JP2018030908A - Polycarbonate resin composition, and molding made of this resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition with an excellent balance between impact resistance, transparency, low light transmittance, color tone, optical properties, moist heat resistance and dry heat resistance.SOLUTION: A polycarbonate resin composition comprises: a component (X), which is polycarbonate resin at least comprising a constitutional unit derived from a dihydroxy compound represented by the general formula (1) in the figure; and a component (Y), which is at least one of a block copolymer comprising A and B blocks and a hydrogenated block copolymer thereof, where the A block is a polymer of an aromatic hydrocarbon with a vinyl group, and the B block is a polymer of a linear unsaturated hydrocarbon with an intramolecular double bond.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition excellent in balance with respect to impact resistance, transparency (total light transmittance), color tone, wet heat resistance, and dry heat resistance.

Polycarbonate resins are generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for providing polycarbonate resins using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. There is a need for the development of such polycarbonate resins.
For example, it has been proposed to use isosorbide (ISB) as a plant-derived monomer and obtain a polycarbonate resin by transesterification with diphenyl carbonate (for example, see Patent Document 1).

  Polycarbonate resins obtained from dihydroxy compounds such as isosorbide not only have excellent optical properties, but also have excellent weather resistance and surface hardness compared to conventionally used aromatic polycarbonate resins, whereas tensile elongation or stress There is a need for further improvement in mechanical properties such as impact resistance in the area where the concentration is concentrated. As a technique for improving the impact resistance, it is known that the impact resistance is improved by adding a core-shell type elastomer to the polycarbonate resin (see, for example, Patent Document 2).

  On the other hand, studies have been made that tensile properties can be improved by incorporating a styrene-based elastomer with respect to conventionally used aromatic polycarbonate resins. Furthermore, it is also known that a metal catalyst can be used to cause a part of the polycarbonate and the elastomer to react with each other (for example, see Patent Document 3).

  Furthermore, in order to improve the characteristics of the amorphous polyolefin resin (A), the amorphous polyolefin resin (A) and a block copolymer (B) composed of an aromatic vinyl compound polymer block and an isobutylene polymer block are used. ), And the amorphous polyolefin resin (A) is composed of both monomers of ethylene and cyclic olefin, or an addition copolymer (A-1) composed of both of them and further α-olefin Or a hydrogenated product (A-2) of a ring-opening polymer of a cyclic olefin, and the weight ratio of (A) / (B) is in the range of 95/5 to 50/50 It is known that a resin composition excellent in impact resistance, transparency and gas barrier properties can be obtained (see, for example, Patent Document 4).

British Patent No. 1079686 JP 2012-214666 A JP-A-11-49944 JP-A-9-124854

According to the study by the present inventors, as in Patent Document 2, a resin composition containing a core-shell type elastomer in a polycarbonate resin using isosorbide as a monomer is as follows:
Excellent impact resistance can be obtained. However, there is a problem that the optical properties of the polycarbonate resin originally using isosorbide as a monomer are impaired. Further, the resin composition has a remarkable change in the color tone of the resin under a high temperature environment, and further improvement has been demanded for long-term use in an environment where the temperature change is large.
Further, as described in Patent Document 3, when a styrene elastomer is contained in an aromatic polycarbonate resin, optical properties such as transparency of the polycarbonate resin are impaired due to the influence of the styrene elastomer. Moreover, although compatibility can be improved by using a metal catalyst and transparency can be improved, hue deterioration such as yellowness, which is considered to be caused by various heterogeneous structure formation as a side reaction by the metal catalyst, has been a problem.

  Furthermore, in Patent Document 4, in order to obtain a practical impact strength, the amount of the block copolymer is increased, and as a result, the haze value is inevitably deteriorated and a practical impact strength and transparency are provided in a balanced manner. There was a problem that it was difficult to do.

  That is, an object of the present invention is to provide a resin composition having a good balance between impact resistance, transparency (total light transmittance), color tone, wet heat resistance, and dry heat resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors can solve the above problems by using a polycarbonate resin composition containing a specific block copolymer in a polycarbonate resin having a specific structure. As a result, the present invention has been completed.

  That is, the gist of the present invention is the following [1] to [7].

［２］前記ポリカーボネート樹脂が前記式（１）で表されるジヒドロキシ化合物以外のジヒドロキシ化合物に由来する構成単位を含む、［１］に記載のポリカーボネート樹脂組成物。
［３］前記ポリカーボネート樹脂が、全ジオールに由来する構成単位１００モル％に対して前記式（１）で表される化合物に由来する構成単位を３０モル％以上含む、［１］または［２］に記載のポリカーボネート樹脂組成物。
［４］前記成分（Ｙ）中のＡブロックの割合が１０〜５０重量％である、［１］〜［３］のいずれか１つに記載の樹脂組成物。
［５］前記Ａブロックが、水素化ポリスチレンブロックである、［１］〜［４］のいずれか１つに記載のポリカーボネート樹脂組成物。
［６］前記Ｂブロックを構成する重合体がイソブチレンに由来する構成単位を含む重合体である、［１］〜［５］のいずれか１つに記載のポリカーボネート樹脂組成物。
［７］［１］〜［６］のいずれか１つに記載のポリカーボネート樹脂組成物を含む成形体
。 [1] A polycarbonate resin composition comprising the following component (X) and component (Y).
Component (X): Polycarbonate resin containing at least a structural unit derived from the dihydroxy compound represented by the following general formula (1) Component (Y): Block copolymer comprising the following A block and B block and this hydrogenated block At least one of the copolymers A block: polymer of aromatic hydrocarbon having vinyl group B block: polymer of chain-like unsaturated hydrocarbon having double bond in the molecule

[2] The polycarbonate resin composition according to [1], wherein the polycarbonate resin includes a structural unit derived from a dihydroxy compound other than the dihydroxy compound represented by the formula (1).
[3] The polycarbonate resin contains 30 mol% or more of a structural unit derived from the compound represented by the formula (1) with respect to 100 mol% of a structural unit derived from all diols. [1] or [2] The polycarbonate resin composition described in 1.
[4] The resin composition according to any one of [1] to [3], wherein the proportion of the A block in the component (Y) is 10 to 50% by weight.
[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the A block is a hydrogenated polystyrene block.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the polymer constituting the B block is a polymer containing a structural unit derived from isobutylene.
[7] A molded article comprising the polycarbonate resin composition according to any one of [1] to [6].

  Since the resin composition of the present invention is excellent in balance in impact resistance, transparency (total light transmittance), color tone, wet heat resistance, and dry heat resistance, it can be used in a wide range of applications as molding materials for various products.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this invention, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

The present invention is a polycarbonate resin composition comprising the following component (X) and component (Y).
Component (X): Polycarbonate resin containing at least a structural unit derived from the dihydroxy compound represented by the following general formula (1) Component (Y): Block copolymer comprising the following A block and B block and this hydrogenated block At least one of the copolymers A block: polymer of aromatic hydrocarbon having vinyl group B block: polymer of chain-like unsaturated hydrocarbon having double bond in the molecule

[Component (X)]
The polycarbonate resin of component (X) used in the present invention is a polycarbonate resin having a structural unit derived from at least a compound represented by the following general formula (1). As will be described later, the structural unit derived from the dihydroxy compound represented by the following formula (1) in a proportion exceeding 30 mol% with respect to 100 mol% of the structural unit derived from all diols (this is appropriately referred to as “structural unit”). A polycarbonate resin containing (a) ") is preferred. The polycarbonate resin may be a homopolycarbonate resin of the structural unit (a) or a copolymerized polycarbonate resin containing a structural unit other than the structural unit (a). From the viewpoint of superior impact resistance, a copolymer polycarbonate resin is preferred.

Examples of the dihydroxy compound represented by the formula (1) include isosorbide (ISB), isomannide, and isoidet which are in a stereoisomeric relationship. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the dihydroxy compounds represented by the formula (1), isosorbide (ISB) obtained by dehydrating condensation of sorbitol produced from various starches that are abundantly present as plant-derived resources, Most preferred from the standpoints of availability and production, weather resistance, optical properties, moldability, heat resistance and carbon neutral.

  In addition, the dihydroxy compound represented by the formula (1) is easily oxidized by oxygen. Therefore, during storage or handling during production, it is preferable to prevent moisture from entering in order to prevent decomposition by oxygen, and to use an oxygen scavenger or in a nitrogen atmosphere.

