JP2023139354A - Polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

To provide a polycarbonate resin composition which has good releasability in molding, causes little change of hue under high temperature environment, has a long life and excellent dry heat resistance, and is excellent in such recyclability (reproduction property) as to cause less change of the hue even when a molded article and molding waste are re-melted and molded, and a molded article comprising the same.SOLUTION: A polycarbonate resin composition contains, with respect to 100 pts.wt. of (A) a polycarbonate resin (component A), 0.001-0.2 pt.wt. of (B) a benzofuranone derivative (component B), and 0.01-1.0 pt.wt. of (C) an ester compound (component C) obtained from polyhydric alcohol having 3 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition having excellent mold releasability, dry heat resistance and reproducibility, and a molded article made from the same. More specifically, polycarbonate has good mold releasability during molding, has a long life with little change in hue in high-temperature environments, and has excellent recyclability with little change in hue even when molded products and molding waste are remelted and molded. The present invention relates to a resin composition and a molded article made from the same.

Due to its excellent properties such as transparency, mechanical properties, dimensional stability, and flame retardancy, polycarbonate resin is used in many applications such as optical parts, mechanical parts, automobile parts, electrical and electronic parts, and office equipment parts. There is. In recent years, issues such as the consumption of limited resources and environmental issues due to carbon dioxide emissions have come into focus, and even for polycarbonate resin, studies are being conducted to extend the lifespan of products and to recycle products by collecting and reusing them. It is being said. However, polycarbonate resin has a problem in that if it is exposed to a high temperature environment for a long time or subjected to heat history such as repeated melt molding, the polycarbonate resin turns yellow and its hue deteriorates.

For example, Patent Document 1 discloses that a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer restores the impact strength of degraded recycled materials; There is no mention of changes in . Patent Document 2 discloses that a polycarbonate resin composition in which a (meth)acrylate copolymer, a phosphorus stabilizer, and a sulfur antioxidant are blended with a polycarbonate resin has little change in hue when repeatedly molded. However, there is no mention of long-term heat exposure. Patent Document 3 exemplifies that a polypropylene resin containing a benzofuranone derivative shows little change in hue when repeatedly extruded, but the effect on polycarbonate resin is unclear. Patent Document 4 exemplifies that a composition in which a benzofuranone derivative is blended with a polycarbonate resin exhibits little change in hue when exposed to heat over a long period of time, but there is no description regarding change in hue or moldability when subjected to repeated thermal hysteresis. do not have.

Japanese Patent Application Publication No. 2018-145439 Japanese Patent Application Publication No. 2012-36264 Japanese Patent Application Publication No. 2012-193158 Special Publication No. 2021-503021

The purpose of the present invention is to have good mold release properties during molding, little change in hue in high-temperature environments, long life, excellent dry heat resistance, and little change in hue even when molded products and molding waste are remelted and molded. An object of the present invention is to provide a polycarbonate resin composition with excellent recyclability (reproducibility) and a molded article made from the same.

As a result of intensive research aimed at achieving the above object, the present inventor found that a polycarbonate resin composition in which a specific benzofuranone derivative and a specific ester compound are blended with a polycarbonate resin achieves the above object, and the present invention reached.
That is, according to the present invention, the following configurations (1) to (10) are provided.

(1) (A) 100 parts by weight of polycarbonate resin (component A), (B) 0.001 to 0.2 parts by weight of a benzofuranone derivative (component B), and (C) a polycarbonate resin having 3 to 30 carbon atoms. A polycarbonate resin composition characterized by containing 0.01 to 1.0 parts by weight of an ester compound (component C) obtained from a hydric alcohol and an aliphatic carboxylic acid having 10 to 22 carbon atoms.
(2) The polycarbonate resin composition according to the above item (1), wherein component B is a benzofuranone derivative represented by the following formula [1].

[In formula [1], R ¹ , R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, R ⁵ , R ⁶ , R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷ represents a hydrogen atom or a hydroxyl group, and n is 0, 1 , represents an integer of 2 or 3. ]

(3) The preceding item (1) in which the C component is an ester compound obtained from an aliphatic alcohol having 3 to 5 carbon atoms and 3 to 5 hydroxyl groups and a saturated aliphatic carboxylic acid having 14 to 22 carbon atoms. Or the polycarbonate resin composition described in (2).
(4) The polycarbonate resin composition according to any one of (1) to (3) above, wherein component C is an ester compound obtained from glycerin or pentaerythritol and a saturated aliphatic carboxylic acid having 14 to 22 carbon atoms. .
(5) The polycarbonate resin according to any one of (1) to (4) above, which contains 0.001 to 0.5 parts by weight of an organic phosphorus antioxidant based on 100 parts by weight of the polycarbonate resin (component A). Composition.
(6) The polycarbonate resin composition according to the above item (5), wherein the organic phosphorus antioxidant is at least one compound selected from the group consisting of phosphite compounds, phosphonite compounds, and phosphine compounds.
(7) The polycarbonate resin composition according to any one of (1) to (6) above, which contains 0.01 to 5 parts by weight of an ultraviolet absorber based on 100 parts by weight of the polycarbonate resin (component A).
(8) The polycarbonate according to the preceding item (7), wherein the ultraviolet absorber is at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and malonic acid ester ultraviolet absorbers. Resin composition.
(9) The polycarbonate resin composition according to any one of (1) to (8) above, which does not contain a hindered phenolic antioxidant.
(10) A molded article made of the polycarbonate resin composition according to any one of (1) to (9) above.

