JP2002020607A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which exhibits a good thermal stability even when a thermal load is applied for a long time under an atmosphere containing oxygen of some concentration, especially a polycarbonate resin composition suitable for rotational molding. SOLUTION: This polycarbonate resin composition is prepared by compounding 100 pts.wt. polycarbonate resin (ingredient A) with 0.0001-1 pt.wt. specific phosphorus compound (ingredient B), 0.0001-1 pt.wt. phenolic antioxidant (ingredient C), and 0.0001-1 pt.wt. sulfur-base antioxidant (ingredient D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition containing a specific stabilizer in combination. More specifically, the present invention provides a polycarbonate resin composition suitable for a use that is exposed to heat for a long time in the presence of oxygen. Such a resin composition is particularly suitable for a method of melt-processing a resin in the presence of a certain amount of oxygen, such as rotational molding.

[0002]

2. Description of the Related Art Polycarbonate resins are used in a wide range of fields because of their excellent properties such as transparency and impact resistance. For example, optical information media, optical lenses, glazing materials for buildings and vehicles, lighting covers, and the like. And light guide plates. These are mainly used as various molded articles by extrusion molding, injection molding, heat compression molding and the like. Among them, injection molding is widely used today because it can form complicated shapes.

[0003] However, injection molding also has problems.
Injection molding is performed using high pressure. For this reason, a mold to be filled with a resin is required to have a toughness corresponding to the mold. Such a mold requires a large number of manufacturing steps and is expensive. In the case of producing small-quantity multi-products or large-sized molded products, there is a case where a cheaper mold is required.

[0004] Also, extremely precise parts such as IC and LS
When injection molding is performed by inserting an I, an optical lens, a liquid crystal glass or the like, or a very fragile part, for example, a glass material, into a mold, the high pressure required for the injection molding may deteriorate or damage these parts. Is generated. In particular, in a polycarbonate having a high melt viscosity, such a problem of deterioration in function or damage is likely to occur. Therefore, there is a need for a method capable of molding at a low pressure, instead of injection molding in some cases.

[0005] One of such molding methods is a rotational molding method. In the rotational molding method, the pressure applied to the resin is only the centrifugal force due to its own weight. Other examples include a molding method in which resin particles are filled in a high-temperature mold and the resin is melted. Preferably, it is a molding method in which a mold is compressed in a molten state. In such a case, a pressure for mold compression is required, but such pressure is extremely low as compared with the filling pressure of the resin in injection molding.

However, in these molding methods,
The resin is heated to an extremely high temperature in an atmosphere where oxygen is present to some extent. Therefore, unlike the case of extrusion molding, injection molding, and the like, the molding that enables these low pressures has a problem that the polycarbonate resin is susceptible to oxidative deterioration and the polycarbonate resin is apt to yellow.

JP-A-4-120614 describes a polycarbonate resin composition comprising a polycarbonate resin containing a specific dye and a specific sulfur-containing carboxylic acid ester. However, the resin composition described in this publication does not solve the above-mentioned problems in rotational molding and the like.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having good thermal stability even when subjected to a thermal load for a long time in a certain oxygen atmosphere. Especially when melt processing in the presence of some oxygen,
For example, it is an object of the present invention to provide a polycarbonate resin composition having good thermal stability when performing rotational molding. The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a polycarbonate resin composition containing a specific stabilizer in combination can solve the above problems, and have reached the present invention.

[0009]

According to the present invention, at least one of the following general formulas (1), (2), (3) and (4) is used with respect to 100 parts by weight of a polycarbonate resin (component (A)). Phosphorus compound (component B) 0.0001-1
Parts by weight, phenolic antioxidant (component C) 0.000
1 to 1 part by weight, and sulfur antioxidant (D component)
The present invention relates to a polycarbonate resin composition containing 0.0001 to 1 part by weight.

