JP2011001455A - Method for producing polycarbonate composition, composition produced by the method, and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a composition of a polycarbonate derived from a dihydric alcohol and a layered silicate, having excellent practical characteristics, and the composition, to provide a method for producing a polycarbonate composition further having good transparency, and the composition, and to provide a method for producing a composition of the polycarbonate derived from the dihydric alcohol, having good characteristics even when the layered silicate substantially not subjected to organization treatment is compounded.SOLUTION: The method for producing the polycarbonate composition containing 0.01-50 pts.wt. of the layered silicate (component B) having 50-200 meq./100 g of cation exchange capacity based on 100 pts.wt. of a polycarbonate (component A) is regulated as follows. (I) The component A contains ≥10 mol% of a carbonate constituent unit derived from the dihydric alcohol (component A-1) based on 100 mol% of the whole constituent units. (II) The component B is the layered silicate substantially not subjected to the organization treatment and having <1 pt.wt. of an organization agent based on 100 pts.wt. of the layered silicate. (III) The component B is dispersed in the component A by (III-1) a method for producing the component A by carrying out a melt polymerization reaction in the coexistence of the component B and the dihydric alcohol (component A-1) while stirring, and/or (III-2) a method for melt-kneading the component A with the component B by using an extruder.

Description

  The present invention relates to the production of a polymer composition comprising a polycarbonate having a structural unit derived from a specific difunctional alcohol (hereinafter sometimes referred to simply as “polycarbonate derived from a bifunctional alcohol”), and a layered silicate. The present invention relates to a method, a composition from the method and a molded article from the composition. Specifically, the composition is excellent in both rigidity and strength, toughness, and heat resistance, and thus has practically preferable characteristics and excellent transparency. Furthermore, particularly preferred difunctional alcohols from which carbonate building blocks are derived can be produced from materials originating from organisms such as plants. Therefore, according to the present invention, there is provided a bifunctional alcohol-derived polycarbonate material that is excellent in practical properties and can be adapted to the reduction and increase in price of petroleum resources that are of concern in the future.

  In recent years, in order to respond to the formation of a sustainable development society and higher prices of petroleum-derived raw materials, there is a strong demand for plastic materials from raw materials that can be easily manufactured from substances originating from organisms such as plants. . As such a plastic material, there is a polycarbonate derived from a bifunctional alcohol. However, since polycarbonates derived from bisphenol A, which are widely used, have high practical strength and toughness, generally, polycarbonate materials are generally expected to have the same characteristics. Therefore, improvement of practical strength and toughness is often required even for polycarbonate derived from a bifunctional alcohol.

  On the other hand, a resin composition in which a so-called organic layered silicate is finely dispersed in a resin, represented by a layered silicate in which interlayer ions of the layered silicate are ion-exchanged with various organic onium ions, has already been widely used. Research and suggestions have been made. This is because such a resin composition is expected as a technique capable of improving mechanical properties, particularly rigidity, while maintaining the surface appearance and specific gravity of the molded article in good condition.

  In a composition in which an organic layered silicate is blended with polycarbonate, the present applicant has already obtained an affinity between the polycarbonate, the organic layered silicate and the polycarbonate and a compound having a hydrophilic component (hereinafter referred to as the compound). A resin composition comprising a simple composition (sometimes referred to as a “compatibilizer”) has been proposed (see Patent Document 1). According to this document, it is known that a composition comprising a polycarbonate and an organically modified layered silicate can improve rigidity and thermal stability by blending such a compatibilizing agent.

  However, organic onium ions have relatively poor thermal stability and can decompose polycarbonate. Therefore, the composition containing the ions may also cause problems such as low thermal stability and gas generation during molding. As one method for solving such a problem, a layered silicate-containing composition capable of reducing or not containing organic onium ions is required. On the other hand, the present situation is that even if layered silicate is simply blended, sufficient effects expected for blending such silicate are not exhibited.

  The present applicant has proposed a polycarbonate resin composition polymerized in the presence of a specific layered silicate (see Patent Document 2). However, such proposals did not provide sufficient knowledge about polycarbonates derived from bifunctional alcohols with respect to polycarbonates by interfacial polycondensation.

  With respect to polycarbonate derived from a bifunctional alcohol, it is derived from a diol having a specific cyclic ether skeleton represented by 1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide” in the present specification). It is known that certain polycarbonates can be combined with montmorillonite or the like (see Patent Document 3).

  In addition, a reaction mixture is formed from a nanomaterial, a solvent, a dihydroxy compound, and an activated carbonate, and in the presence of the solvent, the dihydroxy compound and the activated carbonate are polymerized to form a polycarbonate nanocomposite. Methods and nanocomposites from the production methods are known (see Patent Literature 4 and Patent Literature 5). This document discloses, with a specific example, that a nanomaterial surface treatment is important, and a nanocomposite using a silica dispersion treated with isosorbide as a dihydroxy compound and a specific silane compound as a nanomaterial.

  Polymer nanocomposites containing untreated phyllosilicates, delamination agents, swelling agents, and polyorganosiloxane-polycarbonate copolymers are known (see Patent Document 6). More specifically, the literature discloses low molecular weight polycarbonate as such a swelling agent. There is an example of isosorbide as a dihydroxy compound from which the low molecular weight polycarbonate is derived.

  However, none of the conventional techniques has yet been proposed to propose a polycarbonate composition derived from a bifunctional alcohol excellent in both rigidity and strength, toughness, and heat resistance.

International Publication No. 2003/010235 Pamphlet International Publication No. 2005/082972 Pamphlet International Publication No. 2008/093860 Pamphlet International Publication 2008/042496 Pamphlet International Publication No. 2008/091413 Pamphlet Special table 2007-514854 gazette

  An object of the present invention is to solve the above-mentioned problems and to provide a method for producing a composition of a bifunctional alcohol-derived polycarbonate and a layered silicate, which has excellent practical properties, and such a composition. It is another object of the present invention to provide a method for producing the polycarbonate composition having good transparency and such a composition. Another object of the present invention is to provide a method for producing a polycarbonate composition derived from a bifunctional alcohol, which has good characteristics even when a layered silicate that is not substantially organically treated is blended. In addition, another object of the present invention is to provide a method for producing a polycarbonate composition in which the raw material for deriving the polycarbonate can be produced from a substance originating from a living organism such as a plant.

  In order to achieve such an object, the present inventors have conducted extensive studies, and as a result, combined a bifunctional alcohol-derived polycarbonate and a layered silicate, particularly a layered silicate that has not been substantially organically treated, to achieve a specific purpose. It has been surprisingly found that the above problems can be solved by applying the production method. When a layered silicate is blended with a bisphenol A type polycarbonate or the like that is generally used, strength and rigidity generally decrease. From this fact, it was not expected that the layered silicate exerts an effect on improvement of strength, toughness and the like. However, the present inventors have surprisingly found that a result contrary to the expectation can be obtained, and further studies have been made to complete the present invention.

The object of the present invention is (i) layered silicate (component B) 0.01 to 50 parts by weight having a cation exchange capacity of 50 to 200 meq / 100 g per 100 parts by weight of polycarbonate (component A). A process for producing a polycarbonate composition comprising
(I) The component A contains a carbonate structural unit derived from a difunctional alcohol (component A-1) in an amount of 10 mol% or more in 100 mol% of all the structural units,
(II) The component B is a layered silicate that is substantially not organically treated with less than 1 part by weight of the organic agent per 100 parts by weight of the layered silicate,
(III) The component B is (III-1) a method for producing the component A by a melt polymerization reaction with stirring in the presence of the component B and a difunctional alcohol (component A-1) (hereinafter simply referred to as “component B”). And / or (III-2) a method of melt-kneading component A and component B using an extruder (hereinafter sometimes simply referred to as “method-2”). Is achieved by the production method characterized by being dispersed in the component A.

  In the polycarbonate composition of the present invention, the proportion of each component is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, with respect to 100 parts by weight of the A component. More preferably, it is 1-10 weight part. If the B component is less than the lower limit of the range, the improvement in rigidity and strength is not sufficient, and if the B component exceeds the upper limit of the range, the moldability and thermal stability are lowered, and a molded product excellent in practicality is obtained. It becomes difficult to be.

  The component B of the present invention is a layered silicate that is substantially not organically treated and has an organic agent of less than 1 part by weight per 100 parts by weight of the layered silicate. Examples of such organic agents include organic cations such as organic onium ions and imidazolium ions, and coupling agents such as organic titanate compounds and silane coupling agents. The composition ratio of the component B of the present invention is based on the actual amount of layered silicate, that is, the inorganic content.

  Usually, the blending of the inorganic filler often reduces the thermal stability of the polycarbonate and lowers the toughness represented by breaking strain and impact strength. However, the polycarbonate composition of the present invention is excellent in thermal stability, and the toughness as well as the rigidity and strength is improved by the affinity between the A component and the B component. Such an effect cannot be expected from the widely used bisphenol A type polycarbonate.

  As described above, as a method for producing a composition for effectively exhibiting the affinity between the component A and the component B, the method-1 and the method-2 can be mentioned. The former method-1 is a method in which the B component is dispersed in the monomer by utilizing the affinity between the bifunctional alcohol as a monomer and the layered silicate, and the monomer is polymerized in such a dispersed state. By dispersing the layered silicate in a monomer having a low melt viscosity, it is considered that the finely dispersed layered silicate and the resulting polymer are firmly adhered. In the latter method-2, it is considered that the adhesion between the layered silicate finely dispersed by a strong shearing force and the matrix polymer is strengthened. Moreover, the said structure (i) includes the method of melt-kneading the composition obtained by the method-1 with an extruder, and obtaining a composition.

