JP2020193255A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having a good hue, very high fluidity, and excellent impact resistance.
SOLUTION: A polytrimethylene glycol compound (B) having a number average molecular weight of 500 to 5000 is 0.01 to 4 mass by mass with respect to 100 parts by mass of a polycarbonate resin (A) having a terminal structure represented by the following general formula (1). A polycarbonate resin composition containing 0.005 to 0.5 parts by mass of a phosphorus-based stabilizer (C).
[Chemical 1]

[Selection diagram] Fig. 1

Description

The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having a good hue, a high degree of fluidity, and excellent impact resistance.

Polycarbonate resin is a highly functional resin that has excellent physical properties such as impact resistance, heat resistance, weather resistance, and flame retardancy, and has high light transmittance. Utilizing these characteristics, for example, automobiles, electrical and electronic equipment, and housing It is widely used as a material for manufacturing parts in lighting equipment, optical applications and other industrial fields.
In particular, taking advantage of its excellent optical characteristics and flame retardancy, LED light sources have come to be used as optical components for lighting equipment and optical equipment, which are becoming mainstream in recent years.

However, although the polycarbonate resin is excellent in mechanical properties, thermal properties, electrical properties, and weather resistance, there is a problem that the light transmittance is lower than that of polymethylmethacrylate (PMMA) or the like. Further, the polycarbonate resin has a problem that it is more easily yellowed than the PMMA resin.

Patent Document 1 proposes a method for improving light transmittance and brightness by adding an acrylic resin and an alicyclic epoxy. However, in the method of Patent Document 1, although the hue is improved by adding the acrylic resin, the light transmittance and the brightness cannot be increased because it becomes cloudy, and the transmittance is improved by adding the alicyclic epoxy. However, the effect of improving hue is not observed.

On the other hand, it is known that polyethylene glycol or poly (2-methyl) ethylene glycol or the like is blended with a thermoplastic resin such as a polycarbonate resin, and Patent Document 2 describes a γ-ray irradiation resistant polycarbonate resin containing the same. , Patent Document 3 describes a thermoplastic resin composition blended with PMMA or the like, which has excellent antistatic properties and surface appearance.
Then, 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 degree of yellowing (yellow index: YI) are improved.

However, especially recently, 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 material used for these optical components has extremely high fluidity and excellent properties. Optical characteristics are required. However, the method of improving the fluidity by using a low molecular weight polycarbonate resin or adding a fluidity modifier reduces the impact resistance of the material, so it is very difficult to reach the required specifications with the existing technology. It was difficult.

Japanese Unexamined Patent Publication No. 11-158364 Japanese Unexamined Patent Publication No. 1-22959 Japanese Unexamined Patent Publication No. 9-227785 Japanese Patent No. 5699188

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

As a result of diligent studies to achieve the above problems, the present inventor has added a specific amount of a polycarbonate resin having a specific terminal structure and a specific number average molecular weight of polytrimethylene glycol and a phosphorus-based stabilizer. It has been found that a polycarbonate resin composition having extremely high fluidity, excellent hue, and excellent impact resistance can be obtained by blending in combination with, and has completed the present invention.
The present invention relates to the following polycarbonate resin compositions.

[1] 0.01 to 4 parts by mass of a polytrimethylene glycol compound (B) having a number average molecular weight of 500 to 5000 with respect to 100 parts by mass of a polycarbonate resin (A) having a terminal structure represented by the following general formula (1). , A polycarbonate resin composition containing 0.005 to 0.5 parts by mass of a phosphorus-based stabilizer (C).
(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 above [1] in which the viscosity average molecular weight of the polycarbonate resin (A) is 1000 to 20000. ] The polycarbonate resin composition according to.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the terminal structure is the terminal structure represented by the following general formula (1').
[4] R ¹ in the general formula (1) or (1') is one or more selected from the group consisting of an n-octyl group, an iso-octyl group and a t-octyl group. 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 of the polycarbonate resin (A) in the general formula (1) or (1') is a t-octylphenyl group.
[6] Further, any one of the above [1] to [5] containing 0.0005 to 0.2 parts by mass of the epoxy compound and / or the oxetane compound (D) with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition according to.
[7] A molded product made of the polycarbonate resin composition according to any one of the above [1] to [6].
[8] The molded product according to the above [7], which is an optical member.

The polycarbonate resin composition of the present invention has high fluidity, excellent hue, high impact resistance, and less gas generation during molding.
Therefore, the polycarbonate resin composition of the present invention can be particularly suitably used for various optical components.

FIG. 1 is a graph showing the relationship between the Q value (fluidity) and the impact resistance strength in Example II and Comparative Example II of the present invention. FIG. 2 is a plan view of the drop mold used for the evaluation of mold contamination in the examples.

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 which includes the numerical values described before and after it as the lower limit value and the upper limit value unless otherwise specified.