The present invention is a polycarbonate resin composition consisting of a polycarbonate resin, a benzofuranone derivative, and an ester compound, which has good mold release properties during molding, has minimal discoloration even when used in applications that are exposed to heat for a long period of time, and has excellent dry heat resistance. In addition, it is possible to provide a molded product with excellent recyclability (reproducibility), which exhibits extremely little discoloration even when scraps such as sprue generated during molding and the molded product itself are remelted. In other words, the molded product can be used for a long period of time, waste during molding can be reduced, and the molded product can be reused, so the industrial effect is extremely large.

The details of the present invention will be explained below.

<Component A: Polycarbonate resin>
The polycarbonate resin used as component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or by reacting a carbonate prepolymer with a solid phase transesterification method. or by ring-opening polymerization of a cyclic carbonate compound.

The dihydroxy component used here may be one that is normally used as a dihydroxy component of polycarbonate resins, and may be bisphenols or aliphatic diols.

Examples of bisphenols include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1- Phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5 -trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t- Butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl) Propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4- hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis( 4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-Sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy- 3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3, 3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-( 4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5. 2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the following formula [2] Examples include bisphenol compounds having a siloxane structure represented by:

[In the formula, R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and p and q are each 1 -4 is an integer, e is a natural number, f is 0 or a natural number, and e+f is a natural number from 1 to 100. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of aliphatic diols include 2,2-bis-(4-hydroxycyclohexyl)-propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4'-bis(2- hydroxyethoxy)biphenyl, bis{(2-hydroxyethoxy)phenyl}methane, 1,1-bis{(2-hydroxyethoxy)phenyl}ethane, 1,1-bis{(2-hydroxyethoxy)phenyl}-1- Phenylethane, 2,2-bis{(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-methylphenyl}propane, 1,1-bis(2-hydroxyethoxy) phenyl}-3,3,5-trimethylcyclohexane, 2,2-bis{4-(2-hydroxyethoxy)-3,3'-biphenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3 -isopropylphenyl}propane, 2,2-bis{3-t-butyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)phenyl}butane, 2,2- Bis{(2-hydroxyethoxy)phenyl}-4-methylpentane, 2,2-bis{(2-hydroxyethoxy)phenyl}octane, 1,1-bis{(2-hydroxyethoxy)phenyl}decane, 2, 2-bis{3-bromo-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{3,5-dimethyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{ 3-cyclohexyl-4-(2-hydroxyethoxy)phenyl}propane, 1,1-bis{3-cyclohexyl-4-(2-hydroxyethoxy)phenyl}cyclohexane, bis{(2-hydroxyethoxy)phenyl}diphenylmethane, 9,9-bis{(2-hydroxyethoxy)phenyl}fluorene, 9,9-bis{4-(2-hydroxyethoxy)-3-methylphenyl}fluorene, 1,1-bis{(2-hydroxyethoxy) phenyl}cyclohexane, 1,1-bis{(2-hydroxyethoxy)phenyl}cyclopentane, 4,4'-bis(2-hydroxyethoxy)diphenyl ether, 4,4'-bis(2-hydroxyethoxy) -3,3'-dimethyldiphenyl ether, 1,3-bis[2-{(2-hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis[2-{(2-hydroxyethoxy)phenyl} propyl]benzene, 1,4-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 1,3-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 4,8-bis{(2-hydroxyethoxy)phenyl} Tricyclo[5.2.1.02,6]decane, 1,3-bis{(2-hydroxyethoxy)phenyl}-5,7-dimethyladamantane, 3,9-bis(2-hydroxy-1,1-dimethyl) ethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,4:3,6-dianhydro-D-sorbitol (isosorbide), 1,4:3,6-dianhydro-D- Examples include mannitol (isomannide), 1,4:3,6-dianhydro-L-iditol (isooidide), and the like.

Among these, aromatic bisphenols are preferred, and among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxyphenyl)propane. -hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl) propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, the bisphenol compound represented by the above formula [2] is preferable, especially 2,2-bis(4-hydroxyphenyl) Propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, represented by the above formula [2] Bisphenol compounds are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most suitable. Further, these may be used alone or in combination of two or more.

The polycarbonate resin used as component A of the present invention may be made into a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucide, or 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, 26-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1, Trisphenol such as 1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4- Examples include bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl) Ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

These polycarbonate resins are produced by a reaction method known per se for producing ordinary aromatic polycarbonate resins, for example, a method in which an aromatic dihydroxy component is reacted with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of its manufacturing method will be briefly explained.