  One of the preferred embodiments of the present invention is as follows. (Ii) The component A-1 is a bifunctional alcohol that dissolves in water at 20 ° C. in an amount of 1% by weight or more. It is. A polycarbonate obtained from such a monomer having good hydrophilicity has better affinity with the layered silicate. Furthermore, also in the above-mentioned method-1, since the layered silicate is hydrophilic, good dispersion in the monomer is obtained, which is preferable.

  One of the preferred embodiments of the present invention is the above-mentioned constitution (i) or (ii) wherein (iii) the carbonate constitutional unit derived from the component A-1 is contained in 60 mol% or more in 100 mol% of all carbonate constitutional units. This is a method for producing a polycarbonate composition.

  According to this configuration (iii), the A component and the B component have higher affinity, so that the characteristics of the present invention such as compatibility of rigidity and strength are more effectively exhibited. The carbonate constitutional unit derived from the component A-1 is more preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, in 100 mol% of all carbonate constitutional units. Most preferably, the polycarbonate is composed solely of carbonate structural units derived from the component A-1.

  One of the preferred embodiments of the present invention is that (iv) the component A-1 is a group consisting of a cyclic ether diol represented by the following formula (1) and a linear aliphatic diol having 2 to 6 carbon atoms. It is a manufacturing method of the polycarbonate composition of the said structure (i)-(iii) which is the at least 1 sort (s) of bifunctional alcohol selected.

  Such a preferred A-1 component has high hydrophilicity and good affinity with the layered silicate. As a result, good dispersion and adhesion of the layered silicate can be obtained.

  More preferably, (v) the component A-1 is a method for producing a polycarbonate composition of the constitution (iv), which is a cyclic ether diol represented by the formula (1). The carbonate structural unit derived from the above formula (1) is more preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%, in 100 mol% of all carbonate structural units. Most preferred is a polycarbonate consisting only of carbonate constituent units derived from the formula (1).

  One of the preferred embodiments of the present invention is (vi) a method for producing a polycarbonate composition having the above-mentioned constitutions (i) to (v), wherein the component A has a viscosity average molecular weight of 4,000 to 40,000. is there. The viscosity average molecular weight of the component A is more preferably 10,000 to 30,000, still more preferably 12,000 to 25,000. By satisfying such a range, a polycarbonate composition which is excellent in all of moldability, rigidity and strength and suitable as various molding materials by itself can be obtained. The viscosity average molecular weight is a value calculated using the Schnell equation widely used for polycarbonate resins, as will be described later.

  One of the preferred embodiments of the present invention is as follows: (vii) In the method of (III-1), a part or all of the A-1 component and the B component are premixed, and the B component and the A-1 component are mixed. Is a method for producing a polycarbonate composition having the above constitutions (i) to (vi), which is a method for producing the component A by stirring and polymerizing while stirring. In the above method-1, it is more preferable to perform polymerization after sufficiently dispersing the component B in the monomer. As a result of such dispersion, a finer dispersion of the layered silicate and a strong adhesion with the resulting polymer are achieved, resulting in a composition with better mechanical properties and transparency.

  One of the preferred embodiments of the present invention is (viii) solution-mixing the composition obtained by the method of (III-1) and / or (III-2) above in the presence of a solvent of component A. The method for producing a polycarbonate composition having the above constitutions (i) to (vii), wherein a composition in which the B component is dispersed in the A component is produced by removing the solvent. According to this method, good dispersion that cannot be obtained by simple solution mixing is achieved, and a composition excellent in transparency and particularly suitable for a cast film can be obtained.

  Another aspect of the present invention is: (ix) a polycarbonate composition produced from the production method of the above constitutions (i) to (viii), (x) a molding formed by melt-molding the polycarbonate composition of the constitution (ix). Product, and (xi) a molded product obtained by molding the polycarbonate composition having the configuration (ix) by a solution casting method.

  The polycarbonate composition obtained by the production method of the present invention has good rigidity, thermal stability, surface hardness and surface smoothness. Therefore, the composition 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, and miscellaneous goods. The above properties of the composition are suitable for various thin-walled molded products. Specific examples of thin-walled molded products include various housing molded products such as battery housings, lens barrels, memory cards, speaker cones, disk cartridges, surface light emitters, mechanical parts for micromachines, nameplates, personal computer housings, CD and DVD drive Light diffuser for trays and chassis, trays and chassis for copying machines, direct backlights for liquid crystal devices (especially light diffusers for direct backlights for large liquid crystal display devices (large liquid crystal televisions of 15 inches or larger)), light diffusion Examples thereof include a resin window and an IC card. Therefore, the industrial effect that it produces is exceptional.

It is a figure which shows the outline | summary of lamination | stacking hot press molding.

The details of the present invention will be further described below.
<A component: About polycarbonate>
The A component of the present invention contains a carbonate constituent unit derived from a bifunctional alcohol (component A-1) in an amount of 10 mol% or more in 100 mol% of all the constituent units.
A-1 component contains various linear diol and alicyclic diol, and the bifunctional alcohol containing an aromatic ring. The polycarbonate of A component may contain the carbonate structural unit derived | led-out from components other than A-1 component represented by the aromatic diol component.

  Examples of the linear diol of the A-1 component include those having 2 to 6 carbon atoms such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. A linear aliphatic diol is preferably exemplified.

As the alicyclic diol of the component A-1, cyclic ether diol of the following formula (1), cyclohexanedimethanol, cyclohexanediol, tricyclo (5.2.1.0 ^2,6 ) decanedimethanol, norbornane dimethanol , Decalin-2,6-dimethanol, spiroglycol, p-menthane-1,8-diol, 1,2-bishydroxymethyl-3,4-dimethyl-6- (2-methylpropyl) cyclohexane, 1,2 -Bishydroxymethyl-4- (2-methylpentyl) cyclohexane, 1,1-bis (hydroxymethyl) cyclopropane and the like are preferably exemplified.

  Among them, preferred alicyclic diols include cyclic ether diols of the above formula (1), cyclohexanedimethanol, 1,2-bishydroxymethyl-3,4-dimethyl-6- (2-methylpropyl) cyclohexane, and 1,1-bis (hydroxymethyl) cyclopropane may be mentioned. Such a suitable alicyclic diol satisfies the requirement of the above constitution (ii).

  Examples of the bifunctional alcohol containing an aromatic ring include benzene dimethanol, benzene diethanol, biphenyl dimethanol, 2,6-bis (hydroxymethyl) -p-cresol, and 2,4-bis (hydroxymethyl) -1. , 3,5-trimethylbenzene, 1,3-bis (1-hydroxy-1-methylethyl) benzene and the like.

  The more preferable A-1 component of the present invention is selected from the cyclic ether diol represented by the above formula (1) and the straight chain aliphatic diol having 2 to 6 carbon atoms as in the above configuration (iv). At least one bifunctional alcohol.

  Specific examples of the cyclic ether diol of the above formula (1) include isosorbide, isomannide and isoidide represented by the following formulas (b), (c) and (d).

  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. The purification method is not particularly limited, and known methods such as chromatographic separation and distillation can be used.

  In particular, a polycarbonate in which the structural unit of the formula (1) is a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol) is preferable as the component A. 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. . In addition, when manufacturing a polycarbonate from this isosorbide, it is preferable that it is a crystallized solid as a raw material form. The method for obtaining such crystalline isosorbide is not particularly limited, and it is possible to use one obtained by cooling molten isosorbide to form crystalline isosorbide, or by adding an organic solvent to an aqueous solution of isosorbide and crystallizing isosorbide.

  A diol component other than the component A-1 includes an aromatic diol. Examples of the aromatic diol include 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol A”) and 4,4′-biphenol. 4,4′-bis (2,6-dimethyl) diphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1- Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 ′-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) decane, and 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene.

  The aromatic diol can also contain polyorganosiloxane units. The polycarbonate containing the unit is preferably a copolymer having in its molecule a polyorganosiloxane moiety composed of a structural unit represented by the following general formula (α).

Here, R ³¹ , R ³² , R ³³ and R ³⁴ represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different, and is preferably a methyl group. R ³⁵ represents a divalent organic residue derived from an aliphatic or aromatic compound, preferably an o-allylphenol residue (formula (α) is represented by the following formula (α-1)), p-hydroxy A styrene residue (formula (α) is represented by the following formula (α-2)), a 4-allyl-2-methoxyphenol residue (formula (α) is represented by the following formula (α-3)), and It is an isopropenylphenol residue (formula (α) is represented by the following formula (α-4)).

  Among the above, an o-allylphenol residue is particularly preferable. In the above formulas (α) and (α-1) to (α-4), n represents the degree of polymerization of the structural units in parentheses, and the structural units may be a mixture of two or more. The range of n is 1 to 500, preferably 5 to 200, more preferably 10 to 70, and still more preferably 15 to 30 in the number average value. The upper limit of the number of each component n is preferably 500, more preferably 200, and still more preferably 70.

  Particularly suitable as the component A-1 of the present invention is selected from the cyclic ether diol represented by the formula (1) and the linear aliphatic diol having 2 to 6 carbon atoms as described in the above-mentioned configuration (iv). Among them, the cyclic ether diol represented by the formula (1) is preferable in terms of the heat resistance of the polycarbonate, and isosorbide is particularly preferable.

  The polycarbonate of component A of the present invention can be produced from a difunctional alcohol and a carbonic acid diester by a melt polymerization method. Other diols can be used instead of some difunctional alcohols as required.

The reaction temperature in the melt polymerization method is preferably in the range of 180 ° C. to 280 ° C., more preferably in the range of 180 ° C. to 260 ° C. in order to suppress decomposition of the ether diol and obtain a highly viscous polymer with little coloration. 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.