The polycarbonate resin composition of the present invention contains 0 polytrimethylene glycol compound (B) having a number average molecular weight of 500 to 5000 with respect to 100 parts by mass of the polycarbonate resin (A) having the terminal structure represented by the general formula (1). It is characterized by containing 0.01 to 4 parts by mass and 0.005 to 0.5 parts by mass of the phosphorus-based stabilizer (C).
Hereinafter, each component and the like 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:-[-O-X-OC (= O)-]-. In the formula, X is generally a hydrocarbon, but X with a heteroatom or a heterobond introduced may be used to impart 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. Of these, aromatic polycarbonate resins are preferable from the viewpoints 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, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with cyclic ether using carbon dioxide as a carbonate precursor may also be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a copolymer 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 becomes a thermoplastic resin.

Among the monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2'-Dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1 , 7-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other 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 such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4'-Dihydroxydiphenylsulfide,
Dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;

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

4,4'-Dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;
And so on.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (particularly from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferable.
As the aromatic dihydroxy compound, one type may be used, or two or more types may be used in any combination and ratio.

Further, to give an example of a monomer which is a raw material of an aliphatic polycarbonate resin,
Ethan-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diols, butane-1,4-diols, pentane-1,5-diols, hexane-1,6-diols and decane-1,10-diols;

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;

Glycos such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiroglycol;

1,2-Benzene dimethanol, 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- Aralkyldiols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

1,2-Epoxide ethane (ie, ethylene oxide), 1,2-epoxide propane (ie, propylene oxide), 1,2-epoxide cyclopentane, 1,2-epoxycyclohexane, 1,4-epoxide cyclohexane, 1-methyl Cyclic ethers such as -1,2-epoxide cyclohexane, 2,3-epoxide norbornane, and 1,3-epoxide propane; and the like.

Among the monomers used as raw materials for the polycarbonate resin, carbonyl halide, carbonate ester and the like are used as an example of the carbonate precursor. As the carbonate precursor, one kind may be used, or two or more kinds may be used in any combination and ratio.

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

Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditril carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate of dihydroxy compound, monocarbonate of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.

[Manufacturing 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 suitable of these methods will be specifically described.

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

The dihydroxy compound and carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and the 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. Be done. As the organic solvent, one type may be used, or two or more types may be used in any combination and ratio.

Examples of the alkaline compound contained in the alkaline aqueous solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogen carbonate, and alkaline earth metal compounds. Among them, sodium hydroxide and water. Potassium oxide is preferred. As the alkaline compound, one type may be used, or two or more types may be used in any combination and ratio.

The concentration of the alkaline compound in the alkaline aqueous solution is not limited, but is usually used at 5 to 10% by mass in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12. Further, for example, when phosgene is blown, the molar ratio of the bisphenol compound to the alkaline compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Above all, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, and above all, 1: 2.5 or less.

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

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

[Fused transesterification method]
Next, a case where the polycarbonate resin is produced by the molten 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 acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonate such as ditril carbonate. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type of carbonic acid diester may be used, and 2 or more types may be used in arbitrary combination and ratio.

The ratio of the dihydroxy compound to the carbonic acid diester is arbitrary as long as a desired polycarbonate resin can be 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 1.01 mol or more is particularly used. Is more preferable. The upper limit is usually 1.30 mol or less. By setting the range to such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

When producing a polycarbonate resin by the transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, for example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, as a supplement, 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. As the transesterification catalyst, one type may be used, or two or more types may be used in any combination and 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 carried out under the above conditions while removing by-products such as aromatic hydroxy compounds.

The melt polycondensation reaction can be carried out by either a batch method or a continuous method. In the case of batch method, the order of mixing the reaction substrate, reaction medium, catalyst, additives and the like is arbitrary as long as a desired aromatic polycarbonate resin can be obtained, and an appropriate order may be arbitrarily set. However, above all, in consideration of the stability of the polycarbonate resin and the like, it is preferable to carry out the melt polycondensation reaction in a continuous manner.

In the molten transesterification method, a catalytic deactivator may be used if necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds, phosphorus-containing compounds and derivatives thereof. As the catalyst deactivator, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is preferably 5 equivalents or less. Further, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 20 ppm or less, with respect to the polycarbonate resin.

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

In formula (1), n is an integer of 0 or 1, and R ¹ is an alkyl group having 5 to 14 carbon atoms. Since the polycarbonate resin (A) has the terminal structure of the above formula (1), it enables a high degree of fluidity while maintaining strength, and has a good hue. For this reason, it is usual to lower the molecular weight of the polycarbonate resin in order to improve the fluidity, but in the present invention, even if a desired molecular weight is adopted without lowering the molecular weight when designing the material, a high degree of fluidity is achieved. Therefore, good hue and fluidity can be achieved while maintaining high intensity. By containing the polytrimethylene glycol compound (B), the hue and intensity can be further improved.

The alkyl group of R ¹ preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, and preferably 12 or less carbon atoms, and more preferably 10 or less carbon atoms. The alkyl group of R ¹ may be linear or branched.
Among them, R ¹ is preferably one or more 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 the general formula (1). It is particularly preferred that the terminal structure is a t-octylphenyl group (ie, 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 the ortho position, the meta position or the para position, but the para position shown in the following general formula (1') is preferable.