In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a 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 solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, catalysts such as tertiary amines or quaternary ammonium salts can also be used to promote the reaction. At this time, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.

The transesterification reaction using a carbonate diester as a carbonate precursor is carried out by heating and stirring a predetermined proportion of an aromatic dihydroxy component with a carbonate diester under an inert gas atmosphere, and distilling off the alcohol or phenol produced. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage to distill out the alcohol or phenol produced. Furthermore, a catalyst commonly used in transesterification reactions can also be used to promote the reaction. Examples of the diester carbonate used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

In the present invention, a terminal capping agent is used in the polymerization reaction. A terminal capping agent is used to control the molecular weight, and the resulting polycarbonate resin has superior thermal stability compared to a resin that is not terminal-capped. Such terminal capping agents include monofunctional phenols represented by the following general formulas [3] to [5].

[Formula [3], A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the number of carbon atoms in the alkyl part is 1 to 9), a phenyl group or a phenylalkyl group (the carbon atom in the alkyl part) 1 to 9), and r is an integer of 1 to 5, preferably 1 to 3. ]

[In formulas [4] and [5], Y is -R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or has 1 to 10 carbon atoms. , preferably represents a divalent aliphatic hydrocarbon group of 1 to 5, and n represents an integer of 10 to 50. ]

Specific examples of monofunctional phenols represented by the above formula [3] include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol. , and isooctylphenol.

Furthermore, the monofunctional phenols represented by the above formula [4] or [5] are phenols having long-chain alkyl groups or aliphatic ester groups as substituents, and these are used to terminate the terminals of polycarbonate resins. When capped, these not only function as end capping agents or molecular weight regulators, but also improve the melt flowability of the resin, making molding easier, and are also effective in lowering the water absorption rate of the resin, so they are preferably used. be done.

The substituted phenols of the above formula [4] are preferably those in which n is 10 to 30, particularly 10 to 26, and specific examples include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eiko Examples include silphenol, docosylphenol and triacontylphenol.

Further, as the substituted phenols of the above formula [5], compounds in which Y is -R-COO- and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 are suitable. Specific examples include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate.

Among these monofunctional phenols, monofunctional phenols represented by the above formula [3] are preferred, alkyl-substituted or phenylalkyl-substituted phenols are more preferred, and p-tert-butylphenol and p-tert-butylphenol are particularly preferred. It is cumylphenol or 2-phenylphenol.

It is desirable that these monofunctional phenolic end-stopping agents be introduced at least 5 mol%, preferably at least 10 mol%, at the ends of the obtained polycarbonate resin, and the end-stopping agent may be introduced alone. They may be used alone or in combination of two or more.

The polycarbonate resin used as component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or a derivative thereof, as long as it does not impair the spirit of the present invention. good.

The viscosity average molecular weight of the polycarbonate resin used as component A of the present invention is preferably in the range of 11,500 to 50,000, more preferably in the range of 12,500 to 40,000, and more preferably in the range of 13,500 to 35,000. More preferably, the range is from 15,000 to 30,000. If the molecular weight exceeds the above range, the melt viscosity may become too high, resulting in poor moldability, while if the molecular weight is below the above range, problems may arise in mechanical strength. The viscosity average molecular weight in the present invention was first determined by using an Ostwald viscometer to determine the specific viscosity calculated by the following formula from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C. Insert the specific viscosity into the following equation to determine the viscosity average molecular weight Mv.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
η _SP /c=[η]+0.45×[η] ² c (however, [η] is the limiting viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7
The polycarbonate resin used as component A of the present invention preferably has a total Cl (chlorine) content of 0 to 500 ppm, more preferably 0 to 350 ppm. It is preferable that the total amount of Cl in the polycarbonate resin is within the above range because it has excellent hue and thermal stability.

<Component B: benzofuranone derivative>
The benzofuranone derivative used as component B of the present invention can improve the thermal stability of polycarbonate resin molded products during production or molding of polycarbonate resin, and can suppress discoloration of polycarbonate resin. The benzofuranone derivative used in the present invention is particularly preferably at least one benzofuranone derivative selected from the group consisting of compounds represented by the following formula [1].

[In formula [1], R ¹ , R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, R ⁵ , R ⁶ , R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷ represents a hydrogen atom or a hydroxyl group, and n is 0, 1 , represents an integer of 2 or 3. ]
Specifically, compounds represented by the following formulas [6] to [8] are exemplified, with the compound represented by the following formula [7] being particularly preferred.