[0010]

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(In the formula (1), R ¹ and R ² each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. )

[0012]

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(In the formula (2), R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And R ⁸ represents a hydrogen atom or a methyl group. )

[0014]

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(In the formula (3), R ¹² and R ¹⁵ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ¹³ , R ¹⁴ , R ¹⁶ ,
And R ¹⁷ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and Y represents a group derived from dihydric phenol. )

[0016]

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(In the formula (4), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ ,
R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ²² and R ^{28 each} represent a hydrogen atom or a carbon atom And R ²³ and R ^{29 each} represent a hydrogen atom or a methyl group. Also Z
Represents a group derived from dihydric phenol. )

The polycarbonate resin used as the component A in the present invention will be described below. The production method of the polycarbonate resin is not particularly limited, but is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a solid phase transesterification of a carbonate prepolymer. It is obtained by polymerizing by a method or by ring-opening polymerization of a cyclic carbonate compound.

Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) phenyl}
Propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis} (4-
(Hydroxy-3-phenyl) phenyl} propane, 2,
2-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) -3-methylbutane,
2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4- Hydroxyphenyl) -o-
Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy diphenyl ketone, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl ester and the like, and these may be used alone or in combination of two or more. Can be mixed and used.

Among these, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred, and furthermore, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. In particular, a homopolymer of bisphenol A is preferred.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol may be used. May be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -trisphenol such as α, α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ) Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof.
1-tris (4-hydroxyphenyl) ethane, 1,
1,1-Tris (3,5-dimethyl-4-hydroxyphenyl) ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When the composition contains a polyfunctional compound capable of producing such a branched polycarbonate resin, the proportion is 0.001 to 1 mol%, preferably 0.1 to 1 mol%, based on the total amount of the polycarbonate.
005 to 0.5 mol%, particularly preferably 0.01 to 0.
3 mol%. In particular, in the case of the melt transesterification method,
In some cases, a branched structure may occur as a side reaction.
It is preferably from 01 to 1 mol%, preferably from 0.005 to 0.5 mol%, particularly preferably from 0.01 to 0.3 mol%. The ratio can be calculated by ¹ H-NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Also,
To promote the reaction, for example, triethylamine, tetra-n
Catalysts such as tertiary amines such as -butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds can also be used. At that time, the reaction temperature is usually 0 to
40 ° C., reaction time is about 10 minutes to 5 hours, pH during the reaction
Is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (5).

[0027]

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(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. ) Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (6) and (7) as a substituent are preferably used.

[0030]

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[0031]

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(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

As the substituted phenols of the general formula (6), those having n of 10 to 30, especially 10 to 26 are preferred. Specific examples thereof include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (7), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

It is desirable that the terminal terminator is introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually 120 to 350 ° C.
Range. In the late stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

In order to increase the polymerization rate, a polymerization catalyst is used.
The polymerization catalyst can be used, for example, water
Sodium oxide, potassium hydroxide, dihydric phenol
Alkali metal compounds such as thorium and potassium salts, water
Calcium oxide, barium hydroxide, magnesium hydroxide
Alkaline earth metal compounds such as tetramethylammonium
Hydroxide, tetraethylammonium hydroxide
Nitrogen containing sid, trimethylamine, triethylamine, etc.
Basic compounds, alkali metals and alkaline earth metals
Lucoxides, organic alkali metals and alkaline earth metals
Acid salts, zinc compounds, boron compounds, aluminum
Compounds, silicon compounds, germanium compounds, organic
Tin compounds, lead compounds, osmium compounds, ann
Timon compounds, manganese compounds, titanium compounds, di
Normal esterification reactions such as ruconium compounds,
The catalyst used in the exchange reaction can be used. Touch
The medium may be used alone or in combination of two or more.
May be used. The amount of these polymerization catalysts used is
Preferably 1 × 10 ^-8~
1 × 10^-3Equivalent, more preferably 1 × 10^-7~ 5 × 10
^-FourIt is selected within the range of equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Above all, 2-
Chlorophenyl phenyl carbonate, 2-methoxycarbonyl phenyl phenyl carbonate and 2-ethoxycarbonyl phenyl phenyl carbonate are preferred, and 2-methoxy carbonyl phenyl phenyl carbonate is particularly preferred.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. It is used at a rate of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

The viscosity average molecular weight of the polycarbonate resin of the present invention is not particularly limited.
It is preferably from 00 to 23,000. This is because a high pressure is not applied in the rotational molding method, which is a preferable molding method for the resin composition of the present invention, or in the molding method in which the resin particles are filled in a high-temperature mold and the resin is melted. This is because high fluidity is required for the resin. On the other hand, in such a range, the obtained molded product has sufficient strength. More preferably, the viscosity average molecular weight is from 14,000 to 20,000, and still more preferably from 15,000 to 19,500. Methods for controlling the viscosity average molecular weight of the polycarbonate resin and the polycarbonate resin composition have been widely known, and can be appropriately set according to the purpose.

Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, it is of course possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range. For example, a polycarbonate resin having a viscosity average molecular weight of 80,000 or more, more preferably a polycarbonate resin having a viscosity average molecular weight of 100,000 or more is mixed, and the two peak molecular weight distribution is determined by a method such as GPC (gel permeation chromatography). What has it can also be used.

In the present invention, the viscosity average molecular weight is
The polycarbonate resin composition is dissolved in 20 to 30 times the weight of methylene chloride, and the solubles are collected by filtration through celite. The solution is removed and dried sufficiently to obtain a solid of methylene chloride solubles. . From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, a specific viscosity at 20 ° C. calculated by the following equation is determined using an Ostwald viscometer. Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution]

Furthermore, the viscosity average molecular weight M was determined by inserting the specific viscosity determined above into the following equation. η _SP /c=[η]+0.45×[η] ² c [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

The polycarbonate resin composition of the present invention comprises:
The component B contains at least one phosphorus compound selected from the following general formulas (1), (2), (3) and (4). By using such a specific phosphorus compound, the polycarbonate resin composition of the present invention has good hue and mechanical properties even when a certain amount of oxygen is present and the resin is exposed to a high temperature for a long time under a high melting temperature. Can be provided. As described above, such characteristics are required when performing molding at a low pressure such as rotational molding.

The reason why such a specific phosphorus compound satisfies such properties is unclear. However, the present inventors have found that such a phosphorus compound has better thermal stability than other phosphorus compounds, and as a result, the phosphorus compound has a phenol-based antioxidant and a sulfur-based antioxidant. We anticipate that the synergistic effect will be exerted even under more severe conditions.

[0048]

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(In the formula (1), R ¹ and R ² each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
It represents an aryl group or an aralkyl group. )

[0050]

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(In the formula (2), R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And R ⁸ represents a hydrogen atom or a methyl group. )

[0052]

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(In the formula (3), R ¹² and R ¹⁵ represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ¹³ , R ¹⁴ , R ¹⁶ ,
And R ¹⁷ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and Y represents a group derived from dihydric phenol. )

[0054]

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(In the formula (4), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ ,
R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ²² and R ^{28 each} represent a hydrogen atom or a carbon atom And R ²³ and R ^{29 each} represent a hydrogen atom or a methyl group. Also Z
Represents a group derived from dihydric phenol. )

In the formula (1), R ¹ and R ² are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Equation (1)
Specific examples of the compound of (1) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, and tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-t
tert-butylphenyl) phosphite and the like, and particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite.

On the other hand, the phosphorus compound of the formula (2) can be produced by a known method.
And a phenolic compound represented by the following general formula (9) or a reactive derivative thereof are used.

[0058]

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(In the formula (8), R ³ , R ⁴ , R ⁵ and R ⁶
Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁸ represents hydrogen. Indicates an atom or a methyl group. )

[0060]

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(In the formula (9), R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
It represents a cycloalkyl group, an aryl group or an aralkyl group. )

Specific examples of the compound represented by the general formula (8) include 2,2'-methylenebisphenol, 2,2'-methylenebis (4-methylphenol), and 2,2'-methylenebis (6-methylphenol) 2,2′-methylenebis (4,6-dimethylphenol), 2,2′-ethylidenebisphenol, 2,2′-ethylidenebis (4-methylphenol), 2,2′-isopropylidenebisphenol, 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-ter
t-butylphenol), 2,2′-methylenebis (4
-Methyl-6-cyclohexylphenol), 2,2 ′
-Dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethylphenylmethane, 2,2 '
-Methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol) and 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol) and the like, and they can be preferably used.

The compound of the general formula (8) is more preferably 2,2'-methylenebis (4-methyl-6-ter
t-butylphenol), 2,2′-methylenebis (4
-Ethyl-6-tert-butylphenol), 2,
2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), and 2,2'-butylidene-bis (4-methyl- 6-tert-butylphenol).

