WO2021235272A1 - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Abstract

This resin composition contains 0.15-5.0 parts by mass of a malonic acid ester ultraviolet ray absorber (B) per 100 parts by mass of an aromatic polycarbonate resin (A), and is characterized in that the resin composition has excellent weather resistance and superior hue, molding retention stability, and steam resistance.

Description

Aromatic polycarbonate resin composition and its molded product

The present invention relates to an aromatic polycarbonate resin composition and a molded product thereof. In particular, the present invention relates to an aromatic polycarbonate resin composition having good weather resistance, excellent hue, molding retention stability and vapor resistance, which is useful as an outdoor optical transparent member, and a molded product formed from the resin composition. Further, the present invention relates to a light diffusing resin composition having good light transmission, weather resistance, excellent hue, light diffusivity and vapor resistance, and a molded product formed from the resin composition.

Aromatic polycarbonate has a wide range of uses as a thermoplastic resin with excellent impact resistance, heat resistance, and transparency. Furthermore, it is lighter than inorganic glass and has excellent productivity, so it has excellent weather resistance. For applications that require weather resistance, such as light guide plates, diffuser plates, reflectors, protective films, retardation films, and lighting covers, lighting signs, transmissive screens, and various displays for liquid crystal display devices. Can be suitably used.

Conventionally, as a method for improving the weather resistance of aromatic polycarbonate, a method of adding various ultraviolet absorbers is known. For example, Patent Document 1 describes a polycarbonate resin composition containing 5 to 25 parts by weight of a benzotriazole-based ultraviolet absorber and 0.1 to 10 parts by weight of a fluorescent whitening agent with respect to 100 parts by weight of a polycarbonate resin. Proposed. However, since the content of the ultraviolet absorber and the fluorescent whitening agent is high, gas during thermal processing becomes a problem, and the longest absorption wavelength of the ultraviolet absorber is 390 nm, which is close to visible light, so that the hue is poor and the commercial value is high. It was low.

Further, in Patent Document 2, an ultraviolet absorber selected from benzotriazole-based compounds, benzophenone-based compounds and triazine-based compounds having no maximum absorption wavelength in the ultraviolet region of 350 to 400 nm with respect to 100 parts by mass of the polycarbonate resin 0. A polycarbonate resin composition comprising 05 parts by mass or more and less than 2 parts by mass and 0.00001 to 1 part by mass of a fluorescent whitening agent has been proposed. However, when the ultraviolet absorber selected from the benzotriazole-based compound, the benzophenone-based compound and the triazine-based compound having no maximum absorption wavelength at 350 to 400 nm is blended, only a polycarbonate resin composition having a very inferior hue can be obtained.

On the other hand, Patent Documents 3 to 5 disclose a resin composition containing 0.0005 to 0.1 parts by mass of malonic acid esters with respect to 100 parts by mass of a methyl methacrylate-based resin, but aromatic polycarbonate. There is no mention of.

Further, Patent Document 6 discloses a resin composition containing a malonic acid ester in an aromatic polycarbonate resin. However, specifically, it was insufficient to obtain a resin composition having a low content of malonic acid ester and an excellent balance between good weather resistance, hue, molding retention stability and vapor resistance.

Further, Patent Document 7 discloses a light diffusing resin composition containing a light diffusing agent and a malonic acid ester in an aromatic polycarbonate resin. However, it was insufficient to obtain a resin composition having an excellent balance between weather resistance and light diffusivity.

Japanese Unexamined Patent Publication No. 07-196904 Japanese Patent Application Laid-Open No. 2002-003710 Japanese Unexamined Patent Publication No. 2002-105271 Japanese Patent Application Laid-Open No. 2003-025406 Japanese Patent Application Laid-Open No. 2003-0268888 Japanese Unexamined Patent Publication No. 2006-83230 Japanese Unexamined Patent Publication No. 2006-117822

An object of the present invention is an aromatic polycarbonate resin composition that solves all the problems of the prior art and is useful as an outdoor optical transparent member having good weather resistance, hue, molding retention stability and steam resistance. And to provide a molded product formed from the resin composition.

Another object of the present invention is a light-diffusing resin composition and the resin useful as an outdoor optical transparent member having good light transmission, weather resistance, hue, light diffusivity and steam resistance. It is an object of the present invention to provide a molded product formed from a composition.

As a result of diligent studies to solve the above problems, the present inventors have obtained an aromatic polycarbonate resin composition in which a malonate ester-based ultraviolet absorber is blended in a specific ratio with an aromatic polycarbonate resin, and the resin composition. The present invention has been completed by finding that the formed molded product achieves the above object.

In addition, by blending a light diffusing agent and a malonic acid ester-based ultraviolet absorber in a specific ratio with the aromatic polycarbonate resin, the outdoors have excellent light transmission, weather resistance, hue, light diffusivity and steam resistance. The present invention has been completed by finding that a light-diffusing resin composition useful as an optical transparent member or the like and a molded product formed from the resin composition achieve the above object.