The content of the benzofuranone derivative is in the range of 0.001 to 0.2 parts by weight, preferably in the range of 0.005 to 0.15 parts by weight, and 0.008 to 0.1 parts by weight, based on 100 parts by weight of the polycarbonate resin. The range of parts by weight is more preferable, and the range of 0.01 to 0.05 parts by weight is even more preferable. If the amount is less than the above range, the effect of inhibiting discoloration upon exposure to heat (dry heat resistance) will be insufficient, which is not preferable. Further, even if an amount exceeding the above range is blended, no higher effect will be observed, and the dry heat resistance will deteriorate on the contrary, which is not preferable.
Benzofuranone derivatives are commercially available from Chitec as Revonox 501 (trade name) and are easily available.

<Component C: ester compound>
The ester compound used as component C of the present invention is an ester compound obtained from a polyhydric alcohol having 3 to 30 carbon atoms and an aliphatic carboxylic acid having 10 to 22 carbon atoms, and is a compound of the polycarbonate resin of the present invention. The releasability of molded products during molding can be improved without deteriorating dry heat resistance.

The ester compound of the present invention can be produced from a polyhydric alcohol and an aliphatic carboxylic acid by various conventionally known methods. Examples of reaction catalysts include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, sodium carbonate, potassium carbonate, and organotin compounds such as 2-ethylhexyltin. can be mentioned.

The polyhydric alcohol has 3 to 30 carbon atoms, preferably 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 5 carbon atoms. The valence number (number of hydroxyl groups) of the polyhydric alcohol is preferably 3 to 8, more preferably 3 to 6, and still more preferably 3 to 5. The polyhydric alcohol may contain an ether bond in its carbon chain.

Specific examples of polyhydric alcohols include glycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol, among which glycerin, Pentaerythritol and dipentaerythritol are preferred, particularly glycerin or pentaerythritol.

Aliphatic carboxylic acids include, for example, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, and docosanic acid. Mention may be made of saturated aliphatic carboxylic acids such as acids, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid and cetoleic acid. Among the above, those having 14 to 22 carbon atoms are preferred. Among these, saturated aliphatic carboxylic acids are preferred. Particularly preferred are stearic acid and palmitic acid, or a mixed aliphatic carboxylic acid thereof.

Aliphatic carboxylic acids such as stearic acid and palmitic acid are typically produced from natural fats and oils such as animal fats (such as beef tallow and lard) and vegetable fats (such as palm oil). Therefore, aliphatic carboxylic acids such as stearic acid are usually mixtures containing other carboxylic acid components having different numbers of carbon atoms. In the production of the ester compound of the present invention, stearic acid and palmitic acid, which are produced from such natural oils and fats and are in the form of a mixture containing other carboxylic acid components, are preferably used.

The blending amount of the ester compound is 0.01 to 1.0 parts by weight, preferably 0.02 to 0.5 parts by weight, and more preferably 0.03 to 0.3 parts by weight, based on 100 parts by weight of the polycarbonate resin. It is preferably 0.03 to 0.2 parts by weight, and more preferably 0.03 to 0.2 parts by weight. When the amount of the ester compound is less than the above range, the effect of improving mold releasability is not sufficient. On the other hand, if the amount of the ester compound exceeds the above range, it is not preferable because the transparency of the molded article is impaired and the dry heat resistance is reduced.

<Other ingredients>
The polycarbonate resin composition of the present invention may contain additives known per se in order to impart various functions to the molded article or improve its properties, as long as the purpose of the present invention is not impaired. These additives will be specifically explained below.

(I) Heat stabilizer Various known heat stabilizers can be blended into the polycarbonate resin composition of the present invention. Specific examples include organic phosphorus antioxidants and hindered phenol antioxidants.

Specific examples of such organic phosphorous antioxidants include phosphorous acid (phosphite), phosphonite, phosphinite, phosphine, phosphoric acid (phosphate), phosphonate, phosphinate, and phosphine oxide, among which phosphite, phosphonite, Phosphine, phosphonate, and phosphate are preferably used. Specifically, examples of phosphite compounds include trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, and tridecyl phosphite. Phite, trioctyl phosphite, triotadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2 , 2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl) phosphite, tris(di-iso-propylphenyl) phosphite, tris(di-n-butylphenyl) phosphite phyto, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis(2,4-di- tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) ) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like. Furthermore, as other phosphite compounds, those having a cyclic structure that react with dihydric phenols can also be used. For example, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert- butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and the like.

Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Phosphonite, Tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite , Tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, Tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, -n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, etc., tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2, More preferred are 4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of phosphine compounds include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, Examples include trinaphthylphosphine and diphenylbenzylphosphine. A particularly preferred phosphine compound is triphenylphosphine.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferred.

Specific examples of hindered phenolic antioxidants include vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate, 2-tert-butyl-6 -(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-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-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-tert-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-tert-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-tert-butylphenol), 2,4-bis(n-octylthio)-6-(4-hydroxy-3', 5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-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-tert-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-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3',5'-di-tert -butyl-4-hydroxyphenyl)propionate]methane, etc., which can be preferably used.

Among them, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl- 2'-Hydroxybenzyl)-4-methylphenylacrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethyl ethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. Preferred is n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate.

