JP2019214744A - Polycarbonate resin composition - Google Patents

Abstract

To provide a polycarbonate resin composition which has good color tone and very high flowability and is excellent in toughness.SOLUTION: A polycarbonate resin composition contains, based on 100 pts.mass of a polycarbonate resin (A), 0.1 to 4 pts.mass of a polyalkylene glycol compound (B) having a number-average molecular weight from 500 to 5000, and 0.005 to 0.5 pts.mass of a phosphorus-based stabilizer (C), where the polycarbonate resin (A) has a terminal structure represented by a specific general formula, the polyalkylene glycol compound (B) is at least one selected from the group consisting of a polyalkylene glycol represented by a specific general formula, and a polyalkylene glycol copolymer, and the phosphorus-based stabilizer (C) is bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition having good hue, very high fluidity, and excellent toughness.

Polycarbonate resin is a high-performance resin having excellent physical properties such as impact resistance, heat resistance, weather resistance, and flame retardancy, and having a high light transmittance. It is widely used as a material for manufacturing components in lighting equipment, optical applications and other industrial fields.
In particular, utilizing its excellent optical properties and flame retardancy, LED light sources have recently been used as optical components for lighting equipment and optical equipment, which are becoming mainstream.

  However, polycarbonate resins are excellent in mechanical properties, thermal properties, electrical properties, and weather resistance, but have a problem that light transmittance is lower than that of polymethyl methacrylate (PMMA) or the like. Further, there is a problem that the polycarbonate resin is more likely to yellow than the PMMA resin.

  Patent Document 1 proposes a method for improving light transmittance and luminance by adding an acrylic resin and an alicyclic epoxy. However, in the method of Patent Document 1, the hue is improved by the addition of the acrylic resin, but the light transmittance and the luminance cannot be increased due to cloudiness, and the transmittance is improved by adding the alicyclic epoxy. However, the effect of improving the hue is not recognized.

On the other hand, it is known to blend polyethylene glycol or poly (2-methyl) ethylene glycol into a thermoplastic resin such as a polycarbonate resin. Patent Document 2 discloses a gamma-ray irradiation-resistant polycarbonate resin containing the same. Patent Document 3 describes a thermoplastic resin composition blended with PMMA or the like and having excellent antistatic properties and surface appearance.
Patent Document 4 proposes to improve the transmittance and the hue by blending a polyalkylene glycol composed of a linear alkyl group. By blending polytetramethylene ether glycol, the transmittance and the yellowing degree (yellow index: YI) are improved.

  However, recently, particularly in various mobile terminals such as smartphones and tablet terminals, thinning and large-sized thinning are progressing at a remarkable speed, and the polycarbonate resin materials used for these optical components have very high fluidity and excellent properties. Optical characteristics are required. However, using a low-molecular-weight polycarbonate resin or adding a flow modifier to improve fluidity reduces the toughness of the material, making it extremely difficult to achieve the required specifications with existing technologies. there were.

JP-A-11-158364 JP-A-1-22959 JP-A-9-227785 Japanese Patent No. 5699188

  The present invention has been made in view of the above circumstances, and an object (problem) of the present invention is to provide a polycarbonate resin composition having excellent toughness while having extremely high fluidity and excellent hue.

The present inventors have conducted intensive studies to achieve the above object, and as a result, by blending a polyalkylene glycol in a specific amount with respect to a polycarbonate resin having a specific terminal structure, extremely high fluidity and They have found that a polycarbonate resin composition having an excellent hue and an excellent toughness can be obtained, and have completed the present invention.
The present invention relates to the following polycarbonate resin compositions.

[1] With respect to 100 parts by mass of the polycarbonate resin (A), 0.1 to 4 parts by mass of the polyalkylene glycol compound (B) having a number average molecular weight of 500 to 5000 and 0.005 of the phosphorus-based stabilizer (C). ~ 0.5 parts by mass,
A polycarbonate resin composition, wherein the polycarbonate resin (A) has a terminal structure represented by the following general formula (1).
(In the formula, n represents an integer of 0 or 1, and R ¹ represents an alkyl group having 5 to 14 carbon atoms.)
[2] The polycarbonate resin composition according to the above [1], wherein the viscosity average molecular weight of the polycarbonate resin (A) is 10,000 to 18,000.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the terminal structure is a terminal structure represented by the following general formula (1 ′).
[4] ^{R 1} in the general formula (1) or (1 ') is, n- octyl group, iso - 1 or more in which the selected from the group consisting of octyl and t- octyl group [1] - The polycarbonate resin composition according to any one of [3].
[5] The polycarbonate resin composition according to any one of the above [1] to [4], wherein the terminal structure in the general formula (1) or (1 ′) of the polycarbonate resin (A) is a t-octylphenyl group.

[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the polyalkylene glycol compound (B) is a polyalkylene glycol represented by the following general formula (2).
(Wherein, R ² represents an alkyl group having 1 to 3 carbon atoms, X and Y each independently represent a hydrogen atom, an aliphatic acyl group having 1 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, It represents an aryl group having 6 to 22 carbon atoms or an aralkyl group having 7 to 23 carbon atoms, and m represents an integer of 10 to 400.)
[7] The polycarbonate resin composition according to any one of the above [1] to [6], wherein the polyalkylene glycol compound (B) is a polyalkylene glycol represented by the following general formula (3).
(In the formula, X and Y are each independently a hydrogen atom, an aliphatic acyl group having 2 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, an aryl group having 6 to 22 carbon atoms or 7 to 23 carbon atoms. Wherein p represents an integer of 2 to 6, and r represents an integer of 6 to 100.)

