JP2008274203A - Extrusion molded article and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an extrusion molded article excellent in heat resistance, mechanical properties and environmental durability, which comprises a polycarbonate resin prepared by using biomass resources as raw materials; and to provide an optical film being small in wavelength dispersion of phase difference values and high in heat resistance and thermal stability made from the polycarbonate resin having a low photoelastic coefficient. <P>SOLUTION: This extrusion molded article is produced by extrusion molding a resin, composed of a carbonate structural unit expressed by formula (1) and having melt viscosity measured by a capillary rheometer at 250°C ranging 0.2×10<SP>3</SP>to 4.0×10<SP>3</SP>Pa s under a condition of 600 sec<SP>-1</SP>shear rate, at a cylinder temperature range of 220-270°C. This optical film comprises a polycarbonate resin having 150-200°C glass transition temperature, 330-400°C 5% weight reduction temperature and 0.20-0.45 specific viscosity at 20°C of a solution obtained by dissolving 0.7g of the polycarbonate resin in 100 ml of methylene chloride. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an extrusion-molded article and an optical film made of a specific polycarbonate resin. More specifically, the present invention relates to an extruded product and an optical film that are obtained by molding a specific polycarbonate resin under specific extrusion molding conditions and excellent in heat resistance, mechanical properties, and environmental resistance properties.

  In recent years, due to concerns about the depletion of petroleum resources and the problem of increased carbon dioxide in the air that causes global warming, biomass resources that do not depend on petroleum as a raw material and that do not increase carbon dioxide even when burned are formed. In the polymer field, biomass plastics produced from biomass resources are actively developed.

A representative example of biomass plastic is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. Sexuality has also been considered.
However, when polylactic acid is used as an industrial material such as an extruded product, there is a problem that its heat resistance and environmental resistance are insufficient.

  As an amorphous polycarbonate resin that uses biomass resources as a raw material and has high heat resistance, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide has been studied.

に示したエーテルジオールは、たとえば糖類およびでんぷんなどから容易に作られ、３種の立体異性体が知られているが、具体的には下記式（ｂ）

に示す、１，４：３，６ージアンヒドローＤーソルビトール （本明細書では以下「イソソルビド」と呼称する）、下記式（ｃ）

に示す、１，４：３，６ージアンヒドローＤーマンニトール（本明細書では以下「イソマンニド」と呼称する）、下記式（ｄ）

に示す、１，４：３，６ージアンヒドローＬーイジトール（本明細書では以下「イソイディッド」と呼称する）である。 For example, the following formula (a)

The ether diol shown in Fig. 2 is easily made from, for example, sugars and starch, and three stereoisomers are known. Specifically, the following formula (b)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (c)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (d):

1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid” in the present specification).

  Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. In particular, isosorbide homopolycarbonates are described in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2. Among these, Patent Document 1 reports a homopolycarbonate having a melting point of 203 ° C. using a melt transesterification method. In Non-Patent Document 1, a homopolycarbonate having a glass transition temperature of 166 ° C. is obtained in the melt transesterification method using zinc acetate as a catalyst, but the thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. In Non-Patent Document 2, homopolycarbonate is obtained by interfacial polymerization using bischloroformate of isosorbide, but the glass transition temperature is 144 ° C. and heat resistance (particularly heat resistance due to moisture absorption) is not sufficient. On the other hand, as an example of high heat resistance, Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. In this case, in order to obtain a molded product by extrusion molding or the like, there is a problem that since the glass transition temperature is high, the molding processing temperature is high and the decomposition of the polymer is promoted.

  That is, it is a polycarbonate resin using isosorbide as a monomer, and can provide an extruded product having melt flow characteristics and heat stability suitable for extrusion molding, and exhibiting excellent heat resistance, mechanical characteristics, and environmental resistance characteristics Was not yet obtained.

  Further, in recent years, technological advances in liquid crystal display devices have been remarkably used in a wide range of fields from mobile phones and personal computers to televisions. In addition to the TN (twisted nematic) mode that has been used in the past in liquid crystal display devices, recently, a device configuration of a VA (vertical alignment) mode is becoming mainstream, but a retardation film used for viewing angle compensation in this mode. Is required to have low chromatic dispersion in terms of contrast (see Patent Document 3).

  In addition, as the size of TVs has increased, the problem of frame failure, that is, light leakage due to stress generation after panel assembly has become a problem. At present, a material having a low elastic constant is required.

  Aromatic polycarbonate resins containing bisphenol A as a diol component are difficult to satisfy these required characteristics, and improvements have been studied so far. For example, many attempts have been made to make an aliphatic polycarbonate resin having no aromatic component by using an alicyclic diol as a monomer. In many cases, however, the glass transition temperature (Tg), that is, heat resistance is inferior, so that it is used as an optical film. It was difficult to apply. Among them, as an aliphatic polycarbonate resin excellent in heat resistance, one having an alicyclic structure has been proposed (see Patent Document 4). From the examples, polycarbonate resins having a high Tg are obtained, but it is difficult to synthesize and obtain monomers, and there are many problems in practical use.

  Further, as an example of high practicality, there is a proposal of an optical film made of a novel aliphatic polycarbonate resin containing a diol having a specific alicyclic structure (Patent Documents 5 and 6). The optical film obtained in this process has a low photoelastic constant, and the film obtained therefrom has a small wavelength dispersion of the retardation value, but further improvement is required in terms of both thermal stability and heat resistance.

British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet JP 2004-062023 A JP 05-339395 A JP 2006-028441 A Japanese Patent Laid-Open No. 2006-232897 “Journal of Applied Polymer Science”, 2002, 86, p. 872-880. “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  Accordingly, a first object of the present invention is to provide an extruded product made of a polycarbonate resin using as a raw material a biomass resource excellent in heat resistance, mechanical properties, and environmental resistance properties.

  In addition, the second object of the present invention is an optical film having a low wavelength dispersion of retardation value and high both heat resistance and thermal stability, from a polycarbonate resin having a low photoelastic constant made from biomass resources. Is to provide.

  As a result of diligent research to achieve such an object, the present inventors have conducted extrusion molding of polycarbonate resin made from biomass resources having a specific structure and melt flow characteristics under specific conditions. Extruded products with excellent environmental properties can be obtained, and aliphatic homopolycarbonate resins made from biomass resources with specific specific viscosities are sufficiently high in heat resistance and thermal stability and have low photoelasticity The film obtained therefrom has a small wavelength dispersion of the retardation value, and is found to be suitable for optical uses such as a retardation plate and a substrate of a liquid crystal display device, thereby completing the present invention.