The above-mentioned organic phosphorus antioxidants and hindered phenol antioxidants can be used alone or in combination of two or more. The content of these organic phosphorus antioxidants and hindered phenol antioxidants is preferably 0.001 to 0.5 parts by weight, respectively, based on 100 parts by weight of the polycarbonate resin. The amount is more preferably 0.005 to 0.3 parts by weight, and even more preferably 0.01 to 0.1 parts by weight.

In addition, if the hindered phenol antioxidant is blended in a large amount, it may inhibit the effect of the benzofuranone derivative of the present invention, and the blended amount should be 0.02 parts by weight or less per 100 parts by weight of the polycarbonate resin. It is preferably 0.01 parts by weight or less, more preferably 0.005 parts by weight or less, particularly preferably 0.001 parts by weight or less. Further, it is preferable that substantially no hindered phenol antioxidant be included.

(II) Mold release agent The polycarbonate resin composition of the present invention may contain a mold release agent other than the above-mentioned component (C) as necessary within a range that does not impede the effects of the present invention. As such a mold release agent, those known per se can be used. Examples include polyolefin waxes (polyethylene waxes or 1-alkene polymers; those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds, paraffin wax, beeswax, etc. can be mentioned. Among these, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil and fluorine oil are preferred. The content of the mold release agent is preferably 0.01 to 1 part by weight per 100 parts by weight of the polycarbonate resin.

(III) Ultraviolet absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber if necessary. Examples of such ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxybenzophenone. 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-sodium sulfoxybenzophenone, bis Examples include benzophenone ultraviolet absorbers typified by (5-benzoyl-4-hydroxy-2-methoxyphenyl)methane.

Examples of ultraviolet absorbers include 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 -tert-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-tert-butylphenyl)-5-chloro Benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], methyl-3-[3-tert-butyl Examples include benzotriazole ultraviolet absorbers typified by condensates of -5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate and polyethylene glycol.

Examples of ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis-(2,4- Examples include hydroxyphenyltriazine compounds typified by dimethylphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol.

Examples of the ultraviolet absorber include malonic acid ester compounds such as 2-(1-arylalkylidene) malonic acid esters such as Hostavin PR-25 manufactured by Clariant Japan Co., Ltd. and Hostavin B-CAP manufactured by Clariant Japan Co., Ltd. I can do it.

Particularly preferred is at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, triazine UV absorbers, and malonic acid ester UV absorbers.

The content of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, and even more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. and most preferably 0.1 to 0.5 parts by weight.

(IV) Light stabilizer A light stabilizer can be added to the polycarbonate resin composition of the present invention, if necessary. Examples of such light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1 , 2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2n-butylmalonate, 1,2,3,4-butane Condensate of carboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid and 1,2,2,6,6-pentamethyl- Condensate of 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-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8, condensate with 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 condensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6 - Condensate of pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol, poly Examples include hindered amines represented by methylpropyl 3-oxy-[4-(2,2,6,6-tetramethyl)piperidinyl]siloxane.

The content of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin.

(V) Bluing agent A bluing agent can be blended into the polycarbonate resin composition of the present invention in order to cancel out the yellowing caused by ultraviolet absorbers and the like. Any bluing agent that is normally used for polycarbonate resins can be used without any particular problem. Generally, anthraquinone dyes are preferred because they are easily available. As a specific bluing agent, for example, the common name Solvent Violet 13 [CA. No (color index No.) 60725; Trade name "Macrolex Violet B" manufactured by Bayer, "Diaresin Blue G" manufactured by Mitsubishi Chemical, "Sumiplast Violet B" manufactured by Sumitomo Chemical], Generic name Solvent Violet 31 [CA ．． No. 68210; Trade name: Mitsubishi Chemical Corporation "Diaresin Violet D"], Generic name: Solvent Violet 33 [CA. No.60725; Trade name: "Diaresin Blue J" manufactured by Mitsubishi Chemical Corporation], Generic name: Solvent Blue94 [CA. No. 61500; Trade name: "Dia Resin Blue N" manufactured by Mitsubishi Chemical Corporation], Generic name: Solvent Violet 36 [CA. No. 68210; Trade name "Macrolex Violet 3R" manufactured by Bayer AG], generic name Solvent Blue 97 [trade name "Macro Rex Blue RR" manufactured by Bayer AG], and generic name Solvent Blue 45 [CA. No. 61110; trade name "Polysynthrene Blue RLS" manufactured by Clariant), etc., and Macrolex Blue RR, Macrolex Violet B, and Polysynthrene Blue RLS are particularly preferred.

The content of the bluing agent is preferably 0.000005 to 0.001 parts by weight, more preferably 0.00001 to 0.0001 parts by weight, based on 100 parts by weight of the polycarbonate resin.

(VI) Fluorescent brightener In the polycarbonate resin composition of the present invention, the optical brightener is not particularly limited as long as it is used to improve the color tone of the resin to white or bluish-white, such as stilbene-based, Examples include benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Company, and "Hakkor PSR" manufactured by Hakkol Chemical Company. The fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy to the visible region.

