JP5617693B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a polycarbonate resin composition having good fluidity.

  Polycarbonate having bisphenol A as a skeleton is known as an excellent material with high strength and high heat resistance. However, the melt viscosity is high, the fluidity is low, and molding at a high temperature is necessary, and the obtained molded product may be distorted.

  On the other hand, in order to improve fluidity, various additions of plasticizers have been studied, but bleed-out and mold contamination may occur.

  On the other hand, in mixing with other resins, it has been proposed that fluidity is improved by blending ABS with aromatic polycarbonate (Patent Document 1). Further, a transparent polymer alloy comprising an aromatic polycarbonate resin and a poly (1,4-cyclohexanedimethanol-1,4-cyclohexanedicarboxylate) resin (hereinafter abbreviated as PCC resin) has been proposed (patent). References 2, 3).

Japanese Patent Publication No.38-15225 Special Table 2002-517538 JP 2003-176401 A

  However, the polymer alloys described in Patent Documents 1 to 3 are not always satisfactory in transparency and hue.

Then, this invention aims at obtaining the polycarbonate resin which is excellent in heat resistance, has favorable fluidity, and has excellent transparency and initial color tone.

  As a result of intensive studies to solve the above problems, the present inventor mixed a polycarbonate resin and an aromatic polycarbonate resin having a structure represented by the following general formula (1) in the molecule, The present inventors have found that it has excellent heat resistance, good fluidity, excellent transparency and initial color tone, and has reached the present invention.

  That is, a polycarbonate resin (A) containing 15 mol% or more and less than 50 mol% of a structural unit (a) derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure, and an aromatic polycarbonate By using a polycarbonate resin composition comprising a resin (B), wherein the proportion of the polycarbonate (B) is 60% by weight or more, the above problem has been solved.

（但し、上記一般式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

  Moreover, it is good also considering the dihydroxy compound which has the site | part represented by the said General formula (1) in a part of said structure as a dihydroxy compound represented by following General formula (2).

（但し、上記一般式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

Further, the melt viscosity of the polycarbonate resin (A) measured with a capillary rheometer at 240 ° C. is in the range of 4.0 × 10 ^{2 to} 10.0 × 10 ² Pa · s under the condition of a shear rate of 600 sec ^−1. Also good.

  Furthermore, the polycarbonate resin (A) may contain a structural unit derived from an aliphatic hydrocarbon dihydroxy compound and / or a structural unit derived from an alicyclic hydrocarbon dihydroxy compound in an amount of 50 mol% or more and less than 85 mol%. Good.

  Further, a release agent may be contained in an amount of 0.0001 to 2 parts by weight with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B), and an antioxidant is added. You may make it contain 0.001 weight part or more and 1 weight part or less.

  Furthermore, the total light transmittance of a molded body (thickness 3 mm) molded from the polycarbonate resin composition may be 80% to 99%.

  Furthermore, these polycarbonate resin compositions may be molded into polycarbonate resin molded products.

  Since the present invention uses a resin composition in which a polycarbonate having a specific structure and an aromatic polycarbonate are mixed, a resin having excellent heat resistance, good fluidity, and excellent transparency and initial color tone is obtained. be able to.

DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.
In addition, in this specification, when the expression “to” is used, it is used in a sense including numerical values or physical values before and after that.

  The polycarbonate resin composition according to the present invention is a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure (hereinafter sometimes referred to as “main dihydroxy compound”). A resin composition comprising a polycarbonate resin (A) containing a) and an aromatic polycarbonate resin (B).

<Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is polycondensed by a transesterification reaction using a dihydroxy compound containing a dihydroxy compound having a site represented by the following general formula (1) as a part of the structure and a carbonic acid diester as raw materials. This is a resin obtained.

（但し、上記一般式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。） That is, the polycarbonate resin (A) used in the present invention contains 15 mol% or more and less than 50 mol% of a structural unit (a) derived from a dihydroxy compound having a site represented by the following general formula (1).

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

<Dihydroxy compound>
The dihydroxy compound used in the present invention is not particularly limited as long as it has a site represented by the general formula (1) in a part of its structure. Specifically, oxyalkylene glycols, Examples thereof include a dihydroxy compound having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, and a dihydroxy compound having a cyclic ether structure.

  Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

  Examples of the dihydroxy compound having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, -Bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- ( 2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) ) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9 Bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9 -Bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene and the like.

  The dihydroxy compound having a cyclic ether structure is a dihydroxy compound having a plurality of cyclic ether structures. Specifically, an anhydrous sugar alcohol represented by the dihydroxy compound represented by the following general formula (2), the following general formula: (3) and the compound which has cyclic ether structures, such as spiroglycol represented by following formula (4), are mentioned.

  Since the dihydroxy compound having a plurality of cyclic ether structures has a rigid structure, the resulting polymer also tends to be rigid, and has a high surface hardness and high heat resistance.

  Among these, diethylene glycol and triethylene glycol are preferable from the viewpoint of easy availability, handling, reactivity during polymerization, and hue of the obtained polycarbonate resin (A). From the viewpoint of heat resistance, the above general formula Anhydrosugar alcohol typified by the dihydroxy compound represented by (2) and a compound having a cyclic ether structure represented by the above general formula (3) or general formula (4) are preferred. These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin (A) to be obtained.

  Examples of the dihydroxy compound represented by the general formula (2) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. It may be used.

  Among these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the polycarbonate resin (A). Among them, various kinds that are abundant and easily available as plant-derived resources are used. Isosorbide obtained by dehydrating condensation of sorbitol produced from starch is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.

  The polycarbonate resin (A) used in the present invention may contain a structural unit derived from a dihydroxy compound other than the above-mentioned dihydroxy compound (hereinafter sometimes referred to as “other dihydroxy compound”).

  Since the structure derived from the dihydroxy compound having the site represented by the general formula (1), particularly the structure containing a cyclic ether, has a high polarity, the polycarbonate resin (A) has a high polarity as a whole polymer. Since (B) has a relatively low polarity, the resin composition obtained by mixing is poorly compatible, and since the molding defect and the compatibility are poor, unevenness is often observed in the obtained molded piece. Moreover, when there is too little, there exists a tendency for the heat resistance of a mixture to fall.