２．ポリカーボネート樹脂（Ａ成分）は、ガラス転移温度が１４５〜１６５℃の範囲にある前項１項に記載の押出成形品、
３．ポリカーボネート樹脂（Ａ成分）は、下記式（ａ）で示されるエーテルジオールと炭酸ジエステルとを、アルカリ金属塩、アルカリ土類金属塩、及び含窒素塩基性化合物からなる群より選ばれた少なくとも一つの化合物を触媒として溶融重縮合された前項１または２記載の押出成形品、

４．押出成形品が、シートまたはフィルムである前項１〜３のいずれか１項に記載の押出成形品、
５．押出成形品が光学用フィルムである前項１〜３のいずれか１項に記載の押出成形品、
６．下記式（１）で表されるカーボネート構成単位よりなる脂肪族ホモポリカーボネート樹脂であって、樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度が０．２０〜０．４５であり、ガラス転移温度（Ｔｇ）が１５０〜２００℃であり、且つ５％重量減少温度（Ｔｄ）が３３０〜４００℃であることを特徴とするポリカーボネート樹脂からなる光学用フィルム、

７．ポリカーボネート樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度が０．２０〜０．３７である前項６記載の光学用フィルム、
８．上記式（１）で表されるカーボネート構成単位がイソソルビド（１，４：３，６−ジアンヒドロ−Ｄ−ソルビトール）由来のカーボネート構成単位である前項６記載の光学用フィルム、
９．ポリカーボネート樹脂の光弾性定数が２５×１０^−１２Ｐａ^−１以下である前項６記載の光学用フィルム、および
１０．下記式（Ｉ）を満足する前項６記載の光学用フィルム、
１．０１０＜Ｒ（４５０）／Ｒ（５５０）＜１．０７０ （Ｉ）
（式中、Ｒ（４５０）、Ｒ（５５０）はそれぞれ波長４５０ｎｍ、５５０ｎｍにおけるフィルム面内の位相差値である。）
が提供される。 That is, according to the present invention,
1. It consists of a carbonate structural unit represented by the following formula (1), and the melt viscosity measured by a capillary rheometer at 250 ° C. is 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa under the condition of a shear rate of 600 sec ^-1. -Extrusion product obtained by extruding polycarbonate resin (component A) in the range of s in the range of cylinder temperature 220-270 ° C,

2. The polycarbonate resin (component A) is an extrusion-molded article according to the preceding item 1, wherein the glass transition temperature is in the range of 145 to 165 ° C.
3. The polycarbonate resin (component A) is an ether diol represented by the following formula (a) and a carbonic acid diester, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, and nitrogen-containing basic compounds. 3. Extrusion product according to item 1 or 2, which is melt polycondensed using a compound as a catalyst,

4). The extruded product according to any one of items 1 to 3, wherein the extruded product is a sheet or a film,
5. The extruded product according to any one of items 1 to 3, wherein the extruded product is an optical film,
6). An aliphatic homopolycarbonate resin comprising a carbonate constituent unit represented by the following formula (1), wherein a specific viscosity at 20 ° C. of 0.20 to 0.45 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride is 0.20 to 0.45. An optical film comprising a polycarbonate resin, wherein the glass transition temperature (Tg) is 150 to 200 ° C. and the 5% weight loss temperature (Td) is 330 to 400 ° C .;

7). The optical film as described in 6 above, wherein the specific viscosity at 20 ° C. of a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride is 0.20 to 0.37,
8). The optical film according to item 6 above, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).
9. 9. The optical film as described in 6 above, wherein the photoelastic constant of the polycarbonate resin is 25 × 10 ⁻¹² Pa ⁻¹ or less; The optical film as described in 6 above, which satisfies the following formula (I):
1.010 <R (450) / R (550) <1.070 (I)
(In the formula, R (450) and R (550) are in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively.)
Is provided.

  Hereinafter, the extruded product and the optical film made of the polycarbonate resin according to the present invention will be specifically described sequentially.

[Extruded product]
<About component A>
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin composed of the carbonate structural unit of the above formula (1), and the biogenic substance content measured according to ASTM D686605 is 83% to 100%. Preferably, 84% to 100% is more preferable. Particularly preferred is a homopolycarbonate resin comprising only the carbonate structural unit of the above formula (1).

The polycarbonate resin (component A) used in the present invention has a melt viscosity measured by a capillary rheometer at 250 ° C. of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^-1 . It is in the range, more preferably in the range of 0.4 × 10 ^{3 to} 3.0 × 10 ³ Pa · s, and in the range of 0.4 × 10 ^{3 to} 2.0 × 10 ³ Pa · s. More preferably. When the melt viscosity is within this range, extrusion molding can be performed under favorable conditions in which decomposition of the polymer is suppressed, and a molded product excellent in various characteristics can be obtained. If the melt viscosity is less than the lower limit, even if extrusion molding is possible, the mechanical properties are poor. If the upper limit is exceeded, the melt fluidity is inferior, and if the molding processing temperature is raised, the decomposition of the polymer is promoted.

  As the polycarbonate resin (component A) used in the present invention, those having a specific viscosity at 20 ° C. of 0.14 to 0.5 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride can be preferably used. The lower limit of the specific viscosity is more preferably 0.20 or more, and further preferably 0.22 or more. The upper limit is more preferably 0.45 or less, further preferably 0.37 or less, and particularly preferably 0.34 or less. On the other hand, when the specific viscosity is lower than 0.14, it becomes difficult to give sufficient mechanical strength to the molded product obtained from the polycarbonate resin composition used in the present invention. On the other hand, if the specific viscosity is higher than 0.5, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature.

  The lower limit of the glass transition temperature (Tg) of the polycarbonate resin (component A) used in the present invention is preferably 145 ° C or higher, more preferably 150 ° C or higher, and the upper limit is preferably 165 ° C or lower. If the Tg is less than 145 ° C, the heat resistance (particularly heat resistance due to moisture absorption) is poor, and if it exceeds 165 ° C, the melt fluidity during molding using the polycarbonate resin composition used in the present invention is inferior, and the polymer decomposition occurs. Extrusion molding becomes impossible in a small temperature range. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

  The lower limit of the 5% weight loss temperature of the polycarbonate resin (component A) used in the present invention is preferably 330 ° C or higher, more preferably 340 ° C or higher, still more preferably 350 ° C or higher, and the upper limit is It is preferably 400 ° C. or lower, more preferably 390 ° C. or lower, and further preferably 380 ° C. or lower. It is preferable that the 5% weight loss temperature is within the above range since there is almost no decomposition of the resin when molding using the polycarbonate resin composition used in the present invention. In order to increase the 5% weight loss temperature, it is effective to select a preferable compound as a melt polymerization catalyst as described later. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).

で表されるエーテルジオールおよび炭酸ジエステルとから溶融重合法により製造することができる。エーテルジオールとしては、具体的には下記式（ｂ）、（ｃ）および（ｄ）

で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 The polycarbonate resin (component A) used in the present invention has the following formula (a):

It can manufacture with the melt polymerization method from the ether diol and carbonic acid diester represented by these. As the ether diol, specifically, the following formulas (b), (c) and (d)

And isosorbide, isomannide, and isoidide represented by the formula:

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.

  In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .

  The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 260 ° C.

Further, the reaction initially with ether diol and a carbonic acid diester by heating under normal pressure, after pre-reacted, the system to 1.3 × 10 ^-3 gradually to the reaction late in the vacuum ~ 1.3, × 10 ^over A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about ⁵ MPa is preferred. The reaction time is usually about 0.5 to 4 hours.

  Examples of the carbonic acid diester include esters such as an aryl group or aralkyl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, in which a hydrogen atom may be substituted. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Diphenyl carbonate is preferred.