  The reaction may be carried out either continuously or batchwise. The reactor used for melt polymerization is a vertical reactor equipped with an anchor-type stirring blade, a Max blend stirring blade, or a helical ribbon-type stirring blade, or a horizontal reaction equipped with a paddle blade, lattice blade, or spectacle blade. Any of the devices may be used. Furthermore, an extruder type equipped with a screw may be used. In the case of a continuous system, it is preferable to use a combination of such reactors as appropriate.

  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. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, bis (methyl salicyl) carbonate, bis (ethyl salicyl) carbonate, dimethyl carbonate, diethyl carbonate, and Examples include dibutyl carbonate. Of these, diphenyl carbonate is preferred in terms of reactivity and cost.

  The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98, more preferably 1.01 to 0.98, with respect to the total diol including the ether diol of the formula (a). More preferably, it is 1.01-0.99. 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.

  As a polymerization catalyst, the normal polymerization catalyst used when manufacturing a polycarbonate by a melt-polymerization method can be used. However, in the present invention, when the above-mentioned method-1, that is, the melt polymerization of the A-1 component is performed in the presence of the B component, it is preferable to reduce or not include the polymerization catalyst as much as possible. This is because the component B has catalytic activity, so that the alcohol or phenol distillation rate at the initial stage of the reaction becomes too high, and as a result, the reaction is difficult to control.

  Examples of the polymerization catalyst used for the melt polymerization include (i) alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and sodium salt or potassium salt of dihydric phenol, (Ii) alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, and magnesium hydroxide; and (iii) tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine, and triethylamine. And nitrogen-containing basic compounds. These may be used alone or in combination of two or more. When the component A is produced by polymerization in the absence of a layered silicate, 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.

When the component A is produced by polymerization in the absence of a layered silicate, the amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ^{− with respect} to 1 mol of the carbonic acid diester component. It is selected in the range of ³ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁴ equivalents. The reaction system is preferably maintained in an atmosphere of a gas inert to the raw materials, reaction mixture, and reaction product typified by nitrogen. Argon can be mentioned as inert gas other than nitrogen. Furthermore, you may add additives, such as antioxidant, as needed.

  The polycarbonate produced by the melt polymerization reaction usually has a terminal structure as a residue derived from a hydroxy group or a carbonic acid diester. The terminal structure of the A component of the present invention may also be a residue derived from a hydroxy group or a carbonic acid diester. However, in the component A of the present invention, other end groups can be introduced separately as long as the characteristics are not impaired. Such end groups can be introduced by adding the corresponding monohydroxy compound during polymerization. The terminal group is preferably a terminal group represented by the following formula (2) or (3).

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、または前記式（４）であり、特に炭素原子数８〜２０のアルキル基、または前記式（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、中でも単結合、および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 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, it is 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, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, more preferably from the group consisting of a single bond, an ether bond, and an ester bond. At least one kind of bond selected, 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 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 carbon And at least one group selected from the group consisting of an alkyl group having 1 to 10 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. Are 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. The polycarbonate (component A) used in the present invention has a carbonate constitutional unit obtained from a renewable resource ether diol represented by the above formula (a) in the main chain structure, so that monohydroxy used for terminal structure introduction The compounds are also preferably raw materials obtained from renewable resources such as plants. 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 molded article made of the polycarbonate composition of the present invention can obtain a reduction in hygroscopicity and surface modification effects such as antifouling properties and abrasion resistance. The content of these end groups is preferably from 0.3 to 9.0% by weight, more preferably from 0.3 to 7.5% by weight, still more preferably from 0.5 to 9.0%, based on the polymer main chain structure. 6.0% by weight.

  In the present invention, when the melt polymerization is carried out using (III-1) in the above-mentioned constitution (i), that is, the method-1, the layered silicate which is not substantially organically treated is used as the raw material A- It is carried out by supplying it to the reactor together with one component. In the reaction, it is preferable to melt the monomer and carbonic acid diester and sufficiently disperse the layered silicate in the molten state. Further, as described in the above configuration (vii), the method (III-1), that is, the method-1, is a method in which a part or all of the A-1 component and the B component are mixed in advance, In the coexistence of the above, a method for producing the component A by carrying out a melt polymerization reaction with stirring is preferred. In the preliminary mixing of the A-1 component and the B component, it is preferable to mix the liquid A-1 component and the B component. When the A-1 component is liquid at normal temperature, it is mixed with the B component at a temperature higher than normal temperature, and when it is solid at normal temperature, it is mixed with the B component at a temperature higher than the melting point. Various mixing means can be used for such mixing. In the case where the viscosity of the component A-1 is relatively low at 10,000 mPa · s or less, for example, a homomixer, a high-pressure homogenizer, a bead mill (for example, Ultra Apex Mill manufactured by Kotobuki Industries Co., Ltd.), an ultrasonic stirrer, a high pressure Collision type disperser (for example, Ultimateizer (trade name) sold by Sugino Machine Co., Ltd.), thin film swirl type high speed mixer (for example, TK Filmics (trademark) manufactured by Primix Co., Ltd.), and various statics Mixers and motionless mixers can be used. In the case where the viscosity of the A-1 component is relatively high, exceeding 10,000 mPa · s, for example, a twin-shaft planetary stirrer (for example, TK Hibismix (trademark) manufactured by Primix Co., Ltd.), anchor mixer, planetary Type agitation / deaerator (for example, Mazerustar (trade name) sold by Kurashiki Boseki Co., Ltd.), ultramixer (for example, manufactured by Mizuho Kogyo Co., Ltd.), fluid split mixing mixer (for example, ATEC Japan-made distro mix (product) Name)), roll mill, ball mill, etc. can be used. The viscosity of the high-viscosity dispersion when using such an apparatus is preferably 10,000 to 500,000 mPa · s, more preferably 20,000 to 100,000 mPa · s.

  Furthermore, after mixing the solution which dissolved A-1 component in polar solvents like water, and B component and disperse | distributing uniformly, a polar solvent can be removed and it can also utilize for a polymerization reaction. In such a case, the above-mentioned mixing means corresponding to a relatively low viscosity is preferably used.

As described above, the polycarbonate (A component) used in the present invention has a viscosity average molecular weight of preferably 4,000 to 40,000, more preferably 10,000 to 30,000, and still more preferably 12,000 to 25,000. It is. The viscosity average molecular weight of the polycarbonate is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The intrinsic viscosity is obtained from the obtained specific viscosity (η _SP ) by the following formula, and the viscosity average molecular weight M is calculated from the intrinsic viscosity using the Schenll equation.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  In addition, calculation of the viscosity average molecular weight in the composition containing B component is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

<About layered silicate of component B>
Layered silicate of component B is composed of a layer consisting of the octahedral sheet structure including SiO ₄ tetrahedra sheet structure and Al made of SiO ₂ chain, Mg, and Li, etc., distribution of exchangeable cations between the layers Silicate (silicate) or clay mineral (clay). These silicates (silicates) or clay minerals (clays) are typified by smectite minerals, vermiculite, halloysite, and swellable mica. Specifically, examples of the smectite mineral include montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and stevensite. Examples of the swellable mica include Li type fluorine teniolite, Na type fluorine teniolite, and Na type tetrasilicon. Examples include swellable synthetic mica such as fluorine mica and Li-type tetrasilicon fluorine mica. These layered silicates can be either natural products or synthetic products. The synthetic product is produced by, for example, hydrothermal synthesis, melt synthesis, or solid reaction.

  Among the layered silicates, from the viewpoint of cation exchange capacity, they have swelling properties such as smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica. Fluorine mica is preferably used, and montmorillonite obtained by purifying bentonite and synthetic fluorine mica are more preferable in terms of purity. Among these, synthetic fluorine mica that can provide good mechanical properties is particularly preferable.

  The cation exchange capacity (also referred to as cation exchange capacity) of the layered silicate that is the component B of the present invention is required to be 50 to 200 meq / 100 g, preferably 80 to 150 meq / 100 g, More preferably, it is 100-150 meq / 100g. The cation exchange capacity is measured as a CEC value by the modified Schöllenberger method, which is a domestic official method as a soil standard analysis method.

The outline of this method is as follows. Fill the infiltration tube of a soil leaching device with a length of 12 cm and an inner diameter of 1.3 cm with a layered silicate sample to a thickness of about 8 cm, and use 100 ml of 1N aqueous ammonium acetate solution with a pH of 7 for infiltration over 4-20 hours. And leaching exchange cations. It is then washed with 100 ml of 80% methanol at pH 7 to remove excess ammonium acetate. Next, the sample is washed with 100 ml of a 10% aqueous potassium chloride solution, and ammonium ions (NH ₄ ⁺ ) adsorbed on the sample are exchanged and leached. Finally, NH ₄ ⁺ in the leachate is quantified by steam distillation or Conway microdiffusion, and CEC is calculated. What is marketed as a glass set can be used for the soil leaching device. The Schoenberger method, which is the basis of the improved method, is described in Soil Sci. 59, 13-24 (1945).

  In order to obtain good dispersibility in the composition, the cation exchange capacity of the layered silicate in the component B is required to be 50 meq / 100 g or more, but if it exceeds 200 meq / 100 g, the heat deterioration of the polycarbonate Becomes larger. The layered silicate preferably has a pH value of 9 to 11.5. When the value of pH is greater than 11.5, the thermal stability of the composition of the present invention tends to decrease.

<About other additives>
If desired, various additives other than the above components A and B may be added to the polycarbonate composition of the present invention as an additional component.