On the other hand, specific examples of the compound of the general formula (9) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, −ter
t-butyl-4-methylphenol, 2,4-di-te
rt-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl -4-
Ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-
4-s-butylphenol and the like can be mentioned, and they can be preferably used. A more preferred specific example of the compound of the general formula (9) is a case having two or more alkyl substituents.

The phosphorus compound of the formula (3) can be produced by a known method. In this case, a phenol compound having a substituent or a reactive derivative thereof and a dihydric phenol compound or a reactive derivative thereof are used as raw materials.

As the dihydric phenol, various dihydric phenols exemplified as the raw materials for the polycarbonate resin can be used. Preferably bisphenol A, 2,
2-bis {(4-hydroxy-3-methyl) phenyl}
Propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-
Methyl butane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl)- At least one dihydric phenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene can be mentioned.

The phenol compound having a substituent used for producing the phosphorus compound of the formula (3) includes:
2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6
-Dimethylphenol, 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,
6-di-tert-butyl-4-methylphenol,
2,4-dimethyl-6-tert-butylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol,
And 2,6-di-tert-butyl-4-s-butylphenol, among which those in which at least one or more branched alkyl groups are substituted are preferred. More preferably 2,4-di-tert-butylphenol,
2,6-di-tert-butyl-4-methylphenol can be mentioned.

The phosphorus compound of the formula (4) is obtained by using, as raw materials, a bisphenol compound represented by the above formula (8) or a reactive derivative thereof, and a dihydric phenol compound corresponding to Z in the formula (4) or a reactive derivative thereof. Is used. More preferably, the compound of the general formula (8) includes the bisphenol compound described in the formula (2).
As the dihydric phenol compound corresponding to Z, various dihydric phenols exemplified as the raw material of the polycarbonate resin can be used. Preferably bisphenol A,
2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl)
-3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4
-Hydroxyphenyl) -4-methylpentane, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and at least one dihydric phenol selected from the group consisting of α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Can be mentioned.

The polycarbonate resin composition of the present invention comprises C
It contains a phenolic antioxidant as an essential component. Various phenolic antioxidants can be used.

Specific examples of such phenolic antioxidants include, for example, vitamin E, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-ter
t-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-
6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert)
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-cyclohexylphenol), 2,2′-
Dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t
tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-
Hexanediol bis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl 6- (3-te
rt-butyl-5-methyl-2-hydroxybenzyl)
Phenyl] terephthalate, 3,9-bis {2- [3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4 '-Thiobis (6-te
rt-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol),
2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6- Di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-butyl-4-hydroxyhydrocinnamide), N,
N'-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyl] hydrazine,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like, It can be used preferably.

More preferably, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,
10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-te
rt-butyl-4-hydroxyphenyl) propionate] methane, and furthermore n-octadecyl-β- (4 ′
-Hydroxy-3 ', 5'-di-tert-butylfell) propionate is preferred.

The polycarbonate resin composition of the present invention further comprises a sulfur-based antioxidant as an essential component. Specific examples of such sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra (β-
Laurylthiopropionate) ester, bis [2-methyl-4- (3-laurylthiopropionyloxy)-
5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2
-Mercapto-6-methylbenzimidazole, 1,
1'-thiobis (2-naphthol) and the like can be mentioned. More preferably, pentaerythritol tetra (β-laurylthiopropionate) ester can be mentioned.

The polycarbonate resin composition of the present invention comprises the above components A to D in the following proportions. That is, component B is 0.0001 to 1 part by weight, component C is 0.0001 to 1 part by weight, and component D is 0.0001 to 1 part by weight with respect to 100 parts by weight of component A.
The ratio of the component B is 0.00
And preferably 0.5 to 0.5 part by weight, more preferably 0.0 to 0.5 part by weight.
It is 0.01 to 0.2 parts by weight. The proportion of the C component is 10 for the A component.
0.0005 to 0.5 part by weight, preferably 0.001 to 0.2 part by weight, based on 0 part by weight. The ratio of the component D is 0.1 to 100 parts by weight of the component A.
The amount is preferably from 0005 to 0.5 part by weight, more preferably from 0.001 to 0.2 part by weight.

When the amount of the component B or C is less than 0.0001 part by weight, mechanical properties are likely to be degraded due to thermal deterioration. Deterioration is likely to occur. B component, C component,
Alternatively, when the D component exceeds 1 part by weight, the hue is liable to be deteriorated due to thermal deterioration, which is not preferable.