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

The polycarbonate resin (A) of the present invention can be produced by using a monohydric phenol terminal terminator represented by the following general formula (1a) when it is produced by polymerization.
(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 terminator represented by the general formula (1a) include p-pentylphenol, p-hexylphenol, p-heptylphenol, pn-octylphenol, p-iso-octylphenol, and pt-octylphenol. , P-dodecylphenol and p-tetradecylphenol, p-nonylphenol, p-dodecylphenol, amylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, alkylphenols such as myristylphenol, p-hexyloxy Alkoxyphenols such as phenol, pn-octyloxyphenol, p-iso-octyloxyphenol, pt-octyloxyphenol, and p-dodecyloxyphenol can be preferably mentioned, and any one or more of these can be terminated. It can be used as a terminator. In the formula (1a), the position of the − (O) _n R ¹ group bonded to the phenyl group may be the ortho position, the meta position or the para position, but the para position is preferable.
Above all, the use of any or a plurality of pt-octylphenol and pn-octyloxyphenol as a terminal terminator is considered to be easy to obtain in addition to fluidity, strength and heat resistance of the molded product. More preferred from.

Depending on the required properties for the material, two or more types of terminal terminators may be used in combination without departing from the gist of the present invention, or may be used in combination with a structure other than the structure represented by the general formula (1). It is possible.
Other terminal terminators 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 Examples thereof include p-hydroxybenzoic acid alkyl esters such as methyl ester, ethyl ester, propyl ester, butyl ester, amyl ester, hexyl ester and heptyl ester of alkylphenol and p-hydroxybenzoic acid.
It is also possible to use two or more kinds of other terminal inhibitors in combination. In particular, examples of the terminal terminator that may be used in combination with the terminator of the general formula (1a) include pt-butylphenol from the viewpoint of purity and cost.
When another terminal terminator is used, it is preferably 20 mol% or less, more preferably 10 mol% or less of the total terminator of the entire polycarbonate resin containing the polycarbonate resin (A).

The molecular weight of the polycarbonate resin (A) is preferably 1000 to 20000 in terms of viscosity average molecular weight (Mv), more preferably 10500 or more, still more preferably 11000 or more, particularly preferably 11500 or more, and most preferably 12000 or more. , More preferably 19000 or less, further preferably 18500 or less, and particularly preferably 18000 or less. 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, and by setting the viscosity average molecular weight to the upper limit of the above range or less, the present invention It is possible to suppress and improve the decrease in fluidity of the polycarbonate resin composition of the present invention, improve the molding processability, and facilitate the thin-wall molding process.
The polycarbonate resin (A) may be used by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. In this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned suitable range is mixed. You may.

In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin is the ultimate viscosity [η] (unit: dl / g) at a temperature of 25 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent. , Schnell's viscosity formula, that is, a value calculated from η = 1.23 × 10 ^-4 Mv ^0.83 . The ultimate viscosity [η] is a value calculated by the following formula by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

The polycarbonate resin (A) is not limited to the 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 from each other. It may be used in the meaning including the aspect.).

Further, the polycarbonate resin composition of the present invention may be contained in combination with a polycarbonate resin having a 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 pt-butylphenyl group terminal structure, which is typical of commercially available products. When the polycarbonate resin having another terminal structure is contained, the content 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 with respect to 100 parts by mass of the polycarbonate resin (A). , Especially preferably 15 parts by mass or less, and most preferably 10 parts by mass or less.

Further, in the present invention, the polycarbonate resin may be used in combination with another thermoplastic resin. Further, for example, a polycarbonate resin is used as a copolymer with an oligomer or a polymer having a siloxane structure for the purpose of further improving flame retardancy and impact resistance; a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene, etc. to improve the optical properties Even if it is configured as a copolymer mainly composed of a polycarbonate resin, such as a copolymer with an oligomer or a polymer having an olefin structure; a copolymer with a polyester resin oligomer or a polymer 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 this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Further, the contained polycarbonate ligomer 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 raw material but also a polycarbonate resin recycled from a used product (so-called material recycled polycarbonate resin).
However, when the amount of the regenerated polycarbonate resin is contained, it is preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly 20% by mass, of the polycarbonate resin. Below, it is particularly preferable that it is 10% by mass or less. Since the regenerated polycarbonate resin is likely to be deteriorated by heat deterioration, aging deterioration, etc., if such a polycarbonate resin is used in a larger amount than the above range, the hue and mechanical properties can be deteriorated. Because there is sex.

[Polytrimethylene glycol (B)]
The polycarbonate resin composition of the present invention contains polytrimethylene glycol (B).
Polytrimethylene glycol (B) is a polyether having [-CH ₂ CH ₂ CH _2- O-] as a structural unit, and industrially, trimethylene glycol (or 1) in which a methylene group is linearly bonded. , 3-Propanediol) is polycondensed using an acid catalyst. Polytrimethylene glycol (B) is different from the polyether commonly referred to as polypropylene glycol. Polypropylene glycol is a poly (2-alkyl) ethylene glycol usually produced by ring-opening polymerization of propylene oxide, and is a polyether composed of structural units having a methyl branch.

Trimethylene glycol is represented by HOCH ₂ CH ₂ CH ₂ OH, but industrially, 3-hydroxypropionaldehyde was obtained by hydroformylation of ethylene oxide, which was hydrogenated, or acrolein was hydrated. It is produced by a method of hydrogenating 3-hydroxypropionaldehyde with a Ni catalyst or the like. Recently, a bio-method has been used to reduce glycerin, glucose, starch and the like to microorganisms to produce trimethylene glycol.

