JP2008174655A - Polycarbonate resin sheet or film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet or film formed from a polycarbonate resin composition, excellent in transparency, weatherability and hue, causing no forming roll staining by smoking stemming from the decomposition, deterioration, sublimation or the like of an ultraviolet light absorber via a die port when undergoing extrusion. <P>SOLUTION: The sheet or film is formed from the polycarbonate resin composition comprising 100 pts.wt. of a polycarbonate resin, 0.001-2.0 pts.wt. of at least one thioether compound selected from the group consisting of a compound of formula (1) and a compound of formula (2), and 0.05-5 pts.wt. of a cyclic imino ester compound of formula (3), wherein the formulas (1) and (2) are as follows: (R<SP>1</SP>-S-CH<SB>2</SB>-CH<SB>2</SB>-C(O)O-CH<SB>2</SB>)<SB>4</SB>-C (1), (R<SP>2</SP>-O-C(O)-CH<SB>2</SB>-CH<SB>2</SB>-)<SB>2</SB>-S (2). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin sheet or film. More specifically, the present invention relates to a polycarbonate resin sheet or film that is excellent in transparency, weather resistance, and hue, and that the hue is stably maintained even during molding and after long-term use.

Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, etc., and are therefore widely used in electrical, mechanical, automotive, medical applications and the like. However, when the polycarbonate resin is used outdoors for a long time, the weather resistance may be a problem as compared with an acrylic resin or the like. Techniques using various ultraviolet absorbers for improving the weather resistance of polycarbonate resins are widely known. In addition, several methods for further improving the weather resistance by using an ultraviolet absorber in combination with other additives have been proposed.
Benzotriazole-based, benzophenone-based, and triazine-based UV absorbers are widely known as UV absorbers used for polycarbonate resins.

  2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, and 2- (2H-benzotriazol-2-yl) -4,6-bis ( 2- (2H-benzotriazol-2-yl) (al) alkylphenols such as 1-methyl-1-phenylethyl) phenol (the notation of (al) alkylphenol is meant to include both alkylphenols and aralkylphenols) Among the benzotriazole ultraviolet absorbers, the polycarbonate resin composition containing a relatively small amount of blue light has a relatively good hue, but its heat resistance is low, which causes decomposition and sublimation. However, the inherent performance is not fully demonstrated.

  Moreover, the method of using a cyclic imino ester type compound for ultraviolet protection of a resin material and the resin composition which mix | blended this compound with polycarbonate resin are well-known (refer patent document 1-patent document 3).

  When the polycarbonate resin is molded into a sheet or film, a method of extruding a melt obtained by melting the polycarbonate resin at a high temperature of about 300 ° C. from a T die lip and drawing it with a cooling roll is generally performed. In order to mold after melting at a high temperature of about 300 ° C., the polycarbonate resin itself and the additive are required to have high heat resistance. When the heat resistance is low, the polycarbonate resin burns during sheet and film molding, resulting in yellowing of the molded product, or the UV absorber is contaminated with the molding roll by fuming at the resin die mouth due to degradation or sublimation. Appearance defects occur. As a method for solving this problem, a method of sucking a sublimable substance by providing a suction device along the die lip on the outer wall of the T die is shown (see Patent Document 4). Further, Patent Document 5 discloses an example in which a phosphorus-based heat stabilizer is combined with a cyclic imino ester compound in order to solve these problems, but the effect of suppressing the yellowing of a molded product at the time of molding is sufficient. I couldn't say that.

  In addition, UV absorbers are often used to improve the yellowing of molded products because they absorb visible blue light. Further, such hues may be required to be stable after molding or after long-term use. Need to be kept.

  There is a need for a means for obtaining a polycarbonate resin sheet or film containing an ultraviolet absorber having an excellent appearance and a good hue with little yellowing at the time of molding without using an apparatus as shown in Patent Document 4. It was.

