JP6534890B2 - Polycarbonate resin copolymer and molded article - Google Patents

Description

  The present invention relates to a polycarbonate resin copolymer and a molded article which are excellent in low water absorption and improved in weatherability.

  In recent years, in various fields including optical parts and automobile parts, a transparent resin excellent in various performances is required. Conventionally, polycarbonate resins (hereinafter referred to as PC) and methacrylic resins are known as transparent resins, and in the form of molded articles, films and the like, in a wide range of fields such as electric and electronic parts, optical parts, automobile parts, and machine parts It is used. PC has a high elongation at break and is excellent in impact resistance, but has a problem that the surface is very soft (pencil hardness 4B to 2B) and easily scratched. Therefore, a method has been proposed in which an acrylic ester is applied to the surface of a polycarbonate substrate to form a protective film by ultraviolet curing (Patent Document 1). However, there is a problem that cracks due to shrinkage at the time of curing and the process become complicated. In addition, since the main chain contains an aromatic ring, a step of imparting weather resistance is also required.

  On the other hand, methacrylic resin such as polymethyl methacrylate has high transparency and hard surface hardness (pencil hardness H to 3 H), and is often used as an optical material such as a lens or an optical fiber. However, there is a problem that the use to be used is limited due to the high water absorption rate and the low impact resistance.

Recently, it has been proposed to obtain a polycarbonate excellent in weather resistance and surface hardness by transesterification with diphenyl carbonate using isosorbide which is a plant-derived monomer (Patent Document 2). However, due to the high water absorbency derived from the isosorbide skeleton, the dimensional change is large in an environment under high temperature and humidity, and the application may be limited to the use of precision parts and the like.
Therefore, resins and molded articles having all of low water absorption, weather resistance, heat resistance, impact resistance and pencil hardness in a well-balanced manner have not been provided yet.

Japanese Examined Patent Publication No.4-2614 WO 2004/111106 pamphlet

  An object of the present invention is to provide a polycarbonate resin copolymer and a molded article which are excellent in low water absorption, have improved weatherability, and have good impact resistance and pencil hardness.

The inventors of the present invention conducted intensive studies, and as a result, by including the repeating unit (A), polycarbonate resin having excellent low water absorption, improved weatherability, and excellent heat resistance, impact resistance and pencil hardness. It was investigated that a copolymer and a molded body could be obtained, and the present invention was made.
That is, the present invention is as follows.

（式中、Ｘ_１〜Ｘ_４はそれぞれ独立に、水素原子、置換若しくは無置換の炭素原子数１〜２０のアルキル基、置換若しくは無置換の炭素原子数６〜２０のシクロアルキル基、または置換若しくは無置換の炭素原子数６〜２０のアリール基を表し、Ｘ_５は置換若しくは無置換の炭素原子数２〜１０のアルキレン基、置換若しくは無置換の炭素原子数６〜２０のシクロアルキレン基、または置換若しくは無置換の炭素原子数６〜２０のアリーレン基を表し、ｍ及びｎはそれぞれ独立に１〜５の整数を表す。Ｗは単結合、または下記式（Ｗ）で示される２価の有機基のいずれかであり、

ここにＲ_１とＲ_２はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、または炭素原子数７〜１７のアラルキル基を表す。また、Ｒ_１とＲ_２が結合して炭素環または複素環を形成しても良い。Ｒ_３とＲ_４はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、または炭素原子数６〜１２アリール基を表す。Ｒ_５は炭素原子数１〜９のアルキレン基である。ａは０〜２０の整数を表し、ｂは１〜５００の整数を表す。）
２．ガラス転移温度が８０℃〜１４５℃である前項１記載のポリカーボネート樹脂共重合体。
３．２０℃の塩化メチレン溶液で測定された比粘度が０．１５〜１．５である前項１記載のポリカーボネート樹脂共重合体。
４．単位（Ａ）が下記式（Ａ−１）で表される単位（Ａ−１）である前項１記載のポリカーボネート樹脂共重合体。