[8] The polyalkylene glycol compound (B) is selected from linear alkylene ether units represented by the following general formula (4) and units represented by the following general formulas (5-1) to (5-4). The polycarbonate resin composition according to any one of the above [1] to [7], which is a polyalkylene glycol copolymer having a branched alkylene ether unit.
(In the formula (4), p represents an integer of 2 to 6.)
(In the formulas (5-1) to (5-4), R ^{3 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each of the formulas (5-1) to (5- In 4), at least one of R ^{3 to} R ¹² is an alkyl group having 1 to 3 carbon atoms.)

  The polycarbonate resin composition of the present invention can have excellent toughness while having extremely high fluidity and excellent hue.

It is the top view and sectional drawing of the molded article used for the bending test of the Example. It is sectional drawing which shows the shape of the parallel uneven | corrugated pattern provided in the back surface side of the molded product used for the bending test of the Example. It is a key map showing the device used for the bending test of the example.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples.
In addition, in this specification, "-" is used in the meaning including numerical values described before and after it as a lower limit value and an upper limit value, unless otherwise specified.

The polycarbonate resin composition of the present invention comprises 0.1 to 4 parts by mass of a polyalkylene glycol compound (B) having a number average molecular weight of 500 to 5,000 per 100 parts by mass of the polycarbonate resin (A), and a phosphorus-based stabilizer ( (C) in an amount of 0.005 to 0.5 parts by mass, and the polycarbonate resin (A) has a terminal structure represented by the general formula (1).
Hereinafter, each component constituting the polycarbonate resin composition of the present invention will be described in detail.

[Polycarbonate resin (A)]
The polycarbonate resin used in the present invention has a terminal structure represented by the following general formula (1).
(In the formula, n represents an integer of 0 or 1, and R ¹ represents an alkyl group having 5 to 14 carbon atoms.)

  The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula:-[-OXOC (= O)-]-. In the formula, X is generally a hydrocarbon, but X to which a hetero atom or a hetero bond is introduced may be used for imparting various properties.

  Further, the polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, and any of them can be used. Among them, an aromatic polycarbonate resin is preferred from the viewpoint of heat resistance, mechanical properties, electrical properties, and the like.

  The specific type of the polycarbonate resin is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. At this time, a polyhydroxy compound or the like may be reacted in addition to the dihydroxy compound and the carbonate precursor. Further, a method of reacting carbon dioxide with a cyclic ether as a carbonate precursor may be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, as the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected. Usually, such a polycarbonate polymer is a thermoplastic resin.

Among the monomers that are the raw materials of the aromatic polycarbonate resin, examples of the aromatic dihydroxy compound include:
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (that is, resorcinol), and 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl and 4,4′-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, Dihydroxynaphthalenes such as 2,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A);
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes;

9,9-bis (4-hydroxyphenyl) fluorene,
Bisphenols containing a cardo structure such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable. In particular, 2,2-bis (4-hydroxyphenyl) propane ( That is, bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and 2 or more types may be used together by arbitrary combinations and ratios.

In addition, to give examples of monomers used as raw materials for the aliphatic polycarbonate resin,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

  Glycols such as ethylene glycol, 2,2'-oxydiethanol (i.e., diethylene glycol), triethylene glycol, propylene glycol, and spiro glycol;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie, ethylene oxide), 1,2-epoxypropane (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl Cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, 1,3-epoxypropane; and the like.

  Among the monomers used as the raw material of the polycarbonate resin, examples of the carbonate precursor include carbonyl halide and carbonate ester. One type of carbonate precursor may be used, or two or more types may be used in any combination and in any ratio.

  Specific examples of the carbonyl halide include phosgene; a haloformate such as a bischloroformate of a dihydroxy compound and a monochloroformate of a dihydroxy compound.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and cyclic carbonates. And the like, carbonates of dihydroxy compounds and the like.

[Production method of polycarbonate resin]
The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly preferable ones of these methods will be specifically described.

[Interfacial polymerization method]
First, a case where a polycarbonate resin is produced by an interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually maintained at 9 or more in the presence of an organic solvent and an aqueous alkaline solution which are inert to the reaction, and the dihydroxy compound is reacted with a carbonate precursor (preferably, phosgene). A polycarbonate resin is obtained by performing interfacial polymerization in the presence. In addition, an antioxidant may be added to the reaction system to prevent oxidation of the dihydroxy compound, if necessary.

  The dihydroxy compound and the carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene, and xylene. Can be One type of organic solvent may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the alkali compound contained in the aqueous alkali solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and 2 or more types may be used together by arbitrary combinations and ratios.

  Although the concentration of the alkali compound in the aqueous alkali solution is not limited, it is usually used at 5 to 10% by mass in order to control the pH in the aqueous alkali solution of the reaction to 10 to 12. For example, when phosgene is blown, the molar ratio of the bisphenol compound to the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to 10 to 12, preferably 10 to 11. In particular, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, particularly preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; and alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N'-dimethylaniline and N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanine; guanidine salts; and the like. One type of polymerization catalyst may be used, or two or more types may be used in any combination and in any ratio.

At the time of the reaction, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additives and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as a carbonate precursor, the terminator is not particularly limited as long as it is between the time of the reaction (phosgenation) of the dihydroxy compound and phosgene and the time of the start of the polymerization reaction. It is preferred to add following the filling step.
The reaction temperature is usually from 0 to 40 ° C., and the reaction time is usually from several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

[Molten transesterification method]
Next, a case where a polycarbonate resin is produced by a melt transesterification method will be described.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl carbonate. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type of carbonic acid diester may be used and 2 or more types may be used together by arbitrary combinations and ratios.