A method for producing polytrimethylene glycol from trimethylethylene glycol is described in, for example, US Patent Application Publication No. 2002007043 and 2002010374, and polycondensation of trimethylene glycol using an acid catalyst. Can be manufactured by. Examples of the acid catalyst include sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphoric acid and trifluoromethanesulfonic acid, and a particularly preferable catalyst is sulfuric acid.

The polytrimethylene glycol (B) may be a homopolymer or a copolymer with one or more alkylene glycols other than trimethylene glycol. As the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected.

Further, the terminal group of polytrimethylene glycol (B) is preferably a hydroxyl group. In addition, even if one end or both ends are sealed with an alkyl ether, an aryl ether, an aralkyl ether, a fatty acid ester, an aryl ester, etc., the performance is not affected, and the etherified product or the esterified product can be used in the same manner. ..

As the alkyl group constituting the alkyl ether, either a linear group or a branched alkyl group can be used, and an alkyl group having 1 to 22 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a lauryl group, etc. It is a stearyl group or the like, and methyl ether, ethyl ether, butyl ether, lauryl ether, stearyl ether and the like of polytrimethylene glycol can be preferably exemplified.

The aryl group constituting the aryl ether is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, and further preferably 6 to 10 carbon atoms, and for example, a phenyl group, a tolyl group, or a naphthyl group. Etc., and phenyl group, tolyl group and the like are preferable. The aralkyl group is preferably an aralkyl group having 7 to 23 carbon atoms, more preferably 7 to 13 carbon atoms, still more preferably 7 to 11 carbon atoms, and examples thereof include a benzyl group and a phenethyl group. Especially preferable.

The fatty acid constituting the fatty acid ester can be either linear or branched, and may be a saturated fatty acid or an unsaturated fatty acid.
The fatty acids constituting the fatty acid ester include monovalent or divalent fatty acids having 1 to 22 carbon atoms, for example, monovalent saturated fatty acids, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and enanthic acid. , Capricic acid, capric acid, lauric acid, myristic acid, pentadecic acid, palmitic acid, heptadecic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid and monovalent unsaturated fatty acids such as oleic acid, ellaic acid, Unsaturated fatty acids such as linoleic acid, linolenic acid, and arachidonic acid, and divalent fatty acids having 10 or more carbon atoms, such as sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, tapsia acid and decenoic acid, undecene. Diacid and dodecene diic acid.

The aryl group constituting the aryl ester is preferably an aryl group having 6 to 22 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, and for example, a phenyl group, a tolyl group, or a naphthyl group. Etc., and phenyl group, tolyl group and the like are preferable. Since the end-sealing group exhibits good compatibility with polycarbonate even if it is an aralkyl group, it can exhibit the same action as an aryl group, and the aralkyl group preferably has 7 to 23 carbon atoms, more preferably. An aralkyl group having 7 to 13 carbon atoms, more preferably 7 to 11 carbon atoms is preferable, and examples thereof include a benzyl group and a phenethyl group, and a benzyl group is particularly preferable.

In the present invention, the polytrimethylene glycol (B) used has a number average molecular weight Mn of 500 to 5000. Mn is preferably 700 or more, more preferably 1000 or more, still more preferably 1500 or more, still more preferably 4000 or less, still more preferably 3000 or less. If it exceeds the upper limit of the above range, the compatibility is lowered, which is not preferable, and if it is less than the lower limit of the above range, gas is generated during molding, which is not preferable.
The number average molecular weight Mn of polytrimethylene glycol referred to here is a number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K1577.

The content of polytrimethylene glycol (B) is 0.01 to 4 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). The preferable content is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, particularly 0.3 parts by mass or more, particularly 0.4 parts by mass or more, particularly 0 It is preferably 5.5 parts by mass or more, preferably 3.5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2.5 parts by mass or less, and particularly 2 parts by mass or less, particularly 1.5 parts by mass. Part or less is preferable. If the content is less than 0.01 parts by mass, the hue and yellowing are not sufficiently improved, and if it exceeds 4 parts by mass, the transmittance is lowered due to the white turbidity of the polycarbonate resin, and at the time of melt-kneading by an extruder. , Strand breakage occurs frequently, making it difficult to prepare resin composition pellets.

[Phosphorus stabilizer (C)]
The polycarbonate resin composition of the present invention contains a phosphorus-based stabilizer. By containing a phosphorus-based stabilizer, the hue of the polycarbonate resin composition of the present invention is further improved, and the heat-resistant discoloration property is further improved.
Any known phosphorus-based stabilizer can be used. Specific examples include phosphoric acid, phosphonic acid, phosphite, phosphinic acid, polyphosphoric acid and other phosphorus oxo acids; acidic sodium pyrophosphate, potassium pyrophosphate, acidic calcium pyrophosphate and other acidic pyrophosphate metal salts; phosphoric acid. Phosphates of Group 1 or Group 2B metals such as potassium, sodium phosphate, cesium phosphate, zinc phosphate; phosphate compounds, phosphite compounds, phosphonite compounds and the like can be mentioned, with phosphite compounds being particularly preferred. By selecting the 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 phosphite compounds include triphenylphosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl-phenyl) phosphite, and tris (2,4-di-tert-butylphenyl) phos. Fight, monooctyldiphenylphosphite, dioctylmonophenylphosphite, monodecyldiphenylphosphite, didecylmonophenylphosphite, tridecylphosphite, trilaurylphosphite, tristearylphosphite, distearylpentaerythritol diphosphite, Bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butylphenyl) octylphosphite, 2,2-methylenebis (4,6-di) -Tert-Butylphenyl) octylphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphite, 6- [3- (3-tert-butyl-hydroxy-5-methyl) Phenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] -dioxaphosfepine and the like.