５．さらに下記式（Ｂ）で表される単位（Ｂ）を含む前項１記載のポリカーボネート樹脂共重合体。

６．ＪＩＳ Ｋ５６００−５−４に準拠して測定した鉛筆硬度がＦ以上である前項１記載のポリカーボネート樹脂共重合体。
７．飽和吸水率が１．７％以下である前項１記載のポリカーボネート樹脂共重合体。
８．単位（Ａ−１）を誘導する原料として使用されるモノマー成分である２，２−ビス（４−（２−ヒドロキシエトキシ）シクロヘキシル）プロパンのモノマー純度が９０％以上である前項４記載のポリカーボネート樹脂共重合体。
９．前項１記載のポリカーボネート樹脂共重合体を素材とする成形品。
１０．前項１記載のポリカーボネート樹脂共重合体を素材とするフィルム。 1. The polycarbonate resin copolymer in which a repeating unit contains 1-50 mol% of units (A) represented by following formula (A) in all the repeating units.

(Wherein, X _{1 to} X ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituent Or an unsubstituted aryl group having 6 to 20 carbon atoms, X ₅ is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, m and n each independently represents an integer of 1 to 5. W is a single bond or a divalent group represented by the following formula (W) One of the organic groups,

Here, R ₁ and R ₂ each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, 6 to 6 carbon atoms 12 represents an aryl group, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. Also, R ₁ and R ₂ may combine to form a carbocyclic ring or a heterocyclic ring. R ₃ and R ₄ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 to 12 carbon atoms Represents an aryl group. R ₅ is an alkylene group having 1 to 9 carbon atoms. a represents the integer of 0-20, b represents the integer of 1-500. )
2. 2. Polycarbonate resin copolymer of the preceding clause 1 whose glass transition temperature is 80 degreeC-145 degreeC.
3. The polycarbonate resin copolymer according to the above 1, wherein the specific viscosity measured with a methylene chloride solution at 20 ° C. is 0.15 to 1.5.
4. 3. Polycarbonate resin copolymer of the preceding clause 1 whose unit (A) is a unit (A-1) represented by a following formula (A-1).

5. The polycarbonate resin copolymer according to the above item 1, further comprising a unit (B) represented by the following formula (B).

6. The polycarbonate resin copolymer according to the above item 1, wherein the pencil hardness measured according to JIS K5600-5-4 is F or more.
7. 3. Polycarbonate resin copolymer of the preceding clause 1 whose saturated water absorption is 1.7% or less.
8. The polycarbonate resin according to the aforementioned item 4, wherein the monomer purity of 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane which is a monomer component used as a raw material for deriving the unit (A-1) is 90% or more Copolymer.
9. The molded article which uses the polycarbonate resin copolymer of the preceding clause 1 as a raw material.
10. The film which makes the polycarbonate resin copolymer of the preceding clause 1 a raw material.

  The polycarbonate resin copolymer of the present invention is excellent in low water absorption and has improved weatherability by reacting a monomer component having a biscyclohexane ring with other monomer components and a carbonate precursor in a specific ratio. By using a specific aliphatic diol or alicyclic diol as another monomer component, it has become possible to obtain a polycarbonate resin copolymer having characteristics such as good impact resistance and good pencil hardness. Therefore, its industrial effects are outstanding.

Hereinafter, the present invention will be described in detail.
<Polycarbonate resin copolymer>
The polycarbonate resin copolymer of the present invention is composed of a carbonate unit containing a repeating unit (A).

(Repeating unit (A))
In the present invention, as shown in the following formula (A), the repeating unit (A) is a carbonate unit having a biscyclohexane ring.

Here, in the formula, X _{1 to} X ₄ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X ₅ is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted cycloalkylene having 6 to 20 carbon atoms And a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, m and n each independently represents an integer of 0 to 5;

ここでＲ_１とＲ_２はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、または炭素原子数７〜１７のアラルキル基を表す。また、Ｒ_１とＲ_２が結合して炭素環または複素環を形成しても良い。Ｒ_３とＲ_４はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、または炭素原子数６〜１２アリール基を表す。Ｒ_５は炭素原子数１〜９のアルキレン基である。ａは０〜２０の整数を表し、ｂは１〜５００の整数を表す。 W is either a single bond or a divalent organic group represented by the following formula (W):

Here, R ₁ and R ₂ each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, 6 to 6 carbon atoms 12 represents an aryl group, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. Also, R ₁ and R ₂ may combine to form a carbocyclic ring or a heterocyclic ring. R ₃ and R ₄ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 to 12 carbon atoms Represents an aryl group. R ₅ is an alkylene group having 1 to 9 carbon atoms. a represents the integer of 0-20, b represents the integer of 1-500.