  The polycarbonate resin is composed of a structural unit (a) derived from the dihydroxy compound represented by the formula (1) and a structural unit derived from a dihydroxy compound other than the dihydroxy compound represented by the formula (1). "Structural unit (b)"), for example, one selected from the group consisting of dihydroxy compounds of aliphatic hydrocarbons, dihydroxy compounds of alicyclic hydrocarbons, ether-containing dihydroxy compounds, and dihydroxy compounds containing aromatic groups A copolymer polycarbonate resin containing a structural unit derived from the above-mentioned dihydroxy compound (hereinafter referred to as “structural unit (b)” as appropriate) is preferable. These dihydroxy compounds are preferably dihydroxy compounds that do not contain an aromatic ring structure because of their good color tone. In particular, since one or more dihydroxy compounds selected from the group consisting of dihydroxy compounds of aliphatic hydrocarbons, dihydroxy compounds of alicyclic hydrocarbons, and ether-containing dihydroxy compounds have flexible molecular structures, these By using a dihydroxy compound as a raw material, the impact resistance of the obtained polycarbonate resin can be improved. Among these dihydroxy compounds, it is preferable to use an aliphatic hydrocarbon dihydroxy compound or an alicyclic hydrocarbon dihydroxy compound having a large effect of improving impact resistance, and to use an alicyclic hydrocarbon dihydroxy compound. Most preferred. Specific examples of the aliphatic hydrocarbon dihydroxy compound, the alicyclic hydrocarbon dihydroxy compound, the ether-containing dihydroxy compound, and the dihydroxy compound containing an aromatic group are as follows.

  As the aliphatic hydrocarbon dihydroxy compound, for example, the following dihydroxy compounds can be employed. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane Linear aliphatic dihydroxy compounds such as diol and 1,12-dodecanediol; aliphatic dihydroxy compounds having a branched chain such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol and hexylene glycol.

  Examples of the alicyclic hydrocarbon dihydroxy compound include the following dihydroxy compounds. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalindi Examples include dihydroxy compounds derived from terpene compounds such as methanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol and limonene. Dihydroxy compounds that are primary alcohols of alicyclic hydrocarbons; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, 2,2,4,4- Tetramethyl-1,3-cyclobutane Illustrated in ol, secondary alcohols or dihydroxy compound is a tertiary alcohol of the alicyclic hydrocarbon.

Examples of the ether-containing dihydroxy compound include oxyalkylene glycols and dihydroxy compounds containing an acetal ring.
Examples of oxyalkylene glycols that can be used include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

  As the dihydroxy compound containing an acetal ring, for example, spiro glycol represented by the following structural formula (2), dioxane glycol represented by the following structural formula (3), and the like can be employed.

As the dihydroxy compound containing an aromatic group, for example, the following dihydroxy compounds can be adopted, but dihydroxy compounds other than these can also be adopted. 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3-phenyl) phenyl) propane, 2,2-bis (4-hydroxy- (3 5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) decane, bis (4-hydroxy-3-nitro Phenyl) methane, 3,3-bis (4-hydroxyphenyl) pentane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4-hydroxy) Phenyl) -2-propyl) benzene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4 ′ -Dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy Aromatic bisphenol compounds such as 3-methylphenyl) sulfide, bis (4-hydroxyphenyl) disulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether; 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) propane, 1,3-bis (2-hydroxyethoxy) benzene, 4,4′-bis Dihydroxy compounds having an ether group bonded to an aromatic group such as (2-hydroxyethoxy) biphenyl and bis (4- (2-hydroxyethoxy) phenyl) sulfone; 9,9-bis (4- (2-hydroxyethoxy) Phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, , 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxypropoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 -Methylphenyl) fluorene, 9,9-bis (4- (2-hydroxypropoxy) -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-hydroxyeth C) -3-Phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 -Dihydroxy compounds having a fluorene ring such as -tert-butyl-6-methylphenyl) fluorene and 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene.

  In the polycarbonate resin, the content of the structural unit (a) with respect to 100 mol% of the structural units derived from all dihydroxy compounds is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol as the lower limit. % Or more is more preferable, 55 mol% or more is especially preferable, and 60 mol% or more is the most preferable. As an upper limit, it is more preferable that it is 95 mol% or less, It is more preferable that it is 90 mol% or less, It is especially preferable that it is 85 mol% or less. In these cases, the biogenic substance content can be further increased, and the heat resistance can be further improved. In addition, although the content rate of the structural unit (a) in polycarbonate resin may be 100 mol%, from a viewpoint of raising molecular weight more and a viewpoint of improving impact resistance more, structural units other than the structural unit (a) are included. It is preferably copolymerized.

  The polycarbonate resin may further contain a structural unit (other dihydroxy compound) other than the structural unit (a) and the structural unit (b). However, since the present invention has a good effect, the content ratio of structural units derived from other dihydroxy compounds is preferably 10 mol% or less with respect to 100 mol% of structural units derived from all dihydroxy compounds. More preferably, it is 5 mol% or less.

  The other dihydroxy compound can be appropriately selected according to the properties required for the polycarbonate resin. Moreover, the said other dihydroxy compound may use only 1 type, and may use multiple types together. By using the other dihydroxy compound in combination with the dihydroxy compound represented by the formula (1), it is possible to obtain effects such as improvement in flexibility and mechanical properties of the polycarbonate resin and improvement in moldability.

The dihydroxy compound used as a raw material of the polycarbonate resin may contain a stabilizer such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer, or a heat stabilizer. In particular, the dihydroxy compound represented by the formula (1) has a property of easily changing in an acidic state. Therefore, by using a basic stabilizer in the synthesis process of the polycarbonate resin, it is possible to suppress the alteration of the dihydroxy compound represented by the formula (1), thereby further improving the quality of the obtained polycarbonate resin composition. Can be made.

  As the basic stabilizer, for example, the following compounds can be employed. Hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates and fatty acid salts of Group 1 or 2 metals in the Long Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005); Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium Hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, Basic ammonium compounds such as traphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide; diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, diethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylamino Pyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2 Methoxy, imidazole, 2-mercaptoimidazole, 2-methylimidazole and the amine-based compounds such as amino quinoline, and di - (tert-butyl) hindered amine compounds such as amine and 2,2,6,6-tetramethyl piperidine.

  Although there is no restriction | limiting in particular in content of the said basic stabilizer in the said dihydroxy compound, Since the dihydroxy compound represented by the said Formula (1) is unstable in an acidic state, of the dihydroxy compound containing a basic stabilizer It is preferable to set the content of the basic stabilizer so that the pH of the aqueous solution is around 7.

  The content of the basic stabilizer with respect to the dihydroxy compound represented by the formula (1) is preferably 0.0001 to 1% by weight. In this case, the effect of preventing the alteration of the dihydroxy compound represented by the formula (1) is sufficiently obtained. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by weight.

  As the carbonic acid diester used as a raw material for the polycarbonate resin, a compound represented by the following general formula (4) can be usually employed. These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (4), A ¹ and A ² are each a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A ¹ and A ² may be the same or different. As A ¹ and A ² , it is preferable to employ a substituted or unsubstituted aromatic hydrocarbon group, and it is more preferable to employ an unsubstituted aromatic hydrocarbon group.

  As the carbonic acid diester represented by the general formula (4), for example, substituted diphenyl carbonate such as diphenyl carbonate (DPC) and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like may be employed. it can. Among these carbonic acid diesters, it is preferable to use diphenyl carbonate or substituted diphenyl carbonate, and it is particularly preferable to use diphenyl carbonate. Carbonic acid diesters may contain impurities such as chloride ions, and impurities may inhibit the polycondensation reaction or deteriorate the color tone of the resulting polycarbonate resin. It is preferable to use one purified by the above.

  The polycarbonate resin can be synthesized by polycondensing the above-described dihydroxy compound and carbonic acid diester by an ester exchange reaction. More specifically, it can be obtained by removing the monohydroxy compound and the like by-produced in the transesterification reaction from the system together with polycondensation.

  The transesterification proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst is referred to as “polymerization catalyst”). The type of polymerization catalyst can greatly affect the reaction rate of the transesterification reaction and the quality of the resulting polycarbonate resin.

  The polymerization catalyst is not limited as long as the transparency, color tone, heat resistance, weather resistance, and mechanical strength of the obtained polycarbonate resin can be satisfied. Examples of the polymerization catalyst include metal compounds of Group I or Group II (hereinafter simply referred to as “Group 1” and “Group 2”) in the long-period periodic table, as well as basic boron compounds and basic compounds. Basic compounds such as phosphorus compounds, basic ammonium compounds and amine compounds can be used, among which group 1 metal compounds and / or group 2 metal compounds are preferred, and group 2 metal compounds are particularly preferred.

As the group 1 metal compound, for example, the following compounds can be employed. Sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, 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, boron phenyl Potassium, lithium borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus 2 lithium hydrogen, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, bisphenol A Disodium salt, dipotassium salt, dilithium salt and dicesium salt.
As the Group 1 metal compound, a lithium compound is preferable from the viewpoint of polymerization activity and the color tone of the obtained polycarbonate resin.