That is, according to the present invention, the following (configuration 1) to (configuration 7) are provided.
(Structure 1)
A resin composition containing 0.15 to 5.0 parts by mass of a malonic acid ester-based ultraviolet absorber (B) with respect to 100 parts by mass of an aromatic polycarbonate resin (A).
(Structure 2)
The resin composition according to composition 1, further containing 0.05 to 10.0 parts by mass of the light diffusing agent (C) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
(Structure 3)
The ratio of the amount (b) of the malonic acid ester-based ultraviolet absorber (b) to the amount (c) of the malonic acid ester-based ultraviolet absorber (B) containing 0.15 to 2.0 parts by mass of the malonic acid ester-based ultraviolet absorber (B) b / The resin composition according to composition 2, wherein c is 0.2 or more.
(Structure 4)
The resin composition according to any one of the above configurations 1 to 3, further containing 0.01 to 0.1 parts by mass of the heat stabilizer (D) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
(Structure 5)
The resin composition according to composition 4, wherein the heat stabilizer (D) is a phosphorus-based stabilizer represented by the following formula (X) and / or a sulfur-based stabilizer represented by the following formula (Y).

(R in formula (Y) represents a dodecyl group.)
(Structure 6)
The resin composition according to any one of configurations 1 to 5, further containing 0.1 to 0.5 parts by mass of the release agent (E) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
(Structure 7)
A molded product formed from the resin composition according to any one of the configurations 1 to 6.

The aromatic polycarbonate resin composition of the present invention is useful as an outdoor optical transparent member having excellent weather resistance, hue, molding retention stability and steam resistance without impairing the original characteristics of aromatic polycarbonate. It is a group polycarbonate resin composition, and its industrial effect is exceptional. Further, the light-diffusing resin composition of the present invention is an outdoor optical transparent material having excellent light transmission, weather resistance, hue, light diffusivity and steam resistance without impairing the original characteristics of aromatic polycarbonate. It is a light-diffusing resin composition useful as a member and the like, and its industrial effect is exceptional.

Hereinafter, the present invention will be described in detail.
(Aromatic Polycarbonate Resin (A))
The aromatic polycarbonate resin used in the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt ester exchange method, or a carbonate prepolymer by a solid phase ester exchange method. It is polymerized or obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

The dihydroxy component used here may be any as long as it is usually used as the dihydroxy component of aromatic polycarbonate, and may be bisphenols or aliphatic diols.

Examples of bisphenols include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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) 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'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy- 3,3'-Didimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3, 3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2-( 4-Hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexa , 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1,3-_) Adamantane diyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the following general formula [1]

(In the above general formula [1], R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, c is a natural number, d is 0 or a natural number, c + d is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)
Examples thereof include a bisphenol compound having a siloxane structure represented by.

Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethyleneglycol, 1,16-hexadecanediol, and 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- Phenylethan, 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-Isopropyl} 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-Cycloxy-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) diphenylether, 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- Dimethyladamantan, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D -Sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol (isoidid) and the like can be mentioned.

Among these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4). -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 are preferred, especially 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most suitable. Moreover, these may be used individually or in combination of 2 or more types.

The polycarbonate resin used in the present invention is preferably a polycarbonate resin composed of repeating units represented by the following general formula [2].

[In the above general formula [2], R ¹ and R ² are independently hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and 6 to 6 carbon atoms, respectively. 20 cycloalkyl groups, 6 to 20 carbon atoms cycloalkoxy groups, 2 to 10 carbon atoms alkenyl groups, 6 to 14 carbon atoms aryl groups, 6 to 14 carbon atoms aryloxy groups, carbon atoms Represents a group selected from the group consisting of an alkoxy group having a number of 7 to 20 and an alkoxy group having a carbon atom number of 7 to 20, a nitro group, an aldehyde group, a cyano group and a carboxyl group. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of the groups represented by the following general formulas [3] and [4]. ..

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, and carbon. Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ and R ¹² are independent hydrogen atoms, halogen atoms, and carbon atoms 1 to 18 respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, cycloalkyl group with 6 to 20 carbon atoms, cycloalkoxy group with 6 to 20 carbon atoms, alkenyl group with 2 to 10 carbon atoms, 6 carbon atoms From an aryl group of up to 14; an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group. Represents a group selected from the group of, and if there are multiple, they may be the same or different, c is an integer of 1 to 10 and d is an integer of 4 to 7)].

(In the above general formula [4], R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or 6 to 12 carbon atoms, respectively. Alternatively, it is an unsubstituted aryl group, c is a natural number, d is 0 or a natural number, c + d is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)
The polycarbonate resin used in the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglucolcin, fluoroglucolside, or 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) hepten-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) Etan, 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} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxy). Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

These polycarbonate resins are produced by a reaction method known per se for producing an ordinary aromatic polycarbonate resin, for example, a method of reacting an aromatic dihydroxy component with a carbonic acid precursor such as phosgene or carbonic acid diester. The basic means for the manufacturing method will be briefly described.