The polycarbonate resin composition of the present invention comprises:
It may contain a phosphate compound or a phosphonite compound as a heat stabilizer. Since these compounds have different effects from the phosphite compounds, they can be appropriately added according to the purpose.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, Dioctyl phosphate,
Diisopropyl phosphate and the like,
Preferably it is trimethyl phosphate. The phosphate compound is particularly effective for improving thermal stability when an inorganic filler is contained in the polycarbonate resin composition.
The amount of the phosphate compound is 0.1 to 100 parts by weight of the component A.
A range of 001 to 0.5 parts by weight is appropriate.

Preferred specific examples of the phosphonite compound include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n-butylphenyl)- 3-phenyl-
Phenylphosphonite, bis (2,4-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl)-
3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite , Bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-te
rt-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite,
Tetrakis (2,4-di-n-butylphenyl) -4,
4'-biphenylenediphosphonite, tetrakis (2,
4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-t
tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso- Propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'-
Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert)
-Butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite and the like. Among them, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite or tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and bis (2,4-di-te) is preferred.
More preferred is (rt-butylphenyl) -phenyl-phenylphosphonite or tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite. The phosphonite compound may be a mixture of two or more.

By replacing a part of the component B with the phosphonite compound, it is possible to improve the wet heat resistance while minimizing the deterioration of the hue due to the heat deterioration. The ratio of the phosphonite compound is as follows: Component A 1
It is suitably 0.0001 to 0.1 part by weight based on 00 parts by weight.

Further, the polycarbonate resin composition of the present invention may contain various thermoplastic resins and additives depending on the purpose.

The thermoplastic resin other than the polycarbonate resin includes, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin, ASA resin,
General-purpose plastics represented by SMA resin, polyalkyl methacrylate resin, etc., polyphenylene ether resin, polyacetal resin, aromatic polyester resin,
Engineering plastics represented by polyamide resin, cyclic polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystal polyarylate), etc.
So-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylenesulfide can be mentioned. Further, thermoplastic elastomers such as styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer can also be used.

Examples of other various additives include reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon,
Milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber,
Metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica,
Ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc., flame retardants (halogen, phosphate ester, metal salt, red phosphorus, silicon, metal) Hydrate, etc., including anti-dripping agents), ultraviolet absorbers, light stabilizers, release agents, lubricants, coloring agents (pigments and dyes such as carbon black and titanium oxide),
Light diffusing agents (crosslinked acrylic particles, crosslinked silicon particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, nucleating agents, inorganic and organic Antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers represented by graft rubber, infrared absorbers, and photochromic agents.

The polycarbonate resin composition of the present invention preferably contains a release agent. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compound (silicone oil) , A silicone resin, etc. Those modified with a functional group-containing compound such as acid modification can also be used), a fluorine compound (fluorine oil represented by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. .

Preferred release agents include saturated fatty acid esters, for example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, and stearate stearates. Lower fatty acid esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is 0.01 per 100 parts by weight of the component A.
It is preferably from 2 to 2 parts by weight.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5
-Benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-amylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-te)
rt-butylphenyl) -5-chlorobenzotriazole, 2,2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
Benzotriazole ultraviolet absorbers represented by condensates with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

Further, as an ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy-phenol.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate,
Condensate of 2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid with 1,2,2 Condensation product of 6,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6
6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,
Condensation product with 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-tetraoxaspiro [5,5]
A condensate with undecane) diethanol and a hindered amine-based light stabilizer represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

The ratio of the ultraviolet absorber and the light stabilizer is as follows:
The amount is 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, per 100 parts by weight of the component A.

Further, a bluing agent can be added to the polycarbonate resin composition of the present invention in order to cancel a yellowish color due to an ultraviolet absorber or the like. As the bluing agent, any one can be used without any particular difficulty as long as it is used for a polycarbonate resin. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, a common name Solv
ent Violet 13 [CA. No. (color index No.) 60725; Trade name “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], general name Solvent Vi
olet31 [CA. No. 68210; brand name "Diaresin Violet D" manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33 [CA. No.607
25; brand name "Diaresin Blue J" manufactured by Mitsubishi Chemical Corporation], and generic name Solvent Blue 94 [CA.
No. 61500; Trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet
36 [CA. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Sol
vent Blue 97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent
Blue 45 [CA. No. 61110; Trade name "Terazole Blue RLS" manufactured by Sando Co., Ltd.], Macrovax Violet and Terrazol Blue RLS manufactured by Ciba Specialty Chemicals, and the like. RLS is preferred.