Japanese Patent Publication No.62-31027 WO03 / 095557 pamphlet JP 2004-137472 A JP-A-11-48306 JP 2006-28442 A

  The object of the present invention is excellent in transparency, weather resistance and hue, and when a sheet or film is melt-extruded, the molding roll is not soiled by fuming due to decomposition degradation or sublimation of the ultraviolet absorber from the die mouth, and the molded product. It is an object of the present invention to provide a sheet or film formed from a polycarbonate resin composition that has a good appearance and can stably maintain the hue of a molded product even during molding and after long-term use.

  A further object of the present invention is a molded article comprising the sheet or film, a transparent member for a vehicle represented by a building member or a glazing material or a surface layer member thereof, a material for a thin display device such as a liquid crystal display or a surface layer member thereof, and The object is to provide eyewear materials such as goggles.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problem can be solved by using a specific amount of a specific cyclic imino ester compound as a UV absorber and a specific thioether compound as a heat stabilizer in a polycarbonate resin. It came to complete.

［式（３）中、Ａｒはヘテロ原子を含有してもよい炭素数６〜１２の二価の芳香族炭化水素残基である。ｎは０または１を示す。］
２．チオエーテル系化合物は、ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネートおよびペンタエリスリトールテトラキス（３−ラウリルチオプロピオネート）からなる群より選ばれる少なくとも１種のチオエーテル化合物である前項１記載のポリカーボネート樹脂シートまたはフィルム、
３．チオエーテル系化合物は、ペンタエリスリトールテトラキス（３−ラウリルチオプロピオネート）である前項１記載のポリカーボネート樹脂シートまたはフィルム、
４．環状イミノエステル系化合物は、２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−（４，４’−ジフェニレン）ビス（３，１−ベンゾオキサジン−４−オン）および２，２’−（２，６−ナフタレン）ビス（３，１−ベンゾオキサジン−４−オン）からなる群より選ばれる少なくとも１種の化合物である前項１記載のポリカーボネート樹脂シートまたはフィルム、および
５．環状イミノエステル系化合物は、２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）である請求項１記載のポリカーボネート樹脂シートまたはフィルム、
が提供される。 That is, according to the present invention,
1. (A) 0.001 to 2.0 parts by weight of at least one thioether compound selected from the group consisting of compounds represented by the following formulas (1) and (2) with respect to 100 parts by weight of the polycarbonate resin And (C) a polycarbonate resin sheet or film having a thickness of 0.1 to 10 mm formed from a polycarbonate resin composition containing 0.05 to 5 parts by weight of a cyclic imino ester compound represented by the following formula (3).
(R ¹ —S—CH ₂ —CH ₂ —C (O) O—CH ₂ ) ₄ —C (1)
[In Formula (1), R ¹ may be the same or different and is a linear or branched alkyl group having 4 to 20 carbon atoms. ]
(R ² —O—C (O) —CH ₂ —CH ₂ —) ₂ —S (2)
[In formula (2), R ² may be the same or different and is a linear or branched alkyl group having 6 to 22 carbon atoms. ]

[In Formula (3), Ar is a C6-C12 bivalent aromatic hydrocarbon residue which may contain a hetero atom. n represents 0 or 1. ]
2. Thioether compounds include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate and pentaerythritol tetrakis (3-laurylthio). 2. The polycarbonate resin sheet or film according to item 1, which is at least one thioether compound selected from the group consisting of propionate),
3. The polycarbonate resin sheet or film according to item 1, wherein the thioether compound is pentaerythritol tetrakis (3-laurylthiopropionate);
4). Cyclic imino ester compounds include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) The polycarbonate resin according to item 1, which is at least one compound selected from the group consisting of -4-one) and 2,2 '-(2,6-naphthalene) bis (3,1-benzoxazin-4-one). 4. Sheet or film, and The polycarbonate resin sheet or film according to claim 1, wherein the cyclic imino ester compound is 2,2'-p-phenylenebis (3,1-benzoxazin-4-one).
Is provided.

Hereinafter, the present invention will be described in detail.
[Polycarbonate resin]
(A) component used as the base material of the polycarbonate resin sheet or film of this invention is polycarbonate resin. A polycarbonate resin (hereinafter, sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor, and as a reaction method, an interfacial polycondensation method, a melt transesterification method, Examples include a solid phase transesterification method of a carbonate prepolymer and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is preferable.