  For this reason, the structural unit (a) derived from the dihydroxy compound having a site represented by the general formula (1), preferably the general formulas (2) to (4), with respect to all structural units derived from the dihydroxy compound. Is preferably 15 mol% or more, more preferably 25 mol% or more, particularly preferably 30 mol% or more, while the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, Especially preferably, it is 40 mol% or less. However, when it has an aromatic ring, a polycarbonate resin having a structure different from that of the polycarbonate resin (B) is used.

  Since the content of the structural unit (a) derived from the dihydroxy compound having the site represented by the general formula (1) is within the above range, the flexibility and moldability of the polycarbonate resin (A) are improved. It is possible to obtain effects such as improvement. On the other hand, when the content of the structural unit (a) derived from the dihydroxy compound having the site represented by the general formula (1) is too small, that is, when the content ratio of the structural unit derived from another dihydroxy compound is too large. In some cases, the mechanical properties may deteriorate and the heat resistance may deteriorate. Moreover, when there is too much content of the structural unit (a) derived from the dihydroxy compound which has a site | part represented by the said General formula (1), ie, there are too few content rates of the structural unit derived from other dihydroxy compounds. The water absorption rate may increase or the flexibility may be reduced.

  Examples of the other dihydroxy compounds include aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and aromatic bisphenols.

  Examples of the aliphatic hydroxy dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, Examples thereof include 1,5-heptanediol and 1,6-hexanediol.

  Examples of the alicyclic hydrocarbon dihydroxy compound include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2 1,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol and the like. .

  As the aromatic bisphenols, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2- Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5- Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1 , 1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4 Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3 '-Dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy- 2-methylphenyl) fluorene and the like.

  These may be used alone or in combination of two or more depending on the required performance of the polycarbonate to be obtained. In addition, the dihydroxy compound containing phenolic OH is not preferable because reactivity with alcoholic OH is greatly different and the color tone of the obtained polymer is inferior.

  Among these, from the viewpoint of light resistance of the polycarbonate resin (A), a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, an aliphatic dihydroxy compound and / or a dihydroxy compound of an alicyclic hydrocarbon is preferable. In particular, as the aliphatic dihydroxy compound, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are particularly preferable. Further, a preferred alicyclic hydrocarbon dihydroxy compound is a compound having a cyclic structure hydrocarbon skeleton and two hydroxy groups, and the hydroxy group may be directly bonded to the cyclic structure. Moreover, you may couple | bond with the cyclic structure through the substituent. Furthermore, the cyclic structure may be monocyclic or polycyclic. As the alicyclic hydrocarbon dihydroxy compound, 1,4-cyclohexanedimethanol and tricyclodecane dimethanol are particularly preferable.

  The content of the structural units derived from the other dihydroxy compounds, particularly the aliphatic hydrocarbon dihydroxy compounds, and the structural units derived from the alicyclic hydrocarbon dihydroxy compounds, with respect to all the structural units derived from the dihydroxy compounds, Preferably, it is at least 50 mol%, more preferably at least 55 mol%, particularly preferably at least 60 mol%, while the upper limit is preferably at most 85 mol%, more preferably at most 80 mol%, particularly preferably at least 75 mol%. % Or less.

  The content of the structural unit derived from the other dihydroxy compound, particularly the structural unit derived from an aliphatic hydrocarbon dihydroxy compound, or the structural unit derived from an alicyclic hydrocarbon dihydroxy compound, with respect to all the structural units derived from the dihydroxy compound. Therefore, it is possible to obtain effects such as improvement in flexibility and moldability of the polycarbonate resin (A). On the other hand, when the content is larger than this range, mechanical properties and heat resistance may be lowered. Moreover, when content is made smaller than this range, a water absorption rate may become high and it may become weak.

  The dihydroxy compound used in the present invention may contain a stabilizer such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer, a heat stabilizer, etc. Since the dihydroxy compound used for this invention is easy to change in quality, it is preferable that a basic stabilizer is included.

  Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide Basic ammonium compounds such as roxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 4-amino Pyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole Amine compounds such as 2-mercaptoimidazole, 2-methylimidazole and aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferred, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferred because of their effects and ease of distillation removal described below.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound used for this invention of these basic stabilizers, if there is too little, there exists a possibility that the effect which prevents the quality change of the dihydroxy compound used for this invention may not be acquired, and too much. Since it may cause modification of the dihydroxy compound used in the present invention, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound used in the present invention. It is.

  When the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger or handle under a nitrogen atmosphere. When isosorbide is oxidized, decomposition products such as formic acid may be generated. For example, when isosorbide containing these decomposition products is used as a polycarbonate resin production raw material, the resulting polycarbonate resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. In some cases, a high molecular weight polymer cannot be obtained.

<Carbonated diester>
The polycarbonate resin (A) used in the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester as raw materials.

  As a carbonic acid diester used, what is normally represented by following General formula (5) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

（上記一般式（５）において、Ａ^１及びＡ^２は、それぞれ独立に、置換若しくは無置換の炭素数１〜炭素数１８の脂肪族基、または、置換若しくは無置換の芳香族基である。）

(In the above general formula (5), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group. )

  Examples of the carbonic acid diester represented by the general formula (5) include substituted diphenyl carbonate such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.

<Transesterification reaction catalyst>
The polycarbonate resin (A) used in the present invention produces a polycarbonate resin by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester represented by the general formula (5) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

  The transesterification catalyst that can be used in the production of the polycarbonate resin (A) used in the present invention (hereinafter sometimes simply referred to as a catalyst or a polymerization catalyst) has an effect on the light transmittance at a wavelength of 350 nm and the yellow index value. Can give.

  As the catalyst used, as long as the light resistance, transparency, hue, heat resistance, thermal stability, and mechanical strength of the manufactured polycarbonate resin (A) can satisfy the light resistance, Although not limited, a metal compound, a basic boron compound, a basic phosphorus compound, and a basic ammonium of Group 1 or 2 (hereinafter, simply referred to as “Group 1” or “Group 2”) in the long-period periodic table Examples thereof include basic compounds such as compounds and amine compounds. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

  It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate 2 potassium potassium phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Among them, lithium compounds are preferable.

