄ＝１〜３）

(A + b + c + d = 1-3)

（ａ＋ｂ＋ｃ＝ｎ（整数），Ｒ：炭化水素基）

(A + b + c = n (integer), R: hydrocarbon group)

（ｎ：整数）

(N: integer)

（Ｒ：炭化水素基）

(R: hydrocarbon group)

（ｎ：整数，Ｒ：炭化水素基）

(N: integer, R: hydrocarbon group)

  Among the alicyclic epoxy compounds, the compound represented by the formula (1), the formula (7) or the formula (10) is superior in compatibility with the PC resin and does not impair the transparency. Preferably used. By blending the alicyclic epoxy compound in the PC resin composition of the present invention, it becomes possible to further improve the transparency and also to improve the hydrolysis resistance. The blending amount of the (D) component alicyclic epoxy compound is usually about 0.01 to 1 part by weight, preferably 0.02 to 0.2 part, per 100 parts by weight of the (A) component PC resin. Part by mass. By adding this amount to 0.01 parts by mass or more, an effect of addition is obtained, and by setting it to 1 part by mass or less, phase separation is not promoted and transparency is obtained.

  The polysiloxane compound of the above component (E) is a reactive silicone compound in which one or more functional groups selected from an alkoxy group (for example, methoxy group, ethoxy group), vinyl group and phenyl group are introduced into a silicone compound. There are organopolysiloxanes. This component (E) is a compound that acts as a stabilizer in the PC-based resin. When the component (E) is blended, yellowing due to thermal deterioration during molding, appearance defects such as silver (silver stripes), and air bubbles are mixed. Can be prevented. (E) The compounding quantity of a component is about 0.01-3 mass parts normally with respect to 100 mass parts of PC-type resin of (A) component, Preferably it is suitably selected from the range of 0.05-2 mass parts. When the amount is 0.01 parts by mass or more, the effect of addition is expressed, and when it is 3 parts by mass or less, the molded article does not become cloudy.

In addition to the above-described components, various additives may be blended with the PC resin composition of the present invention as necessary within a range that does not impair the effects of the present invention. Various additives include, for example, arylphosphine-based, other phosphite-based, phosphate-based, hindered phenol-based antioxidants, benzotriazole-based, benzophenone-based ultraviolet absorbers, hindered amine-based, etc. Light stabilizers, aliphatic carboxylic acid ester compounds, paraffin compounds, silicone oil, polyethylene wax and other internal lubricants, conventional flame retardants, flame retardant aids, mold release agents, antistatic agents, colorants Etc.
The present invention also provides an optical molded article comprising the PC resin composition. There are no particular restrictions on the method for producing the optical molded product of the present invention, and various conventionally known molding methods such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, and foam molding. The method etc. can be used. Examples of the optical molded product include a lens and a light guide plate.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1 [Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate)]
Under nitrogen atmosphere, 100 parts by mass of polytetramethylene glycol (PTMG, Mn (number average molecular weight) = 1000) and 33.4 parts by mass of methyl p-hydroxybenzoate were added at 220 ° C. in the presence of 0.05 part by mass of dibutyltin oxide. And methanol was distilled off.
The reaction system was depressurized, and excess methyl p-hydroxybenzoate was distilled off. 5.0 parts by mass of the reaction product was dissolved in 30 parts by volume of methylene chloride. To this methylene chloride solution, 10 parts by volume of an 8% by mass aqueous sodium hydrogen carbonate solution was added, vigorously mixed for 20 minutes, and then the methylene chloride phase was collected by centrifugation. The methylene chloride phase was concentrated under reduced pressure to obtain polytetramethylene glycol-bis (4-hydroxybenzoate) which is a phenol-modified diol. As a result of quantifying p-hydroxybenzoic acid and methyl p-hydroxybenzoate in polytetramethylene glycol-bis (4-hydroxybenzoate) by the following method by HPLC (high performance liquid chromatography), p-hydroxybenzoic acid was obtained. Was less than 10 mass ppm, and methyl p-hydroxybenzoate was 0.2 mass%.

