JP5644243B2 - Polycarbonate resin composition and polycarbonate resin molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin composition containing a polycarbonate resin and an impact strength modifier, and a polycarbonate resin molded product formed by molding the polycarbonate resin composition.

  Polycarbonate is 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 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 to develop polycarbonate.

Conventionally, various polycarbonates using plant-derived monomers as raw materials have been developed.
For example, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1). Further, as a copolymerized polycarbonate of isosorbide and another dihydroxy compound, a polycarbonate copolymerized with bisphenol A has been proposed (for example, see Patent Document 2), and further, by copolymerizing isosorbide and an aliphatic diol. Attempts have been made to improve the rigidity of homopolycarbonate composed of isosorbide (see, for example, Patent Document 3).

On the other hand, a rubber polymer is obtained by using a polycarbonate obtained by polymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound (see, for example, Patent Documents 4 and 5) or a polycarbonate obtained by transesterification between isosorbide and diphenyl carbonate. A polycarbonate to which is added (for example, see Patent Document 6) has also been proposed.
Furthermore, a polycarbonate obtained by adding a styrene resin to a polycarbonate obtained by transesterification between isosorbide and diphenyl carbonate has been proposed (see Patent Document 7).

GB1079686 Publication JP-A-56-55425 WO 2004/111106 JP-A-6-145336 Japanese Patent Publication No. 63-12896 WO2008 / 146719 JP 2007-70438 A

However, the above-mentioned polycarbonate obtained by transesterification with diphenyl carbonate using isosorbide as a plant-derived monomer is brown and is not satisfactory in terms of transparency.
Moreover, the above-mentioned polycarbonate obtained by polymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound, has a molecular weight as low as about 4000 at most and has a low glass transition temperature.

Further, a polycarbonate obtained by adding a rubbery polymer to a polycarbonate obtained by transesterification between isosorbide and diphenyl carbonate has a low notched Charpy impact strength of about 40 kJ / m ² at most, and a polycarbonate added with a styrenic resin is The total light transmittance is not satisfactory.

  As described above, various polycarbonate resins using raw materials obtained from biomass resources such as plants have been proposed in the past, but the fields of building materials, electrical / electronics, automobiles that are required to have both transparency and strength have been proposed. There was nothing that could be used satisfactorily in the field, optical part field and the like.

  Especially in applications such as transparent covers for protecting switches, lighting switches to prevent forgetting to turn off, resin shields, screens on the front of motorcycles, transparent building materials for daylighting, and carport roofs, both transparency and strength are required. The However, polycarbonate resins using raw materials obtained from biomass resources have not been adequately suited for these applications.

  An object of the present invention is a polycarbonate resin composition that solves the above-mentioned conventional problems, has excellent transparency and strength, and can be suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. The object is to provide a molded article and a polycarbonate resin molded article.

  As a result of investigations by the present inventors, a polycarbonate resin composition comprising a polycarbonate resin containing a predetermined amount of a structural unit derived from a dihydroxy compound having a specific site and an impact strength modifier, the predetermined physical properties of the polycarbonate resin composition If satisfied, the present invention has found that a polycarbonate resin composition excellent in transparency and strength can be realized that can be suitably used in the fields of building materials, electric / electronics, automobiles, optical parts, etc. It came to complete.

（但し、前記一般式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）
[２] 前記ポリカーボネート樹脂１００重量部に対する前記衝撃強度改質剤の含有量が１重量部以上２５重量部未満であることを特徴とする［１］に記載のポリカーボネート樹脂組成物。
[３] 構造の一部に前記一般式（１）で表される部位を有するジヒドロキシ化合物が、複素環基を有するジヒドロキシ化合物であることを特徴とする［１］又は［２］に記載のポリカーボネート樹脂組成物。
[４] 複素環基を有するジヒドロキシ化合物が、下記一般式（２）で表される化合物であることを特徴とする［３］に記載のポリカーボネート樹脂組成物。

[５] 前記ポリカーボネート樹脂が、脂肪族ジヒドロキシ化合物に由来する構造単位を更に含むことを特徴とする［１］〜［４］のいずれかに記載のポリカーボネート樹脂組成物。
[６] 前記脂肪族ジヒドロキシ化合物が、脂環式ジヒドロキシ化合物であることを特徴とする［５］に記載のポリカーボネート樹脂組成物。
[７] 前記ポリカーボネート樹脂において、ビスフェノール化合物に由来する構造単位の含有量は０ｍｏｌ％以上かつ１ｍｏｌ％未満であることを特徴とする［１］〜［６］のいずれかに記載のポリカーボネート樹脂組成物。
[８] 前記ポリカーボネート樹脂組成物が酸化防止剤を含有していることを特徴とする請［１］〜［７］のいずれかに記載のポリカーボネート樹脂組成物。
[９] 前記ポリカーボネート樹脂組成物が離型剤を含有していることを特徴とする［１］〜［８］のいずれかに記載のポリカーボネート樹脂組成物。
[１０] ［１］〜［９］のいずれかに記載のポリカーボネート樹脂組成物を成形してなることを特徴とするポリカーボネート樹脂成形品。
[１１] 前記ポリカーボネート樹脂成形品が、射出成形法により成形されたものであることを特徴とする［１０］に記載のポリカーボネート樹脂成形品。 That is, the gist of the present invention resides in the following [1] to [11].
[1] A polycarbonate resin containing 1 mol% or more and less than 70 mol% of a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure, and an impact strength modifier A polycarbonate resin composition comprising:
Total light transmittance of the molded article molded from the polycarbonate resin composition (thickness 3mm) is Ri der 60%
The polycarbonate resin composition, wherein the impact strength modifier is a butadiene-alkyl acrylate-alkyl methacrylate copolymer .