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, Examples include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc., among which magnesium compounds, calcium compounds and barium compounds are preferred, and polymerization activity and obtained From the viewpoint of the hue of the polycarbonate resin obtained, a magnesium compound and / or a calcium compound is more preferable, and a calcium compound is most preferable.

  Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

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

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

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

  The amount of the polymerization catalyst used is preferably 0.1 μmol to 300 μmol, more preferably 0.5 μmol to 100 μmol, based on 1 mol of all dihydroxy compounds used in the polymerization. In the case of using a compound containing at least one metal selected from the group consisting of Group 2 in the above, particularly when using a magnesium compound and / or a calcium compound, the amount of metal is preferably 1 mol per 1 mol of all the dihydroxy compounds. 0.1 μmol or more, more preferably 0.5 μmol or more, particularly preferably 0.7 μmol or more. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, most preferably 1.5 μmol, and most preferably 1.0 μmol.

  When the amount of the catalyst is too small, the polymerization rate is slowed down. As a result, when trying to obtain a polycarbonate resin (A) having a desired molecular weight, the polymerization temperature must be increased, and the resulting polycarbonate resin (A) The hue and light resistance are deteriorated, the unreacted raw material is volatilized during the polymerization, and the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention to the carbonic acid diester represented by the above general formula (5) collapses. May not reach the molecular weight of. On the other hand, when there is too much usage-amount of a polymerization catalyst, the hue of the polycarbonate resin (A) obtained will be deteriorated and the light resistance of a polycarbonate resin (A) may deteriorate.

  Furthermore, when the polycarbonate resin (A) used in the present invention is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the general formula (5), phenol and substituted phenol are used. By-product and remaining in the polycarbonate resin (A) are inevitable, but not only phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, May cause odor during molding. The polycarbonate resin (A) contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, from the viewpoint of light resistance and odor reduction. Is preferably 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less, using a horizontal reactor excellent in devolatilization performance or an extruder with a vacuum vent. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.

  These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

  Further, Group 1 metals, especially sodium, potassium, and cesium, especially lithium, sodium, potassium, and cesium, may have an adverse effect on the hue when contained in the polycarbonate resin (A) in large quantities. The total amount of these in the polycarbonate resin (A) is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less as the amount of metal, because it may be mixed not only from the catalyst to be used, but also from raw materials and reactors. More preferably, it is 0.7 ppm by weight or less.

  The amount of metal in the polycarbonate resin (A) should be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. I can do it.

<Polycarbonate resin (A) production method>
The polycarbonate resin (A) used in the present invention is obtained by polycondensation of the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester of the general formula (5) by a transesterification reaction. The compound and the carbonic acid diester are preferably mixed uniformly before the transesterification reaction.

  The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often resulting in problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a deterioration of the hue of the polycarbonate resin thus obtained, which may adversely affect light resistance.

  The operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the raw material of the polycarbonate resin (A) used in the present invention, and the carbonic acid diester represented by the general formula (5) is an oxygen concentration of 10 vol% or less, Is preferably carried out in an atmosphere of 0.0001 vol% to 10 vol%, particularly 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol%, from the viewpoint of preventing hue deterioration.

  In order to obtain the polycarbonate resin (A) used in the present invention, the carbonic acid diester represented by the general formula (5) is 0.90 to the dihydroxy compound including the dihydroxy compound used in the present invention used for the reaction. The molar ratio is preferably 1.20, more preferably 0.95 to 1.10.

  When this molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloring occurs during molding, the rate of transesterification reaction is reduced, and the desired high molecular weight. The body may not be obtained.

  Moreover, when this molar ratio becomes large, the speed | rate of transesterification may fall or manufacture of polycarbonate resin (A) of the desired molecular weight may become difficult. The decrease in the transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting polycarbonate resin.

  Furthermore, when the molar ratio of the carbonic acid diester represented by the general formula (5) is increased with respect to the dihydroxy compound including the dihydroxy compound used in the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate resin (A) is increased. They increase, and these may absorb the ultraviolet rays and deteriorate the light resistance of the polycarbonate resin, which is not preferable.

  The concentration of the carbonic acid diester remaining in the polycarbonate resin (A) used in the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. . Actually, the polycarbonate resin (A) may contain an unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.

  In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type. In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoints of hue and light resistance. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used. Usually, the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler. Preferably, it is 80 degreeC-150 degreeC, Most preferably, it is 100 degreeC-130 degreeC. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, but not to impair the hue, thermal stability, light resistance, etc. of the final polycarbonate resin, Selection is important.

  The polycarbonate resin (A) used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst. The reason for carrying out the polymerization in a plurality of reactors is a polymerization reaction. In the initial stage, since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. In the latter stage of the polymerization reaction, the equilibrium is shifted to the polymerization side. Therefore, it is important to sufficiently distill off the monohydroxy compound produced as a by-product. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

  As described above, the number of reactors used in the method of the present invention may be at least two or more. However, from the viewpoint of production efficiency and the like, three or more, preferably 3 to 5, particularly preferably 4 are used. One.

  In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

  In the present invention, the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank. A catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution.

  If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized but also decomposition and coloring of the polycarbonate resin may be promoted.

  Specifically, the reaction in the first stage is performed at 140 to 270 ° C., preferably 180 to 240 ° C., more preferably 200 to 230 ° C. as the maximum internal temperature of the polymerization reactor. The monohydroxy compound generated is removed from the reaction system at a pressure of 1 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 10 kPa (absolute pressure) for 0.1 hours to 10 hours, preferably 0.5 hours to 3 hours. Carried out while distilling.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. 200 Pa or less, maximum internal temperature of 210 ° C. to 270 ° C., preferably 220 ° C. to 250 ° C., usually 0.1 hour to 10 hours, preferably 1 hour to 6 hours, particularly preferably 0.5 hour. Perform for ~ 3 hours.