<Quantification of p-hydroxybenzoic acid and methyl p-hydroxybenzoate>
Quantification was performed by HPLC (high performance liquid chromatography) under the following conditions based on a calibration curve prepared with a standard product.
Column: OD Science ODS-3
Column temperature: 40 ° C
Solvent: 0.5% by mass phosphoric acid aqueous solution and acetonitrile volume ratio 1: 2 mixture Flow rate: 1.0 ml / min

Production Example 2 (Production of PC copolymer)
(1) PC oligomer synthesis step To a 5.6 mass% sodium hydroxide aqueous solution, 2000 mass ppm of sodium dithionite is added to bisphenol A (BPA) to be dissolved later, and the BPA concentration is 13.5. BPA was dissolved so as to have a mass%, and an aqueous sodium hydroxide solution of BPA was prepared. A sodium hydroxide aqueous solution of BPA was continuously passed through a tubular reactor having an inner diameter of 6 mm and a pipe length of 30 m at a flow rate of 40 L / hr and methylene chloride at a flow rate of 15 L / hr, and phosgene was continuously supplied at a flow rate of 4.0 kg / hr. Passed through. 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 liquid sent out from the tubular reactor was continuously introduced into a 40-liter baffled tank reactor equipped with a receding blade, and further BPA sodium hydroxide aqueous solution was added at 2.8 L / hr, A 25% by mass sodium hydroxide aqueous solution was supplied at a flow rate of 0.07 L / hr, water at 17 L / hr, and a 1% by mass triethylamine aqueous solution at a flow rate of 0.64 L / hr, and the reaction was performed at 29 to 32 ° C. The reaction liquid was continuously extracted from the tank reactor and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 329 g / L and a chloroformate group concentration of 0.74 mol / L.

(2) PC copolymer polymerization step PC oligomer 20L / hr obtained in the above synthesis step, methylene chloride 12L / hr, polytetramethylene glycol-bis (4-hydroxybenzoate) 40 obtained in Production Example 1 At a flow rate of 868 kg / hr of 3% by weight methylene chloride solution, 400 ml / hr of 3% by weight triethylamine aqueous solution and 2.3 kg / hr of 6.4% by weight sodium hydroxide aqueous solution, It supplied to K pipeline homomixer 2SL type [made by Primix Co., Ltd.], and it preliminarily polymerized under rotation of 3000 rpm, and the prepolymerization liquid was obtained.
Subsequently, BPA was dissolved in 960 g / hr of a 20 mass% methylene chloride solution of PTBP (p-tert-butylphenol) and PTBP (p-tert-butylphenol) in a 6.4 mass% aqueous sodium hydroxide solution to a concentration of 8.8 mass%. Of aqueous solution 14.1 kg / hr. It supplied to K pipeline homomixer 2SL type [made by Primix Co., Ltd.], and it emulsified under rotation of 3000 rpm, and obtained the emulsion. Subsequently, this emulsion was introduced into a jacketed orifice mixer in which two orifice plates having three holes of 0.8 mm in diameter, which are the second reactor, were inserted into a 19.05 mm (3/4 inch) pipe, Further, as a third reactor, a 50 L paddle blade-equipped three-stage tower-type stirring tank with a jacket was supplied for polymerization. Cooling water at 15 ° C. was allowed to flow through the jacket, and the outlet temperature of the polymerization liquid was set to 30 ° C.
Into a 50 L dilution tank equipped with a paddle type stirring blade, a polymerization liquid overflowing from the column reactor and methylene chloride for dilution were continuously supplied at 11 L / hr. The emulsion obtained from the dilution tank is C. The mixture was introduced into a C centrifugal extractor [trade name, manufactured by Kawasaki Heavy Industries, Ltd., internal volume: 4 L, rotor diameter: 430 mm] and subjected to centrifugal extraction at a rotational speed of 3000 rpm to separate an aqueous layer and an organic layer.

(3) Alkaline washing step The organic layer obtained from the above centrifugal extractor and 0.03 mol / L aqueous sodium hydroxide solution (7.8 L / hr) were added to T.C. It supplied to K pipeline homomixer 2SL type [made by Primix Co., Ltd.], and was stirred and mixed at 3000 rpm. The mixed solution from the homomixer outlet was introduced into a centrifugal extractor, and centrifugal extraction was performed at a rotational speed of 3000 rpm to separate the aqueous layer and the organic layer.
The emulsion obtained from the dilution tank is C. Introduced into C centrifugal extractor [trade name, manufactured by Kawasaki Heavy Industries, Ltd., internal volume 4L, rotor diameter 430mm], centrifugal extraction was performed at 3000 rpm, the aqueous layer and the organic layer were separated, and the organic layer continued Feeded to the acid wash step.
(4) Acid washing process The organic layer obtained from the centrifugal extractor in the alkali washing process and 7.8 L / hr of 0.2 mol / L hydrochloric acid aqueous solution were treated with T.P. It supplied to K pipeline homomixer 2SL type [made by Primix Co., Ltd.], and was stirred and mixed at 3000 rpm. The mixed liquid from the homomixer outlet was introduced into a stationary separation tank to separate the aqueous layer and the organic layer, and the organic layer was supplied to the subsequent first water washing step.