(However, the site represented by the general formula (1) unless it is part of _-CH 2 -O-H.)
[2] The polycarbonate resin composition according to [1], wherein the impact strength modifier is contained in an amount of 1 part by weight or more and less than 25 parts by weight with respect to 100 parts by weight of the polycarbonate resin.
[ 3 ] The polycarbonate according to [1] or [2] , wherein the dihydroxy compound having a site represented by the general formula (1) in a part of the structure is a dihydroxy compound having a heterocyclic group Resin composition.
[ 4 ] The polycarbonate resin composition according to [ 3 ], wherein the dihydroxy compound having a heterocyclic group is a compound represented by the following general formula (2).

[ 5 ] The polycarbonate resin composition according to any one of [1] to [ 4 ], wherein the polycarbonate resin further includes a structural unit derived from an aliphatic dihydroxy compound.
[ 6 ] The polycarbonate resin composition according to [ 5 ], wherein the aliphatic dihydroxy compound is an alicyclic dihydroxy compound.
[ 7 ] The polycarbonate resin composition according to any one of [1] to [ 6 ], wherein the content of the structural unit derived from the bisphenol compound in the polycarbonate resin is 0 mol% or more and less than 1 mol%. .
[8] The polycarbonate resin composition according to any one of [1] to [7], wherein the polycarbonate resin composition contains an antioxidant .
[9] The polycarbonate resin composition according to any one of [1] to [8], wherein the polycarbonate resin composition contains a release agent .
[ 10 ] A polycarbonate resin molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [ 9 ].
[ 11 ] The polycarbonate resin molded product according to [ 10 ], wherein the polycarbonate resin molded product is molded by an injection molding method.

  According to the present invention, there are provided a polycarbonate resin composition and a polycarbonate resin molded article which have excellent transparency and strength and can be suitably used in the building material field, the electric / electronic field, the automobile field, the optical part field and the like. be able to.

  Hereinafter, the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

<Polycarbonate resin composition>
The polycarbonate resin composition has a predetermined structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure (hereinafter sometimes referred to as “the dihydroxy compound of the present invention”). The total light transmittance of the molded product having a thickness of 3 mm is 60% or more.

However, unless moiety represented by the general formula (1) is part of _-CH 2 -O-H.
That is, the said dihydroxy compound says what contains at least the site | part of the said General formula (1) further two hydroxyl groups.

In the polycarbonate resin composition, when the total light transmittance is less than 60%, it may be difficult to suitably use in the building material field, the electric / electronic field, the automobile field, the optical part field, and the like. The total light transmittance is preferably 70% or more, more preferably 80% or more.
From the viewpoint of difficulty of realization, the upper limit of the total light transmittance is 94%.

  The total light transmittance can be controlled by adjusting the molar ratio of the dihydroxy compound in the polycarbonate resin composition, the type or content of the impact strength modifier, and the like.

Hereinafter, the details of the polycarbonate resin composition of the present invention will be described.
<Dihydroxy compound>
The said polycarbonate resin has at least the structural unit derived from the dihydroxy compound which has a site | part represented by the said General formula (1) in a part of structure.
In the polycarbonate resin, the content of the structural unit is 1 mol% or more and less than 70 mol%. If it is less than 1 mol%, the heat resistance is insufficient, and the molded member may be deformed by heat. On the other hand, when it exceeds 70 mol%, the impact resistance is insufficient, and there is a possibility of breaking when using the molded member. The content of the structural unit derived from the dihydroxy compound is more preferably 30 mol% or more, and even more preferably 50 mol% or more. Further, the content of the structural unit derived from the dihydroxy compound is more preferably 65 mol% or less, and still more preferably 60 mol% or less.

The dihydroxy compound having a site represented by the general formula (1) in a part of the structure (the dihydroxy compound of the present invention) includes those represented by the general formula (1) in a part of the molecular structure. Although not particularly limited, specifically, oxyalkylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis ( 4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) ) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3- Phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl- 6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene, etc., has an aromatic group in the side chain and is bonded to the aromatic group in the main chain And a dihydroxy compound in which the ether group is a moiety represented by the general formula (1). In addition, some of the heterocyclic groups such as an anhydrosugar alcohol represented by the dihydroxy compound represented by the following general formula (2) and a compound having a cyclic ether structure such as spiroglycol represented by the following general formula (3) Although the dihydroxy compound which is a site | part represented by the said General formula (1) is mentioned, The dihydroxy compound whose part of a heterocyclic group is a site | part represented by the said General formula (1) is preferable. Examples of the dihydroxy compound represented by the following general formula (2) include isosorbide, isomannide, and isoide which are in a stereoisomeric relationship. Moreover, as a dihydroxy compound represented by the following general formula (3), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) ) Undecane (common name: spiroglycol), 3,9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9- Bis (1,1-dipropyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, dioxane glycol and the like can be mentioned.
These may be used alone or in combination of two or more.
Among these dihydroxy compounds, compounds having a heterocyclic group are more preferred from the viewpoint of being abundant as resources and readily available (claim 3 ), and compounds having the following general formula (2) are particularly preferred. (Claim 4 ) Isosorbide obtained by dehydrating and condensing sorbitol produced from various starches is most preferable from the viewpoints of availability, production, optical properties, and moldability.