  Specifically, 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) ethane, 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, 2,2-bis (4- (4 2-hydroxyethoxy) cyclohexyl) butane, 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) -1-phenylethane, 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) cyclohexane, 1 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) pentane, 2,2-bis (4 -(2-hydroxyethoxy) cyclohexyl) fluorene, 1,1-bis (4- (2-hydroxyethoxy) cyclic Hexyl) -4-isopropyl cyclohexane, and the like. Among them, 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane is preferable from the viewpoint of heat resistance and fluidity. Two or more of these may be used in combination.

(Other repeat unit)
In the present invention, repeating units derived from various diol compounds may be mentioned as repeating units constituting the copolymerization constituent unit other than the unit (A).
The diol compound may be any of an aliphatic diol compound, an alicyclic diol compound, and an aromatic dihydroxy compound, and the diol compound or diethylene glycol described in WO 2004/111106 and WO 2011/021720. And oxyalkylene glycols such as triethylene glycol, tetraethylene glycol and polyethylene glycol.

  As the aliphatic diol compound, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1.9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl- 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl 1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanedio Le, 2-methyl-2-propyl-1,3-propanediol.

  Examples of the alicyclic diol compound include cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecanedimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4, 8, 10-tetraoxaspiro [5.5] undecane etc. are mentioned.

As the aromatic dihydroxy compound, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1 Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, bisphenol A, 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol) AF), and 1,1-bis (4-hydroxyphenyl) decane and the like.
Among them, the following repeating unit (B) is particularly preferable as a copolymerization structural unit.

(Repeating unit (B))
The unit (B) in the present invention is derived from an aliphatic diol having an ether group, as shown in the following formula (B).

In the formula (B), a diol having an ether bond among biomass resources is a material having high heat resistance and high pencil hardness.
Examples of the formula (B) include repeating units (B1), (B2) and (B3) represented by the following formulas in a stereoisomer relationship.

These are ether diols derived from carbohydrates, which can be obtained from natural biomass, and are one of the so-called renewable resources. The repeating units (B1), (B2) and (B3) are respectively called isosorbide, isomannide and isoidid. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and subjecting it to dehydration. The other ether diols can be obtained by the same reaction except for the starting materials.
Among isosorbide, isomannide and isoidide, a repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because of its easiness of production and excellent heat resistance.

(composition)
The polycarbonate resin copolymer of the present invention contains the repeating unit (A), and the molar ratio of the entire polycarbonate to the repeating units is 1 to 50 mol%. When the molar ratio is 1 mol% or more and 50 mol% or less, it is preferable because the low water absorption is excellent, the weather resistance is high, and the impact resistance and the pencil hardness become good. As for the molar ratio which occupies for the repeating unit of the whole polycarbonate, 2-40 mol% is more preferable, 3-35 mol% is more preferable, 5-30 mol% is especially preferable.

In the case of a polycarbonate resin copolymer containing units (A) and units (B), the ratio (molar ratio) of units (A) to units (B) is preferably 1 to 50:50 to 99 mol%. , 2 to 40: 60 to 98 mol% is more preferable, 3 to 35: 65 to 97 mol% is more preferable, and 5 to 30: 70 to 95 mol% is particularly preferable. Within this range, heat resistance and impact resistance are excellent, weather resistance is high, and low water absorption is obtained, which is preferable. The total number of the repeating units of the unit (A) and the unit (B) is preferably 60 mol%, more preferably 70 mol%, still more preferably 80 mol%, particularly preferably 90 mol%, based on all repeating units.
The molar ratio is calculated by measuring with proton NMR of JNM-AL400 manufactured by JEOL.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin copolymer of the present invention is preferably 80 ° C. or more and 145 ° C. or less, more preferably 100 ° C. or more and 135 ° C. or less. When using as an optical molded object as Tg is more than a minimum, heat resistance stability is favorable and it is preferable. When the Tg is less than the upper limit, the moldability is good and preferable. The glass transition temperature (Tg) is measured at a temperature rising rate of 20 ° C./min using a Model 2910 DSC manufactured by TA Instruments Japan Co., Ltd.