  The ratio between the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and particularly to use 1.01 mol or more. Is more preferable. The upper limit is usually 1.30 mol or less. With such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. One transesterification catalyst may be used, or two or more transesterification catalysts may be used in any combination and in any ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be performed under the above conditions while removing by-products such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by any of a batch method and a continuous method. In the case of performing the batch method, the order of mixing the reaction substrate, the reaction medium, the catalyst, the additive, and the like is arbitrary as long as a desired aromatic polycarbonate resin is obtained, and an appropriate order may be set as desired. However, among others, the melt polycondensation reaction is preferably performed in a continuous manner in consideration of the stability and the like of the polycarbonate resin.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, any compound that neutralizes the transesterification catalyst can be used. Examples thereof include sulfur-containing acidic compounds, phosphorus-containing acidic compounds, and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and 2 or more types may be used together by arbitrary combinations and ratios.

  The amount of the catalyst deactivator to be used is usually 0.5 equivalent or more, preferably 1 equivalent or more, and usually 10 equivalent or less, based on the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Further, it is usually at least 1 ppm, usually at most 100 ppm, preferably at most 20 ppm, based on the polycarbonate resin.

As described above, the polycarbonate resin used in the present invention has a terminal structure represented by the following general formula (1).

In the formula (1), n is an integer of 0 or 1, and R ¹ is an alkyl group having 5 to 14 carbon atoms. It has been found that when the polycarbonate resin (A) has the terminal structure of the above formula (1), a high degree of fluidity is possible while maintaining strength, and the hue is also good. For this reason, it is common practice to lower the molecular weight of the polycarbonate resin in order to improve the flowability, but in the present invention, when designing the material, even if a desired molecular weight is adopted without lowering the molecular weight, a high flowability is obtained. Therefore, good hue and fluidity can be achieved while maintaining high strength. The hue and strength can be further improved by containing the polyalkylene glycol compound (B).

The carbon number of the alkyl group of R ¹ is preferably 6 or more, more preferably 7 or more, and preferably 12 or less, and more preferably 10 or less. The alkyl group for R ¹ may be linear or branched.
Among them, R ¹ is preferably at least one selected from the group consisting of an n-octyl group, an iso-octyl group and a t-octyl group, more preferably a t-octyl group, and in general formula (1) It is particularly preferable that the terminal structure be a t-octylphenyl group (that is, a 1,1,3,3-tetramethylbutylphenyl group).

In the above formula (1), the position of the — (O) _n R ¹ group bonded to the phenyl group may be at the ortho, meta or para position, but is preferably at the para position shown in the following general formula (1 ′).

  Specific examples of the group represented by the above formula (1) or (1 ′) include a p-pentylphenyl group, a p-hexylphenyl group, a p-heptylphenyl group, a pn-octylphenyl group, and a p-isopropyl group. -Octylphenyl group, pt-octylphenyl group, p-dodecylphenyl group and p-tetradecylphenyl group, p-nonylphenol, p-dodecylphenol, amylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol , An alkylphenyl group such as dodecylphenol and myristylphenol, a p-hexyloxyphenyl group, a pn-octyloxyphenyl group, a p-iso-octyloxyphenyl group, a pt-octyloxyphenyl group, a p-dodecyloxy group Alkoxy such as phenyl group It can be exemplified preferably a phenyl group.

When the polycarbonate resin (A) of the present invention is produced by polymerization, it can be produced by using a monohydric phenol terminal stopper represented by the following general formula (1a).
(In the formula, n represents an integer of 0 or 1, and R ¹ represents an alkyl group having 5 to 14 carbon atoms.)

Specific examples of the terminal stopper represented by the general formula (1a) include p-pentylphenol, p-hexylphenol, p-heptylphenol, p-n-octylphenol, p-iso-octylphenol, and p-t-octylphenol. P-dodecylphenol and p-tetradecylphenol, p-nonylphenol, p-dodecylphenol, amylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, alkylphenols such as myristylphenol, p-hexyloxy Alkoxy such as phenol, pn-octyloxyphenol, p-iso-octyloxyphenol, pt-octyloxyphenol, p-dodecyloxyphenol Phenol can the mentioned Preferably, these can be used either or a plurality as chain terminator. In the formula (1a), the position of the — (O) _n R ¹ group bonded to the phenyl group may be at the ortho, meta or para position, but is preferably at the para position.
Among them, the use of any one or more of pt-octylphenol and pn-octyloxyphenol as a terminal terminator is advantageous in view of availability in addition to fluidity, strength and heat resistance of a molded article. Is more preferable.

Depending on the required properties of the material, two or more types of terminal stoppers may be used in combination without departing from the gist of the present invention, and may be used in combination with a structure other than the structure represented by the general formula (1). It is possible.
Other terminating agents that may be used in combination include, for example, phenol, p-cresol, o-cresol, 2,4-xylenol, pt-butylphenol, o-allylphenol, p-allylphenol, p-hydroxy Styrene, p-hydroxy-α-methylstyrene, p-propylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-trifluoromethylphenol, eugenol, palmitylphenol, stearylphenol, behenylphenol And alkyl esters of p-hydroxybenzoic acid such as methyl esters, ethyl esters, propyl esters, butyl esters, amyl esters, hexyl esters, and heptyl esters of alkylphenols and p-hydroxybenzoic acid.
Other terminal stoppers can be used in combination of two or more. In particular, as a terminal terminator which may be used in combination with the terminal terminator of the general formula (1a), pt-butylphenol is mentioned from the viewpoint of purity and cost.
When another terminal terminator is used, it is preferably at most 20 mol%, more preferably at most 10 mol%, of the entire polycarbonate resin including the polycarbonate resin (A) in the total terminal stopper.

The polycarbonate resin (A) has a viscosity average molecular weight (Mv) of preferably 10,000 to 18,000, more preferably 10500 or more, further preferably 11,000 or more, particularly preferably 11500 or more, and most preferably 12000 or more. Yes, more preferably 17500 or less, further preferably 17000, particularly preferably 16500. By setting the viscosity average molecular weight to the lower limit of the above range or more, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved. The flowability of the polycarbonate resin composition of the present invention can be suppressed and reduced, and the moldability can be increased to facilitate thin-wall molding.
The polycarbonate resin (A) may be a mixture of two or more types of polycarbonate resins having different viscosity average molecular weights. In this case, the polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range is mixed. May be.

