JP2009144019A - Molded product with metal / inorganic thin film made of polycarbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article comprising a material having good adhesion to a metal-inorganic thin film, scratch resistance, transparency, good mechanical strength, good weatherability and a high glass transition temperature. <P>SOLUTION: The molded article with a metal-inorganic thin film comprises a polycarbonate including a constitutional unit derived from a dihydroxy compound represented by general formula (1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is formed by molding a polycarbonate polymer containing isosorbide which is a biomass resource, is environmentally friendly, has good mechanical strength, high glass transition temperature, high surface hardness, weather resistance, and metal / inorganic thin film. The present invention relates to a molded article having good adhesiveness and having a reflective film or magnetic recording film such as an optical disk, a magnetic disk or a mirror.

  Aromatic polycarbonate resin has excellent mechanical strength, impact strength, dimensional stability, heat resistance, transparency, etc., so that it can be used for reflective films such as optical discs, illumination lamp reflectors, vehicle mirrors, and magnetic films. Used for molded products having metal / inorganic thin films such as recording films and hard coat films.

  However, when an aromatic polycarbonate resin is used for a disk substrate such as an optical disk or a magnetic disk, the adhesion between the substrate and the recording film may be insufficient or the recording film may corrode. And Patent Document 2 shows. Furthermore, in these patent documents, the conventional aromatic polycarbonate resin contains various impurities, but it was used as a low molecular weight component (such as polycarbonate oligomer), unreacted bisphenol (such as bisphenol A) or a solvent. It is described that methylene chloride is abundant and these impurities cause various problems as described above when polycarbonate is used for a disk substrate. In particular, volatile organic components are considered to cause such problems. As a countermeasure, it has been proposed to extract a powdery polycarbonate containing impurities with an organic solvent such as acetone. However, such treatment is impractical because it takes a great deal of cost to remove the organic solvent, and a small amount of the remaining residue causes poor adhesion.

  In addition, in an optical disc, a molded product made of an aromatic polycarbonate resin having a metal / inorganic thin film such as a mirror or a lamp reflector, the surface hardness of the aromatic polycarbonate resin is low, so that the optical disc is easily damaged. Has a problem that reading and recording errors are likely to occur, and the image is unclear on the mirror. A hard coat film is applied to a vehicular lamp lens or the like in which the occurrence of scratches is a serious problem. However, since the cost of the hard coat increases, optical disks, mirrors, and the like are required to have materials with higher surface hardness that can reduce the cost of the hard coat.

  Further, in a molded article such as an illumination lamp reflector, it is preferable that the resin is at least self-extinguishing as a flame retardant property and has little yellowing (light resistance) due to light. Aromatic polycarbonate resins have no problem with self-extinguishing properties, but have the disadvantage of poor light resistance.

  By the way, an aromatic polycarbonate is generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the depletion of petroleum resources, and there is a need to provide electrical and electronic parts from plastics using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. There is a demand for the development of molded products having metal / inorganic thin films made of plastic.

  Conventionally, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (for example, see Patent Document 3). However, the obtained polycarbonate is brown and is not satisfactory. Further, as a copolymerized polycarbonate of isosorbide and other dihydroxy compounds, a polycarbonate obtained by copolymerizing bisphenol A has been proposed (for example, see Patent Document 4), and further by copolymerizing isosorbide and an aliphatic diol. Attempts have been made to improve the rigidity of homopolycarbonate composed of isosorbide (see, for example, Patent Document 5).

  On the other hand, many polycarbonates obtained by polymerizing 1,4-cyclohexanedimethanol which is an alicyclic dihydroxy compound have been proposed (for example, Patent Documents 6 and 7). The molecular weight of these polycarbonates is as low as about 4000 at most. Therefore, many of them have a low glass transition temperature.

Thus, although a polycarbonate polymer using isosorbide has been proposed, these documents disclose only the glass transition temperature and further the basic mechanical properties, and the above-mentioned discs and mirrors. The characteristics of factors that affect the peeling of metal / inorganic thin films are not disclosed.
Japanese Patent Laid-Open No. 6-100653 JP-A-10-241149 GB1079686 Publication JP-A-56-55425 WO 2004/111106 gazette JP-A-6-145336 Japanese Patent Publication No. 63-12896

  The purpose of the present invention is to consider the environment and the preservation of petroleum resources in the construction of a better future society, with good adhesion to metal / inorganic thin films, hardly scratched, transparent, mechanical strength, The object is to provide a molded article made of a material having good weather resistance and a high glass transition temperature.

  In view of the above problems, the present inventors have intensively studied. As a result, the polycarbonate produced by the melt polymerization method (also referred to as transesterification method) with diphenyl carbonate using isosorbide as a plant-derived monomer is transparent, mechanical The present invention has been found to have good mechanical strength and weather resistance, high glass transition temperature and high surface hardness, particularly low volatile organic components, and suitable for molding materials having metal / inorganic thin films. It came to complete. Furthermore, it has been found that a polycarbonate copolymerized with an alicyclic dihydroxy compound has a good balance between glass transition temperature and impact resistance and can be applied to a wide range of the above-mentioned molded products.