(Saturated water absorption rate)
The saturated water absorption of the polycarbonate resin copolymer of the present invention is preferably 1.7% or less, more preferably 1.5% or less. When the water absorption rate is 1.7% or less, dimensional changes and warpage due to water absorption can be reduced in the molded product, which is preferable.

(Specific viscosity: _{SP SP} )
The specific viscosity (η _SP ) of the polycarbonate resin copolymer of the present invention is preferably 0.15 or more and 1.50 or less. When the specific viscosity is higher than the lower limit, the strength and the like are improved, and when lower than the upper limit, the molding and processing characteristics are excellent. More preferably, it is 0.20 or more and 1.00 or less, more preferably 0.25 or more and 0.70 or less, and particularly preferably 0.30 or more and 0.50 or less. In addition, the polycarbonate resin copolymer of the present invention may be used in combination with other resins as long as the effects of the present invention are not impaired.
The specific viscosity as used in the present invention was determined using an Ostwald viscometer from a solution of 0.7 g of a polycarbonate resin copolymer dissolved in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the second drop of methylene chloride, t is the second drop of the sample solution]

  In addition, when measuring the specific viscosity of the polycarbonate resin copolymer of this invention, it can carry out in the following way. That is, the polycarbonate resin copolymer is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble matter is collected by celite filtration, and then the solution is removed and sufficiently dried to obtain a solid of methylene chloride soluble matter. obtain. The specific viscosity at 20 ° C. of a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride is determined using an Ostwald viscometer.

(Pencil hardness)
The polycarbonate resin copolymer used in the present invention preferably has a pencil hardness of HB or more. In terms of excellent scratch resistance, F or more is more preferable, and H or more is more preferable. The pencil hardness can be made hard by increasing the composition of the repeating unit (B) on the basis of all the repeating units. In the present invention, the pencil hardness is a hardness which does not leave a scratch mark even when the resin of the present invention is abraded with a pencil having a specific pencil hardness and the resin is rubbed, and is measured according to JIS K-5600. The pencil hardness used in the surface hardness test of the resulting coating film is used as an index. Pencil hardness softens in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, the hardest being 9H, most The soft one is 6B.

(purity)
90% or more is preferable and 95% or more of the monomer purity of 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane which is a monomer component of the repeating unit (A-1) used in the present invention is More preferable. If it is less than 90%, the weather resistance may be deteriorated. The method for setting the monomer purity to 90% or higher is not particularly limited, but methods such as repulp washing with a solvent (washing with solvent and repeating filtration several times) and methods such as distillation and recrystallization may be mentioned. .

(Method for producing polycarbonate resin copolymer)
The polycarbonate resin copolymer of the present invention is produced by a reaction means known per se which produces a usual polycarbonate resin, for example, a method of reacting a diol component with a carbonate precursor such as diester carbonate. Next, basic means of these manufacturing methods will be briefly described.

  Transesterification using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of an aromatic dihydroxy component is heated and stirred with a carbonic acid diester in an inert gas atmosphere to distill off the alcohol or phenol formed. . The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced and the like, but is usually in the range of 120 to 300 ° C. The reaction is initially completed under reduced pressure to complete the reaction while distilling off the alcohol or phenol formed. Moreover, you may add an end terminator, antioxidant, etc. as needed.

  As a carbonic diester used for the said transesterification, ester, such as a C6-C12 aryl group which may be substituted, an aralkyl group, etc. are mentioned. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate and the like are exemplified. Among them, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol in total of the dihydroxy compound.