In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin refers to the intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using methylene chloride as a solvent and using an Ubbelohde viscometer. , Schnell's viscosity equation, that is, a value calculated from η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value obtained by measuring a specific viscosity [η _sp ] at each solution concentration [C] (g / dl) and calculating the value according to the following equation.

  The polycarbonate resin (A) is a polycarbonate resin (A) alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and includes, for example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights). Used in the sense including the mode).

  Further, the polycarbonate resin composition of the present invention may be contained in combination with a polycarbonate resin having another terminal structure other than the polycarbonate resin (A) as long as the effects of the present invention are not significantly impaired. Examples of such a polycarbonate resin include a polycarbonate resin having a terminal structure of a pt-butylphenyl group, which is a typical commercially available product. The content of the polycarbonate resin having another terminal structure is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, particularly preferably 100 parts by mass of the polycarbonate resin (A). It is at most 15 parts by mass, most preferably at most 10 parts by mass.

  In the present invention, the polycarbonate resin may be used in combination with another thermoplastic resin. Further, for example, a polycarbonate resin is copolymerized with an oligomer or a polymer having a siloxane structure for the purpose of further improving flame retardancy and impact resistance; and a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy. A copolymer with a monomer, oligomer or polymer having the following formula: a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving the thermal oxidation stability; a polystyrene or the like for improving the optical properties Copolymers based on polycarbonate resins, such as copolymers with oligomers or polymers having an olefinic structure; copolymers with polyester resin oligomers or polymers for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight (Mv) of the polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Further, the content of the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin material but also a polycarbonate resin recycled from a used product (a so-called material-recycled polycarbonate resin).
However, the recycled polycarbonate resin is preferably 80% by mass or less of the polycarbonate resin, and more preferably 50% by mass or less. Recycled polycarbonate resin is highly likely to have undergone deterioration such as thermal deterioration or aging deterioration.If such a polycarbonate resin is used in an amount larger than the above range, hue and mechanical properties may be reduced. It is because there is.

[Polyalkylene glycol compound (B)]
The polycarbonate resin composition of the present invention contains the polyalkylene glycol compound (B) having a number average molecular weight of 500 to 5000 in an amount of 0.1 to 4 parts by mass based on 100 parts by mass of the polycarbonate resin (A).
Preferred examples of the polyalkylene glycol compound (B) include a branched polyalkylene glycol compound represented by the following general formula (2) or a linear polyalkylene glycol compound represented by the following general formula (3). . The branched polyalkylene glycol compound represented by the following general formula (2) or the linear polyalkylene glycol compound represented by the following general formula (3) is a copolymer with another copolymer component. However, it is preferably a homopolymer.

(Wherein, R ² represents an alkyl group having 1 to 3 carbon atoms, X and Y each independently represent a hydrogen atom, an aliphatic acyl group having 1 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, It represents an aryl group having 6 to 22 carbon atoms or an aralkyl group having 7 to 23 carbon atoms, and m represents an integer of 10 to 400.)
The branched polyalkylene glycol compound represented by the general formula (2) may be a homopolymer composed of one kind of R ^{2 or a} copolymer composed of different R ² .

(In the formula, X and Y are each independently a hydrogen atom, an aliphatic acyl group having 2 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, an aryl group having 6 to 22 carbon atoms or 7 to 23 carbon atoms. Wherein p represents an integer of 2 to 6, and r represents an integer of 6 to 100.)
The linear polyalkylene glycol compound represented by the general formula (3) may be a homopolymer of one kind of p or a copolymer of different p.

Examples of the branched polyalkylene glycol compound include (2-methyl) ethylene glycol in which X and Y are hydrogen atoms and R ² is a methyl group and (2-ethyl) ethylene glycol in which R ² is a methyl group in the general formula (2). Is preferred.

  Examples of the linear polyalkylene glycol compound include polyethylene glycol in which X and Y are hydrogen atoms in general formula (3) and p is 2, polytrimethylene glycol in which p is 3, and polytetramethylene in which p is 4. Preferred are methylene glycol, polypentamethylene glycol in which p is 5, and polyhexamethylene glycol in which p is 6, more preferably polytrimethylene glycol and polytetramethylene glycol.

  The polyalkylene glycol compound (B) is selected from linear alkylene ether units (P1) represented by the following general formula (4) and units represented by the following general formulas (5-1) to (5-4). A polyalkylene glycol copolymer having a branched alkylene ether unit (P2) is also preferred.

(In the formula (4), p represents an integer of 2 to 6.)
The linear alkylene ether unit represented by the general formula (4) may be a single unit composed of one kind of p or a mixture of plural units composed of different p.

(In the formulas (5-1) to (5-4), R ^{3 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each of the formulas (5-1) to (5- In 4), at least one of R ^{3 to} R ¹² is an alkyl group having 1 to 3 carbon atoms.)

  As the linear alkylene ether unit (P1) represented by the general formula (4), when it is described as a glycol, ethylene glycol in which p is 2; trimethylene glycol in which p is 3; Examples thereof include methylene glycol, pentamethylene glycol having p of 5 and hexamethylene glycol having p of 6, which may be mixed, preferably trimethylene glycol and tetramethylene glycol, and particularly preferably tetramethylene glycol.

  Trimethylene glycol is industrially obtained by hydroformylation of ethylene oxide to give 3-hydroxypropionaldehyde and hydrogenating it, or hydrogenating 3-hydroxypropionaldehyde obtained by hydrating acrolein with a Ni catalyst. Manufactured by the method. Recently, trimethylene glycol has also been produced by reducing glycerin, glucose, starch and the like to microorganisms by a biotechnology.