(I) Phosphorus stabilizer It is preferable that the polycarbonate composition of the present invention further contains a phosphorus stabilizer. Such phosphorus stabilizers greatly improve the thermal stability during production or molding. As a result, mechanical properties, hue, and molding stability are improved. Such phosphorus stabilizers include various phosphite compounds, phosphate compounds, phosphonite compounds, and phosphonate 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. In particular, a pentaerythritol type phosphite compound is preferably blended as the phosphite compound.

  More specifically, examples of the pentaerythritol 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, bis (Nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like can be mentioned. Among them, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl) are preferred. Phenyl) pentaerythritol diphosphite and bis (2,6-di -tert- butyl-4-methylphenyl) pentaerythritol phosphite.

  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 monoorthoxenyl 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.

Further, the phosphorus stabilizer of the present invention includes a tertiary phosphine represented by triphenylphosphine.
Said phosphorus stabilizer can be used individually or in combination of 2 or more types. The compounding amount of the phosphorus stabilizer is preferably 0.0001 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of the component A. Part.

(Ii) Hindered phenol stabilizer and other antioxidants The hindered phenol stabilizer is effective in preventing heat aging of the polycarbonate composition. The A component of the present invention is preferably blended because it has a property of being easily subjected to oxidative degradation as compared with a general-purpose aromatic polycarbonate. Hindered phenol stabilizers include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′- Methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N'-hexamethylenebis- (3,5- -Tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [methylene -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used.

  In addition, antioxidants other than the hindered phenol stabilizers can be used. Examples of such other antioxidants include lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Are described in JP-A-7-233160), and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthio And sulfur-containing stabilizers such as propionate. The hindered phenol stabilizers can be used alone or in combination of two or more. The amount of these stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of component A.

(Iii) Polymer other than component A The polycarbonate composition of the present invention may contain other polymers in addition to the polycarbonate of component A as long as the properties of the present invention are not impaired. Such other polymer is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, and still more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the component A. Examples of such other polymers include (iii-1) polycarbonate other than component A, (iii-2) thermoplastic polymer other than polycarbonate, and (iii-3) rubbery polymer.

(Iii-1) The polycarbonate other than the component A may be any polymer as long as it is a polymer that does not contain the carbonate unit of the formula (1), but the main component is a carbonate constituent unit derived from bisphenol A. Bisphenol A type polycarbonate is preferred. The molecular weight of the polycarbonate other than the component A is preferably 1 × 10 ^{4 to} 5 × 10 ⁵ and more preferably 1.2 × 10 ^{4 to} 5 × 10 ⁴ in terms of viscosity average molecular weight.

  (Iii-2) The thermoplastic polymer other than polycarbonate is not particularly limited. For example, polyethylene (including various copolymers such as LLDPE) and polypropylene (modified with maleic anhydride modification and various graft modifications). Various olefinic polymers and copolymers (including polymers and copolymers), polystyrene, acrylonitrile-styrene copolymers, methylmethacrylate-styrene copolymers, styrene-isoprene copolymers, and phenylmethacrylate-styrene copolymers, polymethylmethacrylate and the like Aromatic polyesters such as copolymers, polyamides, polyphenylene ethers, polyalkylene terephthalates and polyalkylene naphthalates. Arylate), aliphatic polyesters such as polylactic acid and polybutylene succinate, polyurethane, polysulfone, polyethersulfone, cyclic polyolefin, polyetherimide, polyamideimide, polyimide, polyaminobismaleimide, and polyetheretherketone Including.

  (Iii-3) The rubbery polymer is preferably a rubbery graft copolymer in which a graft chain is bonded to a rubber substrate. Here, the rubber substrate is a polymer that has rubber elasticity and has a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower, which becomes a graft trunk of the graft polymer. . Such rubber substrates include, for example, polybutadiene, polyisoprene, styrene-butadiene random or block copolymers, acrylonitrile-butadiene copolymers, acrylic acid alkyl esters or copolymers of methacrylic acid alkyl esters and butadiene, ethylene and α-olefins. Examples include copolymers, copolymers of ethylene and unsaturated carboxylic acid esters, copolymers of ethylene and aliphatic vinyl, ethylene, propylene and non-conjugated diene terpolymers, acrylic rubbers, and silicone rubbers. Preferred examples of the monomer for deriving the graft chain of the rubber graft copolymer include aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid esters, and methacrylic acid esters. Specific examples of the rubbery graft copolymer include SB (styrene-butadiene) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MBS (methyl methacrylate-butadiene-styrene) copolymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene). Copolymer, MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) copolymer, MA (methyl methacrylate-acrylic rubber) copolymer, MAS (methyl methacrylate-acrylic) Rubber-styrene) copolymer, methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate Rate - acrylic-butadiene rubber - styrene copolymers, and methyl methacrylate - and the like (acrylic silicone IPN rubber) copolymer. The rubber substrate is preferably 50% by weight or more in 100% by weight of the rubbery graft copolymer, and more preferably in the range of 55 to 85% by weight.

(Iv) Release agent A release agent can be mix | blended with the polycarbonate composition of this invention as needed. The polycarbonate composition of the present invention often requires high dimensional accuracy. Therefore, the polycarbonate composition is preferably excellent in releasability. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, and beeswax. The release agent is preferably 0.005 to 2 parts by weight with respect to 100 parts by weight of component A.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). In the fatty acid ester, the acid value is preferably 20 or less (can take substantially 0), the hydroxyl value is in the range of 0.1 to 30, and the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

(V) Flame retardant The polycarbonate composition of the present invention may be required to have improved flame retardancy. In such a case, a flame retardant, a flame retardant aid, and an anti-dripping agent are blended. Examples of the flame retardant of the present invention include halogenated flame retardants such as brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene, and phosphate esters such as monophosphate compounds and phosphate oligomer compounds. Organic phosphorus flame retardants other than phosphate ester flame retardants such as flame retardants, phosphinate compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonate alkali (earth) metal salts, borate metal salts And flame retardants, organometallic salt flame retardants such as metal stannate flame retardants, silicone flame retardants, ammonium polyphosphate flame retardants, and triazine flame retardants. Examples of the flame retardant aid include sodium antimonate and antimony trioxide. A typical example of the anti-dripping agent is polytetrafluoroethylene having fibril forming ability. Such polytetrafluoroethylene is blended in order to improve the dispersibility of polytetrafluoroethylene in the conductive polycarbonate composition, in order to improve the dispersibility of the polytetrafluoroethylene, or a dispersion obtained by co-aggregating the dispersion and another polymer, or a dispersion. Alternatively, it may be a premix of a solid and a sliding inorganic filler represented by talc.

  The blending amount of the flame retardant is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the component A, and the blending amount of the flame retardant aid is 0.01 to 10 parts by weight with respect to 100 parts by weight of the component A. Preferably, the amount of the anti-dripping agent (as the net amount of polytetrafluoroethylene having fibril-forming ability) is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of component A.

(Vi) Hydrolysis improver The polycarbonate composition of the present invention can be blended with various hydrolysis improvers within the range not impairing the object of the present invention for the purpose of improving the hydrolysis resistance of the component A. . Examples of such compounds include epoxy compounds, oxetane compounds, silane compounds, and phosphonic acid compounds, with epoxy compounds and oxetane compounds being particularly preferred. Examples of the epoxy compound include an alicyclic epoxy compound represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, and a silicon atom-containing epoxy represented by 3-glycidylpropoxy-triethoxysilane. The compound is preferably exemplified. The content of the hydrolysis improver is preferably in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of component A.

(Vii) Ultraviolet Absorber The polycarbonate composition of the present invention can contain an ultraviolet absorber in order to maintain its hue for a long time. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, benzotriazole compounds include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1 , 3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -Benzotriazol-2-yl] -4-methyl-6-tert-butylphenol and 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol] and the like are preferably exemplified, and as the hydroxyphenyltriazine-based compound, 2- (4,6-diphenyl-1,3,5-triazine-2 -Yl) -5-[(hexyl) oxy] phenol is preferably exemplified, and 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) is preferred as the cyclic imino ester compound. Illustrative examples of cyanoacrylate compounds include 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl). A preferred example is oxy] methyl] propane.

  Furthermore, the ultraviolet absorber is a polymer type copolymer obtained by copolymerizing such an ultraviolet absorbing monomer and a monomer such as alkyl (meth) acrylate by taking the structure of a monomer compound capable of radical polymerization. An ultraviolet absorber may be sufficient. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Among the above, as a suitable ultraviolet absorber when a good hue is required, a cyclic imino ester compound and a cyanoacrylate compound are exemplified, and in the present invention, a cyclic imino ester compound is particularly preferable in terms of excellent thermal stability. . The content of the ultraviolet absorber is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 0.05 to 0.5 parts by weight per 100 parts by weight of the component A. .

  The polycarbonate composition of the present invention can also contain a hindered amine light stabilizer represented by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. The combined use of the hindered amine light stabilizer and the UV absorber effectively improves the weather resistance. In such a combination, the weight ratio (light stabilizer / ultraviolet absorber) of both is preferably in the range of 95/5 to 5/95, more preferably in the range of 80/20 to 20/80. You may use a photostabilizer individually or in mixture of 2 or more types. The content of the light stabilizer is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably 0.05 to 0.5 parts by weight per 100 parts by weight of component A.

(Viii) Blueing agent In the polycarbonate composition of the present invention, the blueing agent is further preferably 5 × 10 ^{−6 to} 3 × 10 ⁻⁴ parts by weight, more preferably 2 × 10 ⁻⁵ per 100 parts by weight of component A. ˜2 × 10 ⁻⁴ parts by weight. By blending the bluing agent, the yellowishness can be reduced and a natural translucent color can be imparted to the resin molded product. Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer, and Polysynthrene Blue RLS manufactured by Clariant.