When various products are formed using the polycarbonate resin composition of the present invention as a raw material, various forms can be used as the raw material. For example, shapes such as powders and granules and pellets can be mentioned. A powder having a particle size of about several μm to 1000 μm can be used.

The polycarbonate resin composition of the present invention comprises:
It is suitable for use in rotational molding. In such a case, the form is a granular material, and 3% by weight of particles larger than 35 mesh obtained by a standard sieving method using a Tyler sieve.
It is preferable that the content of particles smaller than 150 mesh is not more than 5% by weight. More preferably, 2% by weight or less of particles larger than 35 mesh and 15% or less.
It is a powder having 4% by weight or less of particles smaller than 0 mesh. More preferably, it is a powder having 1% by weight or less of particles larger than 35 mesh and 4% by weight or less of particles smaller than 150 mesh (hereinafter, such a condition may be referred to as "condition 1").

Further, according to the present invention, the value of 35 determined by the standard sieving method using a Tyler sieve after the test described below is used.
3% by weight or less, preferably 2%, of particles larger than the mesh
It is more preferable that the content is not more than% by weight (hereinafter, such a condition may be referred to as “condition 2”).

Here, the test method under the condition 2 is 500 ml
Put about 100 g of polycarbonate resin particles in a round flask, and place the flask in an oil bath or the like controlled at a temperature specified below so that the whole particles are below the oil bath liquid level, After the temperature is stabilized, the powder in the flask is stirred for 30 minutes at a rotation speed of about 60 rpm, and then the particle size distribution is measured using a standard sieve. The set temperature here is
According to JIS K7207, the temperature shall be 5 ° C. lower than the deflection temperature under load measured under a load of 1.82 MPa.

As a method for obtaining the polycarbonate resin particles satisfying the above condition 2, the rake angle and the twist angle of the cutter blade of the pelletizer, Alternatively, by adjusting the cutting temperature or the like, it may be mentioned that a beard-like substance is not generated in the obtained granular material. In such a case, an ideal powder can be obtained by obtaining the powder by a so-called hot cut method. In addition, when pulverization is performed to obtain a powdery or granular material, by adjusting the pulverizing blade and rotation speed of the pulverizer, the pulverization temperature, and the like, a whisker-like substance is not similarly generated.

For producing the polycarbonate resin composition of the present invention, any method is employed. For example, component A ~
After sufficiently mixing the D component and optionally other components with a pre-mixing means such as a V-type blender, a Nauta mixer, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc., if necessary, an extrusion granulator or a briquette may be used. Examples of the method include granulating with a ting machine or the like, then melt-kneading with a melt-kneading machine represented by a vent-type twin-screw rudder, and pelletizing with a device such as a pelletizer.

In addition, a method in which the components A to D and optionally other components are independently supplied to a melt kneader typified by a vented twin-screw ruder, a part of the components A to D is premixed. Thereafter, a method in which the remaining components are independently supplied to a melt kneader, or the like, may also be used. In addition, when there is a liquid component to be blended, a so-called liquid injection device or liquid addition device can be used for supply to the melt kneader.

The polycarbonate resin composition of the present invention can obtain a desired molded product by various methods.
As a molding method, various methods known as a usual method for molding a thermoplastic resin composition can be used, and examples thereof include extrusion molding, injection molding, and compression molding. In particular, as described above, the polycarbonate resin composition of the present invention is suitable for rotational molding or a molding method in which resin particles are filled in a high-temperature mold and the resin is melted.

Rotational molding makes it possible to obtain particularly large molded products with low distortion. Rotational molding does not require high pressure, so free-cutting steel can be used and inexpensive manufacturing is possible even for large dies. Therefore, such a rotomolded body is suitable for obtaining various glazing materials, lighting covers, and large containers, and is suitable for aircraft, ships, vehicles,
It is suitably used in a wide range of fields such as electronic / electric equipment and mechanical devices.