In the present invention, in addition to the bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

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

  In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

  The polycarbonate is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid, a copolymer polycarbonate obtained by copolymerizing a bifunctional alcohol (including alicyclic), and the like. The polyester carbonate which copolymerized both bifunctional carboxylic acid and bifunctional alcohol may be sufficient. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

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

  In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is decompressed to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.

As the viscosity average molecular weight of the component (A) polycarbonate, if it is less than 1.0 × 10 ⁴ , the strength and the like will decrease, and if it exceeds 5.0 × 10 ⁴ , the molding process characteristics will decrease. The range of 0.0 × 10 ^{4 to} 5.0 × 10 ⁴ is preferable, the range of 1.2 × 10 ^{4 to} 3.0 × 10 ⁴ is more preferable, and the range of 1.5 × 10 ^{4 to} 2.8 × 10 ⁴ is preferable. A range is further preferred. In this case, it is also possible to mix a polycarbonate having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight exceeding 5.0 × 10 ⁴ can be blended.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., the specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

In addition, when measuring the viscosity average molecular weight of the polycarbonate in the polycarbonate resin composition of this invention, it can carry out in the following way. That is, the resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. . A specific viscosity (η _SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

[Thioether compounds]
The thioether compound used in the present invention is at least one thioether compound selected from the group consisting of compounds represented by the following formula (1) and the following formula (2).
(R ¹ —S—CH ₂ —CH ₂ —C (O) O—CH ₂ ) ₄ —C (1)
[Wherein, R ¹ may be the same or different and is a linear or branched alkyl group having 4 to 20 carbon atoms. ]
(R ² —O—C (O) —CH ₂ —CH ₂ —) ₂ —S (2)
[Wherein, R ² may be the same or different and is a linear or branched alkyl group having 6 to 22 carbon atoms. ]

  The thioether-based compound is known as a stabilizer for polycarbonate resin, but in combination with a cyclic iminoester compound described later, the polycarbonate resin composition of the present invention is formed into a sheet or film by blending a small amount of thioether compound. This is effective for suppressing discoloration during melt molding.

  The content of the thioether compound is in the range of 0.001 to 2.0 parts by weight, preferably in the range of 0.01 to 1.0 parts by weight, and 0.02 to 0.0. A range of 5 parts by weight is most preferred. If it is less than 0.001 part by weight, the discoloration suppressing effect at the time of molding the polycarbonate sheet is insufficient, which is not preferable. Moreover, even if it mix | blends the quantity exceeding 2.0 weight part, the improvement of a higher effect is not seen, but since heat resistance falls on the contrary, it is unpreferable.

In the thioether compound represented by the formula (1), R ¹ is an alkyl group having 4 to 20 carbon atoms, preferably an alkyl group having 10 to 18 carbon atoms. Specific examples include pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate), pentaerythritol tetrakis (3-stearyl thiopropionate), among others. Pentaerythritol tetrakis (3-laurylthiopropionate) and pentaerythritol tetrakis (3-myristylthiopropionate) are preferable, and pentaerythritol tetrakis (3-laurylthiopropionate) is particularly preferable.

In the thioether compound represented by the formula (2), R ² is an alkyl group having 6 to 22 carbon atoms, and preferably an alkyl group having 10 to 18 carbon atoms. Specific examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and among them, dilauryl- 3,3′-thiodipropionate and dimyristyl-3,3′-thiodipropionate are preferable, and dimyristyl-3,3′-thiodipropionate is particularly preferable.
Thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), and the like, and can be easily used.

[About cyclic imino ester compounds]
The cyclic imino ester compound used in the present invention is a cyclic imino ester compound represented by the following formula (3).