  The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98 with respect to the ether diol, more preferably 1.01 to 0.98, and still more preferably 1.01 to 0.8. 99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid diester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

  Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali metal compounds such as sodium salt or potassium salt of dihydric phenol, calcium hydroxide, barium hydroxide, magnesium hydroxide, etc. And alkaline earth metal compounds, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine, and triethylamine. These may be used alone or in combination of two or more. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination. Those polymerized using these catalysts are preferred because the 5% weight loss temperature is kept sufficiently high.

The amount of these polymerization catalysts used is preferably in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of the carbonic acid diester component. Chosen by The reaction system is preferably maintained in an atmosphere of a gas inert to the raw material such as nitrogen, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.

  The polycarbonate resin (component A) obtained by carrying out the reaction as described above has a hydroxyl group or a carbonic acid diester residue as the terminal structure, but the polycarbonate resin (component A) used in the present invention loses its properties. You may introduce | transduce a terminal group separately in the range which is not. Such end groups can be introduced by adding a monohydroxy compound during polymerization. As the monohydroxy compound, a hydroxy compound represented by the following formula (2) or (3) is preferably used.

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（４）であり、特に炭素原子数８〜２０のアルキル基、または上記式（４）が好ましい。Ｘは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。 In the above formulas (2) and (3), R ¹ is an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 4)

Preferably an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the above formula (4), particularly an alkyl group having 8 to 20 carbon atoms, or the above formula. (4) is preferred. X is preferably at least one bond selected from the group consisting of a single bond, ether bond, thioether bond, ester bond, amino bond and amide bond, more preferably selected from the group consisting of a single bond, ether bond and ester bond. It is at least one kind of bond, and among them, a single bond and an ester bond are preferable. a is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is particularly preferable.

In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, and particularly at least one group selected from the group consisting of a methyl group and a phenyl group, respectively. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50. Since the polycarbonate resin (component A) used in the present invention has a carbonate structural unit obtained from the ether diol of the renewable resource represented by the above formula (a) in the main chain structure, these monohydroxy compounds can also be planted. It is preferable that it is a raw material obtained from renewable resources, such as. Examples of monohydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

  By introducing these end groups, the effects of improving the extrusion-molded product made of the polycarbonate resin, in particular, the optical film formation, moisture resistance or surface energy (antifouling property and abrasion resistance), etc. can get. These terminal groups are preferably contained in an amount of 0.3 to 9.0% by weight, more preferably 0.3 to 7.5% by weight, particularly preferably 0.3 to 9.0% by weight based on the polymer main chain structure. 5 to 6.0% by weight is contained.

<About other ingredients>
The extruded product of the present invention may be composed of a resin composition obtained by adding various components to the above-described polycarbonate resin (component A). These usable components are exemplified below.

(I) Inorganic filler In the resin composition constituting the extruded product of the present invention, when an inorganic filler is further blended, a molded product excellent in mechanical characteristics, dimensional characteristics, etc. can be obtained.
As inorganic fillers, various inorganic fillers generally known such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.) Materials can be mentioned. The shape of the inorganic filler can be freely selected from fibrous, flaky, spherical and hollow shapes, and fibrous and flaky materials are suitable for improving the strength and impact resistance of the resin composition.

  Among them, the inorganic filler is preferably an inorganic filler made of a pulverized product of natural mineral, more preferably an inorganic filler made of a pulverized product of a natural mineral of silicate, and from the point of its shape. Are preferably mica, talc, and wollastonite.

  On the other hand, since these inorganic fillers are non-petroleum resource materials compared to petroleum resource materials such as carbon fibers, raw materials with a lower environmental load are used, and as a result, A component with a lower environmental load is used. There is an effect that the significance of use is further enhanced. Furthermore, the above-mentioned more preferable inorganic filler has an advantageous effect that good flame retardancy is exhibited as compared with carbon fiber and the like.

  The mica that can be used in the present invention is preferably 10 to 500 μm in terms of the number average particle size calculated by the average number of 1000 particles whose average particle size is observed with a scanning electron microscope and extracted 1 μm or more. More preferably, it is 30-400 micrometers, More preferably, it is 30-200 micrometers, Most preferably, it is 35-80 micrometers. When the number average particle diameter is less than 10 μm, the impact strength may be lowered. On the other hand, if it exceeds 500 μm, the impact strength is improved, but the appearance tends to deteriorate.

  As the thickness of mica, one having a thickness measured by electron microscope observation of 0.01 to 10 μm can be used. Preferably 0.1-5 micrometers thing can be used. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and a more suitable extruded product is provided.

  In addition, as a method for pulverizing mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica rough ore with a dry pulverizer, followed by adding a grinding aid such as water in a slurry state There is a wet pulverization method in which main pulverization is performed by a wet pulverizer, followed by dehydration and drying. The mica of the present invention can be produced by any pulverization method, but the dry pulverization method is generally lower in cost. On the other hand, the wet pulverization method is effective for pulverizing mica more thinly and finely, but is expensive. Mica may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes, and further granulated with sizing agents such as various resins, higher fatty acid esters, and waxes to form granules. May be.

The talc that can be used in the present invention is a scaly particle having a layered structure, which is a hydrous magnesium silicate in terms of chemical composition, and is generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O. the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a H ₂ O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, the specific gravity is about 2.7, and the Mohs hardness is 1.

  The average particle diameter of talc that can be used in the present invention is preferably 0.5 to 30 μm. The average particle size is a particle size at a 50% stacking rate obtained from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter of talc is more preferably 2 to 30 μm, further preferably 5 to 20 μm, and most preferably 10 to 20 μm. Talc in the range of 0.5 to 30 μm imparts good surface appearance and flame retardancy to the extruded product in addition to rigidity and low anisotropy.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the method by deaeration and compression is preferable because it is simple and does not include unnecessary sizing agent resin components in the molded article of the present invention.

The wollastonite that can be used in the present invention is substantially represented by the chemical formula CaSiO ₃ , usually SiO ₂ is about 50 wt% or more, CaO is about 47 wt% or more, and other Fe ₂ O ₃ , Al ₂ O _3. Etc. Wollastonite is a white acicular powder obtained by crushing and classifying raw wollastonite, and has a Mohs hardness of about 4.5. The average fiber diameter of wollastonite used is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and most preferably 1 to 5 μm. The average fiber diameter is observed by a scanning electron microscope, and is calculated by a number average of a total of 1000 samples having a diameter of 0.1 μm or more extracted.

  The blending amount of these inorganic fillers is preferably 0.3 to 200 parts by weight, more preferably 1.0 to 100 parts by weight, and most preferably 3 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A). When the blending amount is less than 0.3 parts by weight, the reinforcing effect on the mechanical properties of the molded product of the present invention is not sufficient, and when it exceeds 200 parts by weight, the molding processability and hue deteriorate, which is not preferable. .