In a reaction 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, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At that 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 carbonic acid diester as a carbonic acid precursor is carried out by a method of distilling off the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating them in an inert gas atmosphere. .. 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 by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. It is also possible to use catalysts normally used in transesterification reactions to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.
In the present invention, a terminal terminator is used in the polymerization reaction. The terminal terminator is used for molecular weight regulation, and the obtained polycarbonate resin has a closed end, so that it is superior in thermal stability as compared with the non-termination agent. As such a terminal terminator, monofunctional phenols represented by the following general formulas [5] to [7] can be shown.

[In the formula, 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 moiety is 1 to 9), a phenyl group, or a phenylalkyl group (the number of carbon atoms in the alkyl moiety is 1 to 9). And r is an integer of 1 to 5, preferably 1 to 3].

[In the formula, X is -RO-, -R-CO-O- or -RO-CO-, where R is a single bond or 1 to 10 carbon atoms, preferably 1 to 5-2. It indicates a valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]
Specific examples of the monofunctional phenols represented by the general formula [5] are, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Examples include phenol and isooctylphenol. Further, the monofunctional phenols represented by the above general formulas [6] to [7] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and these are used to terminal the polycarbonate resin. When sealed, these not only function as a terminal terminator or a molecular weight modifier, but also improve the melt fluidity of the resin, facilitate the molding process, and have the effect of lowering the water absorption rate of the resin, which is preferable. used. The substituted phenols of the above general formula [6] preferably have n of 10 to 30, particularly 10 to 26, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecylphenol. Examples thereof include eicosylphenol, docosylphenol, and triacylphenol. Further, as the substituted phenols of the above general formula [7], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Is preferable, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eikosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [5] are preferable, alkyl-substituted or phenylalkyl-substituted phenols are more preferable, and p-tert-butylphenol and p are particularly preferable. -Kumilphenol or 2-phenylphenol. It is desirable that the terminal terminator of these monofunctional phenols be introduced into the terminal at least 5 mol%, preferably at least 10 mol% with respect to the total terminal of the obtained polycarbonate resin, and the terminal terminator is used alone. Or a mixture of two or more types may be used.

The polycarbonate resin used in the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired.

The viscosity average molecular weight of the polycarbonate resin used in the present invention is preferably in the range of 13,000 to 50,000, more preferably in the range of 15,000 to 40,000, and further in the range of 16,000 to 30,000. The range of 17,000 to 28,000 is particularly preferable, and the range of 18,000 to 26,000 is most preferable. If the viscosity average molecular weight exceeds 50,000, the melt viscosity may become too high and the moldability may be inferior. If the molecular weight is less than 13,000, sufficient toughness and crack resistance cannot be obtained, and there is a problem in mechanical strength. May occur.

The viscosity average molecular weight of the aromatic polycarbonate resin referred to in the present invention is determined by using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20 ° C. with the specific viscosity calculated by the following formula. The viscosity average molecular weight Mv was calculated by inserting the obtained specific viscosity by the following formula.

Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
η _SP / c = [η] +0.45 × ^{[η] 2} c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7
(Malonic acid ester UV absorber (B))
The ultraviolet absorber used in the present invention is a malonic acid ester-based ultraviolet absorber. As the malonic acid ester-based ultraviolet absorber, 2- (1-arylalkylidene) malonic acid esters are preferably used from the viewpoint of durability. As the malonic acid ester-based ultraviolet absorber, Hostavin PR-25 manufactured by Clariant Japan Co., Ltd., Hostavin B-CAP manufactured by Clariant Japan Co., Ltd., and the like are commercially available.

The amount of the malonate ester-based ultraviolet absorber used is 0.15 to 5.0 parts by mass, preferably 0.25 to 4.5 parts by mass, and 0.27 to 4 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate. .0 parts by mass is more preferable, and 0.3 to 3.5 parts by mass is further preferable. If it is less than 0.15 parts by mass, sufficient weather resistance cannot be obtained, and if it exceeds 5.0 parts by mass, the problem of gas generation during processing due to the bleed-out of the ultraviolet absorber and the decrease in mechanical strength occur. Therefore, it is not preferable.
(Light diffuser (C))
The light diffusing agent used as desired in the present invention may be either organic fine particles typified by polymer fine particles or inorganic fine particles. Typical examples of the polymer fine particles are crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Further, copolymerizable monomers other than such monomers can also be used. Among them, polymer fine particles are preferable, and crosslinked particles can be particularly preferably used.

Examples of the monomer used as the non-crosslinkable monomer in the cross-linked particles include a non-crosslinkable vinyl-based monomer such as an acrylic monomer, a styrene-based monomer, and an acrylonitrile-based monomer, and an olefin-based monomer.