［但し、Ａｒはヘテロ原子を含有してもよい炭素数６〜１２の二価の芳香族炭化水素残基である。ｎは０または１を示す。］

[However, Ar is a C6-C12 bivalent aromatic hydrocarbon residue which may contain a hetero atom. n represents 0 or 1. ]

  The cyclic imino ester compound is used as an ultraviolet absorber for improving the weather resistance of the polycarbonate resin. The content of these cyclic imino ester compounds is in the range of 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin, preferably in the range of 0.1 to 4.0 parts by weight, A range of 3.0 parts by weight is particularly preferred. If the cyclic imino ester compound is less than 0.05 parts by weight with respect to 100 parts by weight of the polycarbonate resin, the ultraviolet absorption performance is small and sufficient ultraviolet resistance cannot be obtained. On the other hand, if the cyclic imino ester compound exceeds 5 parts by weight, surging tends to occur in the extruder, and the resin melted from the T die cannot be stably supplied due to discharge fluctuations during molding. As inferior in transparency and smoothness.

  Specific examples of the cyclic imino ester compound include 2,2′-bis (3,1-benzoxazin-4-one) (when n = 0 in formula (3)), 2,2′-p— Phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5- Naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-( 2-Nitro-p-phenylene) bis (3,1-benzoxazin-4-one And 2,2 '- (2-chloro -p- phenylene) bis (3,1-benzoxazin-4-one) is illustrated. Among them, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred, especially 2,2′-p-phenylenebis (3,1-benzoxazine-4 -On) is preferred. The cyclic imino ester can be used alone or in combination of two or more. The cyclic imino ester can be produced by various methods disclosed in the pamphlet of WO 03/035735. That is, any of a method using isatoic anhydride as a raw material (in particular, a method using recrystallized isatoic anhydride) and a method using anthranilic acid can be used. A cyclic imino ester compound can be obtained by reacting these acid compounds with a carboxylic acid chloride compound. These may be recrystallized after production as disclosed in JP-B-62-31027. Such compounds are commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and from CYTEC as CYASORB UV-3638 (trade name) and can be easily used.

  The cyclic imino ester compound is effective for stabilizing the hue for a long period of time because it is less deteriorated by ultraviolet rays. Furthermore, heat resistance and dispersibility are improved by bringing the melting point close to that of polycarbonate resin due to their molecular structure, and sublimation and decomposition during molding of the sheet or film are reduced, so that contamination such as cloudiness of rolls occurs. These effects are synergistically exhibited and a preferable polycarbonate resin sheet or film is obtained.

[Other additives]
<Release agent>
In the present invention, a release agent can be blended with the polycarbonate resin in order to improve the moldability at the time of molding the sheet and film. As the release agent, 90% by weight or more of an ester of alcohol and fatty acid is preferable. Specific examples of the ester of an alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid and / or a partial ester or a total ester of a polyhydric alcohol and a fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Moreover, as a partial ester or total ester of a polyhydric alcohol and a fatty acid, a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable.

  Examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, and stearyl stearate is particularly preferable.

  As partial ester or total ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, All or partial esters of dipentaerythritol such as pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. Can be mentioned. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferable. In particular, pentaerythritol tetrastearate and stearic acid monoglyceride are preferable.

  Examples of the release agent other than the ester include olefin wax, olefin wax containing carboxyl group and / or carboxylic anhydride group, silicone oil, organopolysiloxane, paraffin wax, beeswax and the like.

  In the present invention, the content of the release agent in the polycarbonate resin sheet or film is preferably in the range of 0.005 to 2.0 parts by weight with respect to 100 parts by weight of the polycarbonate resin, and 0.01 to 0.6 weights. The range of parts is more preferable, and the range of 0.02 to 0.5 parts by weight is particularly preferable.

<Phosphorus heat stabilizer>
The polycarbonate resin sheet or film of the present invention may contain 0.001 to 0.2 parts by weight of a phosphorus heat stabilizer per 100 parts by weight of the polycarbonate resin.

  Examples of phosphorus heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite Phyto, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bi (Nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, Diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2,4-di-t-butylphenyl) -4,4'- Biphenylene diphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2 4-di-t-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-) tert-butylphenyl) -3-phenyl-phenylphosphonite and the like.

  Among them, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3 '-Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite And tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite is particularly preferable.