  When this is described as a glycol as the branched alkylene ether unit represented by the above general formula (5-1), (2-methyl) ethylene glycol, (2-ethyl) ethylene glycol, (2,2-dimethyl) ethylene glycol, etc. These may be mixed, and preferred are (2-methyl) ethylene glycol and (2-ethyl) ethylene glycol.

  When the branched alkylene ether unit represented by the above general formula (5-2) is described as a glycol, (2-methyl) trimethylene glycol, (3-methyl) trimethylene glycol, (2-ethyl) trimethylene glycol , (3-ethyl) triethylene glycol, (2,2-dimethyl) trimethylene glycol, (2,2-methylethyl) trimethylene glycol, (2,2-diethyl) trimethylene glycol (ie neopentyl glycol) , (3,3-dimethyl) trimethylene glycol, (3,3-methylethyl) trimethylene glycol, (3,3-diethyl) trimethylene glycol, and the like, and these may be mixed.

  When the branched alkylene ether unit represented by the general formula (5-3) is described as a glycol, (3-methyl) tetramethylene glycol, (4-methyl) tetramethylene glycol, (3-ethyl) tetramethylene glycol , (4-ethyl) tetramethylene glycol, (3,3-dimethyl) tetramethylene glycol, (3,3-methylethyl) tetramethylene glycol, (3,3-diethyl) tetramethylene glycol, (4,4-dimethyl ) Tetramethylene glycol, (4,4-methylethyl) tetramethylene glycol, (4,4-diethyl) tetramethylene glycol, and the like, and these may be mixed, and (3-methyl) tetramethylene glycol may be used. preferable.

  When this is described as a glycol as the branched alkylene ether unit represented by the above general formula (5-4), (3-methyl) pentamethylene glycol, (4-methyl) pentamethylene glycol, (5-methyl) pentamethylene glycol , (3-ethyl) pentamethylene glycol, (4-ethyl) pentamethylene glycol, (5-ethyl) pentamethylene glycol, (3,3-dimethyl) pentamethylene glycol, (3,3-methylethyl) pentamethylene glycol , (3,3-diethyl) pentamethylene glycol, (4,4-dimethyl) pentamethylene glycol, (4,4-methylethyl) pentamethylene glycol, (4,4-diethyl) pentamethylene glycol, (5,5 -Dimethyl) pentamethylene glycol (5,5-methylethyl) pentamethylene glycol, (5,5-diethyl) such as pentamethylene glycol, and the like, may also be these mixtures.

  As described above, the units represented by the general formulas (5-1) to (5-4) constituting the branched alkylene ether unit have been described using glycol as an example for convenience sake. And these polyether-forming derivatives.

  Preferred examples of the polyalkylene glycol copolymer include a copolymer composed of a tetramethylene ether unit and a unit represented by the general formula (5-3), and particularly a tetramethylene ether unit and 3-methyltetramethylene. Copolymers comprising ether units are more preferred. Further, a copolymer composed of a tetramethylene ether unit and a unit represented by the above general formula (5-1) is also preferable, and particularly a copolymer composed of a tetramethylene ether unit and a 2-methylethylene ether unit, and a tetramethylene ether A copolymer composed of units and 2-ethylethylene ether units is more preferred. Further, a copolymer composed of a tetramethylene ether unit and the general formula (5-2) is also preferable, and a copolymer composed of a 2,2-dimethyltrimethylene ether unit, that is, a neopentyl glycol ether unit is also preferable.

  The polyalkylene glycol copolymer may be a random copolymer or a block copolymer.

The linear alkylene ether unit (P1) represented by the general formula (5) and the branched alkylene ether unit (P2) represented by the general formulas (5-1) to (5-4) of the polyalkylene glycol copolymer ) Is a molar ratio of (P1) / (P2), preferably from 95/5 to 5/95, more preferably from 93/7 to 40/60, even more preferably 90/10. -65/35, and the linear alkylene ether unit (P1) is more preferably rich.
In addition, a molar fraction is measured using a deuterated chloroform as a solvent using a < ¹ > H-NMR measuring apparatus.

  Further, as the polyalkylene glycol compound (B), even if one or both ends thereof are blocked with a carboxylic acid or alcohol, the performance of the polyalkylene glycol compound is not affected, and an esterified product or an etherified product can be used similarly. Therefore, X and / or Y in the general formulas (2) and (3) represent an aliphatic acyl group having 2 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, an aryl group having 6 to 22 carbon atoms or a carbon number. It may be 7 to 23 aralkyl groups.

Examples of the esterified product include a fatty acid ester, and any of a linear or branched fatty acid ester can be used. The fatty acid constituting the fatty acid ester may be a saturated fatty acid or an unsaturated fatty acid. In addition, those in which a part of hydrogen atoms are substituted with a substituent such as a hydroxyl group can be used.
As the fatty acid constituting the fatty acid ester, a monovalent or divalent fatty acid having 1 to 23 carbon atoms, for example, a monovalent saturated fatty acid, specifically, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid , Enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and monovalent unsaturated fatty acids, specifically, Unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, and arachidonic acid, and divalent fatty acids having 10 or more carbon atoms, specifically, sebacic acid, undecandioic acid, dodecandioic acid, and tetradecandioic acid , Tapsiaic acid and decenedioic acid, undecenedioic acid, dodecenedioic acid.
These fatty acids can be used alone or in combination of two or more. The fatty acids also include fatty acids having one or more hydroxyl groups in the molecule.

Specific preferred examples of fatty acid esters of polyalkylene glycols, in general formula (2), R ² is a methyl group, polypropylene glycol stearate X and Y is an aliphatic acyl group of 18 carbon atoms, R ² is a methyl group , X and Y are aliphatic acyl groups having 22 carbon atoms. Preferred specific examples of the fatty acid ester of the linear polyalkylene glycol include polyalkylene glycol monopalmitate, polyalkylene glycol dipalmitate, polyalkylene glycol monostearate, polyalkylene glycol distearate, and polyalkylene glycol. (Monopalmitic acid / monostearic acid) ester, polyalkylene glycol behenate and the like.