(5) First water washing step An organic layer obtained from a centrifugal extractor and 7.8 L / hr of pure water were treated with T.W. It supplied to K pipeline homomixer 2SL type [made by Primix Co., Ltd.], and was stirred and mixed at 3000 rpm. The mixed solution from the homomixer outlet was introduced into a centrifugal extractor and subjected to centrifugal extraction at a rotational speed of 3000 rpm to separate the aqueous layer and the organic layer, and the organic layer was supplied to the subsequent second water washing step.
(6) Second water washing step The organic layer obtained from the centrifugal extractor and 7.8 L / hr of pure water were treated with T.W. It supplied to K pipeline homomixer 2SL type [made by Primix Co., Ltd.], and was stirred and mixed at 3000 rpm. The mixed solution from the homomixer outlet was introduced into a centrifugal extractor, and centrifugal extraction was performed at a rotational speed of 3000 rpm to separate the aqueous layer and the organic layer to obtain a purified polycarbonate methylene chloride solution (organic layer).
(7) Concentration and drying step The purified polycarbonate methylene chloride solution was concentrated and pulverized, and the obtained flakes were dried at 105 ° C under reduced pressure. The properties of the obtained polycarbonate flakes were as follows.
The amount of polytetramethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 4.0% by mass.
The viscosity number measured according to ISO 1628-4 (1999) was 36.9 (Mv = 13000). The flow value (Q value) measured by the following method was 96 × 10 ⁻² mL / s. The BPA content was 130 ppm, the methylene chloride content was 1300 ppm, the chloride ion content was less than 0.3 ppm, and the sodium content was less than 0.1 ppm.

<Flow value (Q value)>
Using an elevated flow tester, the amount of molten resin (mL / sec) flowing out from a nozzle having a diameter of 1 mm and a length of 10 mm was measured under a pressure of 280 ° C. and 15.7 MPa according to JIS K7210. The flow value (Q value) increases with decreasing melt viscosity.

Example 1
100 parts by mass of the PC copolymer obtained in Production Example 2 and the phosphite compound were blended in the parts by mass shown in Table 1, and granulated at a resin temperature of 260 ° C. by a 40 mmφ extruder with a vent to obtain pellets. .
Using the obtained pellets, a 35 mm × 25 mm × 2 mm flat plate was injection molded under the following molding conditions.
<Molding conditions>
Molding machine: Toshiba Machine Co., Ltd., EC40N (trade name)
Molding machine cylinder temperature: 340 ° C or 350 ° C
Residence time in cylinder: 8 minutes

Five molded products from the 13th shot and after were collected, YI (yellow index) was measured using each, and the average value was obtained. Moreover, the average value of 5 sheets was also obtained for Tt (total light transmittance). The results are shown in Table 1. YI and Tt were measured by the following methods. In Table 1, the numerical values of 340 and 350 indicate the cylinder temperature of the molding machine when a molded product is produced.
(1) YI
A molded product having a thickness of 2.0 mm was prepared by injection molding, and measured with a spectrocolorimeter Σ90 manufactured by Nippon Denshoku Industries Co., Ltd., with a measurement area of 30φ and a C2 light source transmission method.
(2) Tt
A molded product having a thickness of 2.0 mm was prepared by injection molding and measured with a direct reading haze meter HGM-20DP D65 light source manufactured by Suga Test Instruments Co., Ltd.

Examples 2-6
Table 1 shows 75 parts by mass of the PC copolymer obtained in Production Example 2, 25 parts by mass of Taflon FN 1500 (trade name, manufactured by Idemitsu Kosan Co., Ltd., Bis-A polycarbonate, viscosity number = 39.5), and phosphite compound. And granulated at a resin temperature of 260 ° C. by a 40 mmφ extruder with a vent to obtain pellets. YI and Tt were measured in the same manner as in Example 1 using the obtained pellets. The results are shown in Table 1. In Table 1, HP-10 represents ADK STAB HP-10 (trade name, manufactured by ADEKA, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-ethylhexyl) phosphite). ), PEP-8 refers to ADK STAB PEP-8 (trade name, manufactured by ADEKA Corporation, distearyl pentaerythritol diphosphite).