That is, the gist of the present invention resides in the following [1] to [6].
[1] A molded article having a metal / inorganic thin film made of polycarbonate containing a structural unit derived from a dihydroxy compound represented by the following general formula (1).

[2] The molded article having a metal / inorganic thin film according to [1], wherein the polycarbonate has a glass transition temperature of 80 ° C. or higher.
[3] The molded article having a metal / inorganic thin film according to [1] or [2], wherein the polycarbonate further contains a structural unit derived from an alicyclic dihydroxy compound.
[4] The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound contained in the polycarbonate is 100: 0 to 30. : The molded article having a metal / inorganic thin film according to [3], which is in a range of 70.
[5] The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound contained in the polycarbonate is 90:10 to 40. : The molded article having the metal / inorganic thin film according to [3], which is in a range of 60.
[6] The metal according to any one of [1] to [5], comprising a fatty acid ester-based compound having at least one hydroxyl group and a molecular weight of 200 or more, or a silicone oil having an epoxy group. Molded product with inorganic thin film.

  The molded article having a metal / inorganic thin film made of the polycarbonate of the present invention using a plant-derived monomer has good environmental / petroleum resource conservation, low volatile organic components, high surface hardness, and glass transition temperature. And a good balance of impact strength, it can be suitably used particularly for light and magnetic disks, illumination lamp reflectors, vehicle mirrors, and the like.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

  In the present invention, it is necessary to have a metal / inorganic thin film on at least a part of the surface of the molded product. These metal / inorganic thin films can be attached to the surface of the molded article by various known methods, for example, metal thin films such as aluminum, chrome, nickel, silver, and gold by vacuum deposition and sputtering, and silicate compounds. And the like, particularly a silicone coating thin film cured by irradiation with vacuum ultraviolet light, and various metal / inorganic thin films by CVD. Although it is preferable to perform primer treatment on a molded product before vapor deposition or the like because the adhesion of the thin film can be improved, the effectiveness of the present invention is more easily felt when primer treatment is not performed. The thickness of the thin film is 5 μm to 300 μm, although it depends on the product application.

  The polycarbonate of the present invention is characterized in that it contains a structural unit derived from a dihydroxy compound represented by the following general formula (1), and a part of the dihydroxy compound is replaced with another type of dihydroxy compound such as a fatty acid. It may be a copolymer substituted with a structural unit derived from an aromatic or aromatic dihydroxy compound, or a copolymerized structural unit such as polyalkylene glycol.

  In the present invention, examples of the dihydroxy compound represented by the general formula (1) include isosorbide, isomannide, and isoidet, which are related to stereoisomers. These may be used alone or in combination of two kinds. A combination of the above may also be used.

  Among these dihydroxy compounds, isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and manufacture, optical properties, moldability From the viewpoint of

Since isosorbide is gradually oxidized by oxygen, in order to prevent decomposition due to oxygen during storage and handling during production, do not mix moisture, use an oxygen scavenger, or use a nitrogen atmosphere. It is important to set it down. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate is produced using isosorbide containing these decomposition products, the resulting polycarbonate is colored or causes a significant deterioration in physical properties. In addition, the polymerization reaction may be affected, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate, or physical properties may be significantly deteriorated. As the stabilizer, a reducing agent or an antacid is used. Among them, examples of the reducing agent include sodium borohydride and lithium borohydride. Examples of the antacid include alkalis such as sodium hydroxide. Addition of such an alkali metal salt also serves as a polymerization catalyst, and if it is excessively added, the polymerization reaction may not be controlled.
In order to obtain isosorbide containing no oxidative decomposition product, isosorbide may be distilled as necessary. Moreover, also when the stabilizer is mix | blended in order to prevent the oxidation and decomposition | disassembly of isosorbide, you may distill isosorbide as needed. In this case, the distillation of isosorbide may be simple distillation or continuous distillation, and is not particularly limited. After the atmosphere is an inert gas atmosphere such as argon or nitrogen, distillation is performed under reduced pressure.
By performing such distillation of isosorbide, in the present invention, it is preferable to use a high purity isosorbide having a formic acid content of less than 20 ppm, more preferably 10 ppm or less, particularly 5 ppm or less.

  On the other hand, the dihydroxy compound of a copolymerization structural unit suitable for use in the present invention may be any of linear aliphatic, cycloaliphatic, and aromatic dihydroxy compounds. Examples of linear aliphatic dihydroxy compounds include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2- Examples thereof include ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like.

  Examples of the cycloaliphatic (alicyclic) dihydroxy compound that can be used in the present invention include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1, Hexanediols such as 4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol And norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol and the like. Of these, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,2-cyclohexanedimethanol are preferred.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxy diphenyl etc. are mentioned, Preferably bisphenol A is mentioned.

  Further, the polyalkylene glycol as the copolymerization unit preferably contains 2 to 40 carbonsyl groups having 2 to 4 carbon atoms per molecule, and examples thereof include polyethylene glycol and polypropylene glycol.