  In addition, in the resin composition which comprises the extrusion molded product of this invention, when using a fibrous inorganic filler and a flaky inorganic filler, the folding inhibitor for suppressing those folding can be included. The folding inhibitor inhibits adhesion between the matrix resin and the inorganic filler, reduces stress acting on the inorganic filler during melt kneading, and suppresses the folding of the inorganic filler. Examples of the effect of the folding inhibitor include (1) improvement of rigidity (increase in aspect ratio of inorganic filler), (2) improvement of toughness, and (3) improvement of conductivity (in the case of conductive inorganic filler). Can do. Specifically, the crease suppressor has (i) a compound having a low affinity with the resin, and (ii) a structure having a low affinity with the resin when the surface of the inorganic filler is directly coated with the compound. It is a compound having a functional group capable of reacting with the surface of the inorganic filler.

  Representative examples of the compound having a low affinity for the resin include various lubricants. Examples of the lubricant include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefinic wax (paraffin wax, polyolefin wax, etc.), polyalkylene glycol, fluorinated fatty acid. Fluorine oils such as esters, trifluorochloroethylene, and polyhexafluoropropylene glycol are listed.

  As a method of directly coating the surface of the inorganic filler with a compound having a low affinity for the resin, (1) a method of directly immersing the compound or a solution or emulsion of the compound in the inorganic filler; A method of passing an inorganic filler in the vapor or powder of a compound, (3) a method of irradiating the inorganic filler with the powder of the compound at high speed, and (4) a mechanochemical that rubs the inorganic filler and the compound. And the like.

  Examples of the compound having a structure having a low affinity with the resin and having a functional group capable of reacting with the surface of the inorganic filler include the above-described lubricants modified with various functional groups. Examples of such functional groups include a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, and an alkoxysilyl group.

  One suitable folding inhibitor is an alkoxysilane compound in which an alkyl group having 5 or more carbon atoms is bonded to a silicon atom. The number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 5 to 60, more preferably 5 to 20, still more preferably 6 to 18, and particularly preferably 8 to 16. The alkyl group is preferably 1 or 2, particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group. Such alkoxysilane compounds are preferred in that they have high reactivity with the inorganic filler surface and excellent coating efficiency. Therefore, it is suitable for a finer inorganic filler.

  One suitable folding inhibitor is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 15,000 in terms of weight average molecular weight. In such a polyolefin wax, the amount of carboxyl group and carboxylic anhydride group is in the range of 0.05 to 10 meq / g per gram of lubricant having at least one functional group selected from carboxyl group and carboxylic anhydride group. Is preferable, more preferably 0.1 to 6 meq / g, and still more preferably 0.5 to 4 meq / g. It is preferable that the ratio of the functional group in the folding inhibitor is the same as the ratio of the carboxyl group and the carboxylic anhydride group in the functional group other than the carboxyl group.

  A particularly preferred example of the folding inhibitor is a copolymer of an α-olefin and maleic anhydride. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  The folding inhibitor is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 0.8 parts by weight per 100 parts by weight of the polycarbonate resin (component A) used in the present invention. Part by weight is more preferred.

(Ii) Organic filler The resin composition constituting the extruded product of the present invention can also contain an organic filler. Examples of the organic filler include synthetic fibers such as aramid fiber, polyester fiber, and nylon fiber, Examples include natural fibers such as kenaf, hemp and bamboo. As for the organic filler, it is preferable to use natural fibers from the viewpoint of environmental load. A preferable blending amount of the organic filler is the same as that of the inorganic filler.

(Iii) Flame retardant A flame retardant can also be mix | blended with the resin composition which comprises the extrusion molded product of this invention. Flame retardants include brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, brominated polyacrylates, halogenated flame retardants such as chlorinated polyethylene, and phosphate ester flame retardants such as monophosphate compounds and phosphate oligomer compounds, Organic phosphorus flame retardants other than phosphate ester flame retardants such as phosphinate compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonate alkali (earth) metal salts, borate metal salt flame retardants And organic metal salt flame retardants such as metal stannate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, and triazine flame retardants. Separately, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), an anti-drip agent (polytetrafluoroethylene having fibril-forming ability, etc.), etc. may be blended and used together with the flame retardant.

  Among the above-mentioned flame retardants, compounds that do not contain chlorine and bromine atoms have reduced features that are undesirable when performing incineration and thermal recycling. It is more suitable as a flame retardant in the molded article of the present invention.

  In the resin composition constituting the extruded product of the present invention, when these flame retardants are blended, the range of 0.05 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A) is preferable. If it is less than 0.05 part by weight, sufficient flame retardancy will not be exhibited, and if it exceeds 50 parts by weight, the strength and heat resistance of the molded product will be impaired.

(Iv) Thermal Stabilizer The resin composition constituting the extruded product of the present invention preferably contains a phosphorus-based stabilizer in order to obtain a better hue and stable fluidity. In particular, a pentaerythritol-type phosphite compound represented by the following general formula (5) is preferably blended as a phosphorus stabilizer.

［式中Ｒ^２１、Ｒ^２２はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、または炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていてもよい。］

[Wherein R ²¹ and R ²² are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]

  More specifically, examples of the pentaerythritol type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples thereof include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc. Among them, distearyl pentaerythritol diphosphite, bis (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite and bis (2,6-di -tert- butyl-4-methylphenyl) pentaerythritol diphosphite.

  Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) 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, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

  Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

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

  Said phosphorus stabilizer can be used individually or in combination of 2 or more types, It is preferable to mix | blend an effective amount of a pentaerythritol type | mold phosphite compound at least. The phosphorus stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin (component A). Partly formulated.

(V) Elastic polymer In the resin composition constituting the extruded product of the present invention, an elastic polymer can be used as an impact modifier. Examples of the elastic polymer include natural rubber or glass transition temperature. One or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith are copolymerized with a rubber component of 10 ° C. or less. And graft copolymers. A more preferable elastic polymer is a core-shell type graft copolymer in which one or more shells of the above-mentioned monomer are graft-copolymerized on the core of the rubber component.

  Moreover, the rubber component and the block copolymer of the said monomer are also mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomers (hydrogenated styrene / isoprene / styrene elastomers) and hydrogenated styrene / butadiene / styrene elastomers. Furthermore, various elastic polymers known as other thermoplastic elastomers such as polyurethane elastomers, polyester elastomers, polyether amide elastomers and the like can also be used.

  A core-shell type graft copolymer is more suitable as an impact modifier. In the core-shell type graft copolymer, the core particle size is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and more preferably 0.1 to 0.5 μm in weight average particle size. Is more preferable. If it is in the range of 0.05 to 0.8 μm, better impact resistance is achieved. The elastic polymer preferably contains 40% or more of a rubber component, and more preferably contains 60% or more.

  Rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene- Acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds may include halogen atoms because of concerns about the generation of harmful substances during combustion. No rubber component is preferable in terms of environmental load.

  The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. As the rubber component, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable. The composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure entangled with each other so as not to be separated.

  Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, and styrene is particularly preferable. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, etc., and examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, methacrylic acid. Examples thereof include butyl, cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of 100% by weight of the shell in the case of the core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. Is done.

  The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It can be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. Furthermore, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size. In the case of a core-shell type graft polymer, the reaction may be one stage or multistage for both the core and the shell.