In the general formula _(3), R 1 ~R ₄ are each independently an alkyl group having a carbon number of 1 to 3 carbon atoms.

  Isosorbide is easily oxidized gradually by oxygen. For this reason, when storing or handling during production, it is important to prevent moisture from being mixed, to use an oxygen scavenger, or to be in a nitrogen atmosphere in order to prevent decomposition by oxygen. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate resin is produced using isosorbide containing these decomposition products, the resulting polycarbonate resin is colored or causes a significant deterioration in physical properties. Moreover, it may affect the polymerization reaction, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate resin, or the physical properties may be significantly deteriorated. A reducing agent or an antacid is used as the stabilizer. Among these, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the antacid include alkalis such as sodium hydroxide. Addition of such an alkali metal salt is not preferable because an alkali metal may serve as a polymerization catalyst, and if it is added excessively, the polymerization reaction cannot be controlled.

  In order to obtain isosorbide containing no oxidative decomposition product, isosorbide may be distilled as necessary. Moreover, also when the stabilizer is mix | blended in order to prevent the oxidation and decomposition | disassembly of isosorbide, you may distill isosorbide as needed. In this case, the distillation of isosorbide may be simple distillation or continuous distillation, and is not particularly limited. Distillation is carried out under reduced pressure in an inert gas atmosphere such as argon or nitrogen. By performing such distillation of isosorbide, it is possible to use high purity isosorbide having a formic acid content of 20 ppm or less, particularly 5 ppm or less.

In addition, the measuring method of formic acid content in isosorbide is performed according to the following procedures using an ion chromatograph.
About 0.5 g of isosorbide is precisely weighed and collected in a 50 ml volumetric flask and made up to volume with pure water. A sodium formate aqueous solution is used as a standard sample, and the peak having the same retention time as that of the standard sample is defined as formic acid.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As a measurement column, AG-15 is used for a guard column manufactured by Dionex, and AS-15 is used for a separation column. A measurement sample is injected into a 100 μl sample loop, and 10 mM NaOH is used as an eluent, and the measurement is performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor is used as the suppressor, and a 12.5 mM-H ₂ SO ₄ aqueous solution is used as the regenerating solution.

It is preferable that the polycarbonate resin further includes a structural unit derived from an aliphatic dihydroxy compound in addition to a structural unit derived from a dihydroxy compound having a site represented by the general formula (1) in a part of the structure. 5 ), preferably further comprising a structural unit derived from an alicyclic dihydroxy compound (claim 6 ). In this case, flexibility can be imparted.

<Aliphatic dihydroxy compound>
Examples of the aliphatic dihydroxy compound include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 2-ethyl. 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, alicyclic dihydroxy compounds described below, etc. Is mentioned.

<Alicyclic dihydroxy compound>
Although it does not specifically limit as an alicyclic dihydroxy compound, Usually, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. When the alicyclic dihydroxy compound has a 5-membered ring structure or a 6-membered ring structure, the heat resistance of the obtained polycarbonate resin may be increased. The six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Carbon number contained in an alicyclic dihydroxy compound is 70 or less normally, Preferably it is 50 or less, More preferably, it is 30 or less. When the number of carbon atoms is excessively large, the heat resistance becomes high, but synthesis tends to be difficult, purification becomes difficult, and cost tends to be high. The smaller the carbon number, the easier it is to purify and the easier it is to obtain.

Specific examples of the alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II).
_{HOCH 2 -R 5 -CH 2 OH (} I)
_HO-R 6 -OH (II)
(However, in formula (I) and formula (II), R ₅ and R ₆ each independently represent a divalent group containing a substituted or unsubstituted cycloalkyl structure having 4 to 20 carbon atoms. )

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the general formula (I), in general formula (I), R ₅ represents the following general formula (Ia) (wherein R ³ represents a hydrogen atom, or Represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like.

Examples of tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which are alicyclic dihydroxy compounds represented by the above general formula (I), include, in general formula (I), R ₅ represents the following general formula (Ib) (in the formula: , N represents 0 or 1).

As decalin dimethanol or tricyclotetradecane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), in general formula (I), R ₅ is represented by the following general formula (Ic) (wherein m represents 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, and the like.

Moreover, as norbornane dimethanol which is an alicyclic dihydroxy compound represented by the general formula (I), various isomers in which R ₅ is represented by the following general formula (Id) in the general formula (I) Include. Specific examples thereof include 2,3-norbornane dimethanol, 2,5-norbornane dimethanol and the like.

The adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), includes various isomers in which R ₅ is represented by the following general formula (Ie) in the general formula (I). Specific examples of such a material include 1,3-adamantane dimethanol.