As the group 2 metal compound, for example, the following compounds can be employed. Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate,
Barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.
As the group 2 metal compound, a magnesium compound, a calcium compound or a barium compound is preferable. From the viewpoint of polymerization activity and the color tone of the obtained polycarbonate resin, a magnesium compound and / or a calcium compound is further preferable, and a calcium compound is most preferable.

  In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound can be used in combination with the above-mentioned Group 1 metal compound and / or Group 2 metal compound. However, it is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  As said basic phosphorus compound, the following compounds are employable, for example. Triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt and the like.

  As said basic ammonium compound, the following compounds are employable, for example. 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 and butyltriphenylammonium hydroxide Rokishido like.

  As said amine compound, the following compounds are employable, for example. 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxy Imidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, guanidine and the like.

  The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, and particularly preferably 1 to 50 μmol per 1 mol of all dihydroxy compounds used in the reaction.

  When a compound containing at least one metal selected from the group consisting of Group 2 metals and lithium in the long-period periodic table is used as the polymerization catalyst, for example, selected from the group consisting of magnesium compounds, calcium compounds and barium compounds When using a compound containing at least one metal, particularly when using a magnesium compound and / or a calcium compound, the amount of polymerization catalyst used is the total amount of dihydroxy used in the reaction as the amount of metal atoms of the compound containing the metal. The amount is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more per 1 mol of the compound. The upper limit is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.

Since the polymerization rate can be increased by adjusting the amount of the polymerization catalyst used within the above range, a polycarbonate resin having a desired molecular weight can be obtained without necessarily increasing the polymerization temperature. Deterioration of color tone can be suppressed. Moreover, since it can prevent that the unreacted raw material volatilizes in the middle of superposition | polymerization and the molar ratio of a dihydroxy compound and a carbonic acid diester collapse | crumbles, resin of a desired molecular weight can be obtained more reliably. Furthermore, since side reactions can be suppressed, deterioration of the color tone of the polycarbonate resin or coloring during molding can be further prevented.

  Considering the adverse effect of sodium, potassium, or cesium on the color tone of the polycarbonate resin among the Group 1 metals and the adverse effect of iron on the color tone of the polycarbonate resin, sodium, potassium, cesium, and iron in the polycarbonate resin (A) The total content is preferably 1 ppm by weight or less. In this case, the deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be further improved. From the same viewpoint, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is more preferably 0.5 ppm by weight or less. In addition, these metals may mix not only from the catalyst to be used but from a raw material or a reaction apparatus. Regardless of the source, the total amount of these metal compounds in the polycarbonate resin is preferably in the above-mentioned range as the total content of sodium, potassium, cesium and iron.

(Synthesis of polycarbonate resin)
The polycarbonate resin is obtained by polycondensing a dihydroxy compound used as a raw material, such as the dihydroxy compound represented by the formula (1), and a carbonic acid diester by an ester exchange reaction in the presence of a polymerization catalyst.

  The raw material dihydroxy compound and 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 usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, with 100 ° C. or higher and 120 ° C. or lower being preferred. In this case, the dissolution rate can be increased or the solubility can be sufficiently improved, and problems such as solidification can be sufficiently avoided. Furthermore, in this case, the thermal deterioration of the dihydroxy compound can be sufficiently suppressed, and the resulting color tone of the polycarbonate resin can be further improved, and the weather resistance can be improved. Become.

  The operation of mixing the raw material dihydroxy compound and the carbonic acid diester is performed in an atmosphere having an oxygen concentration of 10 vol% or less, further 0.0001 to 10 vol%, particularly 0.0001 to 5 vol%, and particularly 0.0001 to 1 vol%. It is preferable. In this case, the color tone can be improved and the reactivity can be increased.

  In order to obtain a polycarbonate resin, it is preferable to use a carbonic acid diester in a molar ratio of 0.90 to 1.20 with respect to all dihydroxy compounds used in the reaction. In this case, since the increase in the amount of terminal hydroxyl groups of the polycarbonate resin can be suppressed, the thermal stability of the polymer can be improved. Therefore, coloring at the time of shaping | molding can be prevented further, or the speed | rate of transesterification can be improved. Moreover, it becomes possible to obtain a desired high molecular weight body more reliably. Furthermore, by adjusting the usage-amount of carbonic acid diester in the said range, the speed | rate of transesterification reaction can be suppressed, and the more reliable manufacture of polycarbonate resin of a desired molecular weight is attained. Further, in this case, since an increase in heat history during the reaction can be suppressed, the color tone and weather resistance of the polycarbonate resin can be further improved. Furthermore, in this case, the amount of residual carbonic acid diester in the polycarbonate resin can be reduced, and generation of dirt and odor during molding can be avoided or alleviated. From the same viewpoint as above, the amount of carbonic acid diester used relative to all dihydroxy compounds is more preferably 0.95 to 1.10.

  The method of polycondensing a dihydroxy compound and a carbonic acid diester is performed in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. There are batch, continuous or batch / continuous methods of reaction, but it is possible to obtain a polycarbonate resin with less heat history and adopt a continuous method with excellent productivity. preferable.

  From the viewpoint of controlling the polymerization rate and the quality of the obtained polycarbonate resin, it is important to appropriately select the jacket temperature, the internal temperature, and the pressure in the reaction system according to the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the latter stage of the reaction. In this case, distillation of unreacted monomers is suppressed, and the molar ratio of the dihydroxy compound and the carbonic acid diester can be easily adjusted to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed. In addition, a polymer having a desired molecular weight and terminal group can be obtained more reliably.

  In addition, the polymerization rate in the polycondensation reaction is controlled by the balance between the hydroxy group terminal and the carbonate group terminal. Therefore, if the balance of the end groups varies due to the distillation of the unreacted monomer, it becomes difficult to control the polymerization rate to be constant, and the molecular weight of the resulting resin may vary greatly. Since the molecular weight of the resin correlates with the melt viscosity, when the resulting resin is melt processed, the melt viscosity varies, and it may be difficult to keep the quality of the molded product constant. Such a problem is likely to occur particularly when the polycondensation reaction is carried out continuously.

  In order to suppress the amount of unreacted monomer to be distilled off, it is effective to use a reflux condenser for the polymerization reactor, and shows a high effect particularly in the initial stage of the reaction with a large amount of unreacted monomer. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. By adjusting the refrigerant temperature within these ranges, the reflux amount can be sufficiently increased, the effect can be sufficiently obtained, and the distillation efficiency of the monohydroxy compound to be distilled off can be sufficiently improved. As a result, a decrease in the reaction rate can be prevented, and coloring of the resulting resin can be further prevented. 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 improve the color tone of the obtained polycarbonate resin while maintaining the polymerization rate appropriately and suppressing the distillation of the monomer, it is important to select the kind and amount of the aforementioned polymerization catalyst.

  The polycarbonate resin is usually produced through two or more steps using a polymerization catalyst. The polycondensation reaction may be carried out in two or more stages by using a single polycondensation reactor and changing the conditions sequentially. However, from the viewpoint of production efficiency, a plurality of reactors are used and the respective conditions are changed. It is preferable to carry out in multiple stages.

  From the viewpoint of efficiently performing the polycondensation reaction, it is important to suppress the volatilization of the monomer while maintaining the necessary polymerization rate at the initial stage of the reaction in which a large amount of the monomer is contained in the reaction solution. In the later stage of the reaction, it is important to shift the equilibrium toward the polycondensation reaction side by sufficiently distilling off the by-produced monohydroxy compound. Therefore, the reaction conditions suitable for the early stage of the reaction are usually different from those suitable for the later stage of the reaction. Therefore, by using a plurality of reactors arranged in series, the respective conditions can be easily changed, and the production efficiency can be improved.

As described above, the number of polymerization reactors used for the production of the polycarbonate resin may be at least two, but from the viewpoint of production efficiency, the number is three or more, preferably 3 to 5, particularly preferably 4. One. If there are two or more polymerization reactors, a plurality of reaction stages with different conditions may be further performed in each polymerization reactor, or the temperature and pressure may be continuously changed.

  The polymerization catalyst can be added to the raw material preparation tank or the raw material storage tank, or can be added directly to the polymerization reactor. From the viewpoint of supply stability and control of the polycondensation reaction, it is preferable to install a catalyst supply line in the middle of the raw material line before being supplied to the polymerization reactor and supply the polymerization catalyst in an aqueous solution.

  By adjusting the temperature of the polycondensation reaction, it is possible to improve productivity and avoid an increase in the thermal history of the product. Furthermore, it is possible to further prevent the volatilization of the monomer and the decomposition and coloring of the polycarbonate resin. Specifically, the following conditions can be adopted as reaction conditions in the first stage reaction. That is, the maximum internal temperature of the polymerization reactor is usually set in the range of 150 to 250 ° C, preferably 160 to 240 ° C, and more preferably 170 to 230 ° C. Moreover, the pressure (henceforth an absolute pressure) of a polymerization reactor is 1-110 kPa normally, Preferably it is 5-70 kPa, More preferably, it sets in the range of 7-30 kPa. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.5 to 3 hours. The first stage reaction is preferably carried out while distilling off the generated monohydroxy compound out of the reaction system.