As the acrylic monomer, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate and the like are used alone or mixed. It is possible to use it. Of these, methyl methacrylate is particularly preferable.

Further, as the styrene-based monomer, alkyl styrene such as styrene, α-methyl styrene, methyl styrene (vinyl toluene), and ethyl styrene, and halogenated styrene such as bromoized styrene can be used, and styrene is particularly preferable. ..

As the acrylonitrile-based monomer, acrylonitrile and methacrylonitrile can be used. Further, as the olefin-based monomer, ethylene, various norbornene-type compounds and the like can be used. Further, as other copolymerizable monomers, glycidyl methacrylate, N-methylmaleimide, maleic anhydride and the like can be exemplified. The organic crosslinked particles of the present invention can also have units such as N-methylglutarimide as a result.

On the other hand, examples of the crosslinkable monomer for such a non-crosslinkable vinyl-based monomer include divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and propylene glycol. (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, dicyclopentanyldi (meth) acrylate , Dicyclopentenyldi (meth) acrylate, N-methylol (meth) acrylamide and the like. In addition, examples of other crosslinked particles include silicone crosslinked particles typified by polyorganosylsesquioxane.

The average particle size of the light diffusing agent is preferably 0.01 to 50 μm, more preferably 1 to 30 μm, and even more preferably 2 to 30 μm. If the average particle size is less than 0.01 μm or more than 50 μm, the light diffusivity may be insufficient. The average particle size is represented by a 50% value (D50) of the integrated distribution of the particle size obtained by the laser diffraction / scattering method. The particle size distribution may be single or plural. That is, it is possible to combine two or more kinds of light diffusing agents having different average particle sizes. However, a more preferred light diffusing agent has a narrow particle size distribution. It is more preferable to have a distribution in which 70% by mass or more of the particles are contained in the range of 2 μm before and after the average particle size. From the viewpoint of light diffusivity, the shape of the light diffusing agent is preferably close to a spherical shape, and more preferably a shape close to a true spherical shape. Such a sphere includes an ellipsoidal sphere.

The refractive index of the light diffusing agent is preferably in the range of 1.30 to 1.80, more preferably 1.33 to 1.70, and even more preferably 1.35 to 1.65. These exhibit a sufficient light diffusing function when blended in the resin composition.

The content of the light diffusing agent is preferably 0.05 to 10.0 parts by mass, more preferably 0.1 to 7.0 parts by mass, and even more preferably 0.1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin component. It is 0.15 to 5.0 parts by mass, particularly preferably 0.2 to 2.0 parts by mass. When the content of the light diffusing agent is not less than the lower limit, sufficient light diffusivity is obtained, and when it is not more than the upper limit, the total light transmittance and weather resistance are good.

When a light diffusing agent is used, the amount of the malonate ester-based ultraviolet absorber (B) used is in the range of 0.15 to 2.0 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). The range of 0.2 to 1.6 parts by mass is more preferable, the range of 0.25 to 1.0 parts by mass is further preferable, and the range of 0.3 to 0.5 parts by mass is particularly preferable. When it is above the lower limit, sufficient weather resistance can be obtained, and when it is below the upper limit, gas generation during processing due to bleed-out of the ultraviolet absorber is suppressed, and the total light transmittance, weather resistance and mechanical strength are lowered. Is less likely to occur.

When light is transmitted through a molded product made of a light-diffusing resin composition containing a light-diffusing agent, the light is diffused in the molded product and the light transmission path becomes longer as compared with the molded product made of transparent resin. Therefore, it is necessary to use a sufficient UV absorber for light diffusivity. Specifically, the ratio b / c of the amount (b) of the malonic acid ester-based ultraviolet absorber used to the amount (c) of the light diffusing agent is preferably 0.2 or more, preferably 0.25 or more. Is more preferable, 0.3 or more is further preferable, and 0.5 or more is particularly preferable. When b / c is 0.2 or more, sufficient weather resistance can be obtained.
(Heat stabilizer (D))
The heat stabilizer (D) preferably used in the present invention is preferably a phosphorus-based heat stabilizer and / or a sulfur-based heat stabilizer.

As the phosphorus-based heat stabilizer, phosphite ester or phosphoric acid ester is preferable. Examples of the phosphite ester include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonylphosphite, tridecylphosphite, and trioctylphosphite. , Trioctadecylphosphite, distearylpentaerythritol diphosphite, tricyclohexylphosphite, monobutyldiphenylphosphite, monooctyldiphenylphosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butyl) Phosphite) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, etc. Examples thereof include triesters, diesters and monoesters of phosphorous acid.

The phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and tetrakis (2,4-). Di-tert-butylphenyl) -4,4-diphenylene phosphonite and the like can be mentioned.

Among the phosphorus-based heat stabilizers, tris (2,4-di-tert.-butylphenyl) phosphite represented by the above formula (1) is preferable. Specifically, "IRGAFOS 168 FF" manufactured by BASF is commercially available.