The content of the optical brightener is preferably 0.001 to 0.1 part by weight, more preferably 0.001 to 0.05 part by weight, based on 100 parts by weight of the polycarbonate resin.

(VII) Epoxy compound The polycarbonate resin composition of the present invention may contain an epoxy compound as necessary. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol; Examples include (2-oxiranyl)cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate.

The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.1 parts by weight, and even more preferably 0.005 parts by weight, based on 100 parts by weight of the polycarbonate resin. ~0.05 part by weight.

(VIII) Organometallic Salt The polycarbonate resin composition of the present invention may contain an organometallic salt compound. Such organic metal salts are blended for the purpose of imparting flame retardancy, and are preferably alkali (earth) metal salts of organic acids having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms. Preferably, organic sulfonic acid alkali (earth) metal salts are more preferable. The organic sulfonic acid alkali (earth) metal salts include fluorine-substituted alkyl sulfones such as metal salts of perfluoroalkyl sulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and alkali metals or alkaline earth metals. Included are metal salts of acids and metal salts of aromatic sulfonic acids having from 7 to 50 carbon atoms, preferably from 7 to 40 carbon atoms, with alkali metals or alkaline earth metals. Alkali metals constituting the metal salt include lithium, sodium, potassium, rubidium, and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. More preferred are alkali metals. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are preferred when transparency is required, but they are not widely used and are difficult to purify, resulting in lower costs. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. The alkali metal in the alkali metal sulfonate can be selected depending on these considerations, but potassium sulfonate is the most suitable because it has excellent balance of properties in all respects. Such a potassium salt and an alkali metal sulfonic acid salt consisting of another alkali metal can also be used in combination.

Specific examples of alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluorobutanesulfonate. Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Examples include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. The number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8. Among these, potassium perfluorobutanesulfonate is particularly preferred. A considerable amount of fluoride ions are usually mixed into the alkali (earth) metal salt of perfluoroalkylsulfonic acid made of an alkali metal. Since the presence of such fluoride ions can be a factor in reducing flame retardancy, it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, particularly preferably 10 ppm or less. Further, in terms of manufacturing efficiency, it is preferable that the content is 0.2 ppm or more. Such an alkali (earth) metal salt of perfluoroalkylsulfonic acid with a reduced amount of fluoride ions can be produced by using a known production method and contained in the raw materials for producing the fluorine-containing organic metal salt. Methods for reducing the amount of fluoride ions, methods for removing hydrogen fluoride etc. obtained by the reaction by using gas generated during the reaction or heating, and purification methods such as recrystallization and reprecipitation for producing fluorine-containing organometallic salts. It can be manufactured by a method of reducing the amount of fluoride ions using fluoride ions. In particular, organic metal salt flame retardants are relatively easily soluble in water, so use ion-exchanged water, especially water that satisfies an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS/cm or less. , and is preferably manufactured by a process of dissolving and washing at a temperature higher than room temperature, and then cooling and recrystallizing.

Specific examples of aromatic sulfonic acid alkali (earth) metal salts include, for example, disodium diphenylsulfide-4,4'-disulfonate, dipotassium diphenylsulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecyl phenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate , polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, poly(2-fluoro- 6-Butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-calcium disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, diphenylsulfone-3,4'-disulfonic acid Dipotassium, α,α,α-sodium trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Examples include calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Among these alkali (earth) metal salts of aromatic sulfonic acids, potassium salts are particularly preferred. Among these alkali (earth) metal salts of aromatic sulfonates, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferred, and in particular mixtures thereof (the former and the latter) are preferred. The weight ratio of 15/85 to 30/70) is suitable.

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfuric esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfuric esters, mention may be made in particular of alkali (earth) metal salts of sulfuric esters of monohydric and/or polyhydric alcohols; Examples of sulfuric esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono-, di-, tri-, and tetra-sulfate ester, and lauric acid monoglyceride sulfate. Examples include esters, sulfuric esters of palmitic acid monoglyceride, and sulfuric esters of stearic acid monoglyceride. Preferred examples of the alkali (earth) metal salts of these sulfuric esters include alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N-(N'-benzylaminocarbonyl)sulfanylimide, and N-( Examples include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide.

The content of the organic metal salt is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and even more preferably 0.01 to 0.3 part by weight based on 100 parts by weight of the polycarbonate resin. parts, particularly preferably 0.03 to 0.15 parts by weight.

(IX) Others In addition to the above, the resin composition of the present invention includes a reinforcing filler, a sliding agent (for example, PTFE particles), a coloring agent, a fluorescent dye, an inorganic phosphor (for example, an aluminate as a mother crystal). phosphors), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g. fine titanium oxide, fine zinc oxide), light diffusing agents, flow modifiers, radical generators, infrared absorbers (heat ray absorbent), photochromic agent, etc. can be blended.