  Such elastic polymers are commercially available and can be easily obtained. For example, as rubber components mainly composed of butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber, Kane Ace B series (for example, B-56 etc.) of Kanegafuchi Chemical Industry Co., Ltd. and Metabrene of Mitsubishi Rayon Co., Ltd. C series (for example, C-223A), W series (for example, W-450A), paraloid EXL series (for example, EXL-2602) by Kureha Chemical Industry, HIA series (for example, HIA-15), BTA series (E.g., BTA-III), KCA series, Rohm and Haas Paraloid EXL series, KM series (e.g., KM-336P, KM-357P, etc.), and UCL modifier resin series (UMG)・ ABS's MG AXS Resin Series) and the like, and those mainly composed of acrylic-silicone composite rubber as the rubber component are those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name Methbrene S-2001 or SRK-200. It is done.

  The composition ratio of the impact modifier is preferably 0.2 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (component A), preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts by weight. Such a composition range can give good impact resistance to the composition while suppressing a decrease in rigidity.

(Vi) Other additives In the resin composition constituting the extrusion molded article of the present invention, other thermoplastic resins (for example, other polycarbonate resins, aromatic polyester resins, Aliphatic polyester resin, polyarylate resin, liquid crystalline polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, Polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polystyrene resin, high impact polystyrene resin, syndiotactic polystyrene tree Oils, polymethacrylate resins, phenoxy or epoxy resins, etc.), antioxidants (eg hindered phenol compounds, sulfur antioxidants, etc.), UV absorbers (benzotriazoles, triazines, benzophenones, etc.) ), Light stabilizers (such as HALS), mold release agents (saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes, fluorine compounds, paraffin wax, beeswax, etc.), flow modifiers (such as polycaprolactone), colorants ( Carbon black, titanium dioxide, various organic dyes, metallic pigments, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, inorganic and organic Antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorption Agents, and the like photochromic agent ultraviolet absorber may be blended. These various additives can be used in known blending amounts when blended with a thermoplastic resin such as polycarbonate made of bisphenol A.

<About the manufacturing method of a resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition which comprises the extrusion molded product of this invention. For example, each component and optionally other components can be premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component and optionally other components can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed. The cylinder temperature at the time of melt kneading is preferably in the range of 220 to 270 ° C, more preferably in the range of 230 to 260 ° C, and still more preferably in the range of 230 to 250 ° C. When the cylinder temperature exceeds 270 ° C., the progress of thermal decomposition of the polycarbonate used in the present invention increases.

<Manufacture of extruded products>
The extruded product in the present invention is a molded product shaped by the shape of an extruder die by a melting process, and is generally provided in the form of a sheet, a film, a rod, a tube or the like. Here, the sheet refers to a sheet having a thickness of about 0.5 to 20 mm obtained by extruding a molten polymer from a die or the like into a sheet shape and cooling, and the drawing process may not be performed specially. On the other hand, the film has a thickness of about 5 to 500 μm obtained by extruding a molten polymer from a die or the like and cooling it, or by sequentially or simultaneously stretching a sheet or film in a uniaxial direction or a biaxial direction and orienting molecular chains. Point to.

  The extrusion molded product of the present invention can be produced by using an ordinary known production method. For example, when producing a film and a sheet, a monoaxial or biaxial screw to which a T die or an I die is connected via a gear pump, for example. The raw material polycarbonate resin is supplied to the hopper of the extruder, melted in the cylinder of the extruder, extruded from a die into a sheet, and cooled by a casting roll. About a casting roll, it is preferable to stick a sheet | seat using an electrostatic contact | adherence apparatus or an air knife from the point of being able to prevent thickness spots and air entrainment.

  When the extruded product of the present invention is a stretched film, it can be carried out by a conventionally known method for producing a film used for a polycarbonate resin. For example, an extrusion molding method using a T die or an I die, an inflation extrusion molding method using a ring die, a casting molding method, a calendar molding method, a press molding method, etc. can be mentioned. It is preferable to form using any stretching method of axial stretching. Examples of biaxial stretching include sequential biaxial stretching and simultaneous biaxial stretching.

The extruded product of the present invention is obtained by extrusion molding at a cylinder temperature of 220 to 270 ° C. In order to suppress coloration and molecular weight reduction due to polymer decomposition, the temperature range is more preferably 230 to 260 ° C, and further preferably 230 to 250 ° C. When the cylinder temperature exceeds 270 ° C., the decomposition of the polymer is greatly accelerated.
The extruded product of the present invention can be used not only for structural members, packaging materials, industrial materials such as electrical and electronic applications and automobiles, but can also be used as a material for thermoforming.

  Sheets include optical materials such as automobile window glass and roofs, retardation plates, polarizing plates, and light diffusers, wall materials, flooring materials, arcade roofing materials, veranda waistboards, windproof and snowproof plates, and other exhibition materials. Can be suitably used for a case, a show window, various trays, various nameplates (instrument protective covers, etc.), a helmet shield, and the like. The film can be suitably used for a retardation film or a film for a liquid crystal display device, a film for a light transmission layer of a Blu-ray disc, a surface protective film such as a protective film for a polarizing plate, an insulating film, or the like.

  Further, the extruded product of the present invention can be further provided with other functions by surface modification. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for extrusion products, such as a normal sheet | seat and a film, is applicable.

[Optical film]
A polycarbonate resin having a low photoelastic constant made from biomass resources used in the present invention is suitably used as an optical film having a small wavelength dispersion of retardation values and high both heat resistance and thermal stability. .

The optical film of the present invention is an optical film made of an aliphatic homopolycarbonate resin composed of a carbonate constituent unit represented by the following formula (1).

  The polycarbonate resin used in the optical film of the present invention has a specific viscosity at 20 ° C. of 0.20 to 0.45 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride, preferably 0.20 to 0.37. And more preferably 0.22 to 0.34. When the specific viscosity is lower than 0.20, it becomes difficult to give the obtained optical film sufficient mechanical strength. On the other hand, when the specific viscosity is higher than 0.45, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for film formation by the melt film-forming method becomes higher than the decomposition temperature, which is not preferable.

The polycarbonate resin used for the optical film of the present invention has a melt viscosity measured by a capillary rheometer at 250 ° C. of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^-1 . is preferably one in the range, more preferably in the range of ^{0.4 × 10 3 ~3.0 × 10 3} Pa · s, the range of ^{0.4 × 10 3 ~2.0 × 10 3} Pa · s More preferably. When the melt viscosity is within this range, extrusion molding can be performed under favorable conditions in which decomposition of the polymer is suppressed, and a molded product excellent in various characteristics can be obtained. If the melt viscosity is less than the lower limit, even if extrusion molding is possible, the mechanical properties are poor. If the upper limit is exceeded, the melt fluidity is inferior, and if the molding processing temperature is raised, the decomposition of the polymer is promoted.