Examples of the sulfur-based heat stabilizer include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, and distearyl. -3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3-) Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyldisulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis (2-naphthol) and the like can be mentioned.

Among the sulfur-based heat stabilizers, pentaerythritol tetrakis (3-laurylthiopropionate) represented by the above formula (2) is preferable. Specifically, "Sumilyzer TP-D" manufactured by Sumitomo Chemical Co., Ltd. is commercially available.

The amount of the heat stabilizer used is preferably 0.01 to 0.1 parts by mass, more preferably 0.02 to 0.08 parts by mass, and 0.03 to 0.07 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. The unit is more preferable. Within the above range, sufficient thermal stability can be obtained and steam resistance is excellent.
(Release agent (E))
As the mold release agent preferably used in the present invention, for example, fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc., and those modified with a functional group-containing compound such as acid modification are also used. ), Fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin wax, beeswax, etc. can be mentioned. Among these, fatty acid esters are preferable from the viewpoint of easy availability, releasability and transparency.

The ratio of the release agent to be contained is preferably 0.1 to 0.5 parts by weight, more preferably 0.15 to 0.4 parts by weight, based on 100 parts by mass of the aromatic polycarbonate resin. More preferably, it is 0.2 to 0.3 parts by weight. Within the above range, mold releasability is good, steam resistance is excellent, and mold contamination during molding is reduced.

Among the above mold release agents, fatty acid esters are preferably used. Fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having a divalent value or higher. The carbon number of the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacanthanol and the like. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In fatty acid esters, polyhydric alcohols are more preferred.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid and icosanoic acid. And saturated aliphatic carboxylic acids such as docosanoic acid (bechenic acid), and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid. can. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Since such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats and oils (such as beef tallow and lard) and vegetable fats and oils (such as palm oil), these aliphatic carboxylic acids usually have carbon atoms. It is a mixture containing other carboxylic acid components different from each other. Therefore, it is also produced from such natural fats and oils in the production of aliphatic carboxylic acids, and is in the form of a mixture containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (substantially 0 can be taken). However, in the case of all esters (full esters), it is preferable to contain not a small amount of free fatty acids in order to improve releasability, and in this respect, the acid value of full esters is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (substantially 0 can be taken). These characteristics can be obtained by the method specified in JIS K0070.

The fatty acid ester described above may be either a partial ester or a full ester, but a partial ester is preferable in terms of better releasability and durability, and a glycerin monoester is particularly preferable. The glycerin monoester is mainly composed of a monoester of glycerin and a fatty acid, and suitable fatty acids include saturated fatty acids such as stearate, partiminic acid, bechenic acid, araquinic acid, montanic acid, and lauric acid, and oleic acid and linoleic acid. , And unsaturated fatty acids such as sorbic acid, and those containing glycerin monoesters of stearic acid, behenic acid, and partiminic acid as main components are particularly preferable. The fatty acid is synthesized from a natural fatty acid and is a mixture as described above. Even in such a case, the ratio of the glycerin monoester in the fatty acid ester is preferably 60% by weight or more.

Partial esters are often inferior to full esters in terms of thermal stability. In order to improve the thermal stability of the partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, still more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by a usual method and then purifying it by molecular distillation or the like.

Specifically, after removing gas and low boiling point substances with a spray nozzle type degassing device, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a downflow membrane type distillation device. Distillation of high-purity fatty acid partial ester under the conditions of distillation temperature 160-230 ° C. and vacuum degree 0.01-0.2 Torr after removing polyhydric alcohols such as Sodium metal can be removed as a distillation residue. By repeatedly performing molecular distillation on the obtained distillate, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to thoroughly clean the inside of the molecular distillation apparatus by an appropriate method in advance and to prevent the mixing of sodium metal components from the external environment by improving the airtightness. Such fatty acid esters can be obtained from specialists (for example, Riken Vitamin Co., Ltd.).

The aromatic polycarbonate resin composition of the present invention may contain, for example, other ultraviolet absorbers (benzophenone-based, benzotriazole-based, hydroxyphenyltriazine-based, cyclic iminoester-based, cyanoacrylate-based, etc.) and antistatic agents, if necessary. , Colorants, fluidity improvers, flame retardants, anti-aggregation agents and the like may be further added.

Mixing and kneading of the aromatic polycarbonate resin composition of the present invention may be carried out by a method applied to ordinary thermoplastic resins, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single shaft screw extruder, 2 It can be performed by a shaft screw extruder, a multi-screw screw extruder, or the like. The temperature condition for kneading is usually 260 to 320 ° C.

A general thermoplastic resin molding method can be applied to the aromatic polycarbonate resin composition of the present invention, and for example, injection molding, injection compression molding, or extrusion molding from a pellet resin composition is possible from the viewpoint of productivity. .. Further, the desired molded product can be obtained by vacuum forming, compressed air forming, or the like from the extruded sheet-shaped molded product.