<Hindered phenol heat stabilizer>
You may mix | blend 0.001-0.1 weight part with hindered phenolic antioxidant with respect to 100 weight part of polycarbonate resin in the polycarbonate resin sheet or film of this invention.

  Examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinna Id), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1 , 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, etc. And octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferred.

<Antistatic agent>
An antistatic agent can be blended in the polycarbonate resin sheet or film of the present invention. Examples of the antistatic agent include polyetheresteramide, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride, carbon, graphite, and metal powder. Moreover, “partial ester of polyhydric alcohol and saturated fatty acid” such as glycerin monostearate can be mentioned. The blending amount of the antistatic agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

<Bluing agent>
The polycarbonate resin sheet or film of the present invention can be blended with a bluing agent as long as the object of the invention is not impaired. The bluing agent is effective for eliminating the yellow color of the polycarbonate resin sheet or film. In particular, when weather resistance is imparted, a specific amount of UV absorber is blended, so there is a reality that the sheet or film tends to be yellowish due to the "action and color of the UV absorber", giving a natural transparency In order to achieve this, the blending of the bluing agent is very effective.

The blending amount of the bluing agent in the present invention is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm with respect to the polycarbonate resin.
Examples of the brewing agent include Bayre's Macrolex Violet B and Macrolex Blue RR, Clariant's Polysynthremble-RLS, and the like.

<Flame Retardant>
In the polycarbonate resin sheet or film of the present invention, an amount of flame retardant that does not impair the object of the present invention can be used. Examples of flame retardants include brominated epoxy resins, brominated polystyrene, brominated polycarbonate, brominated polyacrylates, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, sulfonates, etc. Organic acid metal salts, silicone flame retardants and the like can be mentioned, and one or more of them can be used. The said flame retardant can mix | blend a well-known quantity with respect to a polycarbonate resin, respectively.

<Compound with heat ray shielding ability>
In the polycarbonate resin sheet or film of the present invention, a compound having a heat ray shielding ability in an amount that does not impair the object of the present invention can be used. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Various metal compounds having excellent near-infrared absorptivity such as an absorber and carbon fillers are suitable. Furthermore, metallic pigments (for example, metal oxide-coated plate-like fillers, metal-coated plate-like fillers, metal flakes, etc.) mainly reflect heat rays and exhibit heat ray shielding ability.

  As the phthalocyanine-based near infrared absorber, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial, and whisker), carbon fiber (including those produced by vapor phase growth), carbon nanotube, and fullerene. Carbon black and graphite. These can be used alone or in combination of two or more. The blending amount of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, still more preferably 0.001 to 0 parts per 100 parts by weight of the polycarbonate resin. .07 parts by weight. The compounding amount of the metal oxide near-infrared absorber and the metal boride-based near infrared absorber is preferably in the range of 0.1 to 200 ppm (weight ratio) with respect to the polycarbonate resin, and more preferably in the range of 0.5 to 100 ppm. preferable. The blending amount of the carbon filler is preferably in the range of 0.05 to 5 ppm (weight ratio) with respect to the polycarbonate resin. The compounding amount of the metallic pigment is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.8 part by weight per 100 parts by weight of the polycarbonate resin.

<Fluorescent dye>
Since the polycarbonate resin sheet or film of the present invention has good transparency, it can impart higher light transmission and natural transparency by further containing a fluorescent brightening agent. Moreover, the design effect which utilized the luminescent color can be provided by including the fluorescent dye which emits fluorescent whitening agent and other than that.

  Fluorescent dyes (including fluorescent brighteners) include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, xanthene fluorescent dyes, xanthone fluorescent dyes, thiols Examples thereof include xanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin. In particular, a coumarin fluorescent dye, that is, a fluorescent dye composed of a coumarin derivative is preferable from the viewpoint of maintaining good characteristics even in combination with a cyclic imino ester.

  The blending amount of the fluorescent dye (including the fluorescent brightening agent) is preferably 0.0001 to 3 parts by weight, more preferably 0.0005 to 1 part by weight, and still more preferably 0.001 to 100 parts by weight of the polycarbonate resin. 001 to 0.5 parts by weight. Within this range, better UV resistance and hue, thermal stability and light transmittance are compatible.