A molding method in which resin particles are filled in a high-temperature mold and the resin is melted has the same advantages as rotational molding. Such a molding method is particularly advantageous when performing molding by inserting a precision component or a component that is easily damaged. Therefore, such a molded product is suitable for obtaining an optical sensor, a micromotor, and the like, and is suitably used in a wide range of fields such as electronic / electric devices and mechanical devices.

Various methods can be used for heating or cooling these dies, such as heating with a fluid medium such as oil, dielectric heating, and ultrasonic heating. Heating by a fluid medium is suitable for rotational molding, and ultrasonic heating or the like is suitable for a molding method in which resin particles are filled in a high-temperature mold to melt the resin.

[0101]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. Note that the present invention is not limited to the embodiment. The evaluation was based on the following method. (1) Hue of molded article After drying a part of the obtained pellets at 120 ° C for 5 hours using a hot air circulating dryer, the cylinder temperature was 300 ° C by an injection molding machine [FANUC T-150D]. ,
70mm length × 50mm width × 2m thickness at mold temperature 70 ℃
m plate-shaped test pieces were formed. On the other hand, the obtained pellets were pulverized and classified as described below to obtain powders and granules, and then dried and subjected to spin molding to obtain spin-molded articles. A part of the rotomolded body is cut, and is again placed in a hot air drier at 160 ° C. for 3 hours.
Heat treatment was performed for 0 minutes to obtain a substantially plate-shaped test piece.

The hue of the test piece obtained by the injection molding and the test piece obtained from the rotomolded product were measured with a color difference meter (Color Analyzer TR-1800MK-I manufactured by Tokyo Denshoku Industries Co., Ltd.).
It measured according to JISZ8722 using I).
The hue of the rotomolded body with respect to the hue of the test piece obtained by the injection molding was shown by a Hunter color system color difference (ΔE). (2) Screening test for whether or not the condition 2 was satisfied About 100 g of the polycarbonate resin powder was placed in a 500 ml round flask, and the flask was immersed in an oil bath at 130 ° C. as shown in FIG. After confirming that the temperature of the granular material reached 130 ° C. (about 15 minutes was required), the granular material in the flask was further cooled to 60 ° C. for 30 minutes.
After stirring at rpm, the obtained granules were subjected to standard particle size distribution using a Tyler sieve to determine the particle size distribution.

[Examples 1 to 3 and Comparative Examples 1 and 2] The raw materials shown in Table 1 were charged into a V-type blender in the amounts shown in the table, and then mixed to obtain a uniform mixture. Such a mixture having a diameter of 30
mm biaxial ruder [Kobe Steel, Ltd. KTX-30]
The mixture was extruded at a cylinder temperature of 270 ° C. while venting with a vacuum of 3000 Pa to obtain pellets. A part of the obtained pellet was sampled for injection molding, and the rest was ground by the following grinding method (Method A) and classified using a sieve to obtain a powder.

The obtained polycarbonate resin composition powder was dried at 120 ° C. for 5 hours using a hot-air dryer, and then subjected to rotational molding using “GYRO SPACE” manufactured by Gangnam Special Sangyo Co., Ltd. After setting the mold set temperature to about 330 ° C. through the oil of 330 ° C., the powder 1 is placed in the mold.
kg. At such a temperature, the rotation speed of the main shaft is 50 rpm
m, the small shaft rotating together with the main shaft was rotated at a rotation speed of 50 rpm, and rotated for about 15 minutes. After that, rotation was continued for about 18 minutes while adding the oil at room temperature and gradually cooling the mold temperature to around room temperature. After stopping the rotation, the molded product was taken out from the mold and subjected to the above evaluation. .

The symbols for each polycarbonate resin composition shown in Table 1 and the grinding method are as follows. PC1: viscosity average molecular weight 1 produced by phosgene method
8,100 polycarbonate resin B1: Tris (2,4-di-tert-butylphenyl phosphite) (Irgaf manufactured by Ciba-Geigy Japan)
os168) B2: a compound of the following formula (10) produced according to the description in JP-A-3-77895. The purity of the compound was 73%.