In the aromatic polycarbonate resin composition of the present invention, the spectral light transmittance at a wavelength of 350 nm when made into a molded product having a thickness of 2 mm is preferably 5% or less, more preferably 3% or less, and 1%. The following is more preferable. Further, the spectral light transmittance at a wavelength of 380 nm is preferably 30% or more, more preferably 40% or more, still more preferably 45% or more. The molded product obtained from the aromatic polycarbonate resin composition of the present invention is characterized by having a low light transmittance in the ultraviolet region and a high light transmittance in the visible light region.

Examples of the molded product of the present invention include optical members such as a lighting cover and a lighting lens, and among them, they can be suitably used as an outdoor transparent optical member.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
(Aspect I)
The raw materials used in the following examples and comparative examples are as follows.
(Aromatic Polycarbonate Resin (A))
A-1: Teijin Limited Panlite L-1225WX (polycarbonate resin made from bisphenol A, viscosity average molecular weight 19,700)
(Malonic acid ester UV absorber (B))
B-1: Hostavin B-CAP manufactured by Clariant Japan Co., Ltd.
B-2: Hostavin PR-25 manufactured by Clariant Japan Co., Ltd.
(Other UV absorbers (comparative example))
b-1: Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd. (benzotriazole-based UV absorber)
b-2: BASF's Tinuvin 234 (benzotriazole-based UV absorber)
b-3: BASF's Tinuvin1577ED (triazine-based UV absorber)
b-4: SEESORB703 (benzotriazole-based UV absorber) manufactured by Cipro Kasei Co., Ltd.
b-5: ADEKA ADEKA STAB LA-31 (benzotriazole-based UV absorber) manufactured by ADEKA Corporation
(Heat stabilizer (D))
D-1: Hostanox P-EPQ (phosphorus heat stabilizer) manufactured by Clariant Japan Co., Ltd.
D-2: BASF IRGAFOS 168FF (phosphorus heat stabilizer, compound of formula (1))
D-3: Sumitomo Chemical Co., Ltd. Sumilyzer TP-D (sulfur-based heat stabilizer, compound of formula (2))
(Release agent (E))
E-1: Unistar H-476-S (fatty acid ester) manufactured by NOF CORPORATION
The evaluation methods used in the examples and comparative examples are as follows.
(1) Preparation of test piece Using a J85ELIII molding machine manufactured by Japan Steel Works, Ltd., the test piece (50 mm (width) x 90 mm (length) with a thickness of 1 mm at a cylinder temperature of 350 ° C and a mold temperature of 80 ° C. 2 mm and 3 mm three-stage plates) were prepared, and the following measurements were carried out.
(2) Spectral ray transmittance (350 nm, 380 nm)
The light transmittance of the test piece (thickness 2 mm portion) molded in (1) above was measured using a UV-Vis-NIR spectrophotometer Cary5000 manufactured by Agilent Technologies.
(3) Hue evaluation The hue of the test piece molded in (1) above was measured with a spectrophotometer CE-7000A manufactured by Sakata Inx Engineering Co., Ltd. using a C2 light source and a two-degree visual field transmission method, and the YI of the test piece was measured. Was calculated. The smaller the YI value, the more preferable.
(4) Molding retention stability When molding the test piece in (1) above, the hues of the test piece taken out immediately from the mold and the test piece taken out after staying in the mold for 10 minutes are manufactured by Sakata Inx Engineering Co., Ltd. The ΔE of the test piece was calculated by measuring with a spectrophotometer CE-7000A of the above, using a transmission method of a D65 light source and a 10-degree field of view. The smaller the ΔE value, the more preferable.
(5) Steam resistance The test piece molded in (1) above was subjected to a wet heat treatment at 120 ° C. for 24 hours with SN-510 manufactured by Autoclave Yamato Scientific Co., Ltd. for laboratories, and the viscosity average molecular weight of the test piece after the treatment was obtained. The difference in viscosity average molecular weight before treatment (ΔMv × 10 ^-3 ) was calculated. The smaller the ΔMv value, the more preferable.

The viscosity average molecular weight Mv was first determined by using an Ostwald viscometer from a solution obtained by cutting and dissolving 0.7 g of a test piece in 100 ml of methylene chloride at 20 ° C. _{for the specific viscosity (η SP) calculated by the following formula.}
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the data solution to fall]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _{SP) by the following formula.}
η _SP / c = [η] +0.45 × ^{[η] 2} c (However, [η] is the limit viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7
[Examples A1 to A16 and Comparative Examples A1 to A6]
After blending the raw materials at the ratios shown in Table 1, they were melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder TEX30α with a vent manufactured by Japan Steel Works, Ltd. with a screw diameter of 30 mm, and pelletized by strand cutting. After the pellet was dried at 120 ° C. for 5 hours, an evaluation test piece was formed under the above conditions, the above evaluation was performed, and the evaluation results are shown in Table 1.