  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. It is preferable to make it 1 kPa or less. Moreover, the maximum temperature of the internal temperature of a polymerization reactor is normally set in the range of 200-260 degreeC, Preferably it is 210-250 degreeC. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.3 to 6 hours, particularly preferably 0.5 to 3 hours.

  From the viewpoint of further suppressing the coloration and thermal deterioration of the polycarbonate resin and obtaining a polycarbonate resin (A) having a better color tone, the maximum internal temperature of the polymerization reactor in all reaction stages is 210 to 240 ° C. It is preferable to do. In addition, in order to suppress a decrease in polymerization rate in the second half of the reaction and minimize deterioration due to thermal history, use a horizontal reactor with excellent plug flow and interface renewability at the final stage of the polycondensation reaction. Is preferred.

  In continuous polymerization, in order to control the molecular weight of the finally obtained polycarbonate resin to a certain level, it is preferable to adjust the polymerization rate as necessary. In that case, adjusting the pressure in the final stage polymerization reactor is a method with good operability.

  In addition, as described above, the polymerization rate varies depending on the ratio of the hydroxyl group terminal to the carbonate group terminal, so one end group is intentionally reduced to suppress the polymerization rate, and the pressure in the final stage polymerization reactor is reduced accordingly. By maintaining a high vacuum, it is possible to reduce residual low molecular components in the resin including the monohydroxy compound. However, in this case, if the number of terminals on one side is too small, the reactivity of the polycarbonate resin may be extremely low and the molecular weight of the resulting polycarbonate resin may not reach the desired molecular weight, even if the terminal group balance slightly fluctuates. . In order to avoid such a problem, the polycarbonate resin obtained in the final polymerization reactor preferably contains 10 mol / ton or more of both the hydroxyl group terminal and the carbonate group terminal. On the other hand, when both terminal groups are too many, the polymerization rate increases and the molecular weight becomes too high. Therefore, one terminal group is preferably 60 mol / ton or less.

Thus, the residual amount of the monohydroxy compound in the resin can be reduced at the outlet of the polymerization reactor by adjusting the amount of terminal groups and the pressure in the final stage polymerization reactor to a preferable range. The residual amount of the monohydroxy compound in the resin at the outlet of the polymerization reactor is preferably 2000 ppm by weight or less, more preferably 1500 ppm by weight or less, and even more preferably 1000 ppm by weight or less. In this way, by reducing the content of the monohydroxy compound at the outlet of the polymerization reactor, the monohydroxy compound and the like can be easily devolatilized in a later step.

  It is preferable that the residual amount of the monohydroxy compound is small, but if it is attempted to reduce it to less than 100 ppm by weight, the operating conditions are such that the amount of one end group is extremely reduced and the pressure of the polymerization reactor is kept at a high vacuum. I need to take it. In this case, as described above, it is difficult to keep the molecular weight of the obtained polycarbonate resin at a certain level, and therefore it is usually 100 ppm by weight or more, preferably 150 ppm by weight or more.

  The by-produced monohydroxy compound is preferably reused as a raw material for other compounds after purification as necessary from the viewpoint of effective utilization of resources. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A and the like.

  The glass transition temperature of the polycarbonate resin is preferably 90 ° C. or higher. In this case, the heat resistance and biogenic substance content of the polycarbonate resin composition can be improved in a well-balanced manner. From the same viewpoint, the glass transition temperature of the polycarbonate resin is more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. On the other hand, the glass transition temperature of the polycarbonate resin is preferably 170 ° C. or lower. In this case, the melt viscosity can be reduced by the aforementioned melt polymerization, and a polymer having a sufficient molecular weight can be obtained. Further, when the molecular weight is to be increased by increasing the polymerization temperature and decreasing the melt viscosity, the heat resistance of the component (a) is not sufficient, and thus there is a possibility that it may be easily colored. From the viewpoint of improving the molecular weight and preventing coloration in a more balanced manner, the glass transition temperature of the polycarbonate resin is more preferably 165 ° C. or lower, further preferably 160 ° C. or lower, and particularly preferably 150 ° C. or lower.

  The molecular weight of the polycarbonate resin can be represented by a reduced viscosity, and the higher the reduced viscosity, the higher the molecular weight. The reduced viscosity is usually 0.30 dL / g or more, preferably 0.33 dL / g or more. In this case, the mechanical strength of the molded product can be further improved. On the other hand, the reduced viscosity is usually 1.20 dL / g or less, more preferably 1.00 dL / g or less, and still more preferably 0.80 dL / g or less. In these cases, fluidity at the time of molding can be improved, and productivity and moldability can be further improved. The reduced viscosity of the polycarbonate resin was measured using an Ubbelohde viscosity tube at a temperature of 20.0 ° C. ± 0.1 ° C. using a solution in which the concentration of the resin composition was precisely adjusted to 0.6 g / dL using methylene chloride as a solvent. Use the value measured under the conditions. Details of the method for measuring the reduced viscosity will be described in Examples.

The melt viscosity of the polycarbonate resin is preferably 400 Pa · s to 3000 Pa · s. In this case, the molded article of the resin composition can be prevented from becoming brittle, and the mechanical properties can be further improved. Furthermore, in this case, the fluidity at the time of molding can be improved, and the appearance of the molded product can be prevented from being deteriorated or the dimensional accuracy can be prevented from being deteriorated. Furthermore, in this case, coloring and foaming caused by the increase in the resin temperature due to shearing heat generation can be further prevented. From the same viewpoint, the melt viscosity of the polycarbonate resin is more preferably 600 Pa · s to 2500 Pa · s, and still more preferably 800 Pa · s to 2000 Pa · s. In the present specification, the melt viscosity means a melt viscosity at a temperature of 240 ° C. and a shear rate of 91.2 sec ⁻¹ , measured using a capillary rheometer [manufactured by Toyo Seiki Co., Ltd.]. Details of the method for measuring the melt viscosity will be described in Examples described later.

  The polycarbonate resin preferably contains a catalyst deactivator. The catalyst deactivator is not particularly limited as long as it is an acidic substance and has a deactivation function of the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl octyl sulfonate Phosphonium salts such as phosphonium salt, benzenesulfonic acid tetramethylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, p-toluenesulfonic acid tetrabutylphosphonium salt; decylsulfonic acid tetramethylammonium salt; Ammonium salts such as tetrabutylammonium dodecylbenzenesulfonate; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, hexadecyl And the like alkyl esters such as sulfonic acid ethyl.

  The catalyst deactivator includes a phosphorus compound (hereinafter referred to as “specific phosphorus compound”) including any of the partial structures represented by the following structural formula (5) or the following structural formula (6). It is preferable. The specific phosphorus-based compound is added after the polycondensation reaction is completed, that is, for example, in the kneading step or the pelletizing step, to deactivate the polymerization catalyst described later, and the polycondensation reaction is unnecessary thereafter. It is possible to suppress progress. As a result, it is possible to suppress the progress of polycondensation when the polycarbonate resin is heated in the molding step or the like, and consequently, it is possible to suppress the elimination of the monohydroxy compound. Further, by deactivating the polymerization catalyst, coloring of the polycarbonate resin at a high temperature can be further suppressed.

  Specific phosphorus compounds containing the partial structure represented by the structural formula (5) or structural formula (6) include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, acidic Phosphate esters and the like can be employed. Among the specific phosphorus compounds, phosphorous acid, phosphonic acid, and phosphonic acid ester are more excellent in catalyst deactivation and coloring suppression effects, and phosphorous acid is particularly preferable.

As the phosphonic acid, for example, the following compounds can be employed. Phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphone Acids, 4-methoxyphenylphosphonic acid, nitrilotris (methylenephosphonic acid), propylphosphonic anhydride, and the like.

  As the phosphonic acid ester, for example, the following compounds can be employed. Dimethyl phosphonate, diethyl phosphonate, bis (2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate Dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl) phosphonate, diethyl vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl (2-hydroxyethyl) phosphonate, p-methylbenzylphosphonic acid Diethyl, diethylphosphonoacetic acid, diethylphosphonoacetic acid ethyl, diethylphosphonoacetic acid tert-butyl, (4-chlorobenzyl) phosphonic acid die Le, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, 3,5-di -tert- butyl-4-hydroxybenzyl phosphonic acid diethyl, diethyl phosphonoacetate diethyl acetal, (methylthiomethyl) diethyl phosphonic acid.

  As the acidic phosphate ester, for example, the following compounds can be employed. Dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis (butoxyethyl) phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate, distearyl phosphate, Phosphoric diesters such as diphenyl phosphate and dibenzyl phosphate, or a mixture of diester and monoester, diethyl chlorophosphate, zinc stearyl phosphate, and the like.