  The alkyl group constituting the alkyl ether of the polyalkylene glycol may be linear or branched, and may have, for example, a carbon number such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a lauryl group, and a stearyl group. Examples of such a polyalkylene glycol compound include alkyl methyl ether, ethyl ether, butyl ether, lauryl ether, and stearyl ether of a polyalkylene glycol.

  The aryl group constituting the aryl ether of the polyalkylene glycol is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms, such as phenyl group and tolyl. And a naphthyl group, and a phenyl group and a tolyl group are preferred. In addition, the terminal-blocking group, even if it is an aralkyl group, exhibits good compatibility with polycarbonate, so that it can exhibit the same action as an aryl group, and as the aralkyl group, preferably has 7 to 23 carbon atoms. Preferably, it is an aralkyl group having 7 to 13 carbon atoms, more preferably 7 to 11 carbon atoms. Examples thereof include a benzyl group and a phenethyl group, and a benzyl group is particularly preferable.

  Specific examples of the branched polyalkylene glycol compound include, for example, “Uniol D-1000” and “Uniol PB-1000” (trade names, manufactured by NOF CORPORATION).

  Specific examples of the linear polyalkylene glycol compound include, for example, a homopolymer type compound (trade name “PEG # 1000” manufactured by NOF Corporation, “PO3G H1000” manufactured by Alyssa Corporation, Mitsubishi Chemical Corporation) "PTMG1000" manufactured by NOF Corporation and "Polyserin" manufactured by NOF Corp. are exemplified.

  Specific examples of the straight-chain and branched-chain polyalkylene glycol copolymers include, for example, "Polyserin DCB-1000" (trade name, manufactured by NOF Corporation, "PTG-L", manufactured by Hodogaya Chemical Co., Ltd .; Manufactured by “PTXG”.

The number average molecular weight of the polyalkylene glycol compound (B) is 500 to 5,000, preferably 600 or more, more preferably 700 or more, more preferably 4000 or less, further preferably 3000 or less, and particularly preferably 2000 or less. It is. Exceeding the upper limit of the above range is not preferable because the compatibility is reduced, and lowering the lower limit of the above range is not preferable because gas is generated during molding.
The number average molecular weight of the polyalkylene glycol compound is a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1577.

  As the polyalkylene glycol compound (B), one type may be used alone, or two or more types may be used in combination.

[Phosphorus stabilizer (C)]
The polycarbonate resin composition of the present invention contains a phosphorus-based stabilizer. By containing the phosphorus-based stabilizer, the hue of the polycarbonate resin composition of the present invention is further improved, and the heat discoloration resistance is further improved.
Any known phosphorus-based stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid and polyphosphoric acid; metal salts of acidic pyrophosphate such as sodium acid pyrophosphate, potassium acid pyrophosphate and calcium acid pyrophosphate; phosphoric acid Phosphates of Group 1 or 2B metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; phosphate compounds, phosphite compounds, phosphonite compounds, and the like, with phosphite compounds being particularly preferred. By selecting a phosphite compound, a polycarbonate resin composition having higher discoloration resistance and continuous productivity can be obtained.

Here, the phosphite compound is a trivalent phosphorus compound represented by the general formula: P (OR) ₃ , and R represents a monovalent or divalent organic group.
Examples of such a phosphite compound include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonylphenyl) phosphite, and tris (2,4-di-tert-butylphenyl) phosphite. Phyte, monooctyl diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, Bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butylphenyl) octyl phosphite, 2,2-methylene (4,6-di-tert-butylphenyl) octyl phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-diphosphite, 6- [3- (3-tert-butyl) Butyl-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] -dioxaphosphepin.

  Among such phosphite compounds, an aromatic phosphite compound represented by the following formula (6) or (7) is more preferable because the heat-resistant discoloration resistance of the polycarbonate resin composition of the present invention is effectively increased. .

(In the formula, R ¹ , R ² and R ³ may be the same or different, and represent an aryl group having 6 to 30 carbon atoms.)

(In the formula, R ⁴ and R ⁵ may be the same or different, and represent an aryl group having 6 to 30 carbon atoms.)

  As the phosphite compound represented by the above formula (6), triphenyl phosphite, tris (monononylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are preferable. Among them, tris (2,4-di-tert-butylphenyl) phosphite is more preferred. Specific examples of such an organic phosphite compound include, for example, "ADEKA STAB 1178" manufactured by ADEKA, "SUMILIZER TNP" manufactured by Sumitomo Chemical Co., Ltd., "JP-351" manufactured by Johoku Chemical Co., Ltd., and "ADEKA STAB" manufactured by ADEKA 2112 "," IRGAFOS 168 "manufactured by BASF," JP-650 "manufactured by Johoku Chemical Co., Ltd., and the like.

  Among the phosphite compounds represented by the above formula (7), bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert- Those having a pentaerythritol diphosphite structure, such as butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite, are particularly preferred. As such an organic phosphite compound, specifically, for example, “ADEKA STAB PEP-24G” and “ADEKA STAB PEP-36” manufactured by Adeka, “Doverphos S-9228” manufactured by Dover Chemical and the like are preferably exemplified.

Among the phosphite compounds, the aromatic phosphite compound represented by the above formula (7) is more preferable because the hue is more excellent.
In addition, the phosphorus-based stabilizer may contain one kind, or two or more kinds may be contained in an optional combination and ratio.