(Aspect II)
The raw materials used in the following examples and comparative examples are as follows.
(Aromatic Polycarbonate Resin (A))
A-1: Teijin Limited Panlite L-1225WX (polycarbonate resin made from bisphenol A, viscosity average molecular weight 19,700)
A-2: Teijin Limited Panlite L-1225WP (polycarbonate resin made from bisphenol A, viscosity average molecular weight 22,500)
A-3: Polycarbonate resin powder having a branched structure with a viscosity average molecular weight of 25,100 obtained by the following manufacturing method: 2340 parts of ion-exchanged water and 947 parts of 25% sodium hydroxide aqueous solution in a reactor with a thermometer, agitator and a reflux cooler. , 0.7 part of hydrosulfite was charged, and 710 parts of bisphenol A was dissolved under stirring (bisphenol A solution), then 2299 parts of methylene chloride, 112 parts of 48.5% sodium hydroxide aqueous solution, and 14% concentration of sodium hydroxide. Add 38.1 parts (1.00 mol%) of an aqueous solution prepared by dissolving 1,1,1-tris (4-hydroxyphenyl) ethane at a concentration of 25% to the aqueous solution, and add 354 parts of phosgen at 15 to 25 ° C. for about 90 minutes. The phosgenation reaction was carried out by blowing in. After completion of phosgenation, 219 parts of methylene chloride solution of 11% concentration p-tert-butylphenol and 88 parts of 48.5% sodium hydroxide aqueous solution were added, stirring was stopped, and the mixture was allowed to stand for 10 minutes and then stirred. After 5 minutes of emulsification, it was treated with a homomixer (Special Machinery Chemical Industry Co., Ltd.) at a rotation speed of 1200 rpm and a bath number of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under no stirring conditions to complete the polymerization. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, it is poured into a kneader filled with warm water. Methylene chloride was evaporated with stirring to obtain a polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type dryer to obtain a polycarbonate resin powder having a branched structure.

A-4: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 19,400 obtained by the following production method: Ion-exchanged water 21591 parts, 48.5% water in a reactor with a thermometer, agitator and a reflux cooler. Add 3674 parts of an aqueous sodium oxide solution, and add 3,880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) as the dihydroxy compound (I) constituting the carbonate constituent unit represented by the above formula [1], and hydro. After dissolving 7.6 parts of sulfite, 14565 parts of methylene chloride (14 mol with respect to 1 mol of dihydroxy compound (I)) was added, and 1900 parts of phosgene was blown at 22 to 30 ° C. over 60 minutes with stirring. .. Next, a solution prepared by dissolving 1131 parts of a 48.5% sodium hydroxide aqueous solution and 108 parts of p-tert-butylphenol in 800 parts of methylene chloride is added to form a carbonate constituent unit represented by the above formula [3] while stirring. A solution prepared by dissolving 430 parts of a polydiorganosiloxane compound represented by the following formula [8] in 1600 parts of methylene chloride as a dihydroxyaryl-terminated polydiorganosiloxane (II) having an average number of repetitions of about 37 in dimethylsiloxane units is prepared as dihydroxyaryl. The terminal polydiorganosiloxane (II) was added at a rate of 0.0008 mol / min per 1 mol of the divalent phenol (I) to bring it into an emulsified state, and then the mixture was vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued at a temperature of 26 to 31 ° C. for 45 minutes to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, it is poured into a kneader filled with warm water. Then, methylene chloride was evaporated with stirring to obtain a powder of a polycarbonate-polydiorganosiloxane copolymer resin. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content 8.2%, viscosity average molecular weight 19,400)