The hydroxy compound which is these copolymerization structural units may be used individually by 1 type, and may mix and use 2 or more types. Use of a linear aliphatic dihydroxy compound or polyalkylene glycol as a copolymerization component is not preferable because the glass transition temperature is drastically lowered, and the use as an electrical / electronic component is restricted. When an aromatic dihydroxy compound is used as a copolymerization component, the reactivity is significantly different from that of the dihydroxy compound represented by the general formula (1), and transparency and the like deteriorate.
In general, it is difficult to obtain a polycarbonate resin having a single dihydroxy compound represented by the general formula (1) having a high molecular weight. On the other hand, when a cycloaliphatic (sometimes referred to as alicyclic) dihydroxy compound is used as a copolymerization component, the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy as shown below. The balance of reactivity with the compound is good, the molecular weight is relatively easy, the glass transition temperature is lower than the linear aliphatic dihydroxy compound, and the surface hardness and mechanical strength are sufficiently high. This is desirable.

  As described above, a polycarbonate obtained by copolymerizing a structural unit derived from the dihydroxy compound represented by the general formula (1) and a structural unit derived from the alicyclic dihydroxy compound, which is a preferred polycarbonate in the present invention, has not yet been reported. The details thereof will be described below, but the copolymers with other dihydroxy compounds are basically similar, and can be produced with reference to the above-mentioned patent documents.

  About the content rate of the structural unit derived from the dihydroxy compound represented by General formula (1), and the structural unit derived from an alicyclic dihydroxy compound, it can select in arbitrary ratios. However, when a differential scanning calorimetry (DSC) is performed, a single glass transition temperature is given. The polycarbonate copolymer of the present invention is a dihydroxy compound represented by the general formula (1) and an alicyclic dihydroxy compound. The glass transition temperature can be obtained as a polymer having an arbitrary glass transition temperature from about 45 ° C. to about 155 ° C. depending on the application.

  Therefore, for electrical / electronic parts applications of the present invention, by setting the glass transition temperature to 80 ° C. or higher, heat resistance (usable temperature) of 70 ° C. or higher can be secured, and therefore, represented by the general formula (1). It is necessary to appropriately select the ratio of the structural unit derived from the dihydroxy compound to the structural unit derived from the alicyclic dihydroxy compound. The ratio is preferably 100: 0 to 30:70 (mol%), particularly 90:10 to 40:60 (mol%), more preferably 90:10 to 45:55 (mol%). If the number of structural units derived from the dihydroxy compound represented by the general formula (1) is larger than the above range and the number of structural units derived from the alicyclic dihydroxy compound is small, coloring tends to occur. Conversely, the structural formula is represented by the general formula (1). When the number of structural units derived from the dihydroxy compound is small and the number of structural units derived from the alicyclic dihydroxy compound is large, the molecular weight is difficult to increase and the glass transition temperature tends to decrease.

  The polymerization degree of the polycarbonate of the present invention is such that a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 is used as a solvent, and the polycarbonate copolymer concentration is 1.00 g / dl. As a reduced viscosity (hereinafter simply referred to as “reduced viscosity of polycarbonate (co) polymer”) measured at a temperature of 30.0 ° C. ± 0.1 ° C. with high precision, 0.40 dl / g or more, especially 0 The degree of polymerization is preferably 40 dl / g or more and 2.0 dl / g or less. When the reduced viscosity of the polycarbonate copolymer is extremely low, the mechanical strength when molded into electrical and electronic parts is weak. Further, when the reduced viscosity of the polycarbonate is increased, the fluidity at the time of molding is lowered, the cycle characteristics are lowered, the distortion of the molded product is increased, and it tends to be easily deformed by heat. Accordingly, the reduced viscosity of the polycarbonate of the present invention is preferably in the range of 0.40 dl / g to 2.0 dl / g, particularly 0.41 liter / g to 1.5 dl / g. In particular, in a disk substrate or a mirror, since the occurrence of optical distortion leads to a reading error or image distortion, a material having good fluidity is required.

  The polycarbonate of the present invention can be produced by a generally used polymerization method, and the polymerization method may be either a solution polymerization method using phosgene or a melt polymerization method in which it reacts with a carbonic acid diester. A melt polymerization process in which a dihydroxy compound is reacted with a diester carbonate that is less toxic to the environment is preferred for the purposes of the present invention.

  Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following general formula (2).

(In General formula (2), A and A 'are the C1-C18 aliphatic groups which may have a substituent, or the aromatic group which may have a substituent, A and A ′ may be the same or different.)

  Examples of the carbonic acid diester represented by the general formula (2) include diphenyl carbonate, substituted diphenyl carbonate represented by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Particularly preferred are diphenyl carbonate and substituted diphenyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more.

  The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.10, more preferably 0.94 to 1.04, relative to the dihydroxy compound. When this molar ratio is smaller than 0.90, the terminal OH group of the produced polycarbonate (co) polymer is increased, the thermal stability of the polymer is deteriorated, and when the molar ratio is larger than 1.10, Under the same conditions, the transesterification rate decreases, making it difficult to produce a polycarbonate copolymer having a desired molecular weight, and increasing the amount of residual carbonic diester in the produced polycarbonate copolymer. Carbonic acid diesters are not preferred at the time of molding or cause odor of molded products.