In addition, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), R ₆ is represented by the following general formula (IIa) (wherein R ³ is a hydrogen atom, substituted Or an unsubstituted alkyl group having 1 to 12 carbon atoms). Specific examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

As tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the general formula (II), in general formula (II), R ₆ is represented by the following general formula (IIb) (wherein n Represents 0 or 1).

As decalin diol or tricyclotetradecane diol, which is an alicyclic dihydroxy compound represented by the general formula (II), in general formula (II), R ₆ is represented by the following general formula (IIc) (where m is It represents 0 or 1). Specifically, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol and the like are used as such.

The norbornanediol which is an alicyclic dihydroxy compound represented by the general formula (II) includes various isomers in which R ₆ is represented by the following general formula (IId) in the general formula (II). Specifically, 2,3-norbornanediol, 2,5-norbornanediol, and the like are used as such.

The adamantanediol which is an alicyclic dihydroxy compound represented by the general formula (II) includes various isomers in which R ₆ is represented by the following general formula (IIe) in the general formula (II). Specifically, 1,3-adamantanediol etc. are used as such.

  Among the specific examples of the alicyclic dihydroxy compounds described above, cyclohexane dimethanols, tricyclodecane dimethanols, adamantane diols, and pentacyclopentadecane dimethanols are preferable, and are easily available and easy to handle. From the viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are particularly preferable.

  In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. These alicyclic dihydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  In the polycarbonate resin, the molar ratio between the structural unit derived from the dihydroxy compound having a site represented by the general formula (1) in a part of the structure and the structural unit derived from the alicyclic dihydroxy compound is an arbitrary ratio. However, by adjusting the molar ratio, the impact strength may be improved, and the desired glass transition temperature of the polycarbonate resin can be obtained.

  In the polycarbonate resin, the molar ratio of the structural unit derived from the dihydroxy compound having a site represented by the general formula (1) in a part of the structure to the structural unit derived from the alicyclic dihydroxy compound is 80:20. It is preferably ˜30: 70, more preferably 70:30 to 40:60. When the proportion of the structural unit derived from the dihydroxy compound having the site represented by the general formula (1) in a part of the structure is larger than the above range, coloring tends to occur, and conversely, the general formula (1 ) If the proportion of the structural unit derived from the dihydroxy compound having the moiety represented by () is small, it will be difficult to achieve a high molecular weight, it will be difficult to improve impact strength, and the glass transition temperature will tend to decrease. is there.

  In the polycarbonate resin, a structural unit derived from a dihydroxy compound having a site represented by the general formula (1) in a part of the structure, a structural unit derived from an aliphatic dihydroxy compound, a structure derived from an alicyclic dihydroxy compound In addition to the units, structural units derived from other dihydroxy compounds may be included. Other dihydroxy compounds include aromatic dihydroxy compounds.

  Examples of aromatic dihydroxy compounds include bisphenol compounds (including substituted and unsubstituted in the present invention), and specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl). ) Ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4- Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis ( 4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxy) Phenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1, Bisphenol compounds having no substituent on the aromatic ring such as 1-bis (4-hydroxyphenyl) cyclohexane; bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-) Aryl group as a substituent on an aromatic ring such as hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane Bisphenol compounds having: bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydro Ci-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy- 3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy) -3-isopropylphenyl) propane, 2,2-bis (4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydro Xyl-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, , 1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) Ethane, 2,2-bis (4-hydroxy-3,6-dimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2, 3,5-trimethylphenyl) ethane, 2,2-bis (4-hydroxy-2,3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5- Limethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane, etc. Bisphenol compounds having an alkyl group as a substituent on the aromatic ring: bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) dibenzylmethane and the like bisphenol compounds having an aryl group as a divalent group connecting aromatic rings 4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-te Bisphenol compounds in which aromatic rings such as lamethyl-4,4′-dihydroxydiphenyl ether are connected by an ether bond; 4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4′- Bisphenol compounds in which aromatic rings such as dihydroxydiphenylsulfone are linked by sulfone bonds; aromatics such as 4,4′-dihydroxydiphenyl sulfide and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide Examples thereof include bisphenol compounds in which group rings are linked by a sulfide bond, and preferably 2,2-bis (4-hydroxyphenyl) propane (hereinafter, abbreviated as “bisphenol A”). ).

The content of the structural unit derived from the bisphenol compound is preferably 0 mol% or more and less than 1 mol% (Claim 7 ), more preferably 0 mol% or more and less than 0.8 mol%, 0 mol% or more and 0.5 mol%. Less than is even more preferred. When there is too much content of the structural unit derived from a bisphenol compound, there exists a possibility that coloring may become remarkable.

  The above-mentioned other hydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

(Carbonated diester)
The polycarbonate resin in the present invention can be produced by a generally used polymerization method, and the polymerization method may be any of an interfacial polymerization method using phosgene, a melt polymerization method in which a transesterification reaction with a carbonic acid diester is performed, A melt polymerization method in which a dihydroxy compound is reacted with a diester carbonate having lower toxicity to the environment in the presence of a polymerization catalyst is preferred.
The polycarbonate resin can be obtained by a melt polymerization method in which the above-described dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester are transesterified.
As a carbonic acid diester used, what is normally represented by following General formula (4) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (4), A1 and A2 are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group.
Examples of the carbonic acid diester represented by the general formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.