  The content of the phosphorus-based stabilizer (C) is 0.005 to 0.5 part by mass, preferably 0.007 part by mass or more, more preferably 0.1 part by mass, based on 100 parts by mass of the polycarbonate resin (A). 008 parts by mass or more, particularly preferably 0.01 parts by mass or more, preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, further more preferably 0.2 parts by mass or less, and particularly preferably 0 part by mass or less. 0.1 part by mass or less. When the content of the phosphorus-based stabilizer (C) is less than 0.005 parts by mass, the hue and heat-resistant discoloration become insufficient. When the content exceeds 0.5 parts by mass, the heat-resistant discoloration deteriorates. In addition, the wet heat stability is reduced.

[Epoxy compound (D)]
The resin composition of the present invention preferably also contains an epoxy compound (D). By containing the epoxy compound (D) together with the polyalkylene glycol polymer (B), the heat discoloration resistance can be further improved.

As the epoxy compound (D), a compound having one or more epoxy groups in one molecule is used. Specifically, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl -3 ', 4'-Epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) Butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6' -Methylsilohexyl carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis- Epoxy ethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxy tartrate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2 -Epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxy , N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy -5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3', 4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxy Rate, di-n-veh Le -3-t-butyl-4,5-epoxy - cis-1,2-cyclohexyl dicarboxylate, epoxidized soybean oil, can be preferably exemplified such as epoxidized linseed oil.
The epoxy compounds may be used alone or in combination of two or more.

  Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is particularly preferred.

  The preferable content of the epoxy compound (D) is 0.0005 to 0.2 part by mass, more preferably 0.001 part by mass or more, and further preferably 0.1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). The amount is at least 003 parts by mass, particularly preferably at least 0.005 parts by mass, more preferably at most 0.15 parts by mass, further preferably at most 0.1 parts by mass, particularly preferably at most 0.05 parts by mass. When the content of the epoxy compound (D) is less than 0.0005 parts by mass, the hue and heat discoloration resistance tend to be insufficient, and when it exceeds 0.2 parts by mass, the heat discoloration resistance tends to worsen, Hue and wet heat stability are also likely to decrease.

[Additives, etc.]
The polycarbonate resin composition of the present invention may contain other additives other than those described above, for example, a release agent, an antioxidant, an ultraviolet absorber, a fluorescent brightener, a pigment, a dye, a polymer other than the polycarbonate resin, It may contain additives such as a flame retardant, an impact modifier, an antistatic agent, a plasticizer, and a compatibilizer. One or more of these additives may be blended.

[Method for producing polycarbonate resin composition]
The method for producing the polycarbonate resin composition of the present invention is not limited, and any of the known methods for producing a polycarbonate resin composition can be widely used. The polycarbonate resin (A), the polyalkylene glycol compound (B), and the phosphorus-based stabilizer (C) And, if necessary, other components to be blended, for example, beforehand mixed using various mixers such as a tumbler and a Henschel mixer, then a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, and a twin-screw kneading extrusion. Melt kneading with a mixer such as a mixer or a kneader. The temperature of the melt-kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

  The polycarbonate resin composition of the present invention can be formed into various molded products by molding pellets obtained by pelletizing the above-described polycarbonate resin composition by various molding methods. Also, the resin melt-kneaded by an extruder can be directly molded into a molded product without passing through a pellet.

Since the polycarbonate resin composition of the present invention exhibits extremely high fluidity, excellent hue, and excellent toughness, it is suitably used for molding optical parts, particularly thin optical parts, by an injection molding method. The resin temperature at the time of injection molding is preferably, particularly in the case of a thin molded article, molded at a resin temperature higher than 260 to 300 ° C., which is a temperature generally applied to injection molding of a polycarbonate resin. A resin temperature of ３380 ° C. is preferred. The resin temperature is more preferably 310 ° C. or higher, still more preferably 315 ° C. or higher, particularly preferably 320 ° C. or higher, and more preferably 370 ° C. or lower. When the conventional polycarbonate resin composition is used, when the resin temperature during molding is increased to mold a thin-walled molded article, there is also a problem that yellowing of the molded article is likely to occur, but the resin of the present invention By using the composition, it is possible to produce a molded product having a good hue, particularly a thin optical component, even in the above temperature range. In addition, although the reduction of the molecular weight of the polycarbonate resin has been conventionally performed in order to form a thin molded product, the polycarbonate resin composition of the present invention has good fluidity, so that thin molding can be performed without reducing the molecular weight. Thus, it is possible to obtain a molded article having higher strength.
When it is difficult to directly measure the resin temperature, the resin temperature is grasped as a barrel set temperature.

  Here, the thin molded article refers to a molded article having a plate-shaped portion having a wall thickness of usually 1 mm or less, preferably 0.8 mm or less, more preferably 0.6 mm or less. Here, the plate-shaped portion may be a flat plate or a curved plate, may be a flat surface, may have irregularities or the like on the surface, and has a cross section having an inclined surface. Or a wedge-shaped cross section.

Examples of the optical component include components of equipment and appliances that directly or indirectly use a light source such as an LED, an organic EL, an incandescent lamp, a fluorescent lamp, and a cathode ray tube.
The optical component using the polycarbonate resin composition of the present invention can be suitably used in the fields of a liquid crystal backlight unit, various display devices, and lighting devices. Examples of such devices include mobile phones, mobile notebooks, netbooks, slate PCs, tablet PCs, smartphones, various mobile terminals such as tablet terminals, cameras, watches, notebook computers, various displays, lighting devices, and the like. Can be

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.

  The raw materials and evaluation methods used in the following Examples and Comparative Examples are as follows. The method for measuring the viscosity average molecular weight of the polycarbonate resin is as described above.

(Examples 1 to 12, Comparative Examples 1 to 3)
[Production of resin composition pellets]
Each component described in Table 1 above was blended in the ratio (parts by mass) described in Table 2 below, mixed by a tumbler for 20 minutes, and then vented single-screw extruder having a screw diameter of 40 mm (Tanabe Plastic Machinery Co., Ltd.) (VS-40)), melt-kneaded at a cylinder temperature of 240 ° C., and obtained pellets by strand cutting.