[0106]

Embedded image

B3: Tris (nonylphenyl phosphite) C1: Phenolic antioxidant (Irganox 1076, manufactured by Nippon Ciba Geigy Co., Ltd.) D1: Sulfur antioxidant (Sumilyzer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) ST-1 : Other phosphorus-based stabilizer (Sandoz Co., San
dostab P-EPQ) ST-2: Other phosphorus-based stabilizer (T manufactured by Daihachi Chemical Co., Ltd.)
MP) UV1: Benzotriazole-based UV absorber (Chemisorb 79 manufactured by Chemipa Kasei Co., Ltd.) UV2: Benzotriazole-based UV absorber (ADEKA STAB LA-31 manufactured by Asahi Denka Kogyo KK) L1: Release agent (RIKEN Vitamin ( LIQUEMAR S-1
00A) L2: Release agent (Rikemar SL- manufactured by Riken Vitamin Co., Ltd.)
900) LS1: Bead-shaped crosslinked acrylic particles (MBX-5 [average particle size: 5 μm] manufactured by Sekisui Chemical Co., Ltd.) FL1: Fluorescent brightener (Hostalcus KS manufactured by Hoechst)
N) CL1: Dye (Macrolex Violet B manufactured by Bayer AG)

Pulverization method-A method: The polycarbonate resin pellets were pulverized by a pulverizer, and the pulverized product was subjected to sieve classification.

[0109]

[Table 1]

As is clear from Table 1, when the specific stabilizer of the present invention is used in combination, the resin is molded by rotational molding, that is, when it is exposed to a high temperature for a long time in the presence of a certain amount of oxygen. It can be seen that even if there is, it has the same hue as an injection molded product molded under ordinary conditions.

[0111]

The polycarbonate resin composition of the present invention contains a specific stabilizer in combination and has excellent thermochromic properties, and is particularly suitable for molding subjected to long-term heat exposure such as rotational molding. Rotational molding is particularly suitable for obtaining various types of glazing materials, lighting covers, large containers, etc., because large-sized molded products can be obtained with low distortion, especially for aircraft, ships, vehicles, and electronic and electrical equipment. It is suitably used in a wide range of fields such as mechanical devices.

[Brief description of the drawings]

FIG. 1 is a front view of a molded container.

FIG. 2 is a bottom side view of a molded container.

FIG. 3 is a diagram illustrating an outline of a screening test apparatus for whether text condition 2 is satisfied.

[Explanation of symbols]

 1 container-shaped molded product main body (open ball type; thickness of about 2 mm) 2 container-shaped molded product front center line (vertical direction) 3 molded product diameter (360 mm) 4 bottom-opened ball (opening) portion 5 bottom-opened ball (opening) ) Partial diameter (140 mm) 6 Round flask (500 ml) 7 Stirring motor 8 Thermometer (at the time of stirring, it is on the upper side) 9 Stirrer blade 10 Silicon oil bath 11 Sample powder and granules

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J002 CG011 CG021 EJ007 EJ027 EJ037 EJ047 EN107 EP017 EU147 EU187 EU197 EV028 EV048 EV068 EV077 EV088 EW047 EW066 FA040 FD010 FD040 FD050 FD060 FD066 FD000 FD078 FD130 G

Claims (1)

[Claims] 1. Polycarbonate resin (component A) 100
0.0001 to 1 part by weight of at least one phosphorus compound (component B) selected from the following general formulas (1), (2), (3) and (4) based on part by weight, a phenolic antioxidant A polycarbonate resin composition comprising (C component) 0.0001 to 1 part by weight and a sulfur-based antioxidant (D component) 0.0001 to 1 part by weight. Embedded image (In the formula (1), R ¹ and R ² each have 1 carbon atom.
To 12 alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups. ) (In the formula (2), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, Represents an aralkyl group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁸ represents a hydrogen atom or a methyl group.) (In the formula (3), R ¹² and R ^{15 each} have 1 to 1 carbon atoms.
2 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, wherein R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
It represents a cycloalkyl group, an aryl group or an aralkyl group, and Y represents a group derived from dihydric phenol. ) (In the formula (4), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²⁴ , R ²⁵ ,
R ²⁶ and R ²⁷ each represent a hydrogen atom or a carbon atom having 1 to 1;
12 alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, R ^22, R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^23, R ²⁹
Represents a hydrogen atom or a methyl group. Z represents a group derived from dihydric phenol. )