<Light diffuser and white pigment for highly reflective light>
Since the polycarbonate resin sheet or film of the present invention is excellent in transparency, hue and light resistance, the light diffusion function by the light diffusing agent and the high light reflection function by the white pigment are more effectively exhibited. Therefore, the polycarbonate resin sheet or film of the present invention provides a resin sheet or film having better characteristics even by blending a light diffusing agent or a white pigment. Examples of the light diffusing agent include fine polymer particles (preferably acrylic crosslinked particles and silicone crosslinked particles having a particle diameter of 1 to 20 μm), low refractive index inorganic fine particles, and composites thereof. Preferably it is 0.005-20 weight part with respect to 100 weight part of resin, More preferably, it is 0.01-10 weight part. The white pigment is particularly preferably a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment, and the proportion thereof is preferably 1 to 30 parts by weight, more preferably 2 to 2 parts by weight based on 100 parts by weight of the polycarbonate resin. 20 parts by weight.

<Other resins and elastomers>
In the polycarbonate resin composition of the present invention, other resins and elastomers can be blended in a small proportion within a range where the object of the present invention is not impaired.

  Examples of other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. Examples thereof include polyolefin resins, polystyrene resins, acrylonitrile / styrene copolymers (AS resins), acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethacrylate resins, phenol resins, and epoxy resins.

  As the elastomer, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. ) Rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber and the like.

[Production method of polycarbonate resin sheet or film]
The polycarbonate resin sheet or film of the present invention is produced by melt-kneading each component including a polycarbonate resin (component A), a thioether compound (B component) and a cyclic imino ester compound (C component). It is preferable.
Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, an extruder, and the like. Among these, an extruder is preferable from the viewpoint of kneading efficiency.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  As a method for supplying the component A, component B, component C and other additives (hereinafter simply referred to as “additives”) to the extruder, (i) supplying the additives into the extruder independently of the polycarbonate resin. (Ii) a method in which the additive and the polycarbonate resin powder are premixed using a mixer such as a super mixer and then supplied to the extruder; and (iii) the additive and the polycarbonate resin are previously melt-kneaded. And a method of forming a master pellet.

  In the case of melt extrusion, it is preferable to extrude by reducing the melting zone of the extruder to 1.33 to 66.5 kPa. Moreover, it is preferable to adjust the cylinder temperature of an extruder to the range of Tm + 20-Tm + 80 degreeC by making melting | fusing point of polycarbonate resin into Tm degreeC. The melt-extruded molten resin is formed into a sheet or film having a predetermined thickness.

  As a method of forming the molten resin to a predetermined thickness, a polycarbonate resin composition that has been melt-extruded is sandwiched between a first roll (such as a mirror roll or rubber roll) and a second roll (such as a mirror roll or rubber roll). Then, a method is adopted in which the sheet is pressed by the two rolls and, if desired, the sheet is taken up by a take-up roll while contacting the sheet with a third roll (mirror surface roll).

  The roll diameters of the first roll, the second roll and the third roll used here are not particularly limited, and it is not necessary to unify them into the same roll diameter, but the roll diameter is usually 200 mm or more, particularly 250 to 500 mm. Those having the same diameter are preferably used.

  Further, the linear pressure when the melt-extruded polycarbonate resin composition is sandwiched between the first roll and the second roll and pressed by the two rolls is preferably in the range of 4 to 8 MPa · cm. More preferably, it is in the range of 5-7 MPa · cm.

  Furthermore, when the glass transition temperature of the polycarbonate resin to be used is Tg, the roll temperatures of the first roll and the second roll are preferably adjusted to a range of Tg-50 to Tg + 20 ° C. When the polycarbonate resin to be used is a polycarbonate resin obtained from bisphenol A, the roll temperatures of the first roll and the second roll are preferably adjusted to a range of 95 to 165 ° C.