  Moreover, as a polymerization catalyst (transesterification catalyst) in melt polymerization, an alkali metal compound and / or an alkaline earth metal compound is used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with an alkali metal compound and / or an alkaline earth metal compound. It is particularly preferred to use only metal compounds and / or alkaline earth metal compounds.

  Examples of the alkali metal compound used as the polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate. , Lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, Cesium borohydride, sodium phenyl borohydride, potassium phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, benzoic acid Cium, 2 sodium hydrogen phosphate, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, Sodium, potassium, lithium, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like.

  Examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

  These alkali metal compounds and / or alkaline earth metal compounds may be used alone or in combination of two or more.

  Specific examples of basic boron compounds used in combination with alkali metal compounds and / or alkaline earth metal compounds include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethyl Sodium salt such as phenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, butyltriphenyl boron, potassium salt, lithium Examples thereof include salts, calcium salts, barium salts, magnesium salts, and strontium salts.

  Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

  Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

  These basic compounds may be used alone or in combination of two or more.

  When the alkali metal compound and / or alkaline earth metal compound is used, the polymerization catalyst is used in an amount of metal with respect to 1 mol in total of the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy compound. As a conversion amount, it is normally used within the range of 0.1 to 100 μmol, preferably within the range of 0.5 to 50 μmol, and more preferably within the range of 1 to 25 μmol. If the amount of the polymerization catalyst used is too small, the polymerization activity necessary to produce a polycarbonate copolymer having a desired molecular weight cannot be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the resulting polycarbonate (co) The hue of the polymer deteriorates and by-products are generated, resulting in a decrease in fluidity and the generation of gel, making it difficult to produce a polycarbonate (co) polymer having a target quality.

  In the production of the polycarbonate of the present invention, the dihydroxy compound such as the dihydroxy compound represented by the general formula (I) may be supplied as a solid, or heated and supplied in a molten state. Alternatively, it may be supplied as an aqueous solution. When these raw material dihydroxy compounds are supplied in a molten state or in an aqueous solution, there is an advantage that they can be easily measured and transported when industrially produced.

  In the present invention, the method of reacting the dihydroxy compound represented by the general formula (I) or the copolymer component with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in two or more multistage processes. Specifically, the first stage reaction is carried out at a temperature of 140 to 220 ° C, preferably 150 to 200 ° C for 0.1 to 10 hours, preferably 0.5 to 3 hours. From the second stage onward, the reaction temperature is raised while gradually reducing the pressure of the reaction system from the pressure of the first stage, and at the same time, the phenol generated at the same time is removed from the reaction system. Is 200 Pa or less and a polycondensation reaction is performed under the temperature range of 210-280 degreeC.

  In the pressure reduction in this polycondensation reaction, it is important to control the balance between temperature and pressure in the reaction system. In particular, if either one of the temperature and the pressure is changed too quickly, unreacted monomers are distilled out, the molar ratio of the dihydroxy compound and the carbonic acid diester may be changed, and the degree of polymerization may be lowered. For example, when isosorbide and 1,4-cyclohexanedimethanol are used as the dihydroxy compound, 1,4-cyclohexanedimethanol is used when the molar ratio of 1,4-cyclohexanedimethanol to the total dihydroxy compound is 50 mol% or more. Since methanol easily distills out as a monomer, the reaction is carried out under a reduced pressure of about 13 kPa while the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour, and further up to about 6.67 kPa. When the temperature is increased at a temperature increase rate of 40 ° C. or less per hour under the pressure of, and finally the polycondensation reaction is performed at a temperature of 200 to 250 ° C. at a pressure of 200 Pa or less, the degree of polymerization is sufficiently increased The obtained polycarbonate (co) polymer is preferable.

  In addition, when the molar ratio of 1,4-cyclohexanedimethanol is less than 50 mol% with respect to all dihydroxy compounds, particularly when the molar ratio is 30 mol% or less, 1,4-cyclohexanedimethanol Compared with the case where the molar ratio is 50 mol% or more, the viscosity rises rapidly. For example, the temperature is increased at a rate of 40 ° C. or less per hour until the pressure in the reaction system is reduced to about 13 kPa. And the reaction is carried out at a pressure of up to about 6.67 kPa while increasing the temperature at a rate of temperature rise of 40 ° C. or more, preferably at a rate of temperature rise of 50 ° C. or more per hour. When a polycondensation reaction is finally performed at a temperature of 220 to 290 ° C. under a reduced pressure of 200 Pa or less, a polycarbonate copolymer having a sufficiently increased degree of polymerization is obtained. Arbitrariness.

  The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  When the polycarbonate of the present invention is produced by a melt polymerization method, a phosphoric acid compound or a phosphorous acid compound can be added during polymerization for the purpose of preventing coloring.

  As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound components. When the addition amount of the phosphorus compound is less than the above lower limit, the effect of preventing coloring is small, and when it is more than the above upper limit, haze is increased, or on the contrary, the coloring is promoted or the heat resistance is lowered.