  In particular, in order to obtain a polycarbonate resin (A) having good hue and light resistance by suppressing coloring and thermal deterioration of the polycarbonate resin (A), the maximum internal temperature in all reaction stages is less than 250 ° C, particularly from 225 ° C to It is preferable that it is 245 degreeC. In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

  In order to obtain a polycarbonate resin (A) having a predetermined molecular weight, if the polymerization temperature is increased and the polymerization time is too long, the ultraviolet transmittance decreases and the YI value tends to increase.

  The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.

  The polycarbonate resin (A) used in the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like.

  The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Alternatively, a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.

  At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded. The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. is there. When the melt kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin (A) is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal deterioration of the polycarbonate becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

  When the polycarbonate resin (A) used in the present invention is produced, it is desirable to install a filter in order to prevent foreign substances from entering. The filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 μm or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 μm or less, more preferably 10 μm or less.

  Extrusion of the polycarbonate resin (A) used in the present invention is preferably a clean room having a higher degree of cleanliness than Class 7 as defined in JIS B 9920 (2002), more preferably a clean room in order to prevent foreign matter from being mixed after extrusion. It is desirable to implement in. Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. The opening of the filter to be used is preferably 10 μm to 0.45 μm as 99% removal filtration accuracy.

  The molecular weight of the polycarbonate resin (A) used in the present invention thus obtained can be represented by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more. The upper limit of the reduced viscosity is more preferably 1.20 dL / g or less and 1.00 dL / g or less, still more preferably 0.80 dL / g or less.

  If the reduced viscosity of the polycarbonate resin (A) is too low, the mechanical strength of the molded product may be small. If it is too large, the fluidity at the time of molding tends to decrease and the productivity and moldability tend to decrease. .

  The reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ± 0.1 ° C., precisely prepared at a polycarbonate concentration of 0.6 g / dL using methylene chloride as a solvent.

  Furthermore, the lower limit of the concentration of the terminal group represented by the following general formula (6) in the polycarbonate resin (A) used in the present invention is usually 20 μeq / g, preferably 40 μeq / g, particularly preferably 50 μeq / g. The upper limit is usually 160 μeq / g, preferably 140 μeq / g, particularly preferably 100 μeq / g.

  If the concentration of the end group represented by the following general formula (6) is too high, even if the hue at the time of polymerization or molding is good, the hue after exposure to ultraviolet light may be deteriorated. Thermal stability may be reduced. In order to control the concentration of the terminal group represented by the following general formula (6), the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention as the raw material and the carbonic acid diester represented by the general formula (5) is set. In addition to controlling, a method for controlling the kind and amount of the catalyst at the time of the transesterification reaction, the polymerization pressure and the polymerization temperature can be used.

In addition, when the number of moles of H bonded to the aromatic ring in the polycarbonate resin (A) used in the present invention is (C) and the number of moles of H bonded to other than the aromatic ring is (D), it is bonded to the aromatic ring. The ratio of the number of moles of H to the number of moles of total H is expressed by C / (C + D). However, as described above, there is a possibility that an aromatic ring having an ultraviolet absorbing ability affects the light resistance. Therefore, C / (C + D) is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.02 or less, and preferably 0.01 or less. C / (C + D) can be quantified by ¹ H-NMR.

  The polycarbonate resin composition (A) of the present invention can be formed into a molded product by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method. In addition, the polycarbonate resin (A) used in the present invention is, as necessary, a heat stabilizer, a neutralizer, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, and a lubricant before performing various moldings. Additives such as lubricants, plasticizers, compatibilizers, and flame retardants can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder or the like.

  The glass transition temperature of the polycarbonate resin (A) is preferably 75 ° C. or higher and 105 ° C. or lower, more preferably 80 ° C. or higher and 105 ° C. or lower, and 85 ° C. or higher and 105 ° C. or lower. preferable. By using the polycarbonate resin (A) within the range where the glass transition temperature is applied, a molded product having excellent heat resistance can be provided.

<Aromatic polycarbonate resin (B)>
The aromatic polycarbonate resin (B) used in the present invention is a polycarbonate resin in which structural units derived from a dihydroxy compound are connected by a carbonate bond, and has any conventionally known one as long as it has an aromatic ring in the structure. May also be used, and may include a structural unit derived from a dihydroxy compound having a site represented by the general formula (1). However, when it contains a structural unit derived from a dihydroxy compound having a site represented by the formula (1), a polycarbonate resin having a structure different from that of the polycarbonate resin (A) is used.

  The aromatic polycarbonate resin (B) used in the present invention may be either a homopolymer or a copolymer. Moreover, the aromatic polycarbonate resin (B) may have a branched structure.

More specifically, a polycarbonate resin having a repeating structure represented by the following general formula (7) can be given.
— [— O—Ar ¹ —X—Ar ² —] — OC (═O) — (7)
(In the general formula (7), Ar ¹ and Ar ² each independently represent an arylene group which may have a substituent, and X represents a single bond or a divalent group.)

  The arylene group which may have a substituent is not particularly limited as long as it is an arylene group, but is preferably an arylene group having 3 or less aromatic rings, more preferably a phenylene group. is there.

As the substituent that Ar ¹ and Ar ² may independently have, the alkyl group having 1 to 10 carbon atoms which may have a substituent and the carbon number which may have a substituent Examples thereof include an alkoxy group having 1 to 10 carbon atoms, a halogen group, a halogenated alkyl group having 1 to 10 carbon atoms, and an aromatic group having 6 to 20 carbon atoms which may have a substituent. Among these substituents, an alkyl group having 1 to 10 carbon atoms which may have a substituent or an aromatic group having 6 to 20 carbon atoms which may have a substituent is preferable, and more preferably. An alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group.

Examples of the divalent group represented by X include an alkylene group having a chain structure having 1 to 6 carbon atoms which may have a substituent, and a chain having 1 to 6 carbon atoms which may have a substituent. An alkylidene group having a ring structure, an alkylene group having a cyclic structure having 3 to 6 carbon atoms which may have a substituent, an alkylidene group having a cyclic structure having 3 to 6 carbon atoms which may have a substituent, -O —, —S—, —CO— or —SO ₂ — can be mentioned, and among these, an alkylidene group having a chain structure of 3 carbon atoms is particularly preferable. As the substituent that the alkylene group having a chain structure having 1 to 6 carbon atoms has, an aryl group is preferable, and a phenyl group is particularly preferable.