  The carbonic acid diester is preferably used in a molar ratio of 0.96 to 1.10, particularly preferably in a molar ratio of 0.98 to 1.04, based on all dihydroxy compounds used in the melt polymerization. is there. When this molar ratio is less than 0.96, the terminal hydroxyl group of the produced polycarbonate resin is increased, and the thermal stability of the polymer is deteriorated. When the molar ratio is larger than 1.10, The rate of the transesterification reaction is reduced, making it difficult to produce a polycarbonate resin having a desired molecular weight, and the amount of residual carbonic acid diester in the produced polycarbonate resin is increased. This is not preferable because it causes odor of the molded product.

<Transesterification reaction catalyst>
The polycarbonate resin can be produced by transesterifying the dihydroxy compound containing the dihydroxy compound of the present invention and the carbonic acid diester represented by the general formula (4) as described above. More specifically, it can be obtained by transesterification to remove by-product monohydroxy compounds and the like out of the system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

Examples of the transesterification catalyst (hereinafter sometimes referred to as “catalyst”) that can be used in the production of the polycarbonate resin include Group 1 or Group 2 in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005) ( In the following, basic compounds such as metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds, and the like are simply referred to as “Group 1” and “Group 2”. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.
It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
In addition, the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

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

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like, among which magnesium compounds, calcium compounds and barium compounds are preferred, magnesium compounds and / or Or a calcium compound is still more preferable.

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

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

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

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

  In the case of a Group 1 metal compound and / or a Group 2 metal compound, the amount of the catalyst used is usually in the range of 0.1 μmol to 100 μmol as a metal conversion amount with respect to 1 mol of all dihydroxy compounds used in the polymerization. Preferably, it is in the range of 0.5 μmol to 50 μmol, and more preferably in the range of 1 μmol to 25 μmol. If the amount of the catalyst used is too small, the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight may not be obtained, and sufficient breaking energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only the hue of the resulting polycarbonate resin will deteriorate, but also by-products will be generated, resulting in a decrease in fluidity and the occurrence of gels, which causes brittle fracture. In some cases, it may be difficult to produce a polycarbonate resin having a target quality.

The polycarbonate resin is obtained by melt-polymerizing a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester by an ester exchange reaction. The raw material dihydroxy compound and the carbonic acid diester are uniformly mixed before the ester exchange reaction. It is preferable to do.
The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. The hue of the polycarbonate resin thus obtained may deteriorate, which may adversely affect light resistance.

The polycarbonate resin is preferably produced by melt polymerization in multiple stages using a plurality of reactors using a catalyst, but the reason for carrying out melt polymerization in a plurality of reactors is the initial stage of the melt polymerization reaction. Because there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. This is because it is important to sufficiently distill off the monohydroxy compound produced as a by-product. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of reactors arranged in series. As described above, the number of the reactors may be at least two, but from the viewpoint of production efficiency, the number of reactors is three or more, preferably 3 to 5, and particularly preferably four.
In the production of the polycarbonate resin, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed. Good.

In the production of the polycarbonate resin, the catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the reactor, but from the viewpoint of supply stability and control of melt polymerization, the reactor A catalyst supply line is installed in the middle of the raw material line before being supplied to, and is preferably supplied as an aqueous solution.
If the temperature of the transesterification reaction is too low, it may lead to a decrease in productivity and an increase in the thermal history of the product, and if it is too high, it may not only cause vaporization of the monomer but also promote the decomposition and coloring of the polycarbonate resin. .

  In the production of the polycarbonate resin, a method of transesterifying a dihydroxy compound containing a dihydroxy compound having a site represented by the general formula (1) in a part of the structure and a carbonic acid diester in the presence of a catalyst, It is performed in a multistage process of two or more stages. Specifically, the transesterification temperature of the first stage (hereinafter sometimes referred to as “internal temperature”) is usually 140 ° C. to 220 ° C., preferably 150 ° C. to 200 ° C., and the residence time is usually 0. It is carried out for 1 hour to 10 hours, preferably 0.5 hour to 3 hours. In the second and subsequent stages, the transesterification reaction temperature is raised, usually at a temperature of 210 ° C. to 270 ° C., and the pressure of the reaction system is changed to the pressure of the first stage while removing the phenol generated simultaneously from the reaction system. The polycondensation reaction is finally carried out under a pressure of 200 Pa or less while the pressure is gradually lowered. When the transesterification reaction temperature is excessively high, the hue is deteriorated when formed into a molded product, which may easily cause brittle fracture. When the transesterification reaction temperature is too low, the target molecular weight does not increase, the molecular weight distribution becomes wide, and the impact strength may be inferior. Further, if the residence time of the transesterification reaction is excessively long, brittle fracture may occur easily. If the residence time is too short, the target molecular weight may not increase and the impact strength may be inferior.

  In particular, in order to obtain a good polycarbonate resin having a high impact strength by suppressing the coloring, heat deterioration or burning of the polycarbonate resin, the maximum internal temperature in all reaction stages is less than 255 ° C., particularly 225 ° C. to 250 ° C. Is preferred. In addition, a horizontal reactor with excellent plug flow and interface renewability is used at the final stage of the reaction in order to suppress a decrease in the polymerization rate in the latter half of the polymerization reaction and to minimize thermal degradation of the polycarbonate resin due to thermal history. It is preferable to do.