  The polycarbonate resin used for the optical film of the present invention has a glass transition temperature (Tg) having a lower limit of 150 ° C. or higher, preferably 155 ° C. or higher. The upper limit is 200 ° C. or less, preferably 190 ° C. or less, more preferably 168 ° C. or less, and even more preferably 165 ° C. or less. When the Tg is less than 150 ° C., heat resistance (particularly heat resistance due to moisture absorption). If the temperature exceeds 200 ° C., the melt fluidity when the optical film of the present invention is formed by the melt film-forming method is inferior. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

The polycarbonate resin used for the optical film of the present invention has a 5% weight reduction temperature of 330 to 400 ° C, preferably 340 to 390 ° C, more preferably 350 to 380 ° C. A 5% weight loss temperature within the above range is preferable because there is almost no decomposition of the resin during film formation by the melt film forming method. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).
About the manufacturing method and additive of this polycarbonate resin, it is the same as that of what was mentioned above. However, the additive is appropriately used within a range in which the object of the present invention such as transparency of the optical film is achieved.

  The optical film production method of the present invention includes a solution casting method using a resin solution obtained by dissolving the polycarbonate resin used in the present invention in a solvent, and a melt film forming method in which the polycarbonate resin used in the present invention is melted and cast as it is. Is mentioned.

  When producing a film by the solution casting method, the solvent used is most preferably a halogen-based solvent, especially methylene chloride from the viewpoint of versatility and production cost, and the solution composition is 60% by weight of methylene chloride. What dissolved 10 weight part of aliphatic polycarbonate resin with respect to 15-90 weight part of solvent contained above is preferable. If the amount of solvent is more than 90 parts by weight, it may be difficult to obtain a cast film having a large film thickness and excellent surface smoothness. If the amount of solvent is less than 15 parts by weight, the solution viscosity is too high and the film is too high. Manufacturing can be difficult.

  In addition to methylene chloride, other solvents may be added as necessary as long as film formation is not hindered. For example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, chloroform, 1,2 -Halogen solvents such as dichloroethane, aromatic solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as ethylene glycol dimethyl ether It is done.

  In this invention, after casting the solution composition (dope) of this aliphatic polycarbonate resin on a support substrate, a film can be obtained by heating and evaporating a solvent. A glass substrate, a metal substrate such as stainless steel or ferrotype, a plastic substrate such as PET, or the like is used as the support substrate, and the dope is uniformly cast on the support substrate with a doctor blade or the like. Industrially, a method of continuously extruding a dope from a die onto a belt-like or drum-like support substrate is common.

  It is preferable that the dope cast on the support substrate is gradually heated and dried from a low temperature so that foaming does not occur. The dope is peeled off from the support substrate after removing most of the solvent by heating to form a self-supporting film. Further, it is preferable to remove the remaining solvent by heating and drying from both sides of the film. In the drying process after peeling from the substrate, there is a high possibility that stress will be applied to the film due to dimensional changes due to thermal shrinkage. Therefore, a product that requires precise control of optical properties like an optical film used in liquid crystal display devices is required. In the membrane, it is necessary to pay attention to the drying temperature, film fixing conditions, and the like. In general, in drying after peeling, it is preferable to take a method of drying while raising the temperature stepwise in the range of (Tg-100 ° C.) to Tg of the polycarbonate to be used. Drying at Tg or higher is not preferable because thermal deformation of the film occurs, and (Tg-100 ° C.) or lower is not preferable because the drying temperature is remarkably slowed.

  The amount of residual solvent in the film obtained by the solution casting method is preferably 2% by weight or less, more preferably 1% by weight or less. When the amount of residual solvent is 2% by weight or more, the glass transition point of the film is remarkably lowered, which is not preferable.

  When a film is produced by a melt film forming method, the film is generally formed by extruding a melt from a T die. The film-forming temperature (cylinder temperature at the time of melt-kneading) is determined from the molecular weight of polycarbonate, Tg, melt flow characteristics, etc., but is preferably in the range of 220 to 270 ° C, more preferably in the range of 230 to 260 ° C. The range of 230 to 250 ° C. is more preferable. If the temperature is too low, the viscosity may increase and polymer orientation and stress strain may remain. On the other hand, if the temperature is too high, problems such as thermal deterioration, coloring, and die lines (stripe) from the T-die are likely to occur. Sometimes.

  The film thickness of the unstretched film thus obtained is not particularly limited and is determined according to the purpose, but is preferably 10 to 300 μm, more preferably 20 to 200 μm from the viewpoint of film production, physical properties such as toughness, and cost. .

  As the optical film of the present invention, a film obtained by aligning the polymer by a known stretching method such as uniaxial stretching or biaxial stretching of the unstretched film is also suitable. Such stretching can be used, for example, as a retardation film of a liquid crystal display device. The stretching temperature is usually in the range of (Tg−20 ° C.) to (Tg + 20 ° C.) near the Tg of the polymer, and the stretching ratio is usually 1.02 to 3 times in the case of longitudinal uniaxial stretching. The film thickness of the stretched film is preferably in the range of 20 to 200 μm.

The polycarbonate resin constituting the optical film of the present invention preferably has a photoelastic constant of 25 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 20 × 10 ⁻¹² Pa ⁻¹ or less. When the photoelastic constant is higher than 25 × 10 ⁻¹² Pa ⁻¹ , a phase difference appears due to the tension when the optical film is laminated, or stress caused by a difference in dimensional stability with other materials. A phase difference is likely to occur, and as a result, phenomena such as light leakage and a decrease in contrast may occur, resulting in poor long-term stability.

The optical film of the present invention has a wavelength dispersion of the retardation value represented by the following formula (I):
1.010 <R (450) / R (550) <1.070 (I)
Preferably satisfying the following formula (II)
1.010 <R (450) / R (550) <1.060 (II)
Is more preferable.

  Here, R (450) and R (550) are in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively. When such a retardation film having a small wavelength dispersion of retardation values is used, a film having excellent viewing angle characteristics and contrast can be obtained particularly in a VA (vertical alignment) mode of a liquid crystal display device.

In addition, the optical film of the present invention has a value obtained by dividing the retardation by the film thickness (Δn = R (550) / film film thickness (μm)) in the unstretched state (III)
Δn <0.2 (III)
Preferably satisfying the following formula (IV)
Δn <0.15 (IV)
Is more preferable. The lower limit is not particularly limited as long as it is in a range larger than 0 (zero).

Furthermore, when stretched in the range of (Tg−10 ° C.) to (Tg + 10 ° C.) in the vicinity of the Tg of the polymer, the following formula (V)
a ≧ 8 (V)
It is preferable to satisfy the following formula (VI)
a ≧ 8.5 (VI)
Is more preferable. In the above formula, a is a value that satisfies Δn (s) = aXs + b (s is the draw ratio, Δn (s) is Δn at the draw ratio s, a is the slope, and b is a constant). Although an upper limit is not specifically limited, A performance will be fully demonstrated if it is 100 or less.
An optical film having characteristics satisfying the above-described ranges of Δn and a easily develops a retardation after stretching, has good retardation controllability, and is industrially suitable.

  In the optical film of the present invention, the total light transmittance is preferably 88% or more, and more preferably 90% or more. Further, the haze value is preferably 5% or less, more preferably 3% or less. The optical film of the present invention is suitable as an optical film because of its excellent transparency.