Among such phosphite compounds, the aromatic phosphite compound represented by the following formula (2) or (3) is more preferable because the heat-resistant discoloration property of the polycarbonate resin composition of the present invention is effectively enhanced. ..

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

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

As the phosphite compound represented by the above formula (2), triphenylphosphine, tris (monononylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are preferable, among others. Tris (2,4-di-tert-butylphenyl) phosphite is more preferred. Specific examples of such an organic phosphite compound include "ADEKA STUB 1178" manufactured by ADEKA, "Sumilyzer TNP" manufactured by Sumitomo Chemical Co., Ltd., "JP-351" manufactured by Johoku Chemical Industry Co., Ltd., and "ADEKA STAB" manufactured by ADEKA Corporation. 2112 ”,“ Irgaphos 168 ”manufactured by BASF,“ JP-650 ”manufactured by Johoku Chemical Industry Co., Ltd., and the like.

Examples of the phosphite compound represented by the above formula (3) include bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl). Those having a pentaerythritol diphosphite structure such as -4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are particularly preferable. Specific preferred examples of such an organic phosphite compound include "ADEKA TAB PEP-24G" and "ADEKA STAB PEP-36" manufactured by ADEKA, and "Doverphos S-9228" manufactured by Doverchemical.

Among the phosphite compounds, the aromatic phosphite compound represented by the above formula (3) is more preferable because it has a more excellent hue.
The phosphorus-based stabilizer may contain one type, or two or more types may be contained in any combination and ratio.

The content of the phosphorus-based stabilizer (C) is 0.005 to 0.5 parts by mass, preferably 0.007 parts by mass or more, and more preferably 0. parts by mass with respect to 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, still more preferably 0.2 parts by mass or less, particularly 0. . 1 part by mass or less. If the content of the phosphorus-based stabilizer (C) is less than 0.005 parts by mass, the hue and heat-resistant discoloration property will be insufficient, and if it exceeds 0.5 parts by mass, the heat-resistant discoloration property will only worsen. Not only that, but also the wet and thermal stability is reduced.

[Epoxy compound or oxetane compound (D)]
The polycarbonate resin composition of the present invention further preferably contains an epoxy compound and / or an oxetane compound (D).

<Epoxy compound>
The resin composition of the present invention also preferably contains an epoxy compound. By containing the epoxy compound together with the polytrimethylene glycol compound (B), the heat-resistant discoloration property can be further improved.

As the epoxy compound, a compound having one or more epoxy groups in one molecule is used. Specifically, phenylglycidyl ether, allylglycidyl ether, t-butylphenylglycidyl ether, 3,4-epoxidecyclohexylmethyl-3', 4'-epoxidecyclohexylcarboxylate, 3,4-epoxide-6-methylcyclohexylmethyl. -3', 4'-epoxide-6'-methylcyclohexylcarboxylate, 2,3-epoxidecyclohexylmethyl-3', 4'-epoxidecyclohexylcarboxylate, 4- (3,4-epoxide-5-methylcyclohexyl) Butyl-3', 4'-epoxide cyclohexylcarboxylate, 3,4-epoxide cyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxide cyclohexylcarboxylate, 3,4-epoxide-6-methylcyclohexylmethyl-6'-methylsilohexyl Carboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxide dicyclopentadienyl ether, bis-epoxide ethylene glycol, Bis-epoxycyclohexyl adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxide, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-Methyl-5-t-Butyl-1,2-epoxide cyclohexane, octadecyl-2,2-dimethyl-3,4-epoxidecyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxidecyclohexyl Carboxylate, Cyclohexyl-2-methyl-3,4-epoxidecyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxide-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxidecyclohexylcarboxylate, 2-Ethylhexyl-3', 4'-epoxide cyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxide cyclohexyl-3', 4'-epoxide cyclohexylcarboxylate, 4,5-epoxide anhydride tetrahydrophthalic acid, 3 -T-Butyl-4,5-epoxide tetrahydrophthalic anhydride, diethyl4,5-epoxide-cis-1,2-cyclohexyldicarboxy Preferable examples include rate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, epoxidized soybean oil, epoxidized linseed oil and the like.
The epoxy compounds may be used alone or in combination of two or more.