  When adding a phosphorous acid compound, the heat stabilizer shown below can be selected arbitrarily and used. In particular, trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) One or more of pentaerythritol diphosphites can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compound component. It is preferable to do. If the amount of the phosphite compound is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, it may cause haze to increase, or conversely promote coloring or reduce heat resistance. Sometimes.

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, and the total hydroxy compound component described above, It is preferable to set it as 0.0001 mol% or more and 0.005 mol% or less, More preferably, it is 0.0003 mol% or more and 0.003 mol% or less. If the amount added is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the above upper limit, haze may be increased, or conversely, coloring may be promoted or heat resistance may be lowered.

  The polycarbonate of the present invention thus produced can be blended with a heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue during molding.

  Examples of the heat stabilizer 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, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert Butylphenyl) octyl phosphite, bis (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, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate , Diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate, and further blending a phosphorous acid compound by a blending method described later, an increase in haze during polymerization, coloring, and By avoiding a decrease in heat resistance, more heat stabilizers can be blended, and hue deterioration can be prevented.

  The blending amount of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.2 part by weight when polycarbonate is 100 parts by weight. Part is more preferred.

  In addition, the polycarbonate (co) polymer of the present invention can be blended with an antioxidant generally known for the purpose of preventing oxidation.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, 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 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 -Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, One type or two or more types such as 4,8,10-tetraoxaspiro (5,5) undecane may be mentioned.

  The blending amount of these antioxidants is preferably 0.0001 to 0.5 parts by weight when the polycarbonate is 100 parts by weight.

  Moreover, in order to further improve the releasability from the mold at the time of injection molding, the polycarbonate of the present invention can be blended with a release agent as long as the object of the present invention is not impaired.

  As the release agent in the present invention, known plastic release agents can be used, but fatty acid ester compounds and silicone compounds are particularly preferable in that they do not easily inhibit metal / inorganic film adhesion. Among the fatty acid ester compounds, one or more compounds selected from fatty acid esters represented by glycerin fatty acid esters and sorbitan fatty acid esters and partially saponified products thereof are added. It is possible. Particularly preferred are fatty acid ester compounds containing at least one hydroxyl group and having a molecular weight of 200 or more. In addition, the silicone compound is preferably of a type that is modified from the viewpoint of compatibility with the resin, etc. The modified silicone oil is a silicone oil in which an organic group is introduced into the side chain of the polysiloxane, or both ends of the polysiloxane. And / or silicone oil having an organic group introduced at one end thereof. Examples of the organic group include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group. The modified silicone oil is preferably a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane.

  The compounding amount of the release agent is preferably 0.01 to 1 part by weight when the polycarbonate is 100 parts by weight. More preferably, it is 0.02-0.5 weight part.

  Furthermore, in order to improve hydrolyzability and thin film adhesion, the polycarbonate of the present invention can be blended with an epoxy compound as long as the object of the present invention is not impaired.

  Epoxy stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3,4-Epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy -6-Methylcyclohexylmethyl-6'-methylsiloxycarboxylate Bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxy dicyclopentadienyl ether, bis-epoxy ethylene glycol, bis-epoxy cyclohexyl Adipate, butadiene diepoxide, tetraphenylethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl- 5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl -2-methyl-3,4- Epoxycyclohexyl carboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate , 4,6-dimethyl-2,3-epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride Acids, diethyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyl dicarboxylate, etc. Is mentioned. Bisphenol A diglycidyl ether is preferable from the viewpoint of compatibility.

  Such an epoxy stabilizer is in the range of 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, and more preferably 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate. Desirably blended

  The blending of the polycarbonate of the present invention and various additives as described above includes, for example, a method of mixing with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc. This is not particularly limited, and any method may be used as long as it is a commonly used polymer blend method.

  The polycarbonate of the present invention thus obtained or the polycarbonate composition obtained by adding various additives to the polycarbonate as it is or after being once pelletized by a melt extruder, injection molding method, extrusion molding method, compression molding method, etc. The molded article can be formed by a generally known method.

  In order to increase the miscibility of the polycarbonate of the present invention and obtain stable physical properties, it is preferable to use a single screw extruder or a twin screw extruder in the melt extrusion. A method using a single screw extruder or a twin screw extruder does not use a solvent or the like, has a small environmental load, and can be preferably used from the viewpoint of productivity. In the case of the polycarbonate (co) polymer of the present invention, the melt kneading temperature of the extruder is usually 200 to 300 ° C, preferably 220 to 270 ° C. When the melt-kneading temperature is lower than 200 ° C., the melt viscosity of the polycarbonate (co) polymer is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate is likely to be deteriorated, and the color of the polycarbonate is yellowed or the molecular weight is lowered, so that the strength is deteriorated.

  When using an extruder, it is desirable to install a filter in order to prevent polycarbonate from being burned and foreign matters from being mixed during extrusion. The size (opening) of the filter for removing foreign substances depends on the required optical accuracy, but is preferably 100 μm or less. In particular, in the case of dislike mixing foreign substances, it is preferably 40 μm or less, more preferably 10 μm or less. Further, the extrusion of the polycarbonate (co) polymer is desirably performed in a clean room in order to prevent foreign matter from being mixed after the extrusion.