  The structural unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) used in the present invention is obtained by removing a hydrogen atom from the hydroxyl group of the dihydroxy compound. Specific examples of the dihydroxy compound corresponding to this include biphenyl compounds, bisphenol compounds, halogenated bisphenol compounds, and the like.

  Examples of the biphenyl compound include 4,4′-biphenol, 2,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-dimethyl-2, 4′-dihydroxy-1,1′-biphenyl, 3,3′-di- (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 3,3 ′, 5,5′-tetra Methyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3 ′, 5,5′-tetra- (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 2, 2 ', 3,3', 5,5'-hexamethyl-4,4'-dihydroxy-1,1'-biphenyl and the like.

  Examples of the bisphenol compound include bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1, 1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy) -3-methylphenyl) propane, 2,2-bis- (4-hydroxyphenyl) butane, 2,2-bis- (4-hydroxyphenyl) pentane, 2,2-bis- (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis- (4-hydroxyphenyl) hexane, 2,2-bis- (4-hydroxyphenyl) -4-methylpenta 1,1-bis- (4-hydroxyphenyl) cyclopentane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, bis- (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis- (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis- (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis- (3-phenyl-4-hydroxyphenyl) propane, 1, 1-bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis- (4-hydroxy-3-ethylphenyl) propane, 2,2-bis- (4-hydroxy-3-isopropylphenyl) Propane, 2,2-bis- (4-hydroxy-3-sec-butylphenyl) propane, 1,1-bis- (4-hydroxy-3,5-dimethyl) Phenyl) ethane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis- (4-hydroxy-3,6-dimethylphenyl) ethane, bis- (4-hydroxy) -2,3,5-trimethylphenyl) methane, 1,1-bis- (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis- (4-hydroxy-2,3,5) -Trimethylphenyl) propane, bis- (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis- (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, 1, 1-bis- (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane, bis- (4-hydroxyphenyl) phenylmethane, 1,1-bis- (4-hydride) Loxyphenyl) -1-phenylethane, 1,1-bis- (4-hydroxyphenyl) -1-phenylpropane, bis- (4-hydroxyphenyl) diphenylmethane, bis- (4-hydroxyphenyl) dibenzylmethane, 4 , 4 ′-[1,4-phenylenebis (1-methylethylidene)] bis- [phenol], 4,4 ′-[1,4-phenylenebismethylene] bis- [phenol], 4,4 ′-[ 1,4-phenylenebis (1-methylethylidene)] bis- [2,6-dimethylphenol], 4,4 ′-[1,4-phenylenebismethylene] bis- [2,6-dimethylphenol], 4 , 4 ′-[1,4-phenylenebismethylene] bis- [2,3,6-trimethylphenol], 4,4 ′-[1,4-phenylenebis (1-methyl ester) Ridene)] bis- [2,3,6-trimethylphenol], 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bis- [2,3,6-trimethylphenol], 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl ether, 3,3', 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide, phenolphthalein, 4,4 ′-[1 , 4-phenylenebis (1-methylvinylidene)] bisphenol, 4,4 ′-[1,4-phenylenebis (1-methylvinyl) Redene)] bis [2-methylphenol], (2-hydroxyphenyl) (4-hydroxyphenyl) methane, (2-hydroxy-5-methylphenyl) (4-hydroxy-3-methylphenyl) methane, 1,1 -(2-hydroxyphenyl) (4-hydroxyphenyl) ethane, 2,2- (2-hydroxyphenyl) (4-hydroxyphenyl) propane, 1,1- (2-hydroxyphenyl) (4-hydroxyphenyl) propane Etc.

  Further, examples of the halogenated bisphenol compound include 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane. It is done.

  Among these, preferred dihydroxy compounds include bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2- Bis- (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, bis- (4-hydroxyphenyl) phenylmethane, 1,1-bis- (4- Hydroxyphenyl) -1-phenylethane, 1,1-bis- (4-hydroxyphenyl) -1-phenylpropane, bis- (4 Bisphenol compounds in which phenols are linked by an alkylidene group, such as hydroxyphenyl) diphenylmethane, 2-hydroxyphenyl (4-hydroxyphenyl) methane, and 2,2- (2-hydroxyphenyl) (4-hydroxyphenyl) propane It is done. These are preferable in terms of heat resistance and mechanical properties.

  Furthermore, among these, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, bis- (4-hydroxy-3,5-dimethylphenyl) methane, 2,2 -Bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) propane, Bisphenol compounds having an alkylidene group having 6 or less carbon atoms, such as 1,2-bis- (4-hydroxyphenyl) cyclohexane, are particularly preferred in terms of versatility and low cost.

<Method for producing aromatic polycarbonate resin (B)>
As a method for producing the aromatic polycarbonate resin (B) used in the present invention, any conventionally known method such as a phosgene method, a transesterification method, a pyridine method or the like may be used. As an example, a method for producing an aromatic polycarbonate resin (B) by a transesterification method will be described below.

  The transesterification method is a production method in which a dihydroxy compound and a carbonic acid diester are added with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added, and melt transesterification condensation polymerization is performed. Examples of the dihydroxy compound include the biphenyl compounds and bisphenol compounds exemplified above.

  Representative examples of carbonic acid diesters include diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, and dibutyl carbonate. And dialkyl carbonates such as dicyclohexyl carbonate. Of these, diphenyl carbonate is particularly preferably used.

  The viscosity average molecular weight of the aromatic polycarbonate resin (B) used in the present invention is usually 8,000 or more and 30,000 or less, preferably 10,000 or more and 25,000, from the balance of mechanical properties and molding processability. The range is as follows. The reduced viscosity of the aromatic polycarbonate resin (B) was measured at a temperature of 20.0 ° C. ± 0.1 ° C. using methylene chloride as a solvent and the polycarbonate concentration was precisely adjusted to 0.60 g / dl. Usually, it is 0.23 dl / g or more and 0.72 dl / g or less, preferably 0.27 dl / g or more and 0.61 dl / g or less.

  In the present invention, the aromatic polycarbonate resin (B) may be used alone or in combination of two or more.