(Light diffuser (C))
C-1: Bead-shaped crosslinked acrylic particles (manufactured by Sekisui Plastics Co., Ltd .: MBX-5 (trade name), average particle diameter 5 μm)
C-2: Beaded cross-linked silicone (manufactured by Momentive Performance Materials Japan GK: TSR9002 (trade name), average particle size 2 μm)
(Malonic acid ester UV absorber (B))
B-1: Hostavin B-CAP manufactured by Clariant Japan Co., Ltd.
B-2: Hostavin PR-25 manufactured by Clariant Japan Co., Ltd.
(Other UV absorbers (comparative example))
b-1: Chemisorb 79 manufactured by Chemipro Kasei Co., Ltd. (benzotriazole-based UV absorber)
b-2: BASF's Tinuvin 234 (benzotriazole-based UV absorber)
b-3: BASF's Tinuvin1577ED (triazine-based UV absorber)
b-4: SEESORB703 (benzotriazole-based UV absorber) manufactured by Cipro Kasei Co., Ltd.
b-5: ADEKA ADEKA STAB LA-31 (benzotriazole-based UV absorber) manufactured by ADEKA Corporation
(Heat stabilizer (D))
D-1: Hostanox P-EPQ (phosphorus heat stabilizer) manufactured by Clariant Japan Co., Ltd.
D-2: BASF IRGAFOS 168FF (phosphorus heat stabilizer, compound of formula (1))
D-3: Sumitomo Chemical Co., Ltd. Sumilyzer TP-D (sulfur-based heat stabilizer, compound of formula (2))
(Release agent (E))
E-1: Unistar H-476-S (fatty acid ester) manufactured by NOF CORPORATION
(Other ingredients)
F-114P: Potassium perfluorobutane sulfonic acid salt (manufactured by Dainippon Ink and Chemicals Co., Ltd .: Megafuck F-114P (trade name))
SN3307 :: Mixture consisting of polytetrafluoroethylene particles and a styrene-acrylic copolymer (manufactured by Shine Polymer: SN3307 (trade name))
(1) Preparation of test piece Using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U / S-MIV], the molding temperature is 280 ° C, the mold temperature is 80 ° C, the width is 50 mm, the length is 90 mm, and the thickness is A three-stage plate having a length of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm) was formed from the gate side.
(2) Total light transmittance, haze For the total light transmittance and haze of the test piece (thickness 2 mm portion) molded in (1) above, use the reflection / transmittance meter HR-100 manufactured by Murakami Color Technology Research Institute Co., Ltd. It was measured according to JIS-K 7136 used.
(3) Spectral ray transmittance (350 nm, 380 nm)
The light transmittance of the test piece (thickness 2 mm portion) molded in (1) above was measured using a UV-Vis-NIR spectrophotometer Cary5000 manufactured by Agilent Technologies. When the spectral light transmittance at 350 nm is low and the spectral light transmittance at 380 nm is high, the hue is excellent.
(4) Weather resistance The test piece molded in (1) above was placed on an Atlas Ci4000 manufactured by Toyo Seiki Seisakusho, where the black panel temperature was 63 ° C, the humidity was 50%, and the irradiance was 0.35 W / m ^{2 (340 nm).} It was installed so as to irradiate one side, and was taken out after 500 hours. The taken-out test piece was measured with a spectrophotometer CE-7000A manufactured by Sakata Inx Engineering Co., Ltd. using a D65 light source and a transmission method with a 10-degree field of view, and the ΔE of the test piece was calculated. The smaller the ΔE value, the more preferable.
(5) Steam resistance The test piece molded in (1) above was subjected to a wet heat treatment at 120 ° C. for 24 hours with SN-510 manufactured by Autoclave Yamato Scientific Co., Ltd. for laboratories, and the viscosity average molecular weight of the test piece after the treatment was obtained. The difference in viscosity average molecular weight before treatment (ΔMv × 10 ^-3 ) was calculated. The smaller the ΔMv value, the more preferable.

The viscosity average molecular weight Mv was first determined by using an Ostwald viscometer from a solution obtained by cutting and dissolving 0.7 g of a test piece in 100 ml of methylene chloride at 20 ° C. _{for the specific viscosity (η SP) calculated by the following formula.}
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the data solution to fall]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _{SP) by the following formula.}
η _SP / c = [η] +0.45 × ^{[η] 2} c (However, [η] is the limit viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7
[Examples B1 to B19 and Comparative Examples B1 to B6]
After blending the raw materials at the ratios shown in Table 1, they were melt-kneaded at a cylinder temperature of 280 ° C. using a twin-screw extruder TEX30α with a vent manufactured by Japan Steel Works, Ltd. with a screw diameter of 30 mm, and pelletized by strand cutting. After the pellet was dried at 120 ° C. for 5 hours, an evaluation test piece was formed under the above conditions, the above evaluation was performed, and the evaluation results are shown in Table 1.

The aromatic polycarbonate resin composition of the present invention is excellent in good weather resistance, hue, molding retention stability and vapor resistance, and is useful as an outdoor optical transparent member.

Claims (7)

1. A resin composition containing 0.15 to 5.0 parts by mass of a malonic acid ester-based ultraviolet absorber (B) with respect to 100 parts by mass of an aromatic polycarbonate resin (A).
2. The resin composition according to claim 1, further containing 0.05 to 10.0 parts by mass of the light diffusing agent (C) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
3. The ratio of the amount (b) of the malonic acid ester-based ultraviolet absorber (b) to the amount (c) of the malonic acid ester-based ultraviolet absorber (B) containing 0.15 to 2.0 parts by mass of the malonic acid ester-based ultraviolet absorber (B) b / The resin composition according to claim 2, wherein c is 0.2 or more.
4. The resin composition according to any one of claims 1 to 3, further containing 0.01 to 0.1 parts by mass of the heat stabilizer (D) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
5. The resin composition according to claim 4, wherein the heat stabilizer (D) is a phosphorus-based stabilizer represented by the following formula (X) and / or a sulfur-based stabilizer represented by the following formula (Y).
   

   

   

   (R in formula (Y) represents a dodecyl group.)
6. The resin composition according to any one of claims 1 to 5, further containing 0.1 to 0.5 parts by mass of the release agent (E) with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
7. A molded product formed from the resin composition according to any one of claims 1 to 6.