  In addition, in order to obtain a polycarbonate resin with high impact strength and to obtain a polycarbonate resin with high molecular weight, the polymerization temperature may be increased as much as possible, and the polymerization time may be lengthened. It tends to break down. Therefore, in order to satisfy both the high impact strength and the difficulty of brittle fracture, the polymerization temperature must be kept low, the use of a highly active catalyst for shortening the polymerization time, and the appropriate reaction system pressure. Is preferable. Furthermore, it is preferable to remove foreign matters or burns generated in the reaction system by a filter or the like in the middle of the reaction or at the end of the reaction in order to make brittle fracture difficult.

The polycarbonate resin is usually cooled and solidified after melt polymerization as described above, and pelletized with a rotary cutter or the like.
The method of pelletization is not limited, but the polycarbonate resin is drawn out from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or the molten state from the final polymerization reactor is uniaxial or biaxial. After supplying resin to the extruder of the shaft and melt-extruding, cooling and solidifying to pelletize, or after extracting from the final polymerization reactor in a molten state, cooling and solidifying in the form of strands and once pelletizing Examples thereof include a method in which a resin is again supplied to a single-screw or twin-screw extruder, melt-extruded, and then cooled and solidified to be pelletized.
At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.

  The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin, but is usually 150 ° C to 300 ° C, preferably 200 ° C to 270 ° C, more preferably 230 ° C to 260 ° C. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate is severely thermally deteriorated, and foreign matter and burns are generated. It is preferable to install a filter for removing the foreign matters and burns in the extruder or at the exit of the extruder.

The opening of the filter is usually 400 μm or less, preferably 200 μm or less, particularly preferably 100 μm or less. If the opening of the filter is excessively large, leakage may occur in the removal of foreign matters and burns, and when polycarbonate resin is molded, brittle fracture may occur.
Further, a plurality of the filters may be used in series, or a filtration device in which a plurality of leaf disk polymer filters are stacked may be used.

  When the extruded polycarbonate resin is cooled to form chips, it is preferable to use a cooling method such as air cooling or water cooling. The air used for air cooling should be air from which foreign substances in the air have been removed in advance with a HEPA filter (a filter specified in JIS Z8112), etc., to prevent reattachment of foreign substances in the air. desirable. When using water cooling, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. There are various openings of the filter to be used, but those having a filter of 10 to 0.45 μm are preferable.

  The degree of polymerization of the polycarbonate resin was determined by precisely adjusting the polycarbonate concentration to 1.00 g / dl by using a mixed solvent of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 as a solvent. The reduced viscosity measured at 30.0 ° C. ± 0.1 ° C. (hereinafter sometimes simply referred to as “reduced viscosity”) is preferably 0.40 dl / g or more, more preferably 0.60 dl / g or more, Particularly preferred is 0.85 dl / g or more. Further, it is preferably 2.0 dl / g or less, more preferably 1.7 dl / g or less, and particularly preferably 1.4 dl / g or less. If the reduced viscosity of the polycarbonate resin is excessively low, the mechanical strength may be weakened. If the reduced viscosity of the polycarbonate resin is excessively high, the fluidity at the time of molding is reduced, the cycle characteristics are reduced, and the molded product is reduced. Tends to be deformed by heat.

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

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

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

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, and the total hydroxy compound component described above, The content is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less. If this addition amount is less than the lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, it may cause a decrease in transparency, or conversely promote coloring or reduce heat resistance. .

  In addition, the polycarbonate resin produced in this way may be blended with one or more thermal stabilizers in order to prevent a decrease in molecular weight and a deterioration in hue at the time of molding or the like.

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl Diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di) -Tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , Trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), dimethylbenzenephosphonate , Diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate resin, if a phosphorous acid compound is further blended by a blending method described later, transparency during polymerization is reduced, coloring Further, it is possible to blend more heat stabilizers while avoiding a decrease in heat resistance, and it is possible to prevent deterioration of hue.

  The content of these heat stabilizers is preferably 0.0001 parts by weight to 1 part by weight, more preferably 0.0005 parts by weight to 0.5 parts by weight, and 0.001 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Part to 0.2 parts by weight is more preferable.

<Impact strength modifier>
The polycarbonate resin composition of the present invention contains the polycarbonate resin and an impact strength modifier.
In the polycarbonate resin, it is preferable that the content of the impact strength modifier with respect to 100 parts by weight of the polycarbonate resin is 1 part by weight or more and less than 25 parts by weight.
When the content of the impact strength modifier is less than 1 part by weight, a sufficient impact strength modification effect cannot be obtained, and the molded member may be broken. On the other hand, when it exceeds 25 parts by weight, good moldability is impaired, and there is a risk that burns will occur during molding.

  Examples of the impact strength modifier include SB (styrene-butadiene) copolymer, SBS (styrene-butadiene-styrene block) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MBS (methyl methacrylate-). Butadiene-styrene) copolymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer, MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer, AES (acrylonitrile) -Ethylene propylene rubber-styrene) copolymer, MA (methyl methacrylate-acrylic rubber) copolymer, MAS (methyl methacrylate-acrylic rubber-styrene) copolymer, methyl methacrylate-acrylic-butadiene Ngomu copolymer, methyl methacrylate - acrylic - butadiene rubber - styrene copolymer, methyl methacrylate - can be used - (acryl silicone IPN rubber) copolymer, and natural rubber.