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

When the epoxy compound is contained, the content is preferably 0.0005 to 0.2 parts by mass, more preferably 0.001 parts by mass or more, still more preferably 0.001 parts by mass, based on 100 parts by mass of the polycarbonate resin (A). 0.003 parts by mass or more, particularly preferably 0.005 parts by mass or more, more preferably 0.15 parts by mass or less, still more preferably 0.1 parts by mass or less, particularly preferably 0.05 parts by mass or less. is there. If the content of the epoxy compound is less than 0.0005 parts by mass, the hue and heat-resistant discoloration are likely to be insufficient, and if it exceeds 0.2 parts by mass, the heat-resistant discoloration is likely to deteriorate and the hue and wet heat stability are likely to deteriorate. Also tends to decrease.

<Oxetane compound>
The resin composition of the present invention also preferably contains an oxetane compound. By containing the oxetane compound together with the polytrimethylene glycol compound (B), the heat-resistant discoloration property can be further improved.

As the oxetane compound, any compound having one or more oxetane groups in the molecule can be used, and a monooxetane compound having one oxetane group in the molecule and a monooxetane compound having two or more oxetane groups in the molecule can be used. Any bifunctional or higher functional polyoxetane compound can be used.
By containing the oxetane compound, good hue and high heat-resistant discoloration can be further improved.

As the monooxetane compound, a compound represented by the following general formulas (4), (5) or (6) can be preferably exemplified.

(In the formula, R ¹ represents an alkyl group, R ² represents an alkyl group or a phenyl group, R ³ represents a divalent organic group which may have an aromatic ring, and n represents 0 or 1.)

In the above general formulas (4), (5) and (6), R ¹ is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group, and particularly preferably ethyl. It is a group.
Further, R ² is an alkyl group or a phenyl group, preferably an alkyl group having 2 to 10 carbon atoms, and may be any of a chain alkyl group, a branched alkyl group and an alicyclic alkyl group. Alternatively, it may be a chain or branched alkyl group having an ether bond (ether-based oxygen atom) in the middle of the alkyl chain. Specific examples of R ² include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl group, nonyl group, decyl group, 3-Okishipenchiru group, a cyclohexyl group, a phenyl The group can be mentioned. Of these, R ² is preferably a ² -ethylhexyl group, a phenyl group, or a cyclohexyl group.

Specific examples of the compound of the general formula (4) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl-3-3. Normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane and the like can be preferably mentioned. Among them, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane and the like are particularly preferable.
As a specific example of the compound of the general formula (5), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and the like are particularly preferable.

In the general formula (6), R ³ is a divalent organic group which may have an aromatic ring, and examples thereof include an ethylene group, a propylene group, a butylene group, a neopentylene group and an n-pentamethylene group. a linear or branched alkylene group having 1 to 12 carbon atoms such as n- hexamethylene group, a phenylene group, the ^formula: -CH ² -Ph-CH 2 - or ^{-CH 2 -Ph-Ph-CH 2} - (Here, Ph indicates a phenyl group), a divalent group, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, and a tricyclode. Candimethanol residues and the like can be mentioned.

Specific examples of the compound of the general formula (6) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, and bis (3-propyl-3-oxetanylmethyl). Ether, bis (3-butyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3 {[(3-ethyloxetane-3-3) Il) methoxy] methyl} oxetane, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, etc. It can be mentioned particularly preferably.

The oxetane compound may be used alone or in combination of two or more.

When the oxetane compound is contained, the content is preferably 0.0005 to 0.2 parts by mass, more preferably 0.001 parts by mass or more, still more preferably 0.001 parts by mass, based on 100 parts by mass of the polycarbonate resin (A). 0.003 parts by mass or more, particularly preferably 0.005 parts by mass or more, more preferably 0.15 parts by mass or less, still more preferably 0.1 parts by mass or less, particularly preferably 0.05 parts by mass or less. is there. If the content of the oxetane compound (E) is less than 0.0005 parts by mass, the hue and heat-resistant discoloration tend to be insufficient, and if it exceeds 0.2 parts by mass, the heat-resistant discoloration tends to deteriorate. Gas is likely to be generated during molding.

The epoxy compound and the oxetane compound are preferably contained together, and the total content when both are contained is 0.0005 to 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Is preferable.

[Additives, etc.]
The polycarbonate resin composition of the present invention has other additives other than those described above, such as a mold release agent, an antioxidant, an ultraviolet absorber, an optical brightener, a pigment, a dye, and a polymer other than the polycarbonate resin. It can contain additives such as flame retardants, impact resistant improvers, antistatic agents, plasticizers, and compatibilizers. These additives may be used alone or in combination of two or more.

[Manufacturing method of polycarbonate resin composition]
The method for producing the polycarbonate resin composition of the present invention is not limited, and a known method for producing the polycarbonate resin composition can be widely adopted, and the polycarbonate resin (A), the polytrimethylene glycol compound (B), and the phosphorus-based stabilizer (C) can be widely adopted. ), And other ingredients to be blended as needed, are premixed using various mixers such as tumblers and henschel mixers, and then Banbury mixers, rolls, brabenders, single-screw kneading extruders, and twin-screw kneading. Examples thereof include a method of melt-kneading with a mixer such as an extruder or a kneader. The temperature of 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 produce various molded products by molding pellets obtained by pelletizing the above-mentioned polycarbonate resin composition by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without passing through pellets.