In the melt polymerization method, a polymerization catalyst can be used to accelerate the polymerization rate, and examples of such a polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, metal compounds and the like.
As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides and the like of alkali metals and alkaline earth metals are preferably used, and these compounds are It can be used alone or in combination.

  As an alkali metal compound, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples thereof include dilithium hydrogen oxide, disodium phenylphosphate, disodium salt of bisphenol A, dipotassium salt of disodium cesium, dilithium salt of disodium, sodium salt of potassium, potassium salt, cesium salt, lithium salt and the like.

  As an alkaline earth metal compound, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetic acid Barium etc. are illustrated.

  As nitrogen-containing compounds, quaternary ammonium hydroxides having alkyl such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, etc., aryl groups etc. It can be mentioned. Also, tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole can be mentioned. In addition, bases such as ammonia, tetramethyl ammonium borohydride, tetrabutyl ammonium borohydride, tetrabutyl ammonium tetraphenyl borate, tetraphenyl ammonium tetraphenyl borate and the like or basic salts are exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organic tin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds. These compounds may be used alone or in combination of two or more.
The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² equivalents, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × to 1 mole of the diol component. It is chosen in the range of 10 ⁻⁷ to 1 × 10 ⁻³ equivalents.

  A catalyst deactivator can also be added later in the reaction. As the catalyst deactivator to be used, known catalyst deactivators are effectively used, and among these, ammonium salts of sulfonic acid and phosphonium salts are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of p-toluenesulfonic acid such as tetrabutylammonium salt of p-toluenesulfonic acid are preferable.

  As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Preferably, octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are used. Among them, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is most preferably used.

When at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably 0.5 to 50 moles per mole of the catalyst. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.
In addition, heat stabilizers, plasticizers, light stabilizers, polymeric metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, mold release agents, etc., depending on the use and necessity. Additives can be blended.

<Molded body>
The molded article formed using the polycarbonate resin copolymer of the present invention is molded by any method such as, for example, an injection molding method, a compression molding method, an extrusion molding method, a solution casting method. Since the polycarbonate resin copolymer of the present invention is excellent in moldability and heat resistance, it can be used as various molded articles. In particular, structural materials of optical components such as optical lenses, optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, displays, etc., electrical and electronic components such as exteriors and front plates of personal computers and mobile phones It can be advantageously used as a molded article suitable for automotive applications such as automotive headlamps and windows, or functional material applications.

<Film>
Specifically, the film using the polycarbonate resin copolymer of the present invention is a surface protection film, a film for decoration, a front plate, a retardation film, a placel substrate film, a polarizing plate protection film, an antireflective film, a luminance Applications such as lifting films, protective films for optical disks, and diffusion films can be mentioned.
Examples of the method for producing an optical film include known methods such as a solution cast method, a melt extrusion method, a heat press method, and a calendar method. Among them, the solution casting method and the melt extrusion method are preferable, and the melt extrusion method is particularly preferable in terms of productivity.

  In the melt extrusion method, a method of extruding resin using a T-die and feeding it to a cooling roll is preferably used. The temperature at this time is determined from the molecular weight, Tg, melt flow characteristics, etc. of the polycarbonate resin copolymer, and is in the range of 180 to 350 ° C., and more preferably in the range of 200 ° C. to 320 ° C. When the temperature is lower than 180 ° C., the viscosity becomes high, and the orientation of the polymer and the stress strain tend to remain, which is not preferable. If the temperature is higher than 350 ° C., problems such as thermal deterioration, coloring, and die lines (strips) from the T die tend to occur.

  In addition, since the polycarbonate resin copolymer of the present invention has good solubility in organic solvents, a solution casting method can also be applied. In the case of the solution casting method, methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dioxolane, dioxane and the like are suitably used as the solvent. The amount of residual solvent in the film obtained by the solution casting method is preferably 2% by weight or less, more preferably 1% by weight or less. When the amount of residual solvent exceeds 2% by weight, the decrease in the glass transition temperature of the film becomes remarkable, which is not preferable in terms of heat resistance.