<Polycarbonate resin composition>
The polycarbonate resin composition in the present invention includes a polycarbonate resin (A) containing a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure, and an aromatic polycarbonate resin (B). A polycarbonate resin composition comprising:

（但し、上記一般式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

  The ratio of the aromatic polycarbonate resin (B) in the polycarbonate resin composition comprising the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is usually 60% by weight or more, preferably 65% by weight. Above, more preferably 70% by weight or more, particularly preferably 80% by weight or more. On the other hand, it is preferably 95% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less.

  By the way, generally, when aromatic polycarbonates (B) having different viscosities are mixed with each other, the melt viscosity of the mixture is additive, so that a large viscosity reduction does not occur.

  On the other hand, the structure derived from the dihydroxy compound having the site represented by the above general formula (1) in the polycarbonate resin (A), particularly the structure containing a cyclic ether is highly polar and sterically bulky. Furthermore, in the polycarbonate resin (A) having a structural unit derived from a dihydroxy compound of an aliphatic hydrocarbon and / or a structure derived from a dihydroxy compound of an alicyclic hydrocarbon, the entire polymer becomes more sterically bulky. Therefore, the mixture of the aromatic polycarbonate resin (B) and the polycarbonate resin (A) tends to repel sterically and electronically, creating a microscopic space between the polymers, resulting in plasticization as a whole polymer. , The melt viscosity tends to decrease.

  For these reasons, when the ratio of the aromatic polycarbonate resin (B) in the polycarbonate resin composition is too large, the effect of improving the fluidity tends to be thinned. Moreover, when the ratio of polycarbonate resin (B) is too small, the heat resistance and the mechanical property will tend to decrease.

  The polycarbonate resin composition in the present invention preferably has a single glass transition temperature from the viewpoint of maintaining the transparency of the polycarbonate resin composition and the polycarbonate resin molded product.

  Further, the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the polycarbonate resin composition only need to be different types, and the polycarbonate resin (A) preferably has a ring structure, Of these, those containing isosorbide are particularly preferred.

<Resin other than polycarbonate resin>
The polycarbonate resin composition of the present invention and a molded product obtained using this polycarbonate resin can be blended with resins other than polycarbonate resins and additives other than resins.

  Specific examples of resins other than polycarbonate resins that are compounded for the purpose of further improving and adjusting molding processability and various physical properties include resins such as polyester resins, polyethers, polyamides, polyolefins, polymethyl methacrylates, and core-shell types. And rubber-like modifiers such as graft-type or linear random and block copolymers.

  The blending amount of the resin other than the polycarbonate resin is a ratio of 1 part by weight or more and 30 parts by weight or less with respect to 100% by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferably blended at a ratio of 3 parts by weight or more and 20 parts by weight or less, more preferably 5 parts by weight or more and 10 parts by weight or less.

<Heat stabilizer>
In the polycarbonate resin composition and the polycarbonate resin molded product of the present invention, a heat stabilizer can be blended in order to prevent a decrease in molecular weight and a deterioration in hue during molding. Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert -Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl Phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), benzenephosphonic acid Examples thereof include dimethyl, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used.

  These heat stabilizers may be used alone or in combination of two or more. The blending amount of the heat stabilizer is 0.0001 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix, more preferably 0.0005 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. preferable. By blending the heat stabilizer within such a range, it is possible to prevent a decrease in molecular weight or discoloration of the resin without causing bleeding of the additive.

<Antioxidant>
Moreover, the antioxidant generally known for the purpose of antioxidant can be mix | blended with the polycarbonate resin composition and polycarbonate resin molded product of this invention. Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3, 5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis (2, 4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2 , 4,8,10-tetraoxaspiro (5,5) undecane and the like.

  The blending amount of the antioxidant is 0.0001 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix, more preferably 0.0005 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. preferable. By blending the antioxidant in such a range, the oxidation deterioration of the resin can be prevented without causing the bleeding of the antioxidant on the surface of the molded body and the deterioration of the mechanical properties of various molded products.

<Ultraviolet absorber>
In order to further improve the weather resistance of the polycarbonate resin composition and the polycarbonate resin molded product of the present invention, an ultraviolet absorber can be blended. Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo. Triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′- Examples include methylene bis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one) and the like.

  The melting point of the ultraviolet absorber is particularly preferably in the range of 120 to 250 ° C. When an ultraviolet absorber having a melting point of 120 ° C. or higher is used, fogging due to gas on the surface of the molded article is reduced and improved. Specifically, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, and other benzotriazole ultraviolet absorbers Among these, in particular, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyrate) )-6-(2H-benzotriazol-2-yl) phenol is preferred. These ultraviolet absorbers may be used alone or in combination of two or more.

  The blending amount of the ultraviolet absorber is 0.0001 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix, more preferably 0.0005 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. preferable. Within such a range, the weather resistance of the resin composition and the molded article can be improved without causing bleeding of the ultraviolet absorbent on the surface of the molded article of the ultraviolet absorbent and deterioration of mechanical properties of various molded articles.

<Hindered amine light stabilizer>
Moreover, a hindered amine light stabilizer can be mix | blended in order to further improve the weather resistance of the polycarbonate resin composition and the polycarbonate resin molded product of the present invention. Such hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidylamino) -6-chloro-1,3,5-triazine condensate, dibutylamine, 1,3,5-triazine, N, N'- Bis (2,2,6,6) -tetrame Le 4-piperidyl-1,6-hexamethylene diamine and N-(2,2,6,6-tetramethyl-4-piperidyl) polycondensate butylamine, and the like. Of these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are preferred.

  The amount of the hindered amine light stabilizer is 0.001 part by weight or more and 1 part by weight or less based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix | blend in a ratio, It is still more preferable to mix | blend in the ratio of 0.005 weight part or more and 0.5 weight part or less, It mix | blends in the ratio of 0.01 weight part or more and 0.2 weight part or less. Is particularly preferred. By blending the hindered amine light stabilizer within such a range, the polycarbonate resin composition of the present invention can be molded without causing bleeding of the hindered amine light stabilizer on the surface of the polycarbonate resin composition and deterioration of mechanical properties of various molded products. The weather resistance of the molded product formed can be improved.