  The said specific phosphorus type compound may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.

  The content of the specific phosphorus compound in the polycarbonate resin is preferably 0.1 ppm to 5 ppm by weight as phosphorus atoms. In this case, the effects of catalyst deactivation and coloring suppression by the specific phosphorus compound can be sufficiently obtained. In this case, the polycarbonate resin can be further prevented from being colored, particularly in an endurance test at high temperature and high humidity.

  Further, by adjusting the content of the specific phosphorus compound according to the amount of the polymerization catalyst, it is possible to more reliably obtain the effects of catalyst deactivation and coloring suppression. The content of the specific phosphorus compound is preferably 0.5 times mol or more and 5 times mol or less, and 0.7 times mol or more and 4 times mol as the amount of phosphorus atoms with respect to 1 mol of the metal atom of the polymerization catalyst. More preferably, it is more preferably 0.8 times mol or more and 3 times mol or less.

[Component (Y)]
The component (Y) used in the present invention is at least one of a block copolymer composed of the following A block and B block and this hydrogenated block copolymer.
A block: polymer of aromatic hydrocarbon having vinyl group B block: polymer of chain-like unsaturated hydrocarbon having double bond in the molecule

  In the above block copolymer, the A block which is a polymer of aromatic hydrocarbon having a vinyl group is a hard segment, and the B block which is a polymer of chain unsaturated hydrocarbon having a double bond in the molecule is soft. Configure the segment.

A typical example of the block copolymer has a copolymer structure represented by A-B or A-B-A,
A block copolymer in which the double bond of the A and / or B block may be partially or completely hydrogenated, and is generally known as a styrenic thermoplastic elastomer.

  Specific examples of the aromatic hydrocarbon having a vinyl group in the A block include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, 4-chloromethylstyrene, 4-hydroxymethylstyrene, 4-t-butoxystyrene, dichloro Examples include styrene, 4-monofluorostyrene, 4-phenylstyrene, vinylnaphthalene, vinylanthracene, and the like. Styrene, α-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-chloromethylstyrene, vinylnaphthalene Are preferably used, and styrene, α-methyl Styrene, 4-methylstyrene, 4-t-butylstyrene are preferred, most preferably styrene is used. These aromatic hydrocarbons having a vinyl group may be used alone or in combination of two or more.

The chain unsaturated hydrocarbon polymer having a double bond in the molecule constituting the B block is not particularly limited as long as it exhibits elastomeric properties. It is only necessary that the structural unit of the chain unsaturated hydrocarbon polymer having a chain includes a structural unit derived from the chain unsaturated hydrocarbon having a double bond in the molecule.
The number of carbon atoms of the chain-like unsaturated hydrocarbon having a double bond in the molecule is not particularly limited, but is preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less.
The number of double bonds of the chain-like unsaturated hydrocarbon having a double bond in the molecule is preferably 2 or less from the viewpoint of enhancing the elastomeric property of the B component. When the number of double bonds is one, a long molecular chain is disadvantageous for polymer formation, and therefore, the chain hydrocarbon preferably has 4 or less carbon atoms. Furthermore, this double bond may be partially or completely hydrogenated.
Preferred embodiments of the polymer of a chain unsaturated hydrocarbon having a double bond in the molecule constituting the B block include, for example, ethylene, isobutylene, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl- A polymer containing a structural unit derived from one or more monomers of 1,3-butadiene and a portion thereof or a complete hydrogenated product are preferable. Among them, a polymer containing a structural unit derived from isobutylene is more preferable from the viewpoint of transparency and color tone of the obtained polycarbonate resin composition.

The upper limit of the proportion of the A block in the block copolymer is preferably 50% by weight or less, more preferably 45% by weight or less, still more preferably 40% by weight or less, and particularly preferably 35% by weight or less. When the content of the A block is not more than the above upper limit, mechanical properties such as impact resistance can be improved without impairing various properties of the polycarbonate resin of component (X).
On the other hand, the ratio of the A block in the block copolymer is preferably 10% by weight or more, preferably 12% by weight or more, and particularly preferably 15% by weight or more as a lower limit. If the ratio of the A block is less than the lower limit, the flexibility and rubber elasticity are inferior, and thus sufficient impact modifying ability may not be obtained.

  The component (Y) is preferably a hydrogenated block copolymer obtained by hydrogenating the block copolymer. The upper limit of the hydrogen conversion of the aromatic ring in the A block is usually 100% or less when hydrogenation is performed. 30% or more, preferably 50% or more, more preferably 90% or more. When the hydrogenation rate is less than the above range, the transparency and color tone of the obtained polycarbonate resin composition tend to be inferior.

  The block copolymer of component (Y) used in the present invention is excellent in balance in transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, moist heat resistance, and dry heat resistance. This block copolymer also has good compatibility with the polycarbonate resin of component (X), and does not impair the original transparency of the polycarbonate resin as a resin composition with the polycarbonate resin. Since the refractive index of the polymer and the polycarbonate resin are close to each other, a resin composition excellent in transparency can be obtained. For this reason, according to the present invention, it is possible to provide a resin composition that is flexible and excellent in moldability and excellent in impact resistance and transparency.

  As a method for hydrogenating the block copolymer, any production method may be used as long as the above structure is obtained. For example, the aromatic ring of the vinyl aromatic block copolymer obtained by cationic polymerization in an organic solvent using a Lewis acid catalyst or the like is hydrogenated by the method described in JP-A-11-100420. Can be obtained.

  The hydrogenation method and reaction mode of the aromatic ring of the block copolymer are not particularly limited, and may be carried out according to a known method. However, the hydrogenation rate can be increased, and hydrogen with little polymer chain cleavage reaction can be obtained. Is preferred. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, rhenium and the like. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used, and the hydrogenation reaction is preferably performed in an organic solvent.

  The heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like. These may be used alone or in combination of two or more. The supported amount of the catalyst component is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 60% by weight or less, preferably 50% by weight or less based on the total amount of the catalyst component and the carrier.

  As homogeneous catalysts, catalysts combining metal compounds such as nickel, cobalt, titanium or iron and organometallic compounds such as organoaluminum and organolithium; rhodium, palladium, ruthenium, rhenium, titanium, zirconium, hafnium, etc. An organometallic complex of the above can be used.

  As said metal compound, the acetylacetone salt of each metal, a naphthenate, a cyclopentadienyl compound, a cyclopentadienyl dichloro compound, etc. are used. As the organic aluminum, alkyl aluminum such as triethylaluminum and triisobutylaluminum; alkylaluminum halide such as diethylaluminum chloride and ethylaluminum dichloride; alkylaluminum hydride such as diisobutylaluminum hydride and the like are used.

  Examples of organometallic complexes include γ-dichloro-π-benzene complexes, dichloro-tris (triphenylphosphine) complexes, hydrido-chloro-tris (triphenylphosphine) complexes of the above metals.

  These hydrogenation catalysts can be used alone or in combination of two or more. The amount of the hydrogenation catalyst used is usually 0.001 parts by weight or more, preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight, based on 100 parts by weight of the vinyl aromatic block copolymer. It is at least 50 parts by weight, preferably at most 30 parts by weight, more preferably at most 15 parts by weight.

  The hydrogenation reaction is carried out at a pressure of 5 to 25 MPa at a temperature of 100 to 200 ° C., as a solvent, a saturated hydrocarbon solvent such as cyclohexane, methylcyclohexane, n-octane, decalin, tetralin, naphtha, or an ether such as tetrahydrofuran. It is preferable to use a system solvent. Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, it is 100 to 1000 weight part with respect to 100 weight part of block copolymers.

  The method for recovering the hydrogenated block copolymer after completion of the hydrogenation reaction is not particularly limited. The recovery method is usually a steam coagulation method in which the hydrogenated catalyst residue is removed by a method such as filtration or centrifugation, and then the solvent is removed from the solution in which the hydrogenated block copolymer is dissolved by steam stripping, heating under reduced pressure. Direct solvent removal method to remove solvent under, hydrogenated block copolymer by pouring solution into poor solvent of hydrogenated block copolymer such as methanol, ethanol, isopropyl alcohol, water, acetone, methyl ethyl ketone, ethyl acetate A known method such as a coagulation method for precipitating and solidifying can be employed.

  The block copolymer has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, preferably 10,000 or more, more preferably 30000 or more, still more preferably. On the other hand, it is preferably 200000 or less, more preferably 150,000 or less, and further preferably 130,000 or less. When the Mw of the block copolymer is not less than the above lower limit value, the resulting molded article tends to have good mechanical strength, heat resistance, and moldability. The melt viscosity of the resin tends to be low, and the moldability tends to be good.