  As thickness of the unstretched film which uses the polycarbonate resin copolymer of this invention, the range of 30-400 micrometers is preferable, More preferably, it is the range of 40-300 micrometers. When the unstretched film-like material is further stretched to form a retardation film, it may be appropriately determined within the above range in consideration of the desired retardation value and thickness of the optical film.

  The present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight". The resin used and the evaluation method used in the examples are as follows.

1. Polymer composition ratio (NMR)
The polymer composition ratio (molar ratio) was measured by proton NMR of JNM-AL400 manufactured by JEOL.

2. Specific viscosity measurement It measured using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin copolymer 0.7g in 100 ml of methylene chlorides at 20 degreeC.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the second drop of methylene chloride, t is the second drop of the sample solution]

3. Glass transition temperature measurement Using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of a polycarbonate resin copolymer, under a nitrogen atmosphere (nitrogen flow rate: 40 ml) according to JIS K7121 / Min), temperature rising rate: 20 ° C./min.

4. Water Absorption Rate The water absorption rate is obtained by dissolving a polycarbonate resin copolymer pellet in methylene chloride and evaporating methylene chloride, using a cast film having a thickness of 200 μm, drying at 100 ° C. for 12 hours, and then immersing in water at 25 ° C. for 48 hours The weight increase after the treatment was measured, and the water absorption was determined by the following equation.
Water absorption rate (%) = {(resin weight after water absorption-resin weight before water absorption) / resin weight before water absorption} × 100

5. Weathering Discoloring According to JIS B7753, using a Sunshine Weatherometer S80 manufactured by Suga Test Instruments Co., Ltd., set a discharge voltage of 50 V and a discharge current of 60 A with a sunshine carbon arc (ultra long life carbon 4 pair) light source, irradiate and surface spray Irradiated for 500 hours on a square surface of a flat (60 mm wide × 60 mm long × 3 mm thick) injection molded piece under conditions of a black panel temperature of 63 ° C and a relative humidity of 50% (for rainfall). The The surface spray (rainfall) time was 12 minutes / hour. The glass filter used A type. With respect to the test pieces before and after the test, the color difference ΔE was measured using a spectrographic color difference meter SE-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The smaller ΔE, the smaller the color change.

6. High-speed surface impact test High-speed impact tester with 2 mm thick square plate Using Shimadzu HYDROSHOTHITS-P10 (Shimadzu Corporation), test temperature 23 ° C, test speed 7 m / sec, striker diameter 1/2 inch, receiving diameter 1 inch The test was carried out 10 times, and the probability of becoming brittle fracture and the maximum impact energy (average value) were evaluated.

7. Pencil hardness The obtained polycarbonate resin copolymer is vacuum dried at 100 ° C. for 24 hours, and then a 2 mm thick square plate is formed using a 75ton molding machine (JSW J-75 EIII) manufactured by JSW Co., Ltd. It measured by the pencil hardness test method of JISK5600 using a shaping | molding test piece.

8. Monomer Purity 100 mg of a sample was dissolved in 1 ml of chloroform, methylated with 4 volumes of tetramethyl ammonium hydroxide, and reaction pyrolysis was carried out at 600 ° C. with an Agilent Technology 5975 series gas chromatograph / mass detector. The monomer purity was calculated from the obtained peak area ratio.

Example 1
<Production of Polycarbonate Resin Copolymer>
409 parts of isosorbide (hereinafter abbreviated as ISS), 172 parts of 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane (hereinafter abbreviated as HBPE) having a purity of 97.1%, 750 parts of diphenyl carbonate, and as a catalyst 0.8 × 10 ⁻² parts of tetramethylammonium hydroxide and 0.6 × 10 ⁻⁴ parts of sodium hydroxide were heated to 180 ° C. under a nitrogen atmosphere to melt. Thereafter, the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 260 ° C. at a rate of 60 ° C./hr and held at that temperature for 10 minutes, and then the degree of vacuum was reduced to 133 Pa or less over 1 hour. The reaction was carried out under stirring for a total of 6 hours, discharged under nitrogen pressure from the bottom of the reaction vessel, and cut with a pelletizer while cooling in a water bath to obtain pellets. Various evaluation results are shown in Table 1.