  The roll temperature of the third roll is preferably adjusted to a range of Tg-25 to Tg ° C. When the polycarbonate resin to be used is a polycarbonate resin obtained from bisphenol A, the roll temperature of the third roll is preferably adjusted to a range of 120 to 145 ° C.

  The polycarbonate resin sheet or film of the present invention has a thickness of 0.1 to 10 mm, preferably 0.1 to 5 mm. In the present invention, a polycarbonate resin sheet having a thickness exceeding 0.5 mm and 10 mm or less is defined as a polycarbonate resin film having a thickness of 0.1 to 0.5 mm.

  The polycarbonate resin sheet or film of the present invention can suppress discoloration at the time of melt molding, has a good appearance of the molded product without staining the molding roll due to fuming due to decomposition or sublimation of the additive, and the hue of the molded product. Is stable even after long-term use and is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishing materials, transport containers, packaging containers, playground equipment and miscellaneous goods And the industrial effects that it plays are exceptional.

The following examples further illustrate the present invention. The evaluation was based on the following method.
(1) Transparency (haze): The haze of a 2.0 mm thick sheet and a 0.2 mm thick film obtained in the examples was measured according to JIS K7105 using NDH-300A manufactured by Nippon Denshoku Co., Ltd. It was measured. The larger the haze value, the greater the light diffusion and the lower the transparency.

(2) Hue (YI value): Transmitted light of a sheet of 2.0 mm thickness and a film of 0.2 mm thickness obtained in the examples using a color difference meter SE-2000 manufactured by Nippon Denshoku Co., Ltd. Based on ASTM-E1925 from the measured X, Y and Z values, it was calculated using the following formula. It shows that the yellowness of a shaping | molding board is so strong that YI value is large.
YI = [100 (1.28X−1.06Z)] / Y

  (3) Molding heat resistance (retention test): In each example, sheets and films were obtained in the same manner except that the polycarbonate resin composition melted for 10 minutes in the extruder cylinder was retained and then extruded. The YI value of this sheet and film was measured by the same method as in the evaluation (2). The difference ΔYI between the YI value of the sheet and film after 10 minutes of residence and the sheet and film obtained in each example (1 minute residence) was determined.

  (4) Ultraviolet resistance test: A 2.0 mm thick sheet and a 0.2 mm thick film obtained in the examples were applied to a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd .: WEL-SUN: HC- The color (YI value) after processing for 1000 hours in a total of 120 minutes with a black panel temperature of 63 ° C., humidity of 50%, water spraying for 18 minutes and no spraying for 102 minutes using B) was the same as in the evaluation (2) above. Measured by the method. The difference ΔYI between the YI value of the sheet and film after the UV resistance test and the sheet and film obtained in each example (before the UV resistance test) was determined.

  (5) Die pressure fluctuation: The maximum fluctuation width per hour of pressure fluctuation in the extruder was measured at the time of forming a sheet and a film, and 5 MPa or less was evaluated as ◯, 5 MPa to 10 MPa as Δ, and 10 MPa or more as x.

  (6) Roll stains: For the cloudy state of the first roll after continuous 6-hour molding, x when the cloudiness that affects the appearance defect of the product is noticeable, x when the product is not affected but the cloudiness is noticeable When the cloudiness was inconspicuous, the evaluation was made visually.

[Examples 1-6, Comparative Examples 1-6]
Various additives listed in Tables 1 and 2 were mixed in blenders in 100 parts by weight of polycarbonate resin powder produced from bisphenol A and phosgene by an interfacial condensation polymerization method using a blender. Using the apparatus shown in FIG. 1, a polycarbonate resin melted by a T-die extruder with a vent while maintaining an extruder temperature of 250 to 300 ° C., a die temperature of 260 to 300 ° C., and a vacuum degree of the vent portion at 26.6 kPa. The composition was extruded at a width of 1,000 mm, and the first roll to the third roll were all mirror metal rolls (roll diameter 300 mm), and the temperatures of the first roll, the second roll, and the third roll were 140 ° C. and 150 ° C., respectively. C. and 145.degree. C., and the extruded molten polycarbonate resin composition is sandwiched between the first roll and the second roll and pressed with a linear pressure of 6 MPa.cm, and the second roll and the third roll. Pass through the third roll while making contact with the third roll to form a polycarbonate resin sheet (thickness 2 mm) or film (thickness 0.2 mm) of the desired thickness, Ri to obtain a take-up sheet or film. The arithmetic average roughness (Ra) of the obtained sheet and film was 0.03 μm. Various evaluation results of the obtained sheets and films are shown in Tables 1 and 2.