  Further, when cooling the extruded polycarbonate into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. There are various sizes (openings) of filters to be used, but those having a filter of 10 to 0.45 μm are preferable.

  The polycarbonate of the present invention is not limited to the above, and various known additives such as impact resistance improvers, flame retardants, flame retardant aids, inorganic fillers, antistatic agents are within the scope of the present invention. An agent, a foaming agent, and a dye / pigment may be contained. In addition, for example, a polymer alloy kneaded with a synthetic resin such as aromatic polycarbonate, aromatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, or a biodegradable resin such as polylactic acid or polybutylene succinate is used. You can also.

  The molding using the polycarbonate of the present invention can be usually performed in the same manner as the molding method of the bisphenol A type aromatic polycarbonate resin. In the case of injection molding, the mold temperature is preferably 30 ° C to 120 ° C, and the resin temperature is preferably 220 ° C to 330 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded. In the following, the physical properties and characteristics of polycarbonate were evaluated by the following methods.

(1) Reduced viscosity
Using an Ubbelohde viscometer, a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 was used as a solvent, the concentration was precisely adjusted to 1.00 g / dl, and a temperature of 30. Measurement was performed at 0 ° C. ± 0.1 ° C. The higher this number, the greater the molecular weight.

(2) Glass transition temperature (Tg)
Using a differential scanning calorimeter ("DSC822" manufactured by METTLER) with a sample of about 10mg, heated at a rate of temperature increase of 10 ° C / min, measured according to JIS K 7121 (1987). The extrapolated glass transition start temperature Tg, which is the temperature at the intersection of the straight line obtained by extending the line to the high temperature side and the broken line drawn at the point where the slope of the step change portion of the glass transition is maximized, was determined. .

(3) Impact strength
Test using Custom Scientific's minimax injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., a length of 31.5 mm, a width of 6.2 mm, and a thickness of 3.2 mm The piece was injection-molded, and a notch with a depth of 1.2 mm was provided with a notching machine to obtain a test piece.
About this test piece, the Izod impact strength with a notch at 23 degreeC was measured using the custom scientific minimax Izod impact tester "CS-183TI type". It shows that impact resistance strength is so large that this figure is large, and it is hard to break.

(4) Scratch hardness (pencil method) test Using a custom scientific mini-max injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., a length of 31.5 mm and a width of 6 .2mm, 0.8mm thick test piece is injection molded, and the pencil hardness is in the range of 6B to 6H in accordance with JIS K5600-5-4, using a scratch hardness (pencil method) tester manufactured by Co-Tech. Measured with 6B indicates that the surface hardness is low, and 6H indicates that the surface hardness is high.

(5) Weather resistance discoloration test Using a custom scientific mini-max injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., injection-molded length 31.5 mm, width 6. A test specimen with a thickness of 2 mm and a thickness of 0.8 mm was installed on the inclined surface of 45 degrees south in Yokkaichi, Yokkaichi City, Mie Prefecture, and the weather discoloration test was conducted from mid-January to mid-October 2006. Carried out. For the test pieces before and after the test, a color difference ΔE was measured using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller ΔE, the smaller the discoloration.

(6) Flammability test Using a custom scientific mini-max injection molding machine “CS-183MMX” at a temperature of 240 to 300 ° C., a length of 31.5 mm, a width of 6.2 mm, and a thickness A test piece having a thickness of 0.8 mm was injection-molded and measured according to a UL-94 standard horizontal flammability test (HB). However, the combustion state was confirmed by a method in which a test flame was applied to one end of the test piece for 30 seconds and removed. If the fire is extinguished without spreading over the entire specimen, it is judged as a self-extinguishing material. If it spreads, it is judged that it is easy to burn. At the same time, the color of the smoke was checked. White smoke is preferred over black smoke.

(7) Volatile organic component amount 1.5 g of the following polycarbonate pellets are set in a sample tube of a head space device (manufactured by Nippon Analytical Industrial Co., Ltd., JHS-100A), left to stand at 100 ° C. for 30 minutes, and He is used as a carrier gas. Volatiles were adsorbed on the adsorption tube. This adsorbed volatile matter was introduced into a gas chromatograph (manufactured by Yokogawa, HP5890A), helium was used as a carrier gas, the temperature was raised from 40 ° C. to 300 ° C. at 10 ° C./min, and detected by FID. Based on the obtained gas chromatogram and a calibration curve of heptane prepared in advance, the amount of volatile matter in terms of heptane was determined.

(8) Adhesiveness of thin film Mirror pellet mold with pellets dried at 120 ° C for 6 hours before injection molding, using an injection molding machine with clamping force of 75 tons, molding temperature of 265 ° C, and molded product shape of 100mm x 100mm x 3mm And was molded at a mold temperature of 110 ° C. The mold release property at the time of injection molding was good, and the molded product could be taken out without resistance. The appearance of the molded product was observed to observe the release unevenness pattern, and evaluated according to the following criteria. The molded article was subjected to aluminum vapor deposition so as to have an aluminum film thickness of 140 nm without performing primer treatment. The following evaluation was performed about the sample which heat-processed the obtained aluminum vapor deposition sample on the conditions of 70 degreeC x 1 month with the hot air dryer.