<Manufacture of polycarbonate resin composition>
Any method can be used to produce the polycarbonate resin composition of the present invention. For example, components A, B, C, and optionally other components are sufficiently mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, or extrusion mixer, and then extruded as necessary. Examples of methods include granulation using a granulator or briquetting machine, followed by melt-kneading using a melt-kneading machine typified by a vented twin-screw ruder, and pelletizing using a device such as a pelletizer. Alternatively, a method is available in which component A, component B, component C, and optionally other components are each independently fed into a melt kneader represented by a vented twin-screw ruder, and a portion of component A and other components are prepared in advance. After mixing, the remaining components are independently fed to a melt-kneading machine, each or both of the B component and C component is diluted and mixed with water or an organic solvent, and then fed to a melt-kneading machine, or such diluted mixture is fed to a melt-kneading machine. Another example is a method of premixing with other components and then feeding the mixture to a melt kneader. In addition, when there is a liquid component in the blended components, a so-called liquid injection device or liquid addition device can be used to supply the components to the melt-kneading machine.

<Molded product>
Any method can be used to produce a molded article made of the polycarbonate resin composition of the present invention. For example, the polycarbonate resin composition can be kneaded using an extruder, a Banbury mixer, a roll, or the like, and then molded by a conventionally known method such as injection molding, extrusion molding, or compression molding to obtain a molded article.

Specific uses of molded products include housings and components for various lighting devices such as LED lighting installed indoors and outdoors, films and components for display monitors, and buildings for greenhouse films and windows. Parts, parts for electronic and electrical equipment such as computers, game consoles, and printers, parts for electrical appliances such as washing machines and dishwashers, headlamps and windows for cars, windshields for motorcycles, helmet covers, goggles, glasses and cameras. Examples include lenses such as

The mode of the present invention that the present inventor considers to be the best at present is a combination of the preferable ranges of each of the above-mentioned requirements, and representative examples thereof are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to Examples, but the present invention is not limited to these Examples. The details of each component used and the evaluation are as follows.
(A component)
A-1: Bisphenol A type aromatic polycarbonate resin (manufactured by Teijin: L-1225WX, viscosity average molecular weight 19,700)

(B component)
B-1: [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl] 3,5-di-tert-butyl-4-hydroxybenzoate (Chitec Manufactured by: Revonox501)

(C component)
C-1: Glycerin monostearate (manufactured by Riken Vitamin Co., Ltd.: Rikemar S-100A)
C-2: Pentaerythritol tetrastearate (manufactured by NOF Corporation: Unistar H-476-S)

(Other ingredients)
(thermal stabilizer)
D-1: Tris(2,4-di-tert-butylphenyl) phosphite (manufactured by BASF: Irgafos 168)
D-2: Triphenylphosphine (Johoku Kagaku Co., Ltd.: JC-263)
D-3: Hindered phenol antioxidant (manufactured by BASF: Irganox 1010)
(Ultraviolet absorber)
E-1: Benzotriazole ultraviolet absorber (manufactured by BASF: Tinuvin 234)
E-2: Benzotriazole ultraviolet absorber (manufactured by ADEKA: ADEKA STAB LA-31)
E-3: Malonic acid ester ultraviolet absorber (manufactured by Clariant: Hostavin PR-25)
(epoxy compound)
F-1: Copolymer of styrene and glycidyl methacrylate (manufactured by NOF Corporation: Marproof G-0250SP)

(Manufacture of pellets)
The above ingredients were blended in the proportions listed in Table 1, mixed for 15 minutes in a tumbler, and then TEX30α manufactured by Japan Steel Works, Ltd. (fully meshed, rotating in the same direction, double thread screw) using a vented twin screw extruder with a screw diameter of 30 mm. The molten resin composition was melted and kneaded at a cylinder temperature of 280°C, extruded into a strand, solidified by cooling with water, and cut with a pelletizer to obtain pellets of the polycarbonate resin composition (1 extrusion number). Ta.

The polycarbonate resin pellets obtained above were fed to a vented single-screw extruder with a screw diameter of 30 mm, VSK type manufactured by Nakatani Kikai, and melted and kneaded at a cylinder temperature of 285°C. The molten resin extruded into a strand shape was cooled with water. It solidified and was cut into pellets using a pelletizer. The obtained pellets were pelletized under the same extrusion conditions to obtain re-pellets (3 times of extrusion) of the polycarbonate resin composition.

(Evaluation method)
(1) Dry heat resistance The pellets obtained by the above manufacturing method were dried at 120°C for 5 hours in a hot air circulation dryer, and then molded using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.]. A molded plate having a width of 50 mm, a length of 90 mm, and a thickness of 2 mm was molded at 270° C. and a mold temperature of 80° C. This molded plate was heat-treated at 130° C. for 1000 hours in a hot air circulation dryer. The yellowness index (YI) of the molded plate before heat treatment and the molded plate after heat treatment was measured using an integrating sphere spectrophotometer [CE-7000A manufactured by X-Rite Co., Ltd.] in accordance with ASDM D1925. The range of increase in YI (ΔYI) of the formed plate after heat treatment was calculated from the following formula.
ΔYI = YI after heat treatment - YI before heat treatment
The larger the ΔYI, the more likely the color changes to yellow, indicating poor dry heat resistance. Those with ΔYI of 0.5 or less were marked as ○, and those with ΔYI exceeding 0.5 were marked as ×.