(Ix) Light Diffusing Agent Examples of the light diffusing agent include polymer fine particles (preferably acrylic crosslinked particles and silicone crosslinked particles having a particle size of several μm), low refractive index inorganic fine particles, and composites thereof. . From the viewpoint of thermal stability, polymer fine particles are more preferable. In addition, in the case of inorganic fine particles, fine particles whose surfaces are treated with various surface treatment agents for improving thermal stability are preferable. The average particle diameter of the polymer fine particles is preferably in the range of 0.1 to 10 μm, more preferably in the range of 0.1 to 8 μm. The average particle diameter is represented by a 50% value (D ₅₀ ) of the cumulative distribution of particle sizes obtained by the laser diffraction / scattering method. Further, a narrow particle size distribution is preferable, and a particle having an average particle size of ± 2 μm has a distribution of 70% by weight or more of the total particle size. The refractive index of the polymer fine particles is preferably 1.33 to 1.7, more preferably 1.35 to 1.67, still more preferably 1.35 to 1.55, and particularly preferably 1.35. 1.45. The shape of the polymer fine particles is preferably close to a sphere from the viewpoint of light diffusibility, and more preferably a shape close to a true sphere. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight per 100 parts by weight of the component A.

(X) Light Reflecting Agent The polycarbonate composition of the present invention can be blended with titanium dioxide, zinc oxide, and zinc sulfide as a white pigment for the purpose of adjusting the light shielding property and imparting high light reflectivity. Of these white pigments, titanium dioxide is particularly preferred. Such titanium dioxide is preferably surface-treated with an oxide of a metal such as aluminum, silicon, titanium, zirconium, antimony, tin and zinc. As the surface treatment, either a high-density treatment or a low-density (porous) treatment can be applied. Further preferred titanium dioxide is surface treated with an organic compound. As such a surface treatment agent, a surface treatment agent mainly comprising an amine compound, a silicone compound, and a polyol compound is used. In particular, titanium dioxide coated with an alkyl hydrogen polysiloxane is preferably used. In the polycarbonate composition of the present invention, the content of titanium dioxide is 0.0001 to 0.5 parts by weight, more preferably 0.0005 to 0.1 parts by weight, per 100 parts by weight of component A.

(Xi) Other dyes and pigments Various dyes and pigments other than the above can be used in the polycarbonate composition of the present invention as long as the object of the invention is not impaired. Examples of such dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes Examples thereof include dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, fluorescent whitening agents such as bisbenzoxazolyl-stilbene derivatives, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can also be used. In addition, carbon black and metallic pigments (for example, metal oxide-coated plate-like filler, metal-coated plate-like filler, and metal flakes) can be blended. In addition to coloring and design effects, carbon black and metallic pigments can be blended for the purpose of providing a heat ray shielding effect by absorbing or reflecting heat rays when the molded article has light transmittance. The content of such other dyes and pigments varies depending on the purpose, but is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.8 part by weight per 100 parts by weight of component A.

(Xii) Antistatic agent The polycarbonate composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonic acid phosphonium salts such as (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzene sulfonic acid phosphonium salts, and alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less per 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and still more preferably 1.5 parts by weight. It is in the range of ˜3 parts by weight.

  Antistatic agents include, for example: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonate alkali (earth) metal salts. Specifically, for example, metal salts of dodecylbenzenesulfonic acid, metal salts of perfluoroalkanesulfonic acid, and the like are exemplified. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, more preferably 0.005. -0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable. Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salt and arylsulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less, preferably 0.001 to 0.03 parts by weight per 100 parts by weight of component A. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less per 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight.

(Xiii) Compound having heat ray shielding ability For the polycarbonate composition of the present invention, an amount of a compound having heat ray shielding ability which does not impair the object of the present invention can be used. The compounds include phthalocyanine-based near infrared absorbers, metal oxide-based near infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. Further, as described above, metallic pigments (for example, metal oxide-coated plate-like fillers, metal-coated plate-like fillers, metal flakes, and the like) mainly reflect heat rays and exhibit heat ray shielding ability.

As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (including both natural and artificial, and whiskers), carbon fibers (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon. Black and graphite. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and still more preferably 0.001 based on 100 parts by weight of component A. -0.07 weight part. The content of the metal oxide near infrared absorber and the metal borate near infrared absorber is preferably in the range of 1 × 10 ⁻⁵ to 2 × 10 ⁻² parts by weight based on 100 parts by weight of component A. A range of × 10 ⁻⁵ to 1 × 10 ⁻² parts by weight is more preferable. The carbon filler is preferably in the range of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ parts by weight based on 100 parts by weight of component A. The content of the metallic pigment is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.8 part by weight, based on 100 parts by weight of component A.

(Xiv) Reinforcing filler other than B component To the polycarbonate composition of the present invention, a reinforcing filler other than the B component can be further blended within the range where the effects of the present invention are exhibited. Reinforcing fillers include various commonly known fillers such as glass fibers, carbon fibers, glass flakes, wollastonite, kaolin clay, mica, talc and various whiskers (such as potassium titanate whisker and aluminum borate whisker). Available. The shape can be freely selected from a fiber shape, a flake shape, a spherical shape, and a hollow shape. Glass fiber, carbon fiber, glass flake and the like are suitable for improving the strength and impact resistance of the resin molded product. On the other hand, when the good surface appearance (surface smoothness) of the polycarbonate composition of the present invention is utilized more effectively, the size of the reinforcing filler is preferably minute. Specifically, in the case of a fibrous filler, the fiber diameter, and in the case of a plate-like filler or granular filler, the size is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less. preferable. A lower limit of about 0.05 μm is appropriate. Examples of such minute reinforcing fillers include talc, wollastonite, kaolin clay, and various whiskers. The content of the reinforcing filler other than the component B is suitably 50 parts by weight or less, preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the component A. Preferably it is 2-10 weight part.

(Xv) Fluid modifier A fluid modifier can be mix | blended with the polycarbonate composition of this invention. The composition of the present invention is excellent in thermal stability in consideration of blending an inorganic filler. However, since the A component polycarbonate is inferior in thermal stability, it may be required to lower the molding processing temperature. is there. Such flow modifiers include styrene oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types) Preferred examples include branched and hyperbranched aliphatic polyester oligomers, terpene resins, and polycaprolactone. The flow modifier is suitably 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight per 100 parts by weight of component A.

(Xvi) Other additives other than those described above In addition, a nucleating agent (for example, sodium stearate, ethylene-sodium acrylate, etc.), fluorescent whitening agent, antibacterial agent, and photocatalytic antifouling, as long as the object of the present invention is not impaired. An agent, a photochromic agent, and the like may be blended. These various additives can be used in known blending amounts when blended with the resin material.

<About the manufacturing method of a polycarbonate composition>
In the polycarbonate composition of the present invention, the component A and the component B are mixed by the “method-1” and / or “method-2” as described above. Additives to be blended as necessary as described above are the method of blending with the component B in Method-1 or -2 and the method of blending in addition to the composition obtained by Method-1 or -2. Any method can be used.

  In the method of additionally adding the additive, it is preferable to melt and knead each component. Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, and an extruder. Of these, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin-screw extruder is more preferable. By using such a multi-screw extruder, the layered silicate is finely dispersed in the base resin with a strong shearing force. The multi-screw extruder is also preferable as an extruder used in “Method-2”.

  Hereinafter, a more preferable aspect in the twin screw extruder used in the blending of the component B and the blending of other additives in the present invention is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw having a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin screw extruder is preferably 20 to 50, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, whereas when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  When each component is premixed, examples of the premixing method include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator or a briquetting machine as necessary. 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.

  The B component, or a mixture containing the B component, and the reinforcing filler in the optional component can be supplied from a supply port in the middle of the extruder using a side feeder. The melt kneading at the time of producing the polycarbonate composition of the present invention is adjusted so that the resin temperature is preferably 280 ° C. or lower, more preferably 270 ° C. or lower. The lower limit of the extrusion temperature is preferably 210 ° C or higher, more preferably 220 ° C or higher, although the appropriate temperature varies depending on the melt viscosity of the component A.

  The solution casting method is preferably applied to the production of the polycarbonate composition of the present invention. That is, a method of preparing a composition by dissolving and dispersing the component A, component B and optionally other components in a solvent, and then removing the solvent is also preferably applied. The component B does not dissolve in the solvent, so the resulting liquid is a dispersion, but is referred to as “solution casting method” in this specification. As a means for such dissolution and dispersion, a homomixer, a high-pressure homogenizer, a bead mill (for example, Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd.), an ultrasonic stirrer, and a high-pressure collapsible dispersion device (for example, SUGINO MACHINE Co., Ltd.) are sold. Optimizer (trade name, etc.), thin-film swirl type high-speed mixer (for example, TK Filmics (trademark) manufactured by Primics Co., Ltd.), various static mixers, motionless mixers, and the like can be used. In TK film mixing, a PC wheel type stirring unit is preferable. When using these methods, the viscosity of the dispersion is preferably 20,000 mPa · s or less, and more preferably 10 to 10,000 mPa · s. Such mixing may be carried out in any atmosphere in the atmosphere and in an inert gas such as nitrogen gas. The adjustment of the dispersion with such a low viscosity tends to promote the dispersion of the component B, but the life of the dispersed state tends to be shortened. Therefore, after dispersion at such a low viscosity, it is preferable to remove a part of the solvent to increase the solution viscosity. An increase in solution viscosity is also necessary in the production of molded articles such as films by the solution casting method.