  The molecular weight distribution of the block copolymer can be appropriately selected according to the purpose of use, but is preferably a ratio (Mw / Mn) of polystyrene-equivalent Mw and number average molecular weight (Mn) measured by GPC, preferably 4 Below, more preferably 3 or less, particularly preferably 2 or less. It is preferable for Mw / Mn to be equal to or lower than the above upper limit value because a molded article having excellent moldability, heat resistance, transparency, and the like can be easily obtained.

[Other ingredients]
The resin composition of the present invention may contain other components in addition to the components (X) and (Y).

  Additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers such as fillers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, Flame retardants, antistatic agents, conductivity-imparting agents, cross-linking agents, cross-linking aids, metal deactivators, molecular weight regulators, antibacterial agents, antifungal agents, fluorescent whitening agents, organic diffusing agents, inorganic diffusing agents, etc. And the like.

[Physical properties of polycarbonate resin composition]
<Glass transition temperature>
In a polycarbonate-type resin composition, it is preferable that the peak of the glass transition temperature measured by DSC method is single. The glass transition temperature of the polycarbonate resin composition is preferably 100 ° C. or higher and 200 ° C. or lower. In this case, since the heat resistance can be further improved, deformation of the molded product can be further prevented. Moreover, in this case, the thermal deterioration of the component (X) during the production of the resin composition can be further suppressed, and the impact resistance can be further improved. Furthermore, the thermal deterioration of the resin composition during molding can be further suppressed. From the same viewpoint, the glass transition temperature of the polycarbonate resin composition is more preferably 110 ° C. or higher and 190 ° C. or lower, and further preferably 120 ° C. or higher and 180 ° C. or lower.

<Impact strength>
The impact strength of the polycarbonate resin composition can be evaluated by, for example, a notched Charpy impact strength test described in detail in Examples below. The notch tip radius R is 0.50 mm. The notched Charpy impact strength is preferably 10 kJ / m ² or more, more preferably 15
kJ / ^{m 2} or more, more preferably 20 kJ / ^{m 2} or more, and particularly preferably 30 kJ / ^{m 2} or more. By being in this range, it has excellent impact resistance.

<Total light transmittance>
The total light transmittance of the polycarbonate-based resin composition can be evaluated by, for example, a total light transmittance measuring method described in detail in Examples below. The total light transmittance is preferably 90% or more. By being in this range, it has excellent transparency.

<Color tone>
The color tone of the polycarbonate resin composition can be evaluated by, for example, a method for measuring a yellowness YI value described in detail in Examples below. The yellowness YI value is preferably 5.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. By being in this range, it has excellent transparency.

<Long-term wet heat resistance>
The long-term wet heat resistance of the polycarbonate-based resin composition can be evaluated by, for example, the long-term wet heat resistance measurement method described in detail in Examples below. In this evaluation, the smaller the ΔYI value, the smaller the change in color tone when used for a long time in a high-temperature and high-humidity environment. A preferable ΔYI value in this evaluation is 5.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. By being in this range, it has excellent long-term wet heat resistance.

<Long-term dry heat resistance>
The long-term dry heat resistance of the polycarbonate resin composition can be evaluated by, for example, a long-term dry heat resistance measurement method described in detail in Examples below. In this evaluation, the smaller the ΔYI value, the smaller the change in color tone when used for a long period of time in a high-temperature drying environment, indicating that the film has heat resistance that can withstand long-term use. A preferable ΔYI value in this evaluation is 5.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. By being in this range, it has excellent long-term dry heat resistance.

[Method for Producing Resin Composition]
The resin composition of the present invention can be produced, for example, by a method of mechanically melting and kneading the above components. Examples of the melt kneader that can be used here include a single-screw extruder, a twin-screw extruder, a Brabender, a Banbury mixer, a kneader blender, and a roll mill. The lower limit of the kneading temperature is usually 100 ° C. or higher, preferably 145 ° C. or higher, more preferably 160 ° C. or higher. The upper limit of the kneading temperature is usually 350 ° C., preferably 300 ° C., more preferably 250 ° C. When kneading, each component may be kneaded all at once, or a multistage division kneading method may be used in which any component is kneaded and then the other remaining components are added and kneaded.

[Method for Molding Resin Composition]
Examples of the resin composition of the present invention include injection molding (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method, T-die film molding method, laminate molding method, It can be processed into various molded articles by molding methods such as blow molding, hollow molding, compression molding, and calendar molding. There is no restriction | limiting in particular in the shape of a molded object, A sheet | seat, a film, plate shape, particle shape, a lump body, a fiber, a rod shape, a porous body, a foam etc. are mentioned, Preferably it is a sheet | seat, a film, and plate shape. Further, the formed film can be uniaxially or biaxially stretched. Examples of the stretching method include a roll method, a tenter method, and a tubular method. Furthermore, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment and the like which are usually used industrially can also be applied.

[Usage]
Although the use of the molded object containing the resin composition of this invention is not specifically limited, The following uses can be mentioned as an example. That is, coating materials such as electric wires, cords, wire harnesses, insulation sheets, OA equipment displays and touch panels, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, etc. FDD collet, floppy hub, optical disk substrate in optical components field, optical disk pickup lens, optical lens, LCD substrate, PDP substrate, television screen for projection TV, retardation film, fog lamp lens, illumination switch lens, sensor switch lens, fullnel Lens, protective glasses, projection lens, camera lens, sunglasses, light guide plate, camera strobe reflector, LED reflector, headlamp lens for automobile parts, window Car lamp lens, tail lamp lens, resin window glass, meter cover, outer panel, door handle, rear panel, wheel cap, visor, roof rail, sunroof, instrument panel, panels, control cable covering material, air bag cover, mud guard, bumper, Various malls such as boots, air hoses, lamp packings, gaskets, window moldings, site shields, weather strips, glass run channels, grommets, vibration control and sound insulation materials, joint materials in the field of building materials, handrails, windows, table edge materials, Sashes, bathtubs, window frames, signboards, lighting covers, water tanks, stair lumbar boards, carports, highway sound insulation walls, multi-wall sheets, steel wire coverings, lighting lamp globes, switch breakers, protective covers for machine tools, industrial deep drawing vacuum Shaped containers, pump housings, home appliances, various packings in the field of weak electricity, grips, belts, rubber feet, rollers, protectors, suction cups, refrigerators, gaskets, switches, connector covers, game machine covers, pachinko machines, OA Housing, notebook PC housing, HDD head tray, instrument window, transparent housing, roller with OA gear, switch case slider, gas cock knob, clock frame, clock train wheel inset, amber cap, various rolls for OA equipment Tubular molded products such as hoses and tubes, atypical extrusions, leather-like articles, articulating tools, soft tactile dolls, pen grips, straps, suckers, watches, umbrella bones, cosmetic cases, toothbrush patterns, etc. General miscellaneous goods, containers such as houseware, tupperware, cable ties, braces Various types of bottles such as infusion bottles, food bottles, water bottles, cosmetics bottles, and other personal care bottles, medical components, catheters, syringes, syringe gaskets, drip tubes, tubes, ports, caps, rubber stoppers, diamonds Examples include risers, blood connectors, dentures, disposable containers, and the like, and can also be applied to applications using foam molding.
Among the above, the tube is particularly suitable for a medical tube that can prevent the adsorption of medicinal components, and the multilayer tube is most suitable for its inner layer material or intermediate layer material.

Although the usage in the field of the film and sheet of the molded product containing the resin composition of the present invention is not particularly limited, the following usage can be given as an example. That is, stretch film for packaging, wrap film for business use or household use, pallet stretch film, stretch label, shrink film, shrink label, film for sealant, film for retort, sealant film for retort, aroma retaining heat seal film, A- PET sealant, frozen food containers and lids, cap seals, heat-sealing films, heat-bonding films, heat-sealing films, bag-in-box sealant films, retort pouches, standing pouches, spout pouches, laminated tubes, heavy bags , Food packaging such as fiber wrapping film, miscellaneous goods packaging field, house film, multi-film agricultural film field, infusion bag, high-calorie infusion and peritoneal dialysis (CAPD), antibiotic kit bag, etc. , Drainage bags for peritoneal dialysis, blood bags, urine bags, surgical bags, ice pillows, ampoule cases, medical film and sheet fields such as PTP packaging, civil engineering impermeable sheets, waterproofing materials, mats, joint materials, Building materials related fields such as flooring, roofing, decorative film, skin film, wallpaper, leather, ceiling material, trunk room lining, interior skin material, vibration control sheet, sound insulation sheet, etc., display cover, battery case, mouse Pads, mobile phone cases, IC card holders, floppy disk cases, CD-ROM cases, etc., weak electric fields, toothbrush cases, puff cases, cosmetic cases, eye drops and other pharmaceutical cases, tissue cases, face packs, etc. toiletries or sanitary fields, for stationery Film / sheet, clear file, pencil case, notebook cover Desk mats, keyboard covers, book covers, office supplies related fields such as binders, furniture leather, beach ball toys, umbrellas, raincoats, tablecloths, blister packages, bath lids, towel cases, fancy cases, General household use such as tag cases, pouches, amulet bags, insurance card covers, passbook cases, passport cases, knife cases, etc., miscellaneous goods field, retroreflective sheets, synthetic paper, and the like. In addition, as a pressure-sensitive adhesive composition, or as a film / sheet field in which a pressure-sensitive adhesive is applied to a substrate to impart adhesiveness, carrier tape, pressure-sensitive adhesive tape, marking film, semiconductor or glass dicing film, surface protective film, Steel plate / plywood protective film, automotive protective film, adhesive tape for packaging / bundling, office / house adhesive tape, bonding adhesive tape, coating masking adhesive tape, surface protective adhesive tape, sealing adhesive tape, anti-corrosion / waterproof Adhesive tape for electrical insulation, adhesive tape for electrical insulation, adhesive tape for electronic equipment, adhesive film, adhesive tape for medical and sanitary materials such as base material film, identification and decoration adhesive tape, display tape, packaging tape, surgical tape, For example, an adhesive tape for labels.