(2) Reproducibility The pellets and repellets obtained by the above manufacturing method were dried at 120 ° C. for 5 hours in a hot air circulation dryer, and using an injection molding machine [J85-ELIII manufactured by Japan Steel Works, Ltd.], A molded plate having a width of 50 mm, a length of 90 mm, and a thickness of 2 mm was molded at a molding temperature of 270° C. and a mold temperature of 80° C. The hue (L*, a*, b*) of this molded plate was measured using an integrating sphere spectrophotometer [CE-7000A manufactured by X-Rite] under the conditions of light source D65, viewing angle of 10 degrees, and transmission method. did. The range of increase (Δb*) in the b* value of the re-pellet molded plate was calculated using the following formula.
Δb*=Re-pellet molding plate b* value−Pellet molding plate b* value The larger the Δb* value, the more likely it is to turn yellow, indicating poor reproducibility. If the Δb* value was 0.05 or less, it was marked as ○, and if it exceeded 0.05, it was marked as ×.

(3) Mold releasability The pellets obtained by the above manufacturing method were dried in a hot air circulation dryer at 120°C for 5 hours, and molded at a molding temperature of 270°C using an injection molding machine [J180ADS manufactured by Japan Steel Works, Ltd.]. ℃, mold temperature 90℃, a cup-shaped molded product (opening outer diameter: 70 mm, bottom outer diameter: 63 mm, height: 20 mm, thickness: 4 mm) was molded continuously for 20 shots, 11 to 20 shots. The appearance of the eye molded product was visually observed. If deformation or cracks are observed in the molded product, this indicates poor mold releasability. A molded product with no deformation or cracking was marked as ○, and a molded product with deformation or cracking was marked as ×.

[Examples 1 to 11 and Comparative Examples 1 to 5]
Using the pellets and repellets obtained in the above-mentioned resin pellet production, the dry heat resistance, reproducibility, and mold releasability described in the above-mentioned evaluation method were evaluated. The evaluation results are shown in Table 1.

The polycarbonate resin composition of the present invention and the molded products obtained from it have good mold release properties during molding, exhibit very little discoloration even when used in applications that are exposed to heat for a long period of time, and have excellent dry heat resistance. Even if scraps such as sprue and the molded product itself are remelted, molded products with excellent recyclability (reproducibility) with extremely little discoloration can be obtained. It is extremely useful and can be used in various industrial applications such as electronic equipment, automobiles, and building materials.

Claims (10)

(A) 100 parts by weight of polycarbonate resin (component A), (B) 0.001 to 0.2 parts by weight of a benzofuranone derivative (component B), and (C) a polyhydric alcohol having 3 to 30 carbon atoms. A polycarbonate resin composition characterized by containing 0.01 to 1.0 parts by weight of an ester compound (component C) obtained from an aliphatic carboxylic acid having 10 to 22 carbon atoms. The polycarbonate resin composition according to claim 1, wherein component B is a benzofuranone derivative represented by the following formula [1].
[In formula [1], R ¹ , R ² , R ³ and R ⁴ may be the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, R ⁵ , R ⁶ , R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷ represents a hydrogen atom or a hydroxyl group, and n is 0, 1 , represents an integer of 2 or 3. ] 3. The C component is an ester compound obtained from an aliphatic alcohol having 3 to 5 carbon atoms and 3 to 5 hydroxyl groups and a saturated aliphatic carboxylic acid having 14 to 22 carbon atoms. polycarbonate resin composition. The polycarbonate resin composition according to any one of claims 1 to 3, wherein component C is an ester compound obtained from glycerin or pentaerythritol and a saturated aliphatic carboxylic acid having 14 to 22 carbon atoms. The polycarbonate resin composition according to any one of claims 1 to 4, comprising 0.001 to 0.5 parts by weight of an organic phosphorus antioxidant based on 100 parts by weight of the polycarbonate resin (component A). The polycarbonate resin composition according to claim 5, wherein the organic phosphorus antioxidant is at least one compound selected from the group consisting of phosphite compounds, phosphonite compounds, and phosphine compounds. The polycarbonate resin composition according to any one of claims 1 to 6, which contains 0.01 to 5 parts by weight of an ultraviolet absorber per 100 parts by weight of the polycarbonate resin (component A). The polycarbonate resin composition according to claim 7, wherein the ultraviolet absorber is at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and malonic acid ester ultraviolet absorbers. The polycarbonate resin composition according to any one of claims 1 to 8, which does not contain a hindered phenolic antioxidant. A molded article made of the polycarbonate resin composition according to any one of claims 1 to 9.