  On the other hand, a highly viscous dispersion can also be obtained directly. As a mixing means for preparing such a high-viscosity dispersion, a twin-shaft planetary stirrer (for example, TK Hibismix (trademark) manufactured by PRIMIX Co., Ltd.), an anchor mixer, a planetary stirring / defoaming device (for example, Kurashiki Spinning Co., Ltd.) Mazerustar (trade name) sold by Co., Ltd., Ultramixer (for example, manufactured by Mizuho Kogyo Co., Ltd.), fluid split mixing mixer (for example, Distromix (trade name) manufactured by ATEC Japan), roll mill, ball mill, etc. Available. The viscosity of the high-viscosity dispersion when using such an apparatus is preferably 20,000 to 500,000 mPa · s, more preferably 30,000 to 100,000 mPa · s. As a stirring blade in an apparatus using a stirring blade, an anchor type, a dissolver type, or the like can be used.

  As a solvent in the above solution casting method, methylene chloride and 1,3-dioxolane are used alone or as a main component, and a mixed solvent in which about 20% by weight or less of a lower alcohol, acetone, methyl acetate or the like is mixed is used. Also good.

  The weight concentration of the above dispersion is preferably 5 to 30% by weight, more preferably 7 to 25% by weight as the concentration of the component A. In particular, the solution prepared before casting is preferably in the range of 13 to 23% by weight.

<Manufacture of molded product from polycarbonate composition>
The polycarbonate composition of the present invention can produce various products by injection molding the pellets produced as described above. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Further, the polycarbonate composition of the present invention can be used in the form of various shaped extruded products, sheets, films and the like by being extruded. For forming sheets and films, an inflation method, a calendar method, a casting method, and the like can be used. Further, it can be molded as an optical product and a heat-shrinkable product by a specific stretching operation. The polycarbonate composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.

  In addition, the polycarbonate composition of the present invention can produce various products by the solution casting method as described above. In the solution casting method of the present invention, techniques of solution casting methods for various known resin solutions, particularly polycarbonate resin solutions, can be applied. In the solution casting method, a film-shaped molded article is usually obtained through a casting process in which a resin solution is cast on a metal support, and a solvent evaporation and drying process after the process. In the present invention, it is preferable to produce a product by the same process. In the casting step, the dispersion of the composition of the present invention is cast on a drum or band-shaped metal support, and the solvent is evaporated to obtain a web. The surface of the metal support is preferably in a mirror state, and examples thereof include a drum having a chrome-plated surface that is mirror-finished, and a stainless steel belt that is mirror-finished by surface polishing. Examples of the casting of the dispersion onto the metal support include a method of extruding a dispersion having a uniform thickness from a pressure die, a method of making the dispersion uniform with a doctor blade, and a method of using a reverse roll coater. Industrially, a method using a pressure die is preferable, and any one of a coat hanger die and a T die can be suitably used as the pressure die. The amount of the dispersion to be cast is preferably fed from a precision quantitative gear-a pump.

  It is preferable that the solvent of the dispersion cast on the metal support is evaporated by heating the surface temperature of the metal support by passing a temperature control medium through the back surface. Such surface temperature is preferably set to a temperature 1 to 10 ° C. lower than the boiling point of the solvent. The evaporation of the solvent is a method of evaporating a predetermined amount on the metal support, and then peeling it from the metal support and further drying it. Any of the drying methods can be used, but the former method is more preferable. In the drying step, a method of drying the web peeled from the metal support by blowing hot air having a temperature of 60 to 160 ° C. is preferable. After drying in such a temperature range, it is preferable to dry at 100 to 160 ° C. in order to remove the solvent remaining in the web. The shrinkage of the web due to the evaporation of the solvent is preferable because drying can be performed while suppressing the shrinkage as much as possible because the flatness of the film can be improved. The shrinkage of the web can be suppressed by a tenter method in which the drying process is performed while holding the width ends of the peeled web with a clip. The process from the casting process to the winding process may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. It can also be dried using far infrared rays or microwaves.

  The polycarbonate composition of the present invention has good rigidity, thermal stability, surface hardness, and surface smoothness. Therefore, by forming the surface of the molded body with the polycarbonate composition of the present invention, it is possible to produce a molded body having excellent appearance, scratch resistance, rigidity, and cost. As a molding method for constituting the surface with the composition of the present invention, for example, coextrusion, sandwich molding, insert molding and the like can be used. More specifically, according to the present invention, it is a resin molded product formed from the polycarbonate composition of the present invention, and preferably has a value of arithmetic average roughness Ra measured according to JIS B0601 on the surface thereof. There is provided a resin molded product having a modulus of elasticity of 0.1 μm or less and preferably an elastic modulus of 3,500 MPa or more. The elastic modulus is measured as a tensile elastic modulus or a bending elastic modulus depending on whether the plate-shaped portion of the resin molded product is subjected to a tensile test by the same method as ISO527-2 or a bending test by the same method as IS0178, respectively. can do. A highly rigid resin molded product satisfying any one of these elastic moduli, preferably 3,500 MPa or more is provided.

  The value of the arithmetic surface roughness Ra of the resin molded product is more preferably 0.08 μm or less, and still more preferably 0.05 μm or less. The lower limit is largely due to the mold for molding, but about 0.001 μm is appropriate. The value of the elastic modulus is more preferably 3,800 MPa or more, and further preferably 4,000 MPa or more. On the other hand, the upper limit is suitably 8,000 MPa, preferably 7,000 MPa, and more preferably 6,000 MPa. Further, the resin molded product preferably has a pencil hardness measured according to JIS K 5600 of H to 2H.

  The molded product formed from the polycarbonate composition of the present invention can be further imparted with other functions by surface modification. “Surface modification” as used herein means the surface layer of a resin molded product by means of vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, and printing. This means that a new layer is formed on the surface, and a surface modification method used for ordinary resin molded products can be applied.

  Examples of the method for laminating a metal layer or a metal oxide layer on the surface of the resin molded product include physical vapor deposition, chemical vapor deposition, thermal spraying, and plating. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating, and examples of chemical vapor deposition (CVD) include thermal CVD, plasma CVD, and photo CVD. By such a method, it is possible to form a hard film such as diamond-like carbon. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method can be used. Among the above methods, the vapor deposition method and the plating method are preferable for forming the metal layer of the molded article made of the resin composition of the present invention, and the vapor deposition method is preferable for forming the metal oxide layer.

  Moreover, the member excellent in practicality is provided by giving a hard coat to the surface of a resin molded product. Since the polycarbonate composition of the present invention is excellent in affinity with a polar group, the adhesiveness with the hard coat layer is also good. Examples of the hard coating agent include a silicone resin hard coating agent and an organic resin hard coating agent. The hardness of the hard coat layer is not particularly limited. Examples of the organic resin hard coat agent include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate. Among these, an ultraviolet curable hard coat agent is particularly preferable. Furthermore, it is more preferable that the hard coat agent contains a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a light stable monomer. A more suitable organic resin hard coat agent is one in which a hard coat layer is formed by copolymerizing such a monomer and an alkyl (meth) acrylate monomer. Such an ultraviolet curable hard coat agent is preferable in that its processing is simple, and in addition, it is easy to include a structural unit obtained by copolymerizing an ultraviolet absorbing monomer and / or a light stable monomer. This is preferable in that the light resistance of the product can be greatly improved.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the measurement of the various characteristics in an Example was based on the following method.

(I) Evaluation Items of Composition by Melt-Kneading (by Method-2) (I-1) Evaluation of Thermal Stability The viscosity average molecular weight of the injection-molded product was measured and its thermal stability was evaluated. Those having poor thermal stability greatly reduce the molecular weight of the molded product. The molecular weight of the molded product was measured by the method described in the text using the bending test piece (I-3) below. That is, such a pellet or test piece is dissolved in 20 to 30 times the weight of methylene chloride, and after such soluble matter is collected by celite filtration, the solution is removed and dried sufficiently, and the methylene chloride soluble matter is removed. A solid was obtained. The viscosity average molecular weight was calculated from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride.

(I-2) Tensile fracture strength and tensile fracture nominal strain Bending specimens were molded with an injection molding machine (J75EIII type, manufactured by Nippon Steel Co., Ltd.) at a cylinder temperature of 230 ° C, a mold temperature of 90 ° C, and a molding cycle of 40 seconds. (Dimensions: length 175 mm × width 10 mm × thickness 4 mm, but the width of the chuck portion is 20 mm) and stored for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH. Based on 1 and 527-2, the tensile yield strength (unit: MPa) and the tensile fracture nominal strain (unit:%) at 23 ° C. were measured. The test speed was 5 mm / min. A high strength is preferable for practical use, and a large nominal strain indicates that the material has high toughness.

(I-3) Bending elastic modulus and bending strength Molded with an injection molding machine (J75EIII type, manufactured by Nippon Steel Works) at a cylinder temperature of 230 ° C., a mold temperature of 90 ° C., and a molding cycle of 40 seconds. : Length 80 mm × width 10 mm × thickness 4 mm) and stored for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH, and the bending elastic modulus and bending strength are measured in accordance with ISO 178 in the atmosphere. It was measured. It is practically preferable that both the elastic modulus and strength are large.

(I-4) Notched Charpy impact strength A test piece having the same shape as the above (I-3) was prepared under the same conditions, and stored for 24 hours in an atmosphere at a post-molding temperature of 23 ° C. and a relative humidity of 50% RH. did. A notch was made in accordance with ISO standard ISO-179, and a Charpy impact test was conducted. The higher the impact strength, the better for practical use.

(I-5) Deflection temperature under load A test piece having the same shape as the above (I-3) was prepared under the same conditions and stored for 24 hours in an atmosphere at a post-molding temperature of 23 ° C. and a relative humidity of 50% RH. Based on ISO75-1 and 75-2, the deflection temperature under load was measured at a load of 1.80 MPa.