[the film]
The resin composition of the present invention is particularly useful as a film molding material among the above-mentioned various applications due to its excellent transparency, color tone, mechanical properties, heat resistance, moist heat resistance, and dry heat resistance.

The film containing the resin composition of the present invention may be a single layer film made of the resin composition of the present invention, or a laminated film of two or more layers formed by coextrusion with another resin composition. Also good.
Such a film is useful as a raw film for processing and forming into a container to be described later, or as a protective film for a display surface of an electronic device, a mobile phone, a smartphone or the like. The visibility of the display surface is not impaired, and the excellent impact resistance makes the device excellent in protection effect. Furthermore, it can withstand long-term use in various environments because of its excellent long-term wet heat resistance and long-term dry heat resistance.

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

  In the following, various physical properties were measured according to the following methods.

(1) Molecular weight:
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated block copolymer or block copolymer are measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene under the following conditions. It was.
Apparatus: Waters 2690 manufactured by Nippon Waters Co., Ltd.
Detector (RI detection): Waters 2410 manufactured by Nippon Waters Co., Ltd.
Column: Shodex KF-604, KF-603, manufactured by Showa Denko KK
Three each of KF-602.50 were connected in series.
Solvent: Tetrahydrofuran Flow rate: 0.7 mL / min
Temperature: 40 ° C

(2) Hydrogenation rate:
The hydrogenation rate (mol%) of the aromatic ring of the hydrogenated block copolymer was calculated by measuring a ¹ H-NMR spectrum.

(3) Notched Charpy impact test
The ISO test piece for mechanical properties obtained below was subjected to a notched Charpy impact test according to ISO 179 (2000). For the notch, the tip radius R was measured for 0.50 mm. Note that the larger the numerical value of the notched Charpy impact strength, the better the impact resistance strength. However, in the present invention, when the notch tip radius R is 0.50 mm, the component (Y) and other resins are compared to the component (X). By including at least one of the components, the value of the Charpy impact strength with a notch was improved as compared with the component (X).

(4) Measurement of total light transmittance and haze:
The pellets of the polycarbonate-based transparent resin composition were dried at 90 ° C. for 4 hours or longer using a hot air dryer (manufactured by Matsui Seisakusho, box-type dryer PO-80). Next, the dried pellets are supplied to an injection molding machine (Nippon Steel Works J75EII type) and molded under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, whereby an injection molded plate ( Width 100 mm × length 100 mm × thickness 2 mm). In accordance with JIS K7136 (2000), the total light transmittance and Haze of the injection-molded plate were measured with a D65 light source using a Nippon Denshoku Industries Co., Ltd. haze meter “NDH2000”. The larger the total light transmittance, the better the transparency. Moreover, it is evaluated that the smaller the value of Haze, the better the optical characteristics. In the present example, the total light transmittance was 90% or more.

(5) Measurement of Yellowness YI Value The pellets of the polycarbonate-based transparent resin composition were dried at 90 ° C. for 4 hours or more using a hot air dryer (manufactured by Matsui Seisakusho, box type dryer PO-80). Next, the dried pellets are supplied to an injection molding machine (Nippon Steel Works J75EII type) and molded under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, whereby an injection molded plate ( Width 100 mm × length 100 mm × thickness 2 mm). In accordance with JIS K7136 (2000), YI of an injection-molded plate was measured with a C light source using a colorimetric color difference meter “ZE-2000” manufactured by Nippon Denshoku Industries Co., Ltd. In the present example, the YI value was 5.0 or less.

(6) Long-term moisture and heat resistance The pellets of the polycarbonate-based transparent resin composition were dried at 90 ° C. for 4 hours or more using a hot air dryer (manufactured by Matsui Seisakusho, box dryer PO-80). Next, the dried pellets are supplied to an injection molding machine (Nippon Steel Works J75EII type) and molded under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, whereby an injection molded plate ( Width 100 mm × length 100 mm × thickness 2 mm). The molded plate was cut into a width of 50 mm and a length of 50 mm, and then subjected to a static treatment for 960 hours at 85 ° C. and a relative humidity of 85% using ETAC HIFLEX FX224P manufactured by Enomoto Kasei Co., Ltd.
Regarding YI change (ΔYI) before and after the treatment, in accordance with JIS K7136 (2000), a colorimetric color difference meter “ZE-2000” manufactured by Nippon Denshoku Industries Co., Ltd. was used. YI was measured.
In this evaluation, the smaller the ΔYI value, the smaller the change in color tone when used for a long time in a high-temperature and high-humidity environment, indicating that the heat and heat resistance is excellent. In this example, a ΔYI value in this evaluation of 5.0 or less was considered excellent in heat and moisture resistance.

(7) Long-term dry heat resistance The pellets of the polycarbonate-based transparent resin composition were dried at 90 ° C. for 4 hours or more using a hot air dryer (manufactured by Matsui Seisakusho, box-type dryer PO-80). Next, the dried pellets are supplied to an injection molding machine (Nippon Steel Works J75EII type) and molded under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, whereby an injection molded plate ( Width 100 mm × length 100 mm × thickness 2 mm). The molded plate was cut into a width of 50 mm and a length of 50 mm, and then subjected to a static treatment for 960 hours in a vacuum oven VOS-301SD manufactured by Tokyo Rika Kikai Co., Ltd. at 85 ° C. under the condition that no decompression operation was performed.
Regarding YI change (ΔYI) before and after the treatment, in accordance with JIS K7136 (2000), a colorimetric color difference meter “ZE-2000” manufactured by Nippon Denshoku Industries Co., Ltd. was used. YI was measured.
In this evaluation, the smaller the ΔYI value, the smaller the change in color tone when used for a long time in a high-temperature dry environment, and the better the heat resistance. In this example, a ΔYI value in this evaluation of 5.0 or less was considered excellent in dry heat resistance.

[Production Example of Polycarbonate Resin (PC-1, PC-2)]
[Raw materials]
The abbreviations and manufacturers of the compounds used in the following production examples are as follows.
<Dihydroxy compound>
・ ISB: Isosorbide (Rocket Fleure)
CHDM: 1,4-cyclohexanedimethanol [manufactured by SK Chemical]
TCDDM: Tricyclodecane dimethanol [manufactured by OXEA]
<Carbonated diester>
・ DPC: Diphenyl carbonate [Mitsubishi Chemical Corporation]
<Catalyst deactivator>
Phosphorous acid [manufactured by Taihei Chemical Industry Co., Ltd.] (molecular weight 82.0)
<Thermal stabilizer (antioxidant)>
Irganox 1010: pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [manufactured by BASF]
AS2112: Tris (2,4-di-tert-butylphenyl) phosphite [manufactured by ADEKA Corporation] (molecular weight 646.9)
<Release agent>
E-275: ethylene glycol distearate [manufactured by NOF Corporation]

[Production Example 1 Polycarbonate resin (PC-1)]
Polycarbonate resin was polymerized using a continuous polymerization facility comprising three vertical stirring reactors, one horizontal stirring reactor, and a twin screw extruder. Specifically, first, ISB, CHDM, and DPC are melted in tanks, ISB 35.2 kg / hr, CHDM 14.9 kg / hr, DPC 74.5 kg / hr (in terms of molar ratio ISB / CHDM). /DPC=0.700/0.300/1.010) was continuously fed to the first vertical stirring reactor. At the same time, an aqueous solution of calcium acetate monohydrate was supplied to the first vertical stirring reactor so that the addition amount of calcium acetate monohydrate as a catalyst was 1.5 μmol with respect to 1 mol of all dihydroxy compounds. The reaction temperature, internal pressure and residence time of each reactor are as follows: first vertical stirring reactor: 190 ° C., 25 kPa, 90 minutes, second vertical stirring reactor: 195 ° C., 10 kPa, 45 minutes, third vertical type Stirring reactor: 210 ° C., 3 kPa, 45 minutes, fourth horizontal stirring reactor: 225 ° C., 0.5 kPa, 90 minutes. The operation was performed while finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the reduced viscosity of the obtained polycarbonate resin was 0.41 dL / g to 0.43 dL / g.