(8-1) Tape peelability:
About the heat-treated sample, scratches are made on the aluminum-deposited surface with a knife, and cello tape (registered trademark) is pasted on the surface, and the adhesion when the cello tape (registered trademark) is peeled off is determined according to the following criteria. evaluated. ○ The above was judged to be practically acceptable.
(Double-circle): The peeling of an aluminum vapor deposition film is hardly seen.
○: Slight peeling of the evaporated aluminum film is observed.
(Triangle | delta): Some peeling of aluminum vapor deposition film is seen.
X: Peeling of the aluminum deposited film is remarkable.

(8-2) Appearance:
The samples after the heat treatment were visually evaluated according to the following criteria. ○ The above was judged to be practically acceptable.
◎; The reflected image is clear and cloudy.
○: Reflected image is clearly reflected and slightly cloudy.
Δ: Reflected image is blurred and clouded by gas.
X: Clouding by gas is seen. The reflected image is bad.

In addition, the formic acid content of isosorbide used in the following Examples 1 to 7 was 5 ppm. The formic acid contained in isosorbide was quantified by the following method.
<Quantification of formic acid>
The amount of formic acid contained in isosorbide was measured by ion chromatography. 0.5 g of isosorbide was precisely weighed and collected in a 50 ml volumetric flask, and the volume was adjusted with pure water. An aqueous sodium formate solution was used as the standard sample, and the peak having the same retention time as that of the standard sample was formic acid.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As measurement columns, AG-15 was used as a guard column manufactured by Dionex, and AS-15 was used as a separation column. The measurement sample was injected into a 100 μl sample loop, and 10 mM NaOH was used as an eluent, and the measurement was performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor was used as the suppressor, and a 12.5 mM-H2SO4 aqueous solution was used as the regenerating solution.

[Example 1]
13.4-cyclohexanedimethanol (Eastman, hereinafter abbreviated as “1,4-CHDM”) with respect to 27.7 parts by weight (0.516 mol) of isosorbide (Rocket Fleure) 0 parts by weight (0.221 mol), diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “DPC”) 59.2 parts by weight (0.752 mol), and cesium carbonate (Wako Pure Chemical Industries, Ltd.) as a catalyst Manufactured) 2.21 × 10 ⁻⁴ parts by weight (1.84 × 10 ⁻⁶ mol) was put into a reaction vessel, and the heating bath temperature was 150 ° C. as the first step of the reaction under a nitrogen atmosphere. The raw material was dissolved with stirring as necessary (about 15 minutes). Subsequently, the pressure was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while the heating bath temperature was increased to 190 ° C. over 1 hour.

  After maintaining the entire reaction vessel at 190 ° C. for 15 minutes, as a second step, the pressure in the reaction vessel is set to 6.67 kPa, the heating bath temperature is increased to 230 ° C. in 15 minutes, and the generated phenol is removed. It was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was allowed to reach 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was extruded into water to obtain polycarbonate pellets. About the obtained polycarbonate, the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, weather discoloration, flammability, volatile organic component amount, and thin film adhesion were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.

[Example 2]
In Example 1, 19.7 parts by weight (0.363 mol) of isosorbide, 21.6 parts by weight of 1,4-CHDM (0.404 mol), 58.8 parts by weight of DPC (0.741 mol), and carbonic acid as a catalyst. It implemented similarly except having changed into cesium 2.19 * 10 <^-4> weight part (1.82 * 10 <^-6> mol). The obtained results are shown in Table 1.

[Example 3]
In Example 1, 35.9 parts by weight (0.674 moles) of isosorbide, 4.4 parts by weight of 1,4-CHDM (0.083 moles), 59.7 parts by weight of DPC (0.764 moles), carbonic acid as a catalyst. It implemented similarly except having changed to cesium 2.22 * 10 <^-4> weight part (1.87 * 10 <^-6> mol). The obtained results are shown in Table 1.

[Example 4]
In Example 1, 59.9 parts by weight of DPC (0.592 mol, cesium carbonate 2.23 × 10 ⁻⁴ parts by weight (1.45 as a catalyst) with respect to 40.1 parts by weight (0.581 mol) of isosorbide. This was carried out in the same manner except that it was changed to × 10 ⁻⁶ mol), and the obtained results are shown in Table 1.

[Example 5]
In Example 1, 25.8 parts by weight (0.480 moles), 58.6 parts by weight (0.734 moles) DPC, and 15.7 parts by weight (0.288 moles) isosorbide, and The same procedure was performed except that the catalyst was changed to 2.18 × 10 ⁻⁴ parts by weight (1.80 × 10 ⁻⁶ mol) of cesium carbonate. The obtained results are shown in Table 1.