(I-6) Haze measurement Stepped plate shape whose thickness changes from the gate side to 3 mm, 2 mm, and 1 mm in a staircase pattern using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. Using the molded product, the haze at the 1 mm portion was measured. The width of the plate-shaped molded product was 50 mm, the length of the 3 mm portion was 20 mm, the length of the 2 mm portion was 45 mm, and the length of the 1 mm portion was 25 mm. Each sample had a surface roughness Ra of 0.05 μm at a thickness of 2 mm.

(I-7) Measurement of Pencil Hardness of Molded Product Using the 2 mm thickness portion of the plate-shaped molded product of (I-6) above, the pencil hardness of the surface of the plate-shaped molded product was measured using HEIDON-14 manufactured by Shinto Kagaku Co., Ltd. Using a mold, measurement was performed under a load of 750 g in accordance with JIS K 5600.

(II) Manufacture of pellets and molded articles made of a polycarbonate composition [Examples 1 and 2 and Comparative Examples 1 and 2]
The pellet which consists of a polycarbonate composition which consists of a mixture ratio of Table 1 was created in the following ways. According to the charging composition shown in Table 1, each raw material was weighed into a polyethylene bag and the bag was sufficiently rotated in the vertical and horizontal directions to uniformly dry-blend the charged material. The obtained mixture was supplied to the first input port at the rearmost part using a vent type twin screw extruder (KZW15-25MG manufactured by Technobel Co., Ltd.) having a screw diameter of 15 mm. The cylinder temperature and the die temperature were both 210 ° C., the screw rotation speed was 200 rpm, the discharge rate per hour was 2 kg / hour, and the vent vacuum was 3 kPa. In addition, the structure of the screw segment had the kneading | mixing zone comprised with the kneading disk in the upstream and downstream of the position of a vent. The extruded strand was cooled in a water bath, then cut with a pelletizer and pelletized. The obtained pellets were dried with a hot air dryer at 110 ° C. for 6 hours, and then injection-molded as described above to prepare bending test pieces and the like.

The raw materials used in Examples and Comparative Examples are as follows.
(Component A)
PC-ISS: Polycarbonate resin pellets having a viscosity average molecular weight of 13,700 composed of carbonate structural units derived from isosorbide, prepared in Production Example 1 below (polycarbonate other than component A)
PC-A: Polycarbonate resin powder having a viscosity average molecular weight of 15,900 composed of a carbonate constituent unit derived from bisphenol A (Panlite (registered trademark) CM-1000 manufactured by Teijin Chemicals Ltd.)

<Production Example 1: Production of PC-ISS>
1608 parts by weight of isosorbide (PC grade manufactured by Roquette) and 2356 parts by weight of diphenyl carbonate were placed in a reactor, and 0.2 parts by weight of tetramethylammonium hydroxide was used as a polymerization catalyst (2 × 10 2 parts per mole of diphenyl carbonate component). ^-4 mol) and 1.32 × 10 ⁻⁴ parts by weight of sodium hydroxide (0.3 × 10 ⁻⁶ mol per 1 mol of the diphenyl carbonate component), and heated to 180 ° C. under a nitrogen atmosphere at normal pressure. Melted. After 5 minutes from the start of heating, it was confirmed that the raw material had melted, and stirring was started. Thereafter, stirring was continued until the end of the polymerization.
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.

Subsequently, 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 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. Thereafter, the stirrer was stopped, nitrogen gas was supplied to return to normal pressure, and the polymer in a molten state was taken out from the reactor to obtain a bulk polymer. Thereafter, the polymer mass was cut and pulverized to obtain a polymer powder. 0.3 parts by weight of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka Adeka Stub PEP-36) with respect to 100 parts by weight of the obtained polymer powder ) And blended uniformly to obtain a premix. The preliminary mixture was supplied to the first input port at the rearmost part using a vent type twin screw extruder (KZW15-25MG manufactured by Technobel Co., Ltd.) having a screw diameter of 15 mm. The cylinder temperature and the die temperature were both 210 ° C., the screw rotation speed was 200 rpm, the discharge rate per hour was 2 kg / hour, and the vent vacuum was 3 kPa. In addition, the structure of the screw segment was the same as that in the case of manufacturing the above composition. The extruded strand was cooled in a water bath, then cut with a pelletizer and pelletized. The obtained pellets were dried in a hot air dryer at 110 ° C. for 6 hours and used as a raw material PC-ISS.

(B component: layered silicate)
S1ME: synthetic fluorine mica having a cation exchange capacity of 100 milliequivalents / 100 g (S1-ME (trade name) manufactured by Coop Chemical Co., Ltd.)
(Other ingredients)
IRGF: Phosphite heat stabilizer (Ciba Specialty Chemicals, Inc .: Irgafos 168 (trade name))

  As apparent from Table 1 above, the composition of the present invention has a slight increase in flexural modulus, but has increased toughness such as tensile fracture strength, fracture nominal strain and impact strength, and deflection temperature under load. It can be seen that all of them have practically preferable characteristics. Due to such an effect, the composition of the present invention can be applied even to uses that are fragile and cannot be used with the PC-ISS polymer alone. Since the PC-ISS polymer can be produced from plant-derived raw materials, the composition of the present invention can be applied to a wider range of materials having a low environmental impact, thereby contributing to a reduction in the environmental impact. Become.

(III) Evaluation Items of Composition by Mixing During Polymerization (by Method-1) (III-1) Bending Elastic Modulus, Bending Strength, and Deflection Amount From the polymer powder obtained in each of the following Examples and Comparative Examples, vacuum heat Using a press molding machine, a bending specimen (dimensions: length 80 mm × width 10 mm × thickness 4 mm) was molded and stored for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH. In accordance with ISO178, the bending elastic modulus, the bending strength, and the amount of deflection when the bending strength (maximum value of strength) was shown were measured. It is practically preferable that both the elastic modulus and strength are large, and a large amount of deflection indicates excellent toughness.

(III-2) Haze measurement of laminate The haze of a laminate of a cast film and a plate-like injection-molded product produced by the method shown below was used using a Nippon Denshoku Industries Co., Ltd. haze meter NDH-2000. It was measured. The haze reflects the haze of the cast film, and serves as an index indicating dispersibility due to solution mixing of the layered silicate and the polymer.

(III-3) Measurement of pencil hardness of laminate The pencil hardness of the cast film side surface was measured with a load of 750 g in accordance with JIS K 5600 using a HEIDON-14 model manufactured by Shinto Kagaku Co., Ltd.

(IV) Production of polycarbonate composition using Method-1 [Example 3]
Add 876.8 parts by weight of isosorbide (PC grade manufactured by Roquette), 1285.3 parts by weight of diphenyl carbonate, and 21 parts by weight of S1ME (abbreviation as above) to a reactor having an anchor type stirring blade, and remove it sufficiently. After the gas treatment, it was heated to 180 ° C. and melted at normal pressure under a nitrogen atmosphere. After 5 minutes from the start of heating, it was confirmed that the raw material had melted, and stirring was started. Thereafter, stirring was continued until the end of the polymerization.
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 for 20 minutes in this state, the temperature was raised to 200 ° C. over 20 minutes. Next, the pressure was gradually reduced over 20 minutes, the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol, and the temperature was raised to 250 ° C. over 40 minutes, followed by reaction for 20 minutes.

Next, the pressure was gradually reduced and reacted at 2.67 × 10 ⁻³ MPa for 10 minutes, then the temperature was raised to 260 ° C., the pressure was reduced to 1.33 × 10 ⁻³ MPa, and the reaction was continued for 20 minutes. The pressure was reduced and when the pressure reached 4.00 × 10 ⁻⁵ MPa, the reaction was allowed to proceed for 5 minutes. Thereafter, the stirrer was stopped, nitrogen gas was supplied to return to normal pressure, and the polymer in a molten state was taken out from the reactor to obtain a bulk polymer. Thereafter, the polymer mass was cut and pulverized to obtain a polymer powder. The obtained polymer had a specific viscosity of 0.444 (24,600 in terms of viscosity average molecular weight). The inorganic content calculated from the ash measurement was 1.6% by weight.

[Example 4]
1900 parts by weight of isosorbide (PC grade manufactured by Roquette) and 100 parts by weight of S1ME (abbreviation as above) were put into a reactor having an anchor type stirring blade, and after sufficient degassing treatment, normal pressure under nitrogen atmosphere And heated to 90 ° C. to melt isosorbide. Thereafter, the mixture was stirred at a rotational speed of 250 rpm for 3 hours, cooled to room temperature and solidified to prepare “Preliminary mixture-α” in which S1ME was dispersed in isosorbide.
540.8 parts by weight of isosorbide (PC grade manufactured by Roquette), 1285.3 parts by weight of diphenyl carbonate, and 336 parts by weight of the above-mentioned “preliminary mixture-α” were put into a reactor having an anchor type stirring blade and fully desorbed. After the gas treatment, it was heated to 180 ° C. and melted at normal pressure under a nitrogen atmosphere. After 5 minutes from the start of heating, it was confirmed that the raw material had melted, and stirring was started. Thereafter, stirring was continued until the end of the polymerization.

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 for 20 minutes in this state, the temperature was raised to 200 ° C. over 20 minutes. Subsequently, the pressure was gradually reduced over 20 minutes, and the pressure was reduced to 4.00 × 10 ⁻³ MPa while distilling off the phenol. The reaction was performed in this state for 35 minutes, and the temperature was further raised to 250 ° C. over 35 minutes. Next, the pressure was gradually reduced and reacted at 2.67 × 10 ⁻³ MPa for 10 minutes, then the temperature was raised to 260 ° C. and the pressure was reduced to 1.33 × 10 ⁻³ MPa to continue the reaction for 10 minutes. The pressure was reduced, and after reaching 4.00 × 10 ⁻⁵ MPa, the reaction was carried out for 10 minutes. Thereafter, the stirrer was stopped, nitrogen gas was supplied to return to normal pressure, and the polymer in a molten state was taken out from the reactor to obtain a bulk polymer. Thereafter, the polymer mass was cut and pulverized to obtain a polymer powder. The specific viscosity of the obtained polymer was 0.344 (18,700 in terms of viscosity average molecular weight). The inorganic content calculated from the ash measurement was 1.6% by weight.