Since the polycarbonate resin composition of the present invention exhibits extremely high fluidity, excellent hue, excellent impact resistance, and less gas generation during molding, optical parts, particularly thin-walled optics, are subjected to injection molding. It is suitably used for molding parts. The resin temperature at the time of injection molding is preferably higher than 260 to 300 ° C., which is a temperature generally applied to injection molding of polycarbonate resin, particularly in the case of thin-walled molded products, and is preferably 305. A resin temperature of ~ 380 ° C. is preferable. The resin temperature is more preferably 310 ° C. or higher, further preferably 315 ° C. or higher, particularly preferably 320 ° C. or higher, and even more preferably 370 ° C. or lower. When a conventional polycarbonate resin composition is used, there is a problem that yellowing of the molded product is likely to occur if the resin temperature at the time of molding is raised in order to mold the thin-walled molded product. However, the resin of the present invention has a problem. By using the composition, it becomes possible to produce a molded product having a good hue, particularly a thin-walled optical component, even in the above temperature range. Further, although it has been conventionally practiced to reduce the molecular weight of the polycarbonate resin in order to mold a thin-walled molded product, since the polycarbonate resin composition of the present invention has good fluidity, thin-wall molding can be performed without lowering the molecular weight. , It becomes possible to make a molded product with higher strength.
The resin temperature is grasped as the barrel set temperature when it is difficult to measure it directly.

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

Examples of the optical component include components of devices / 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 tube.
The optical component using the polycarbonate resin composition of the present invention can be suitably used in the fields of liquid crystal backlight units, various display devices, and lighting devices. Examples of such devices include various mobile terminals such as mobile phones, mobile notebooks, netbooks, slate PCs, tablet PCs, smartphones, tablet terminals, cameras, watches, notebook computers, various displays, lighting devices, and the like. Be done.

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

The raw materials used in the following Examples and Comparative Examples are shown in Table 1-2 below. The method for measuring the viscosity average molecular weight Mv of the polycarbonate resin is as described above.

(Examples I-1 to 15, Comparative Examples I-1 to 7)
[Manufacturing of resin composition pellets]
Each component listed in Tables 1 and 2 above is blended in the proportions (parts by mass) shown in Tables 3 and 4 below, mixed in a tumbler for 20 minutes, and then a single-screw extruder with a vent having a screw diameter of 40 mm ( It was melt-kneaded at a cylinder temperature of 240 ° C. by Tanabe Plastic Machinery Co., Ltd. “VS-40”), and pellets were obtained by strand cutting.

[Hue (YI) and ΔYI (evaluation of heat-resistant discoloration)]
The obtained pellets are dried at 120 ° C. for 5 to 7 hours with a hot air circulation type dryer, and then long-light path molding is performed with an injection molding machine (“HSP100A” manufactured by Sodick Co., Ltd.) at a resin temperature of 340 ° C. and a mold temperature of 80 ° C. A product (300 mm × 7 mm × 4 mm) was molded.
YI (yellowing degree) was measured with an optical path length of 300 mm for this long optical path molded product. A long optical path spectroscopic transmission chromometer (“ASA 1” manufactured by Nippon Denshoku Kogyo Co., Ltd., C light source, 2 ° field of view) was used for the measurement.
Next, after holding the long optical path molded product at 95 ° C. for 500 hours, YI was measured with an optical path length of 300 mm, the difference ΔYI from the initial YI value was obtained, and the heat discoloration property was evaluated.

[Outflow amount per unit time: Q value (unit: × ^10-2 cm ³ / sec)]
The pellets obtained by the above method are dried at 120 ° C. for 4 hours or more, and then the composition is prepared under the conditions of 280 ° C. and a load of 160 kgf / cm ² using an elevated flow tester in accordance with 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.

[Impact resistance evaluation: Charpy impact strength with notch (unit: kJ / m ² )]
The obtained pellets are dried at 120 ° C. for 5 hours, and then used in an injection molding machine (“NEX80III” manufactured by Nissei Resin Industry Co., Ltd.) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 45 seconds. , ISO179-1, 2 and 3 mm thick impact resistance test pieces were prepared. The obtained test piece was notched at R0.25 mm / depth 2 mm, and the notched Charpy impact strength (kJ / m ² ) was measured in a temperature environment of 23 ° C.

[Gas generation during molding: Mold contamination evaluation (mold deposits)]
Stainability evaluation in injection molding (mold stain)
The pellets obtained above are dried at 120 ° C. for 5 hours, and then a cylinder is used using an injection molding machine (“SE7M” manufactured by Sumitomo Heavy Industries, Ltd.) and a drop mold as shown in FIG. The state of dirt due to white deposits generated on the metal mirror surface on the mold fixing side after 150 shot injection molding under the conditions of a temperature of 340 ° C., a molding cycle of 10 seconds, and a mold temperature of 40 ° C. is as follows. The evaluation was visually evaluated based on the criteria.
A: The amount of deposits on the mold is small, and the mold contamination resistance is extremely good.
B: The amount of mold deposits is slightly seen between A and C.
C: There are many mold deposits, and mold contamination is noticeable.

The drop mold of FIG. 2 is a mold designed so that the resin composition is introduced from the gate G and the generated gas easily accumulates in the tip P portion. The width of the gate G is 1 mm and the thickness is 1 mm. In FIG. 2, the width h1 is 14.5 mm, the length h2 is 7 mm, the length h3 is 27 mm, and the thickness of the molded portion is 3 mm.
The above evaluation results are shown in Tables 3 to 4 below.