The contents of each component indicated by symbols in Tables 1 and 2 are as follows.
(Component A); Polycarbonate resin PC: Polycarbonate resin powder having a viscosity average molecular weight of 23,900 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite (registered trademark) L-1250WP ( Product name) / Melting point: 224 ° C./Tg 145 ° C.)
(Component B); heat stabilizer B-1; pentaerythritol-tetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd .: Sumilizer TP-D (trade name))
B-2: Dimyristyl-3,3′-thiodipropionate (Sumitomo Chemical Co., Ltd .: Sumilizer TPM (trade name))
B-3 (for comparison); Tris (2,4-di-tert-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irgaphos 168)
(C component); UV absorber C-1; 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) (manufactured by Takemoto Yushi Co., Ltd .: CEi-P (trade name) / melting point) : 314 ° C)
C-2 (for comparison); 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Chemipro Kasei Co., Ltd .: Chemisorb 79 (trade name) ) / Melting point: 104 ° C.)
C-3 (for comparison); 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (Asahi Denka Kogyo Co., Ltd.) Co., Ltd .: ADK STAB LA-31 (trade name) / melting point: 195 ° C.)
(Other ingredients)
Mold release agent (PETS); Pentaerythritol tetrastearate (manufactured by Cognis Japan KK: Roxyol VPG861 (trade name))
Blueing agent (MB); anthraquinone compound (manufactured by Bayer Co., Ltd .: Macrolex Violet B (trade name))

It is the schematic which shows an example of the manufacturing apparatus of the polycarbonate resin sheet or film of this invention.

Explanation of symbols

1. T dice 2. First roll (mirror roll)
3. Second roll (mirror roll)
4). Third roll (mirror roll)
5. Take-up roll 6. Melt extruded polycarbonate resin composition

Claims (5)

(A) 0.001 to 2.0 parts by weight of at least one thioether compound selected from the group consisting of compounds represented by the following formulas (1) and (2) with respect to 100 parts by weight of the polycarbonate resin And (C) a polycarbonate resin sheet or film having a thickness of 0.1 to 10 mm formed from a polycarbonate resin composition containing 0.05 to 5 parts by weight of a cyclic imino ester compound represented by the following formula (3).
(R ¹ —S—CH ₂ —CH ₂ —C (O) O—CH ₂ ) ₄ —C (1)
[In Formula (1), R ¹ may be the same or different and is a linear or branched alkyl group having 4 to 20 carbon atoms. ]
(R ² —O—C (O) —CH ₂ —CH ₂ —) ₂ —S (2)
[In formula (2), R ² may be the same or different and is a linear or branched alkyl group having 6 to 22 carbon atoms. ]

[In Formula (3), Ar is a C6-C12 bivalent aromatic hydrocarbon residue which may contain a hetero atom. n represents 0 or 1. ]   Thioether compounds include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate and pentaerythritol tetrakis (3-laurylthio). The polycarbonate resin sheet or film according to claim 1, which is at least one thioether compound selected from the group consisting of propionate).   The polycarbonate resin sheet or film according to claim 1, wherein the thioether compound is pentaerythritol tetrakis (3-lauryl thiopropionate).   Cyclic imino ester compounds include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) The polycarbonate according to claim 1, which is at least one compound selected from the group consisting of -4-one) and 2,2 '-(2,6-naphthalene) bis (3,1-benzoxazin-4-one). Resin sheet or film.   The polycarbonate resin sheet or film according to claim 1, wherein the cyclic imino ester compound is 2,2'-p-phenylenebis (3,1-benzoxazin-4-one).

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