  One optical film of the present invention may be used alone, or two or more films may be laminated and used. Moreover, you may use in combination with the optical film which consists of another raw material. You may use as a protective film of a polarizing plate, and may be used as a film for transparent substrates of a liquid crystal display device.

  The present invention is an extrusion-molded product obtained from a polycarbonate resin using biomass resources as a raw material, and has excellent heat resistance, mechanical properties, and environmental resistance characteristics, and in addition, an extrusion-molded product with reduced environmental load. Therefore, it is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishery materials, transport containers, packaging containers, playground equipment, and miscellaneous goods. The effect is exceptional.

  Further, the optical film of the present invention has a low photoelastic constant, good retardation development and retardation controllability, excellent viewing angle characteristics, and excellent heat resistance and thermal stability. It can use suitably as a protective film of this, and the film for transparent substrates of a liquid crystal display device.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.
[Examples of extruded products]
A polycarbonate resin was produced by the method shown in the following production example. Moreover, each value in an Example was calculated | required with the following method.
(1) Melt viscosity Obtained as a result of measurement using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd. with a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 250 ° C. The melt viscosity at 600 sec ⁻¹ was read from the obtained Shear Rate / Viscosity curve.
(2) Glass transition temperature The glass transition temperature was measured by DSC (model DSC2910) manufactured by TA Instruments.
(3) 5% weight loss temperature Measured with TGA (model TGA2950) manufactured by TA Instruments.

<Production Example 1: Production of Polycarbonate A-1 Component>
1608 parts by weight (11 moles) of isosorbide and 2356 parts by weight (11 moles) of diphenyl carbonate were placed in a reactor, and 1.0 part by weight of tetramethylammonium hydroxide was used as a polymerization catalyst (1 × with respect to 1 mole of diphenyl carbonate component). ^10-4 mol) and 1.1 × 10 ⁻³ parts by weight of sodium hydroxide (0.25 × 10 ⁻⁶ mol with respect to 1 mol of diphenyl carbonate component), and heated to 180 ° C. under a nitrogen atmosphere at normal pressure And melted.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.

Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. The temperature was gradually raised, and the reaction was finally carried out at 250 ° C. and 6.66 × 10 ⁻⁵ MPa for 40 minutes. As a result, a polymer having a glass transition temperature of 156 ° C., a melt viscosity at a shear rate of 600 sec ⁻¹ of 0.53 × 10 ³ Pa · s, and a 5% weight reduction temperature of 360 ° C. was obtained.

<Production Example 2: Production of Polycarbonate A-2 Component>
A polymer was obtained in the same manner as in Production Example 1 except that the reaction was finally carried out at 260 ° C. and 6.66 × 10 ⁻⁵ MPa for 60 minutes. The polymer had a glass transition temperature of 164 ° C. and a shear rate of 600 sec ⁻¹ . The melt viscosity was 1.7 × 10 ³ Pa · s, and the 5% weight loss temperature was 362 ° C.

<Production Example 3: Production of Polycarbonate A-3 Component>
1590 parts by weight (10.88 moles) of isosorbide and 36 parts by weight (0.24 moles) of p-tert-butylphenol were placed in a thermometer and a reactor equipped with a stirrer, purged with nitrogen, and 5500 parts by weight of pyridine well dried beforehand. Then, 32400 parts by weight of methylene chloride was added and dissolved. Under stirring, 1400 parts by weight (14.14 mol) of phosgene was blown in for 100 minutes at 25 ° C. After the completion of phosgene blowing, the reaction was terminated by stirring for about 20 minutes. After completion of the reaction, the product was diluted with methylene chloride, pyridine was neutralized and removed with hydrochloric acid, washed repeatedly with water until the conductivity was almost the same as that of ion-exchanged water, and then methylene chloride was evaporated. As a result, a polymer having a glass transition point of 172 ° C. and a melt viscosity of 5.1 × 10 ³ Pa · s at a shear rate of 600 sec ⁻¹ and a 5% weight reduction temperature of 362 ° C. was obtained.

<Production Example 4: Production of Polycarbonate A-4 Component>
A polymer was obtained in the same manner as in Production Example 1, except that 1608 parts by weight (11 moles) of isosorbide and 2427 parts by weight (11.33 moles) of diphenyl carbonate were used. This polymer had a glass transition temperature of 138 ° C., a melt viscosity at a shear rate of 600 sec ⁻¹ of 0.13 × 10 ³ Pa · s, and a 5% weight loss temperature of 355 ° C.

Extruded articles were produced by the methods shown in the following examples and comparative examples. Moreover, each value in an Example was calculated | required with the following method.
(1) Tensile strength, tensile modulus: The tensile properties of the film were measured according to ISO 527.
(2) Chemical resistance: The film was immersed in toluene, xylene, acetone and trichloroethane for 24 hours at room temperature, and the surface state was observed.
(3) Hydrolysis resistance: The specific viscosity (η _sp ) after the film was treated for 10 days in a constant temperature and humidity chamber at 80 ° C. × 90% relative humidity in terms of the retention rate relative to the value before the treatment. evaluated.

The following were used as raw materials.
(Appendix-1) Antioxidant: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka ADEKA STAB PEP-36)
Further, the following resins were used as comparative resins.
(Ratio-1) Bisphenol A-polycarbonate resin: L-1250 (manufactured by Teijin Chemicals Ltd.)
(Ratio-2) Poly-L-lactic acid resin: LACEA H-100J (manufactured by Mitsui Chemicals, Inc.)

<Examples 1-2 and Comparative Examples 1-5>
A polycarbonate resin and additives dried at 100 ° C. for 12 hours with the composition shown in Table 1 were supplied to an extruder hopper, melted at a melting temperature of 250 ° C., and rotated at a surface temperature of 25 ° C. through a 1 mm slit die. The film was extruded upward and rapidly cooled to obtain a film having a thickness of 0.3 mm. Each characteristic was measured using these films. The bisphenol A-polycarbonate resin was extruded at a cylinder temperature of 310 ° C., and the poly-L-lactic acid was extruded at a cylinder temperature of 220 ° C. Each characteristic was measured using these films. The measurement results are shown in Tables 1 and 2.

  As is apparent from the results of Tables 1 and 2, the polycarbonate resin used in the present invention having a specific molecular weight and glass transition temperature can obtain a good film-like molded product when extruded in a specific temperature range. It can be seen that it has excellent heat resistance and mechanical properties. Furthermore, it has better chemical resistance than bisphenol A-polycarbonate resin, which is the most representative engineering plastic, and has hydrolysis resistance comparable to that, and it is a plastic made from the most representative biomass resource. It has also been found that it has better chemical resistance and hydrolysis resistance than -L-lactic acid, and its environmental resistance is also at a very high level.

[Examples of optical film]
Measurement of physical properties in the following Reference Examples, Examples and Comparative Examples was performed as follows. The melt viscosity, glass transition temperature (Tg), and 5% weight loss temperature (Td) were measured in the same manner as described above.