(Examples II-1 to 3, Comparative Examples II-1 to 5)
[Manufacturing of resin composition pellets]
Each component shown in Tables 1 and 2 is blended at the ratio (parts by mass) shown in Table 5 below, mixed in a tumbler for 20 minutes, and then a single-screw extruder with a vent (Tanabe Plastic) having a screw diameter of 40 mm. It was melt-kneaded at a cylinder temperature of 240 ° C. by “VS-40” manufactured by Kikai Co., Ltd.), and pellets were obtained by strand cutting.

[Hue (YI) and ΔYI (evaluation of heat-resistant discoloration)]
The obtained pellets are dried at 120 ° C. for 5 to 7 hours with a hot air circulation type dryer, and then long-light path molding is performed with an injection molding machine (“HSP100A” manufactured by Sodick Co., Ltd.) at a resin temperature of 340 ° C. and a mold temperature of 80 ° C. A product (300 mm × 7 mm × 4 mm) was molded.
YI (yellowing degree) was measured with an optical path length of 300 mm for this long optical path molded product. A long optical path spectroscopic transmission chromometer (“ASA 1” manufactured by Nippon Denshoku Kogyo Co., Ltd., C light source, 2 ° field of view) was used for the measurement.
Next, after holding the long optical path molded product at 95 ° C. for 500 hours, YI was measured with an optical path length of 300 mm, the difference ΔYI from the initial YI value was obtained, and the heat discoloration property was evaluated.

[Outflow amount per unit time: Q value (unit: × ^10-2 cm ³ / sec)]
The pellets obtained by the above method are dried at 120 ° C. for 4 hours or more, and then the composition is prepared under the conditions of 240 ° C. and a load of 160 kgf / cm ² using an elevated flow tester in accordance with 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.

[Impact resistance evaluation: Charpy impact strength with notch (unit: kJ / m ² )]
The obtained pellets are dried at 120 ° C. for 5 hours, and then used in an injection molding machine (“NEX80III” manufactured by Nissei Resin Industry Co., Ltd.) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 45 seconds. , ISO179-1, 2 and 3 mm thick impact resistance test pieces were prepared. The obtained test piece was notched at R1.0 mm / depth 2 mm, and the notched Charpy impact strength (kJ / m ² ) was measured in a temperature environment of 23 ° C.

[Gas generation during molding: Mold contamination evaluation (mold deposits)]
Stainability evaluation in injection molding (mold stain)
The pellets obtained above are dried at 120 ° C. for 5 hours, and then the cylinder temperature is set to 340 ° C. using an injection molding machine (“SE8M” manufactured by Sumitomo Heavy Industries, Ltd.) and the above-mentioned drop mold. , Molding cycle 10 seconds, 150 shot injection molding under the condition of mold temperature 40 ° C., and the state of dirt due to white deposits generated on the metal mirror surface on the mold fixing side after completion is visually inspected according to the following criteria. Evaluation was made at.
A: The amount of deposits on the mold is small, and the mold contamination resistance is extremely good.
B: The amount of mold deposits is slightly seen between A and C.
C: There are many mold deposits, and mold contamination is noticeable.
The above evaluation results are shown in Table 5 below.

FIG. 1 is a graph showing the relationship between the Q value (fluidity) and the notched Charpy impact strength in Example II and Comparative Example II, where ● is an example and ▲ is a comparative example.
From FIG. 1, it can be seen that in each of the examples, fluidity and impact strength can be achieved in a well-balanced manner, and while having higher fluidity than the comparative example, excellent impact strength is maintained. On the other hand, it can be seen that the comparative example is inferior in its balance.

Since the polycarbonate resin composition of the present invention is a polycarbonate resin material having a good hue, very high fluidity, and excellent impact resistance, it can be suitably used for various optical parts and the like.

Claims (8)

0.01 to 4 parts by mass of the polytrimethylene glycol compound (B) having a number average molecular weight of 500 to 5000 with respect to 100 parts by mass of the polycarbonate resin (A) having the terminal structure represented by the following general formula (1), phosphorus-based A polycarbonate resin composition containing 0.005 to 0.5 parts by mass of a stabilizer (C).
(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 composition according to claim 1, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 1000 to 20000. The polycarbonate resin composition according to claim 1 or 2, wherein the terminal structure is a terminal structure represented by the following general formula (1').
Any of claims 1 to 3 in which R ¹ in the general formula (1) or (1') is at least one selected from the group consisting of an n-octyl group, an iso-octyl group and a t-octyl group. The polycarbonate resin composition according to. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the terminal structure of the polycarbonate resin (A) in the general formula (1) or (1') is a t-octylphenyl group. The polycarbonate resin composition according to any one of claims 1 to 5, further containing 0.0005 to 0.2 parts by mass of the epoxy compound and / or the oxetane compound (D) with respect to 100 parts by mass of the polycarbonate resin (A). Stuff. A molded product made of the polycarbonate resin composition according to any one of claims 1 to 6. The molded product according to claim 7, which is an optical member.