[Example 5]
116.8 parts by weight of isosorbide (PC grade, manufactured by Roquette), 1285.3 parts by weight of diphenyl carbonate, and 800 parts by weight of the above-mentioned “premixture-α” were put into a reactor having an anchor type stirring blade and fully desorbed. After the gas treatment, it was heated to 180 ° C. and melted at normal pressure under a nitrogen atmosphere. After 5 minutes from the start of heating, it was confirmed that the raw material had melted, and stirring was started. Thereafter, stirring was continued until the end of the polymerization.

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 for 20 minutes in this state, the temperature was raised to 200 ° C. over 20 minutes. Subsequently, the pressure was gradually reduced over 20 minutes to 4.00 × 10 ⁻³ MPa while removing phenol, and the temperature was further raised to 250 ° C. over 40 minutes. Next, the pressure was gradually reduced and reacted at 2.67 × 10 ⁻³ MPa for 10 minutes, then the temperature was raised to 260 ° C. and the pressure was reduced to 1.33 × 10 ⁻³ MPa to continue the reaction for 10 minutes. The pressure was reduced, and after reaching 4.00 × 10 ⁻⁵ MPa, the reaction was carried out for 10 minutes. Thereafter, the stirrer was stopped, nitrogen gas was supplied to return to normal pressure, and the polymer in a molten state was taken out from the reactor to obtain a bulk polymer. Thereafter, the polymer mass was cut and pulverized to obtain a polymer powder. The specific viscosity of the obtained polymer was 0.449 (24,900 in terms of viscosity average molecular weight). The inorganic content calculated from the ash content measurement was 3.6% by weight.

[Comparative Example 3]
876.8 parts by weight of isosorbide (PC grade manufactured by Roquette) and 1285.3 parts by weight of diphenyl carbonate were placed in a reactor, and 0.164 parts by weight of tetramethylammonium hydroxide as a polymerization catalyst (based on 1 mol of diphenyl carbonate component). 3 × 10 ⁻⁴ mol) and 7.2 × 10 ⁻⁴ parts by weight of sodium hydroxide (3 × 10 ⁻⁶ mol with respect to 1 mol of diphenyl carbonate component) and 180 ° C. under normal pressure in a nitrogen atmosphere. Heated and melted. After 5 minutes from the start of heating, it was confirmed that the raw material had melted, and stirring was started. Thereafter, stirring was continued until the end of the polymerization.

Thereafter, the reaction was carried out by substantially the same heating and depressurization procedures as in Example 5 to complete the reaction. Thereafter, the stirrer was stopped, nitrogen gas was supplied to return to normal pressure, 21 parts by weight of S1ME was quickly supplied to the reactor, and deaeration and nitrogen atmosphere were performed again. In this state, stirring was carried out in the same manner as in the polymerization to disperse S1ME uniformly to some extent, and then the pressure was reduced and stirring was continued for 2 hours under 4.00 × 10 ⁻⁵ MPa. Thereafter, the stirrer was stopped, nitrogen gas was supplied to return to normal pressure, and the polymer in a molten state was taken out from the reactor to obtain a bulk polymer. Thereafter, the polymer mass was cut and pulverized to obtain a polymer powder. The polymer obtained had a specific viscosity of 0.432 (23,900 in terms of viscosity average molecular weight). The inorganic content calculated from the ash measurement was 1.6% by weight.

(IV-1) Production of bending test piece A bending test piece (size: length 80 mm x width 10 mm x thickness 4 mm) was formed from the polymer powder obtained above using a vacuum hot press molding machine. The vacuum hot press molding machine was a compression molding machine SFV-10 manufactured by Shinfuji Metal Industry Co., Ltd., and the polymer powder was melt-compressed with two metal bars in a metal mold. The molding conditions were as follows: mold temperature: 220 ° C., vacuum degree: 0.2 kPa, primary pressure and time: 0.5 MPa and 2 minutes, and secondary pressure and time: 1.5 MPa and 6 minutes. Here, the primary pressure is a pressure applied at a mold temperature of 220 ° C., and the secondary pressure is a pressure applied from the start of cooling to just before the removal.

(IV-2) Manufacture of cast film To the polymer powder obtained above, methylene chloride (manufactured by Tokuyama Co., Ltd.) is added so that the solid content concentration is 15% by weight, and using a mix rotor (trade name) A homogeneous dispersion was obtained. Using a bar coater, this dispersion was uniformly coated on a smooth glass plate with a thickness of 0.5 mm. After drying at room temperature for 20 minutes and at 45 ° C for 1 hour, the cast film is removed from the glass plate, fixed to a metal frame so that the film is stretched comfortably, and further dried at 120 ° C for 8 hours. A typical cast film was obtained. The thickness of the obtained film was about 75 μm (the thickness variation was about 5 μm).

(IV-3) Manufacture of cast film laminated molded body The cast film obtained above and a polycarbonate plate-shaped molded article previously molded by injection molding are integrated using a vacuum hot press molding machine, and the cast is formed on the surface. A molded body having the composition of the film was obtained. Here, the polycarbonate plate-shaped article was prepared from bisphenol A type polycarbonate having a viscosity average molecular weight of 30,000 (Panlite (registered trademark) K-1300 manufactured by Teijin Chemicals Ltd.). The shape of the plate-shaped molded product was 100 mm in length and width, and 2 mm in thickness. The vacuum heat press molding machine is a compression molding machine SFV-10 manufactured by Shinto Metal Industry Co., Ltd. As shown in FIG. 1, a cast film and a plate-shaped molded product are formed with two metal plates in a metal mold. Crimped. The pressure bonding conditions were as follows: mold temperature: 220 ° C., degree of vacuum: 0.2 kPa, primary pressure and time: 0.5 MPa and 2 minutes, and secondary pressure and time: 1.5 MPa and 3 minutes. Here, the primary pressure is a pressure applied at a mold temperature of 220 ° C., and the secondary pressure is a pressure applied from the start of cooling to just before the removal. The metal plate surface in contact with the film and the molded product was polished with a cloth coated with a silicone release agent to prevent the resin from sticking.

  As is clear from Table 2 above, it can be seen that the composition of the present invention can be obtained by mixing with the layered silicate at the monomer stage to obtain a composition excellent in strength and toughness. This is presumably because the layered silicate is finely dispersed to ensure good adhesion with the polymer. In particular, it can be seen that the effect is remarkable when the monomer and the layered silicate are premixed. It can be seen that the resulting composition has a low haze and excellent transparency.

  The polycarbonate composition obtained by the production method of the present invention 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, and miscellaneous goods. It is.

1 Metal frame 2 Lower plate 3 Upper plate 4 Polycarbonate plate-shaped molded product (thickness 2 mm)
5 Cast film

Claims (11)

Production of polycarbonate composition containing 0.01 to 50 parts by weight of layered silicate (B component) having a cation exchange capacity of 50 to 200 meq / 100 g with respect to 100 parts by weight of polycarbonate (A component) A method,
(I) The component A contains a carbonate structural unit derived from a difunctional alcohol (component A-1) in an amount of 10 mol% or more in 100 mol% of all the structural units,
(II) The component B is a layered silicate that is substantially not organically treated with less than 1 part by weight of the organic agent per 100 parts by weight of the layered silicate,
(III) The component B is (III-1) a method for producing the component A by a melt polymerization reaction with stirring in the presence of the component B and a difunctional alcohol (component A-1), and / or Or (III-2) A method for producing a polycarbonate composition, wherein the component A and the component B are dispersed in the component A by a method of melt-kneading using an extruder.   The method for producing a polycarbonate composition according to claim 1, wherein the component A-1 is a bifunctional alcohol that dissolves in water at 20 ° C. in an amount of 1 wt% or more.   The manufacturing method of the polycarbonate composition of Claim 1 or Claim 2 which contains the carbonate structural unit induced | guided | derived from A-1 component in 100 mol% of all carbonate structural units. The A-1 component is at least one bifunctional alcohol selected from the group consisting of a cyclic ether diol represented by the following formula (1) and a linear aliphatic diol having 2 to 6 carbon atoms. The manufacturing method of the polycarbonate composition of any one of Claims 1-3.

  The method for producing a polycarbonate composition according to claim 4, wherein the component A-1 is a cyclic ether diol represented by the formula (1).   The said A component has the viscosity average molecular weight of 4,000-40,000, The manufacturing method of the polycarbonate composition of any one of Claims 1-5.   In the method of (III-1), a part or all of the A-1 component and the B component are mixed in advance, and a melt polymerization reaction is performed while stirring in the coexistence of the B component and the A-1 component. The manufacturing method of the polycarbonate composition of any one of Claims 1-6 which is a method of manufacturing a component.   The composition obtained by the method of (III-1) and / or (III-2) above is further mixed in the presence of a solvent of component A, and the solvent is removed, whereby component B is contained in component A. The manufacturing method of the polycarbonate composition of any one of Claims 1-7 which manufactures the composition disperse | distributed to.   The polycarbonate composition manufactured from the manufacturing method of any one of Claims 1-8.   A molded article obtained by melt-molding the polycarbonate composition according to claim 9.   A molded article obtained by molding the polycarbonate composition according to claim 9 by a solution casting method.

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