  The polycarbonate resin was withdrawn from the fourth horizontal stirring reactor at an amount of 60 kg / hr, and then the bent twin-screw extruder [TEX30α manufactured by Nippon Steel Works, L / D: 42.0, while the resin was in a molten state] L (mm): screw length, D (mm): screw diameter]. The polycarbonate resin that passed through the extruder was passed through a candle type filter (manufactured by SUS316) having an aperture of 10 μm while being in a molten state, and foreign matters were filtered. Thereafter, the polycarbonate resin was discharged from the die in a strand shape, cooled with water and solidified, and then pelletized with a rotary cutter to obtain a polycarbonate resin having an ISB / CHDM molar ratio of 70/30 mol%. In Table 1, the obtained polycarbonate resin was described as “(PC-1)”.

  The extruder has three vacuum vents, where residual low molecular components in the resin were removed by devolatilization. Before the second vent, 2000 ppm by weight of water was added to the resin to perform water injection and devolatilization. Prior to the third vent, 0.1 part by weight, 0.05 part by weight, and 0.3 part by weight of Irganox 1010, AS2112, and E-275 were added to 100 parts by weight of the polycarbonate resin, respectively. Thus, ISB / CHDM copolymer polycarbonate resin pellets were obtained. 0.65 weight ppm phosphorous acid (0.24 weight ppm as the amount of phosphorus atoms) was added to the polycarbonate resin as a catalyst deactivator. Phosphorous acid was added as follows. A master batch was prepared by mixing the polycarbonate resin pellets obtained in Production Example 1 with a solution of phosphorous acid in an ethanol solution. From the front of the first vent port of the extruder (from the resin supply port side of the extruder), The master batch was supplied at 1 part by weight with respect to 100 parts by weight of the polycarbonate resin in the extruder.

[Production Example 2 Polycarbonate resin (PC-2)]
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / TCDDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ A copolymer polycarbonate resin was obtained in the same manner as in Example 1. In Table 1, the obtained polycarbonate resin was described as “(PC-2)”.
[Production Example of Hydrogenated Block Copolymer (BP-2)]
[Production Example 3 Production of Block Copolymer (BP-2)]
In a stainless steel autoclave equipped with a stirrer, a polystyrene block content of 30% by weight, a copolymer of polystyrene block-polyisobutylene block-polystyrene block of Mw = 111000, Mn = 82100, and 75 parts by weight of tetrahydrofuran And 4 parts by weight of a 5% by weight palladium-supported activated carbon catalyst as a hydrogenation catalyst were mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen gas was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 170 ° C. and a pressure of 10 MPa for 4.5 hours.
After completion of the hydrogenation reaction, the reaction solution was diluted with 100 parts by weight of tetrahydrofuran, and the solution was filtered to remove the hydrogenation catalyst. The filtrate was poured into 1200 parts by weight of methanol with stirring, and the precipitated hydrogenated block copolymer was separated by filtration and dried by a vacuum dryer.
The hydrogenated block copolymer thus obtained was represented by the following formula, the weight average molecular weight (Mw) was 103000, and the number average molecular weight (Mn) was 78200 (Mw / Mn = 1.3). . The hydrogenation rate of the A block was 97%. In Table 1, the obtained hydrogenated block copolymer was described as “(BP-2)”.

[Raw materials used in Examples and Comparative Examples]
The abbreviations of the compounds used in the following examples and comparative examples are as follows.
Polycarbonate resin PC-1: Polycarbonate resin PC-2 produced in Production Example 1 Polycarbonate resin produced in Production Example 2 Block copolymer BP-1: Hydrogenated styrene-isoprene-butadiene-polystyrene copolymer [( Kuraray Septon HG-252] (polystyrene block content: 28% by weight)
BP-2: Block copolymer produced in Production Example 3 BP-3: Hydrogenated styrene-ethylene-butadiene-styrene copolymer [Clayton G1643 manufactured by Kraton Polymer Japan Co., Ltd.] (Polystyrene block content: 16. 6 to 20.6% by weight)
Core-shell rubber CS-1: Methyl methacrylate-butadiene-styrene rubber [Clike Strength E-950 manufactured by Arkema Co., Ltd.]

[Example 1]
After blending 2850 parts by weight of the polycarbonate resin pellet PC-1 obtained in Production Example 1 and 150 parts by weight of the block copolymer BP-1, a 30 mm twin-screw extruder provided with a vacuum vent (KZW- manufactured by Technovel Corp.) 15-30MG) was used to extrude at 230 ° C. while removing the low molecular weight components remaining in the resin by devolatilization to obtain polycarbonate resin composition pellets. Next, after the obtained pellets were dried for 5 hours with a hot air dryer at a temperature of 90 ° C., pellets were injection-molded using a 75-ton injection molding machine (EC-75 manufactured by Toshiba Machine Co., Ltd.). Molding conditions are a mold temperature: 60 ° C. and a cylinder temperature: 240 ° C. In this way, an ISO tensile test piece was obtained by molding a test piece composed of a plate-like molded body having a width of 100 mm, a length of 100 mm, and a thickness of 2 mm, and the like. About the obtained ISO tensile test piece, the Charpy impact test piece which gave 0.5 mm notch was cut out, and the Charpy impact test was implemented. Moreover, about the plate-shaped molded article, the total light transmittance, Haze, and YI were measured about the sample cut into width 50mm x length 50mm.

[Examples 2-3, Comparative Examples 3-4]
The same operation as in Example 1 was performed except that the composition described in Table 1 was changed.

[Comparative Example 1]
About the pellet of polycarbonate resin PC-1 manufactured in Production Example 1, after drying for 5 hours with a hot air dryer at a temperature of 90 ° C., using a 75-ton injection molding machine (EC-75 manufactured by Toshiba Machine Co., Ltd.), The pellets were injection molded. Molding conditions are a mold temperature: 60 ° C. and a cylinder temperature: 240 ° C. In this way, an ISO tensile test piece was obtained by molding a test piece composed of a plate-like molded body having a width of 100 mm, a length of 100 mm, and a thickness of 2 mm, and the like. About the obtained ISO tensile test piece, the Charpy impact test piece which gave 0.5 mm notch was cut out, and the Charpy impact test was implemented. Moreover, about the plate-shaped molded article, the total light transmittance, Haze, and YI were measured about the sample cut into width 50mm x length 50mm.

[Comparative Example 2]
In Comparative Example 1, the same operation as in Comparative Example 1 was performed except that the polycarbonate resin used was changed to PC-2.

From Table 1, it can be seen that the resin composition of the present invention is excellent in all of impact resistance, transparency (total light transmittance), color tone, wet heat resistance, and dry heat resistance. On the other hand, in Comparative Example 1 and Comparative Example 2 that do not contain a block copolymer, the impact resistance is inferior compared to Examples 1-3. Moreover, although the comparative example 3 is excellent in impact resistance, it is inferior to transparency, an optical characteristic, and a color tone compared with Example 1. FIG. Comparative Example 4 is excellent in impact resistance, but inferior in color tone, long-term wet heat resistance, and long-term dry heat resistance as compared to Example 2.

Claims (7)

A polycarbonate resin composition comprising the following component (X) and component (Y).
Component (X): Polycarbonate resin containing at least a structural unit derived from the dihydroxy compound represented by the following general formula (1) Component (Y): Block copolymer comprising the following A block and B block and this hydrogenated block At least one of the copolymers A block: polymer of aromatic hydrocarbon having vinyl group B block: polymer of chain-like unsaturated hydrocarbon having double bond in the molecule

  The polycarbonate resin composition of Claim 1 in which the said polycarbonate resin contains the structural unit derived from dihydroxy compounds other than the dihydroxy compound represented by the said Formula (1).   The polycarbonate resin of Claim 1 or 2 in which the said polycarbonate resin contains 30 mol% or more of structural units derived from the compound represented by the said Formula (1) with respect to 100 mol% of structural units derived from all the diols. Composition.   The resin composition of any one of Claims 1-3 whose ratio of A block in the said component (Y) is 10 to 50 weight%.   The polycarbonate resin composition according to claim 1, wherein the A block is a hydrogenated polystyrene block.   The polycarbonate resin composition according to any one of claims 1 to 5, wherein the polymer constituting the B block is a polymer containing a structural unit derived from isobutylene.   The molded object containing the polycarbonate resin composition of any one of Claims 1-6.