[Example 6]
The following release agent was mixed with the polycarbonate obtained in Example 1 at a ratio of 0.1 part by weight with respect to 100 parts by weight of the polycarbonate, and a twin-screw extruder (Nippon Steel Works Model: TEX-30C) was used. Then, pelletization was performed at a cylinder temperature of 230 ° C. Using this pellet, the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, weather discoloration, flammability, amount of volatile organic components, and thin film adhesion were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.
<Release agent>
-Fatty acid ester (glycerin monostearate): Riken Vitamin brand name Riquemar S100A.

[Example 7]
The following release agent was mixed with the polycarbonate obtained in Example 1 at a ratio of 0.1 part by weight with respect to 100 parts by weight of the polycarbonate, and a twin-screw extruder (Nippon Steel Works Model: TEX-30C) was used. Then, pelletization was performed at a cylinder temperature of 230 ° C. Using this pellet, the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, weather discoloration, flammability, amount of volatile organic components, and thin film adhesion were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.
<Release agent>
Epoxy-modified silicone oil: manufactured by Shin-Etsu Silicon Co., Ltd., KF102, viscosity = 4000 cST. (Hereinafter also referred to as modified silicone)

[Comparative Example 1]
For bisphenol A type polycarbonate resin (Iupilon S3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.), the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, weather discoloration, flammability, volatile organic component amount by the above-described evaluation methods , And thin film adhesion was evaluated. The obtained results are shown in Table 1.

[Comparative Example 2]
To 100 parts by weight of bisphenol A-type polycarbonate resin (Iupilon S3000 manufactured by Mitsubishi Engineering Plastics), the following release agent was mixed at a ratio of 0.1 part by weight, and a twin-screw extruder (manufactured by Nippon Steel Works) : TEX-30C) and pelletizing at a cylinder temperature of 230 ° C. Using this pellet, the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, weather discoloration, flammability, amount of volatile organic components, and thin film adhesion were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.
<Release agent>
-Fatty acid ester (glycerin monostearate): Riken Vitamin brand name Riquemar S100A.

[Comparative Example 3]
To 100 parts by weight of bisphenol A-type polycarbonate resin (Iupilon S3000 manufactured by Mitsubishi Engineering Plastics), the following release agent was mixed at a ratio of 0.1 part by weight, and a twin-screw extruder (manufactured by Nippon Steel Works) : TEX-30C) and pelletizing at a cylinder temperature of 230 ° C. Using this pellet, the reduced viscosity, glass transition temperature, Izod impact value, pencil hardness, weather discoloration, flammability, amount of volatile organic components, and thin film adhesion were evaluated by the evaluation methods described above. The obtained results are shown in Table 1.
<Release agent>
Epoxy-modified silicone oil: manufactured by Shin-Etsu Silicon Co., Ltd., KF102, viscosity = 4000 cST. (Hereinafter also referred to as modified silicone)

Table 1 shows the following.
1) Examples 1 to 5, which are polycarbonate polymers of the present invention, are practically used for heat resistance, mechanical properties, weather resistance, and flame retardancy (self-extinguishing) as compared with Comparative Example 1 which is an aromatic polycarbonate resin. It is a sufficient value, has a high surface hardness, and at the same time has a small amount of volatile organic components, and has good adhesion of the deposited aluminum metal film.
2) In addition, in Examples 6 and 7 in which a release agent was blended, the heat resistance, mechanical strength, surface hardness and the like were hardly changed as compared with Example 1 in which no mold release agent was blended, but vapor deposition was performed. The adhesion of the aluminum metal film was further improved. This tendency is also shown in Comparative Examples 2 and 3 blended with the aromatic polycarbonate resin, but the adhesion of the aluminum metal film was better.
3) Examples 1 to 3 in which the molar ratio of isosorbide to 1,4-CHDM is in the range of 90/11 to 47/53 have good heat resistance and mechanical balance.

From the above results, the molded article having a metal / inorganic thin film made of the polycarbonate (co) polymer of the present invention using a plant-derived monomer has good environmental / petroleum resource conservation and has a volatile organic component. Low adhesion, good adhesion to metal / inorganic thin films, high surface hardness, good weather resistance, and good balance between glass transition temperature and impact strength, especially for light and magnetic disk and lighting lamp reflectors It can be suitably used for a molded article having a metal / inorganic thin film such as a vehicle mirror.

Claims (6)

The molded article which has a metal and an inorganic thin film which consists of a polycarbonate containing the structural unit derived from the dihydroxy compound represented by following General formula (1).

  The molded article having a metal / inorganic thin film according to claim 1, wherein the polycarbonate has a glass transition temperature of 80 ° C or higher.   The molded article having a metal / inorganic thin film according to claim 1 or 2, wherein the polycarbonate further contains a structural unit derived from an alicyclic dihydroxy compound.   The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound contained in the polycarbonate is 100: 0 to 30:70. The molded product having a metal / inorganic thin film according to claim 3, wherein the molded product has a range.   The ratio (mol%) of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound contained in the polycarbonate is 90:10 to 40:60. The molded product having a metal / inorganic thin film according to claim 3, wherein the molded product has a range. The molding having a metal / inorganic thin film according to any one of claims 1 to 5, comprising a fatty acid ester compound having at least one hydroxyl group and a molecular weight of 200 or more, or a silicone oil having an epoxy group. Goods.