Example 2
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was carried out except that ISS of ISS, 344 parts of purity 97.1%, and DPC 750 were used as the raw materials. The results are shown in Table 1.

[Example 3]
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was carried out except that 460 parts of ISS, 115 parts of HBPE having a purity of 97.1%, and 750 parts of DPC were used as the raw materials. The results are shown in Table 1.

Example 4
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was carried out except using ISS 358 parts, HBPE 172 parts having a purity of 97.1%, 76 parts of 1,4-cyclohexanedimethanol (hereinafter CHDM) and DPC 750 parts as raw materials. Did. The results are shown in Table 1.

[Example 5]
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was performed except that the bisphenol A was changed to 678 parts in place of ISS. The results are shown in Table 1.

[Example 6]
<Production of Polycarbonate Resin Copolymer>
The same operation as in Example 1 is carried out except that 172 parts of 89.8% purity 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane (hereinafter abbreviated as HBPE) is used. I made an evaluation. The results are shown in Table 1.

Comparative Example 1
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was carried out except that 501 parts of ISS and 750 parts of DPC were used as the raw materials. The results are shown in Table 1.

Comparative Example 2
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was carried out except that ISS 435 parts, hexanediol (hereinafter HD) 60 parts and DPC 750 parts were used as the raw materials. The results are shown in Table 1.

Comparative Example 3
<Production of Polycarbonate Resin Copolymer>
The same evaluation as in Example 1 was carried out except that ISS 358 parts, CHDM 151 parts and DPC 750 parts were used as raw materials. The results are shown in Table 1.

Comparative Example 4
Various evaluation results are described in Table 1 using a bisphenol A polycarbonate resin (Panalite L1225 manufactured by Teijin Chemicals, Ltd.).

Comparative Example 5
Various evaluation results are shown in Table 1 using a polyacrylic resin (Mitsubishi Rayon Acrippet MF).

  The polycarbonate resin copolymer of the present invention is useful as a structural material of optical parts, electric and electronic parts such as exteriors of personal computers and mobile phones, front plates, etc., films used as retardation films, etc.

Claims (10)

The polycarbonate resin copolymer in which a repeating unit contains 1-50 mol% of units (A) represented by following formula (A) in all the repeating units.

(Wherein, X _{1 to} X ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituent Or an unsubstituted aryl group having 6 to 20 carbon atoms, X ₅ is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, m and n each independently represents an integer of 1 to 5. W is a single bond or a divalent group represented by the following formula (W) One of the organic groups,

Here, R ₁ and R ₂ each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, 6 to 6 carbon atoms 12 represents an aryl group, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. Also, R ₁ and R ₂ may combine to form a carbocyclic ring or a heterocyclic ring. R ₃ and R ₄ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 to 12 carbon atoms Represents an aryl group. R ₅ is an alkylene group having 1 to 9 carbon atoms. a represents the integer of 0-20, b represents the integer of 1-500. )   The polycarbonate resin copolymer according to claim 1, wherein the glass transition temperature is 80 ° C to 145 ° C.   The polycarbonate resin copolymer according to claim 1, wherein the specific viscosity measured with a methylene chloride solution at 20 ° C is 0.15 to 1.5. The polycarbonate resin copolymer according to claim 1, wherein the unit (A) is a unit (A-1) represented by the following formula (A-1).

The polycarbonate resin copolymer according to claim 1, further comprising a unit (B) represented by the following formula (B).

  The polycarbonate resin copolymer according to claim 1, wherein the pencil hardness measured according to JIS K5600-5-4 is F or more.   The polycarbonate resin copolymer according to claim 1, which has a saturated water absorption of 1.7% or less.   The polycarbonate according to claim 4, wherein the monomer purity of 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane which is a monomer component used as a raw material for deriving the unit (A-1) is 90% or more. Resin copolymer.   The molded article which uses the polycarbonate resin copolymer of Claim 1 as a raw material.   A film comprising the polycarbonate resin copolymer according to claim 1 as a material.