<Release agent>
The polycarbonate resin composition of the present invention preferably further contains a release agent in order to further improve the releasability from the mold during melt molding. Release agents include higher fatty acids, higher fatty acid esters of mono- or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, and montan wax. Natural coal wax, olefin wax, silicone oil, organopolysiloxane and the like can be mentioned, and higher fatty acid and higher fatty acid ester of monohydric or polyhydric alcohol are particularly preferable.

  The higher fatty acid ester is preferably a partial ester or a total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

  The higher fatty acid is preferably a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms. Examples of such saturated fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like. One of these release agents may be used alone, or two or more thereof may be mixed and used.

  The content of the release agent is preferably 0.0001 parts by weight or more, more preferably 0.01 parts by weight with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. Part by weight or more, particularly preferably 0.1 part by weight or more, on the other hand, preferably 2 parts by weight or less, more preferably 1 part by weight or less, particularly preferably 0.5 parts by weight or less. If it is smaller than this range, there is a risk that mold release failure will occur. On the other hand, if it is larger than this range, the heat resistance of the molded product may be lowered.

  In this Embodiment, the addition time of the said mold release agent mix | blended with a polycarbonate resin composition and the addition method are not specifically limited. For example, when the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; the polycarbonate resin melted during mixing of the polycarbonate resin and other compounding agents regardless of the polymerization method. A case where it is blended and kneaded with a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like. As an addition method, a method of directly mixing or kneading the release agent with a polycarbonate resin; a high-concentration masterbatch prepared using a small amount of a polycarbonate resin or other resin and the release agent can also be added. .

<Molding>
In the present embodiment, a polycarbonate resin molded product obtained by molding the above-described polycarbonate resin composition is obtained. The molding method of the polycarbonate resin molded product is not particularly limited, but the polycarbonate resin (A), the aromatic polycarbonate resin (B) and, if necessary, other raw materials such as resins and additives are directly mixed, and an extruder or an injection. Either put into a molding machine and mold, or melt and mix the raw materials using a twin-screw extruder, extrude into a strand shape to produce pellets, and then put these pellets into an extruder or injection molding machine Can be mentioned. Moreover, since the polycarbonate resin molded article of the present invention is excellent in light resistance and transparency, it can be used for road sound insulation walls, arcade ceiling sheets, arcade ceiling plates, facility roofs, facility wall materials, and the like.

<Melt viscosity>
The melt viscosity of the polycarbonate resin (A) measured with a capillary rheometer at 240 ° C. is preferably 4.0 × 10 ² Pa · s or more under the condition of a shear rate of 600 sec ⁻¹ and 4.5 × 10 ² Pa. -S or more is preferable. If it is lower than 4.0 × 10 ² , the melt viscosity is low, which may cause a problem of dripping during molding. On the other hand, the upper limit of the melt viscosity is preferably 10.0 × 10 ² Pa · s, and preferably 9.0 × 10 ² Pa · s. If it is higher than 10.0 × 10 ² Pa · s, the melt viscosity is too high, which may cause a problem that molding is difficult.

<Load deflection temperature>
The load deflection temperature in ISO75 of the polycarbonate resin composition according to the present invention is preferably 80 ° C. or higher and preferably 85 ° C. or higher when a load of 1.80 MPa is applied. If it is less than 80 ° C., there is a case where a problem that the molded product is usually deformed during use may occur. On the other hand, the upper limit of the load deflection temperature is preferably 135 ° C, and preferably 130 ° C. When the temperature is higher than 135 ° C., a high temperature is required for melting at the time of molding, and there are cases in which problems such as poor fluidity occur during molding.

<Total light transmittance>
The total light transmittance of the polycarbonate resin composition according to the present invention is measured with a D65 light source in accordance with JSI-K7105 using a test piece made of the polycarbonate resin composition. The total light transmittance of the polycarbonate resin composition according to the present invention measured by this method is preferably 80% or more, and preferably 85% or more. If it is lower than 80%, there is a problem that the molded product becomes opaque and cloudy. On the other hand, the upper limit of the total light transmittance is preferably 99%, and preferably 90%. Although it may be higher than 99%, it is difficult to obtain a material higher than 99%, and 99% is sufficient.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.

[Evaluation of physical properties and characteristics]
In the following, evaluation of physical properties or characteristics of polycarbonate resin, polycarbonate resin composition, molded article and the like was performed by the following method.
(1) Measurement of reduced viscosity A polycarbonate resin sample was dissolved using methylene chloride as a solvent to prepare a polycarbonate solution having a concentration of 0.6 g / dL. Made by Mori Tomo Rika Kogyo Co., Ltd .: Measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde type viscosity tube. From the following equation, the relative viscosity η is calculated from the solvent passage time t ₀ and the solution passage time t _{find rel} ,

η _rel = t / t ₀

From the relative viscosity, the specific viscosity η _sp was determined from the following equation.

η _sp = (η−η ₀ ) / η ₀ = η _rel −1

The reduced viscosity η _sp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

(2) Total light transmittance The polycarbonate resin pellets were dried at 90 ° C. for 10 hours in a nitrogen atmosphere. Next, the dried polycarbonate resin pellets were supplied to an injection molding machine (manufactured by Nippon Steel Co., Ltd .: J75EII type), and injection molded pieces (width 60 mm × length) under conditions of a resin temperature of 220 ° C. and a molding cycle of 23 seconds. The injection molding piece in the thickness direction of the 10th to 20th shots was repeatedly molded according to JIS K7105, and a haze meter (Nippon Denshoku Industries Co., Ltd.) Co., Ltd .: NDH2000) was used, and the total light transmittance and haze of the test piece were measured with a D65 light source.

(3) Deflection temperature under load Based on ISO75, the deflection temperature under load at 1.80 MPa was measured.

(4) Melt viscosity Melt viscosity (Pa · s): A sample dried at 90 ° C. for 10 hours is heated to a constant temperature using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) having a die diameter of 1 mmφ × 10 mmL. was measured between shear rate γ = 9.12~1824 ^{(sec -1)} and were read melt viscosity at 600 sec ^-1.