Comparative Example 1
In Example 1, it granulated like Example 1 except not mix | blending a phosphite compound, and the pellet was obtained. YI and Tt were measured in the same manner as in Example 1 using the obtained pellets. The results are shown in Table 2.
Comparative Examples 2-4
Table 2 shows 75 parts by mass of the PC copolymer obtained in Production Example 2, 25 parts by mass of Taflon FN 1500 (trade name, manufactured by Idemitsu Kosan Co., Ltd., Bis-A polycarbonate, viscosity number = 39.5), and phosphite compound. And granulated at a resin temperature of 260 ° C. by a 40 mmφ extruder with a vent to obtain pellets. YI and Tt were measured in the same manner as in Example 1 using the obtained pellets. The results are shown in Table 2. In Table 2, PEP-36 is ADK STAB PEP-36 (trade name, manufactured by ADEKA, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite) Irg168 indicates Irgaphos 168 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd., tris (2,4-di-t-butylphenyl) phosphite).

Example 7
75 parts by mass of the PC copolymer obtained in Production Example 2, 25 parts by mass of Taflon FN 1500 (trade name, manufactured by Idemitsu Kosan Co., Ltd., Bis-A polycarbonate, VN = 39.5), and dialnal BR83 (trade name, Mitsubishi Rayon Co., Ltd., acrylic resin, molecular weight 40000) 0.1 part by mass, KR511 (trade name, Shin-Etsu Silicone Co., Ltd., organosiloxane having methoxy group and vinyl group) 0.1 part by mass, Celoxide 2021P (Trade name, manufactured by Daicel Chemical Industries, Ltd.) 0.05 parts by mass, Adeka Stub HP-10 (trade name, manufactured by ADEKA Co., Ltd.) 0.085 parts by mass, and the resin temperature by a 40 mmφ extruder with a vent Granulation was performed at 260 ° C. to obtain pellets. YI and Tt were measured in the same manner as in Example 1 using the obtained pellets. The results are shown in Table 2.

  According to the PC resin composition of the present invention, an optical molded product with reduced yellowing can be obtained.

Claims (7)

(A) It has a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), and the content of the repeating unit represented by the general formula (II) is 1 to 30% by mass. 100 parts by mass of a polycarbonate resin containing a polycarbonate copolymer having a viscosity number of 30 to 71 and (B) a phosphite compound represented by the general formula (III) and / or the general formula (IV) A polycarbonate resin composition comprising 0.001 to 1 part by mass of a phosphite compound.

[In the formula, R ¹ and R ² represents an alkyl group having 1 to 6 carbon atoms independently. X is a single bond, 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, -S-, -SO- , —SO ₂ —, —O—, —CO—, or a bond represented by the following formula (V-1) or the following formula (V-2).

R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. a to d are each an integer of 0 to 4, and n is an integer of 2 to 200. R ^{5 to} R ⁷ each independently represents a group selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms. R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ^{10 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Indicates the group to be selected. ] In formula (II), Y _{is, -CH 2 -CH 2 -CH 2 -CH} 2 -, - CH 2 -CH 2 -CH 2 -CH (CH 3) - and -CH ₂ -CH ₂ -CH ₂ The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is one or more selected from −.   The polycarbonate resin composition according to claim 1 or 2, wherein the polycarbonate copolymer contained in the polycarbonate resin as the component (A) has a viscosity number of 37 to 62. The polycarbonate-based resin according to any one of claims 1 to 3, wherein the polycarbonate copolymer contained in the polycarbonate-based resin (A) has a flow value (Q value) at 280 ° C of 30 × 10 ^-2 mL / s or more. Resin composition.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the polycarbonate resin of component (A) comprises a polycarbonate copolymer and a polycarbonate having bisphenol A as a single monomer.   The polycarbonate resin according to any one of claims 1 to 5, comprising (C) 0.01 to 1 part by mass of an acrylic resin having a molecular weight of 200 to 100,000 with respect to 100 parts by mass of the polycarbonate resin as the component (A). Composition.   An optical molded article comprising the polycarbonate resin composition according to claim 1.