Preferably, the impact strength modifier is a copolymer containing butadiene .
In this case, a particularly significant impact strength modification effect can be obtained in combination with the polycarbonate resin.

  Specific examples of butadiene-containing copolymers include SBS (styrene-butadiene-styrene block) copolymers, ABS (acrylonitrile-butadiene-styrene) copolymers, and MBS (methyl methacrylate-butadiene-styrene) copolymers. There are polymers, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) copolymers, MB (methyl methacrylate-butadiene) copolymers, methyl methacrylate-acryl-butadiene rubber copolymers, and the like.

The polycarbonate resin composition can be produced by mixing the polycarbonate resin and the impact strength modifier.
Specifically, for example, the polycarbonate resin composition by mixing the pellet-like polycarbonate resin and the impact strength modifier using an extruder, extruding into a strand, and cutting into a pellet with a rotary cutter or the like You can get things.
The Charpy notched impact strength of the polycarbonate resin composition is preferably 15 kJ / m ² or more, more preferably 20 kJ / m ² or more, even more preferably 25 kJ / m ² or more. From the viewpoint of difficulty of realization, the upper limit of the notched Charpy impact strength of the polycarbonate resin composition is 200 kJ / m ² .
At the time of mixing the polycarbonate resin and the impact strength modifier, additives such as the following antioxidant and mold release agent can be added as necessary.

  In the polycarbonate resin composition, one or more kinds of antioxidants generally known for the purpose of antioxidant can be blended.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4 -Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, 4,8,10-tetraoxaspiro (5,5) undecane and the like.

  The content of these antioxidants is preferably 0.0001 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate.

  In addition, the polycarbonate resin composition has a range that does not impair the purpose of the present invention in order to further improve the release from the cooling roll during sheet molding or the mold release from the mold during injection molding. 1 type (s) or 2 or more types of mold release agents may be mix | blended.

  Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, Examples include organopolysiloxane.

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

  As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

  The content of the release agent is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  Further, the polycarbonate resin composition is significantly less discolored by ultraviolet rays than the conventional polycarbonate resin, but for the purpose of further improvement, it does not impair the purpose of the present invention. Seeds or two or more species may be blended.

  Examples of such ultraviolet absorbers and light stabilizers include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2 , 2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis3-benzoxazin-4-one) and the like.

  The content of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate.

  The polycarbonate resin composition may be blended with one or more blueing agents in order to counteract yellowishness. Any bluing agent can be used without any problem as long as it is used in conventional polycarbonate resins. In general, anthraquinone dyes are preferred because they are readily available.

  As a specific bluing agent, for example, the general name Solvent Violet 13 [CA. (Color Index No.) 60725], generic name Solvent Violet 31 [CA. 68210], general name Solvent Violet 33 [CA. 60725], generic name Solvent Blue 94 [CA. 61500], generic name Solvent Violet 36 [CA. 68210], generic name Solvent Blue 97 [manufactured by Bayer, "Macrolex Violet RR"], and generic name Solvent Blue 45 [CA. 61110] and the like are typical examples.

Usually, the content of these bluing agents is preferably 0.1 × 10 ⁻⁴ parts by weight to 2 × 10 ⁻⁴ parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  In addition to the above-mentioned additives, the polycarbonate resin composition has various known additives such as a flame retardant, a flame retardant aid, a hydrolysis inhibitor, and an antistatic agent, as long as the object of the present invention is not impaired. It may be a resin composition containing an agent, a foaming agent, a dye / pigment, and the like. Also, for example, a resin composition in which a synthetic resin such as aromatic polycarbonate, aromatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, or the like, or a biodegradable resin such as polylactic acid or polybutylene succinate is mixed. May be.

  As a blending method of the above-mentioned polycarbonate resin composition and various additives as described above, for example, mixing and kneading with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc. Or a solution blending method in which the mixture is dissolved in a common good solvent such as methylene chloride. However, this is not particularly limited, and any blending method that is usually used can be used. Various methods may be used.

  Various additives are added to the polycarbonate resin thus obtained, and it is generally known such as an extrusion molding method, an injection molding method, a compression molding method, etc. directly or after being once pelletized by a melt extruder. It can be formed into a desired shape by a forming method.

[Polycarbonate resin molded product]
A polycarbonate resin molded product can be obtained by molding the polycarbonate resin composition as described above.
Preferably, the polycarbonate resin molded product is molded by an injection molding method (claim 9 ).
In this case, the polycarbonate resin molded product having a complicated shape can be produced. And if it shape | molds in a complicated shape, it will become easy to generate | occur | produce a stress concentration part, but since the modification effect of impact strength is acquired as mentioned above in the said polycarbonate resin composition, the fracture | rupture by stress concentration can be suppressed.