[Amount of outflow per unit time: Q value (unit: × 10 ^-2 cm ³ / sec)]
After the pellet obtained by the above method is dried at 120 ° C. for 4 hours or more, the composition is dried at 240 ° C. under a load of 160 kgf / cm ² using an elevated flow tester according to JIS P8115. The outflow amount per unit time (Q value, unit: × 10 ⁻² cm ³ / sec) was measured to evaluate the fluidity. The orifice used had a diameter of 1 mm and a length of 10 mm.

[Measurement of Hue (YI)]
After the obtained pellets were dried at 120 ° C. for 5 to 7 hours by a hot air circulation type dryer, the resin temperature was 340 ° C. and the mold temperature was 80 ° C. by an injection molding machine (“EC100SX-2A” manufactured by Toshiba Machine Co., Ltd.). A long optical path molded product (300 mm × 7 mm × 4 mm) was molded.
With respect to this long optical path molded product, YI (yellowing degree) was measured at an optical path length of 300 mm. A long-path spectral transmission colorimeter (“ASA 1” manufactured by Nippon Denshoku Industries Co., Ltd., C light source, 2 ° field of view) was used for the measurement.

[Molded product three-point bending test]
The obtained pellets were dried at 120 ° C. for 5 to 7 hours by a hot air circulating dryer, and then, at an injection molding machine (“HSP100A” manufactured by Sodick Co., Ltd.), at a resin temperature of 360 ° C. and a mold temperature of 40 ° C. As shown in FIG. 1, a molded product 1 having a size of 61 mm × 112 mm × 0.45 mm in thickness and having an uneven parallel pattern 2 on the back side was formed. As shown in FIG. 2, the parallel uneven pattern 2 provided on the back side of the molded article 1 has a distance between the concave portion and the convex portion of 0.014 mm, the base length of the convex portion is 0.05 mm, and the parallel concave and convex pattern 2 The angle between the concave portion and the convex portion is 120 °.
The obtained molded article 1 was subjected to a three-point bending test under the following conditions using a bending test apparatus shown in FIG. That is, the molded article 1 is placed on the support bases 3 and 3 'provided in parallel with the back surface 2 facing downward and 1200 mm in depth, the span d between the support bases 3 and 3' is set to 5 mm, and the jig is set. (Not shown). A knife-shaped edge 4 having a thickness of 3 mm, a tip angle of 30 °, and a tip of 0.14 mm is provided on the molded article 1 above the center lines of the supports 3 and 3 ′. 4 was pressed down from above the molded product 1 at a rate of 10 mm / min below the center line of the span d, and the molded product 1 was bent by bending until the displacement became 10 mm.
This test was performed 10 times, and the number of fractures (n / 10) when the displacement reached 10 mm was taken as the number of fractures. The smaller the number of fractured pieces, the better the toughness.
The above evaluation results are shown in Table 2 below.

  Since the polycarbonate resin composition of the present invention is a polycarbonate resin material exhibiting excellent toughness while having extremely high fluidity and excellent hue, it can be suitably used for various optical parts and the like, The availability of is very high.

Claims (4)

With respect to 100 parts by mass of the polycarbonate resin (A), 0.1 to 4 parts by mass of the polyalkylene glycol compound (B) having a number average molecular weight of 500 to 5,000, and 0.005 to 0.5 parts by mass of the phosphorus-based stabilizer (C). 5 parts by mass,
Polycarbonate resin (A) have a terminal structure represented by the following general formula (1 '),
The polyalkylene glycol compound (B) is a polyalkylene glycol represented by the following general formula (2), a polyalkylene glycol represented by the following general formula (3), or a polyalkylene glycol represented by the following general formula (4). At least one selected from a polyalkylene glycol copolymer having a chain alkylene ether unit and a branched alkylene ether unit selected from units represented by the following general formulas (5-1) to (5-4);
A polycarbonate resin composition, wherein the phosphorus-based stabilizer (C) is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite .
[In the formula (1 ′), n represents an integer of 0 or 1, and R ^{1 is at} least one selected from the group consisting ^of an n-octyl group, an iso-octyl group, and a t-octyl group. ]
[In the formula (2), R ² represents an alkyl group having 1 to 3 carbon atoms, X and Y each independently represent a hydrogen atom, an aliphatic acyl group having 1 to 23 carbon atoms, It represents an alkyl group, an aryl group having 6 to 22 carbon atoms or an aralkyl group having 7 to 23 carbon atoms, and m represents an integer of 10 to 400. ]
[In the formula (3), X and Y each independently represent a hydrogen atom, an aliphatic acyl group having 2 to 23 carbon atoms, an alkyl group having 1 to 23 carbon atoms, an aryl group having 6 to 22 carbon atoms or a carbon number. Represents an aralkyl group of 7 to 23, p is an integer of 2 to 6, and r is an integer of 6 to 100. ]
[In the formula (4), p represents an integer of 2 to 6. ]
[In the formulas (5-1) to (5-4), R ^{3 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each of the formulas (5-1) to (5- In 4), at least one of R ^{3 to} R ¹² is an alkyl group having 1 to 3 carbon atoms. ]   The polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin (A) is 10,000 to 18,000. The polycarbonate resin composition according to claim 1 or 2 , wherein the terminal structure in the general formula (1 ') of the polycarbonate resin (A) is a t-octylphenyl group. The polyalkylene glycol compound (B) is selected from poly (2-methyl) ethylene glycol, poly (2-ethyl) ethylene glycol, polytetramethylene glycol, and a copolymer composed of tetramethylene ether units and 2-methylethylene ether units. The polycarbonate resin composition according to any one of claims 1 to 3, which is at least one kind selected therefrom.