(5) Appearance When the appearance was observed, “◯” was indicated when no burrs or sink marks were observed on the molded product, and “X” was indicated when burrs or sink marks were observed on the molded product.

[raw materials]
<Polycarbonate resin (A)>
<Manufacturing method of PC1>
The abbreviations of the compounds used in the description of the following examples are as follows.
・ ISB: Isosorbide (Rocket Fleure, trade name: POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Shin Nippon Rika Co., Ltd., SKY CHDM)
・ DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. The mixture was charged so that ISB / CHDM / DPC / calcium acetate monohydrate = 0.40 / 0.60 / 1.00 / 6.5 × 10 ⁻⁷ , and sufficiently substituted with nitrogen. Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 30 minutes.
The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.
The content thus oligomerized is once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was 210 ° C. and the pressure was 200 Pa in 60 minutes. Thereafter, the internal temperature was 220 ° C. over 20 minutes, the pressure was 133 Pa or less, the pressure was restored when the predetermined stirring power was reached, and the molten polycarbonate resin was pelletized with a pelletizer from the outlet of the polymerization reactor to obtain pellets. . The reduced viscosity was 0.63 dl / g.

<Manufacturing method of PC2>
Except that the structural unit derived from isosorbide / the structural unit derived from 1,4-cyclohexanedimethanol = 70/30 mol%, a polycarbonate resin pellet in a molten state was obtained in the same manner as PC1. The reduced viscosity was 0.51 dl / g.

<Manufacturing method of PC3>
Except that the structural unit derived from isosorbide / the structural unit derived from 1,4-cyclohexanedimethanol = 0/100 mol%, a polycarbonate resin pellet in a molten state was obtained in the same manner as PC1. The reduced viscosity was 0.72 dl / g.

<Aromatic polycarbonate resin (B)>
PC4 ... Mitsubishi Engineering Plastics Co., Ltd .: Novalex M7027BF (Aromatic polycarbonate resin having a structure derived only from 2,2-bis- (4-hydroxyphenyl) propane, reduced viscosity 0.56 dl / g)
PC5: manufactured by Mitsubishi Engineering Plastics Co., Ltd .: NOVAREX M7022J (aromatic polycarbonate resin having a structure derived only from 2,2-bis- (4-hydroxyphenyl) propane, reduced viscosity 0.47 dl / g)
PC6: manufactured by Mitsubishi Engineering Plastics Co., Ltd .: Novalex M7020AD2 T-5 (aromatic polycarbonate resin having a structure derived only from 2,2-bis- (4-hydroxyphenyl) propane, reduced viscosity 0.38 dl / g)

Example 1
After PC1 and PC4 were dry blended at a weight ratio of 15:85, they were extruded at a resin temperature of 250 ° C. using a twin screw extruder (TEX30HSS-32) manufactured by Nippon Steel Works, and cooled and solidified with water. Then, it pelletized with the rotary cutter. The pellets were dried at 80 ° C. for 10 hours in a nitrogen atmosphere, and then supplied to an injection molding machine (manufactured by Nippon Steel Works Co., Ltd .: J75EII type). The resin temperature was 250 ° C., the mold temperature was 80 ° C., and the molding cycle was 40 seconds. Under these conditions, an injection-molded plate (width 60 mm × length 60 mm × thickness 3 mm) was molded.
Table 1 shows the results obtained by measuring the total light transmittance, the deflection temperature under load, and the melt viscosity of the obtained sample.

(Example 2)
Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC4 were mixed at a mixing weight ratio of 40:60. The results are shown in Table 1.

Example 3
Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC5 were mixed at a mixing weight ratio of 5:95. The results are shown in Table 1.

Example 4
Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC5 were mixed at a mixing weight ratio of 15:85. The results are shown in Table 1.

(Comparative Example 1)
Samples were prepared and evaluated in the same manner as in Example 1 except that PC2 and PC4 were mixed at a mixing weight ratio of 15:85. The results are shown in Table 1.

(Comparative Example 2)
Samples were prepared and evaluated in the same manner as in Example 1 except that PC3 and PC4 were mixed at a mixing weight ratio of 40:60. The results are shown in Table 1.

(Comparative Example 3)
A sample was prepared in the same manner as in Example 1 except that PC1 and PC4 were mixed at a mixing weight ratio of 1:99, but a molded piece with good appearance could not be obtained due to high melt viscosity. The results are shown in Table 1.

(Comparative Example 4)
A sample was prepared in the same manner as in Example 1 except that PC4 and PC6 were mixed at a mixing weight ratio of 85:15. However, a molded piece with good appearance was not obtained because of high melt viscosity. The results are shown in Table 1.

(Reference Examples 1-6)
Table 2 shows the results of measuring the total light transmittance, the deflection temperature under load, and the melt viscosity for PC1 to PC6 alone.

Claims (6)

The structural unit (a) derived from a dihydroxy compound having a site represented by the following general formula (1) as part of the structure contains 15 mol% or more and less than 50 mol%, and is derived from 1,4-cyclohexanedimethanol A resin comprising a polycarbonate resin (A) having a structural unit of 50 mol% or more and less than 85 mol% and having a reduced viscosity of 0.30 dL / g or more and 0.80 dL / g or less and an aromatic polycarbonate resin (B) A composition comprising:
A polycarbonate resin composition, wherein the ratio of the polycarbonate (B) is 60% by weight or more and 95% by weight or less .

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.) 2. The polycarbonate resin according to claim 1, wherein the dihydroxy compound having a part represented by the general formula (1) in a part of the structure is a dihydroxy compound represented by the following general formula (2). Composition.

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.) The polycarbonate resin (A) has a melt viscosity measured by a capillary rheometer at 240 ° C. in a range of 4.0 × 10 ^{2 to} 10.0 × 10 ² Pa · s under a condition of a shear rate of 600 sec ^−1. Item 3. The resin composition according to Item 1 or 2. The polycarbonate resin composition according to any one of claims 1 to 3 , wherein the proportion of the polycarbonate (B) is 80% by weight or more. The polycarbonate resin composition according to any one of claims 1 to 4, wherein a total light transmittance of a molded body (thickness 3 mm) molded from the polycarbonate resin composition is 80% to 99%. A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 5 .