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

(1) Test piece preparation method The pellet of the polycarbonate resin composition was dried at 80 degreeC for 6 hours using the hot air dryer. Next, the pellets of the dried polycarbonate resin composition are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and the injection molded plate is subjected to a resin temperature of 240 ° C., a mold temperature of 60 ° C. and a molding cycle of 40 seconds. An ISO test piece for mechanical properties (width 60 mm × length 60 mm × thickness 3 mm) was molded.

(2) Total light transmittance and haze measurement The injection molded plate obtained in the above (1) is based on JIS K7105, using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the test piece using a D65 light source. The total light transmittance and haze of were measured.

(3) Notched Charpy impact A notched Charpy impact test was carried out on the ISO test piece for mechanical properties obtained in (1) in accordance with ISO179.

The abbreviations of the compounds used in the description of the following examples and reference examples are as follows.
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (Eastman)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

(Impact strength modifier)
METABLEN C-223A: MBS (Mitsubishi Rayon Co., Ltd.)
Paraloid EXL2603: Butadiene-alkyl acrylate-alkyl methacrylate copolymer (Rohm and Haas Japan)

(Antioxidant)
ADK STAB 2112: Phosphite antioxidant (manufactured by ADEKA)
ADK STAB AO-60: Phenolic antioxidant (manufactured by ADEKA)
(Release agent)
S-100A: Stearic acid monoglyceride (Riken Vitamin Co., Ltd.)

( Reference Example 1)
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × 10 −6, and sufficiently purged with nitrogen (oxygen concentration 0.0005 vol% ~ 0.001 vol%).

  Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes.

  The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant.

  The contents thus oligomerized are once restored to atmospheric pressure and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes. Thereafter, the internal temperature was set to 230 ° C. over 20 minutes, the pressure was set to 133 Pa or less, the pressure was restored when the predetermined stirring power was reached, the contents were extracted in the form of strands, and pelletized (polycarbonate resin) with a rotary cutter.

  Next, pellets of the obtained polycarbonate resin, and further metabrene C-223A as an impact strength modifier, S-100A as a mold release agent, and Adekastab as an antioxidant so as to have the composition shown in Table 1 below. AO-60 and ADK STAB 2112 were extruded in a strand shape using a twin-screw extruder (LABOTEX30HSS-32) manufactured by Nippon Steel Works with two vents so that the resin temperature at the outlet was 250 ° C. After cooling and solidifying, it was pelletized with a rotary cutter. At this time, the vent port was connected to a vacuum pump, and the pressure at the vent port was controlled to be 500 Pa. The analysis result of the obtained pellet-like polycarbonate resin composition and the evaluation result by the method are shown in Table 1 described later.

(Example 1 )
The same operation as in Reference Example 1 was conducted except that 5 parts by weight of paraloid EXL2603 was added as an impact strength modifier.

( Reference Example 2 )
The procedure was the same as Reference Example 1, except that the molar ratio of ISB and CHDM in Reference Example 1 was changed and 10 parts by weight of Methbrene C-223A was added as an impact strength modifier.

(Comparative Example 1)
The same procedure as in Reference Example 1 was performed except that the impact strength modifier of Reference Example 1 was not added.

(Comparative Example 2)
Except for not adding the impact modifier of Example 2 was conducted in the same manner as in Reference Example 2.

As can be seen from Table 1, in Example 1 and Reference Examples 1 and 2 , compared with Comparative Examples 1 and 2, the light transmittance was as high as 60% or more, and a high notched Charpy impact strength was exhibited. Therefore, the polycarbonate resin molded products of Example 1 and Reference Examples 1 and 2 have excellent transparency and impact strength, and can be suitably used in the building material field, electrical / electronic field, automobile field, optical part field, and the like. it can.

Claims (11)

Polycarbonate resin composition comprising a polycarbonate resin containing 1 mol% or more and less than 70 mol% of a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) as part of the structure, and an impact strength modifier A thing,
Total light transmittance of the molded article molded from the polycarbonate resin composition (thickness 3mm) is Ri der 60%
The polycarbonate resin composition, wherein the impact strength modifier is a butadiene-alkyl acrylate-alkyl methacrylate copolymer .

(However, the site represented by the general formula (1) unless it is part of _-CH 2 -O-H.)   2. The polycarbonate resin composition according to claim 1, wherein the content of the impact strength modifier with respect to 100 parts by weight of the polycarbonate resin is 1 part by weight or more and less than 25 parts by weight. The polycarbonate resin composition according to claim 1 or 2 , wherein the dihydroxy compound having a part represented by the general formula (1) in a part of the structure is a dihydroxy compound having a heterocyclic group. The polycarbonate resin composition according to claim 3 , wherein the dihydroxy compound having a heterocyclic group is a compound represented by the following general formula (2).

The polycarbonate resin composition according to any one of claims 1 to 4 , wherein the polycarbonate resin further contains a structural unit derived from an aliphatic dihydroxy compound. The polycarbonate resin composition according to claim 5 , wherein the aliphatic dihydroxy compound is an alicyclic dihydroxy compound. In the said polycarbonate resin, content of the structural unit derived from a bisphenol compound is 0 mol% or more and less than 1 mol%, The polycarbonate resin composition of any one of Claims 1-6 characterized by the above-mentioned. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition contains an antioxidant . The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition contains a release agent . A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 9 . The polycarbonate resin molded article according to claim 10 , wherein the polycarbonate resin molded article is molded by an injection molding method.