(1) Specific viscosity (η _sp )
The pellet was dissolved in methylene chloride, the concentration was about 0.7 g / dL, and the temperature was measured at 20 ° C. using an Ostwald viscometer (device name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 · PC). In addition, specific viscosity (eta) _sp is calculated | required from a following formula.
η _sp = t / t _o −1
t: Flow time of sample solution t _o : Flow time of solvent only (2) Film thickness Measured with a film thickness meter made by Mitutoyo.
(3) Photoelastic constant A film having a width of 1 cm and a length of 6 cm is prepared, and the phase difference of the film in an unloaded state is set to the phase difference of light having a wavelength of 550 nm when loaded with 1N, 2N, and 3N, manufactured by JASCO Corporation. It was obtained by measuring with a spectroscopic ellipsometer “M220” and calculating (phase difference) × (film width) / (load).
(4) Total light transmittance and haze value of the film The film was measured using a turbidimeter NDH-2000 type manufactured by Nippon Denshoku Industries Co., Ltd.
(5) Retardation value (R (450), R (550)) and its chromatic dispersion (R (450) / R (550))
Measurement was performed at a wavelength of 450 nm and a wavelength of 550 nm using a spectroscopic ellipsometer “M220” manufactured by JASCO Corporation. The retardation value was measured by measuring the retardation value with respect to the normal incident light with respect to the film surface.
(6) Amount of residual solvent in the film It was calculated from the weight change before and after the film was heat-dried at 230 ° C. for 6 hours.

[Reference Example 1] (Production of polycarbonate resin used in Examples)
1608 parts by weight (11 moles) of isosorbide and 2356 parts by weight (11 moles) of diphenyl carbonate were placed in a reactor, and 1.0 part by weight of tetramethylammonium hydroxide was used as a polymerization catalyst (1 × with respect to 1 mole of diphenyl carbonate component). ^10-4 mol) and 1.1 × 10 ⁻³ parts by weight of sodium hydroxide (0.25 × 10 ⁻⁶ mol with respect to 1 mol of diphenyl carbonate component), and heated to 180 ° C. under a nitrogen atmosphere at normal pressure And melted.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.

Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. The temperature was gradually raised to 260 ° C., and the reaction was finally carried out at 250 ° C. and 6.66 × 10 ⁻⁵ MPa for 1 hour. The polymer after the reaction was pelletized. The polymer obtained had a specific viscosity of 0.26, a glass transition temperature of 162 ° C., and a 5% weight loss temperature of 357 ° C.

[Reference Example 2] (Production of polycarbonate resin used in Comparative Example)
24.84 parts by weight of isosorbide, 3.55 parts by weight of 1,6-hexanediol, and 42.84 parts by weight of diphenyl carbonate were put into a reactor, and tetramethylammonium hydroxide was used as a polymerization catalyst in an amount of 1.82 × 10 ^−3. Parts (1 × 10 ⁻⁴ mol relative to 1 mol of the diol component), and 27.2 × 10 ⁻⁶ parts by weight of 2,2-bis (4-hydroxyphenyl) propane disodium salt (based on 1 mol of the diol component) 0.5 × 10 ⁻⁶ mol), and a polycarbonate resin was melt-polymerized in the same manner as in Reference Example 1 except that it was charged and melted at 180 ° C. in a nitrogen atmosphere. The polymer obtained had a specific viscosity of 0.28 and a glass transition temperature of 123 ° C.

[Example 3]
The polycarbonate resin obtained in Reference Example 1 was melted into a film by using a KZW15-30MG film forming apparatus (manufactured by Technobel Co., Ltd.) and a KYA-2H-6 roll temperature controller (manufactured by Kato Riki Seisakusho Co., Ltd.). Got. The extruder cylinder temperature was maintained in the range of 220 ° C to 260 ° C, and the roll temperature was 250 ° C. The physical properties of the obtained film are shown in Tables 3 and 4.

[Examples 4 to 6]
The unstretched polycarbonate film obtained in Example 3 was uniaxially stretched at three stretching ratios at a stretching temperature of 170 ° C. using a stretching machine to obtain a stretched film. Table 4 shows the retardation values of these stretched and unstretched films and the physical properties of wavelength dispersion thereof.

[Comparative Example 6]
A melt film-forming film was obtained in the same manner as in Example 3, using Panlite (registered trademark) L1225 manufactured by Teijin Chemicals Limited, which is a polycarbonate resin composed of bisphenol A. Table 3 shows the physical properties of this film. It can be seen that the photoelastic constant is higher than that of the polycarbonate film of Example 3, and the wavelength dispersion of the retardation value is large.

[Comparative Examples 7-9]
The polycarbonate resin obtained in Reference Example 2 was dissolved in methylene chloride to obtain a solution having a concentration of 18% by weight. The solution was cast on a stainless steel substrate and dried by heating at a temperature of 40 ° C. for 20 minutes and at a temperature of 60 ° C. for 30 minutes. Then, the film was peeled off from the substrate, and the periphery of the film was loosely fixed. For 30 minutes, 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 140 ° C. for 1 hour to obtain a film. This polycarbonate film was uniaxially stretched at two stretching ratios at a stretching temperature of 120 ° C. using a stretching machine to obtain a stretched film. Tables 3 and 4 show retardation values of these unstretched films (Comparative Example 7) and stretched films (Comparative Examples 8 and 9) and their physical properties of wavelength dispersion. It can be seen that the photoelastic constant is high as compared with the polycarbonate films of Examples 3 to 6, the wavelength dispersion of the retardation value is large, the retardation after stretching is hardly exhibited, and the retardation controllability is poor.

Claims (10)

It consists of a carbonate structural unit represented by the following formula (1), and the melt viscosity measured by a capillary rheometer at 250 ° C. is 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa under the condition of a shear rate of 600 sec ^-1. Extrusion product obtained by extruding a polycarbonate resin (component A) in the range of s at a cylinder temperature of 220 to 270 ° C.

  The extruded product according to claim 1, wherein the polycarbonate resin (component A) has a glass transition temperature in the range of 145 to 165 ° C. The polycarbonate resin (component A) is an ether diol represented by the following formula (a) and a carbonic acid diester, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, and nitrogen-containing basic compounds. The extrusion molded article according to claim 1 or 2, which has been melt polycondensed using a compound as a catalyst.

  The extruded product according to any one of claims 1 to 3, wherein the extruded product is a sheet or a film.   The extruded product according to any one of claims 1 to 3, wherein the extruded product is an optical film. An aliphatic homopolycarbonate resin comprising a carbonate constituent unit represented by the following formula (1), wherein a specific viscosity at 20 ° C. of 0.20 to 0.45 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride is 0.20 to 0.45. An optical film comprising a polycarbonate resin having a glass transition temperature (Tg) of 150 to 200 ° C. and a 5% weight loss temperature (Td) of 330 to 400 ° C.

  The optical film according to claim 6, wherein a specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride is 0.20 to 0.37.   The optical film according to claim 6, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol). The optical film according to claim 6, wherein the polycarbonate resin has a photoelastic constant of 25 × 10 ⁻¹² Pa ⁻¹ or less. The optical film according to claim 6, which satisfies the following formula (I).
1.010 <R (450) / R (550) <1.070 (I)
(In the formula, R (450) and R (550) are in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively.)