JP2017031346A - Polycarbonate resin copolymer and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin copolymer excellent in low water absorption, having improved weather resistance and further good in impact resistance and pencil hardness and a molded article.SOLUTION: There are provided a polycarbonate resin copolymer having a carbonate unit constituted by a monomer component represented by the formula (A) and having a bis-cyclohexane ring with 1 to 50 mol% of the carbonate unit in total repeating units and a molded article and film containing the same as a raw material.SELECTED DRAWING: None

Description

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

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

  On the other hand, methacrylic acid resins such as polymethyl methacrylate have high transparency and hard surface hardness (pencil hardness H to 3H), and are often used as optical materials such as lenses and optical fibers. However, there is a problem in that the usage is limited because of its high water absorption rate and low impact resistance.

Recently, it has been proposed that isosorbide, a plant-derived monomer, is used to obtain a polycarbonate having excellent weather resistance and surface hardness by transesterification with diphenyl carbonate (Patent Document 2). However, due to the high water absorption derived from the isosorbide skeleton, the dimensional change is large in an environment of high temperature and high humidity, and there are cases where the use is limited to the use of precision parts.
For this reason, a resin and a molded body having a good balance of low water absorption, weather resistance, heat resistance, impact resistance, and pencil hardness have not yet been provided.

Japanese Patent Publication No.4-2614 International Publication No. 2004/111106 Pamphlet

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

As a result of intensive investigations, the present inventors have found that a polycarbonate resin having excellent low water absorption, improved weather resistance, heat resistance, impact resistance and good pencil hardness by including the repeating unit (A). The inventors have determined that a copolymer and a molded body can be obtained, and have reached the present invention.
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０〜５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. A polycarbonate resin copolymer containing 1 to 50 mol% of the repeating unit (A) represented by the following formula (A) in all 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 substituted group. Or an unsubstituted aryl group having 6 to 20 carbon atoms, and 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, and m and n each independently represents an integer of 0 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 are each 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 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. R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring. R ₃ and R ₄ are each 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 an integer of 0 to 20, and b represents an integer of 1 to 500. )
2. 2. The polycarbonate resin copolymer as described in 1 above, wherein the glass transition temperature is 80 ° C. to 145 ° C.
3. The polycarbonate resin copolymer according to item 1, wherein the specific viscosity measured with a 20 ° C. methylene chloride solution is 0.15 to 1.5.
4). 2. The polycarbonate resin copolymer according to item 1, wherein the unit (A) is a unit (A-1) represented by the following formula (A-1).

5). Furthermore, the polycarbonate resin copolymer of the preceding clause 1 containing the unit (B) represented by a following formula (B).

6). 2. The polycarbonate resin copolymer according to item 1, wherein the pencil hardness measured in accordance with JIS K5600-5-4 is F or more.
7). 2. The polycarbonate resin copolymer according to item 1, wherein the saturated water absorption is 1.7% or less.
8). 5. The polycarbonate resin according to 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. A molded article made of the polycarbonate resin copolymer according to item 1 above.
10. A film made of the polycarbonate resin copolymer according to item 1 above.

  The polycarbonate resin copolymer of the present invention reacts with a monomer component having a biscyclohexane ring at a specific ratio with another monomer component and a carbonate precursor, thereby being excellent in low water absorption and improved weather resistance. By using a specific aliphatic diol or alicyclic diol as the other monomer component, it becomes possible to obtain a polycarbonate resin copolymer having characteristics such as good impact resistance and good pencil hardness. Therefore, the industrial effect that it produces is exceptional.

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

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

Here, in the formula, 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 substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein 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. A group, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and 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 are each 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 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. R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring. R ₃ and R ₄ are each 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 an integer of 0 to 20, and b represents an integer of 1 to 500.

  Specifically, 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) ethane, 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, 2,2-bis (4- ( 2-hydroxyethoxy) cyclohexyl) butane, 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) -1-phenylethane, 1,1-bis (4- (2-hydroxyethoxy) cyclohexyl) cyclohexane, , 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) cycl Hexyl) -4-isopropyl cyclohexane, and the like. Of these, 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane is preferred from the viewpoints of heat resistance and fluidity. Two or more of these may be used in combination.

(Other repeat units)
In the present invention, examples of the repeating unit constituting the copolymer structural unit other than the unit (A) include repeating units derived from various diol compounds.
The diol compound may be an aliphatic diol compound, an alicyclic diol compound, or an aromatic dihydroxy compound. The diol compound or diethylene glycol described in International Publication No. 2004/111106 pamphlet, International Publication No. 2011/021720 pamphlet may be used. And oxyalkylene glycols such as triethylene glycol, tetraethylene glycol and polyethylene glycol.

  Examples of the aliphatic diol compound include 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 and the like can be mentioned.

Examples of the aromatic dihydroxy compound include 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.
Especially, the following repeating unit (B) is especially 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 having a stereoisomer relationship.

These are saccharide-derived ether diols that are also obtained from natural biomass and are one of the so-called renewable resources. The repeating units (B1), (B2) and (B3) are called isosorbide, isomannide and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.
Among isosorbide, isomannide, and isoidide, a repeating unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because of ease of production and heat resistance.

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

In the case of a polycarbonate resin copolymer containing the unit (A) and the unit (B), the ratio (molar ratio) of the unit (A) to the unit (B) is preferably 1 to 50:50 to 99 mol%. 2-40: 60-98 mol% is more preferable, 3-35: 65-97 mol% is further more preferable, and 5-30: 70-95 mol% is especially preferable. This range is preferable because it is excellent in heat resistance and impact resistance, has high weather resistance, and has low water absorption. The total repeating unit of the unit (A) and the unit (B) is preferably 60 mol%, more preferably 70 mol%, still more preferably 80 mol%, and particularly preferably 90 mol% in all repeating units.
The molar ratio is measured and calculated by 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 higher and 145 ° C. or lower, more preferably 100 ° C. or higher and 135 ° C. or lower. When the Tg is equal to or higher than the lower limit, the heat stability is good when used as an optical molded article, which is preferable. Moreover, if Tg is below the upper limit, the moldability is good and preferable. The glass transition temperature (Tg) is measured at 29 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan.

(Saturated water absorption)
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. A water absorption of 1.7% or less is preferred because it can reduce dimensional changes and warpage due to water absorption in the molded product.

(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin copolymer of the present invention is preferably from 0.15 to 1.50. When the specific viscosity is not less than the lower limit, the strength and the like are improved, and when the specific viscosity is not more than the upper limit, the molding property is excellent. More preferably, it is 0.20 or more and 1.00 or less, More preferably, it is 0.25 or more and 0.70 or less, Especially preferably, it is 0.30 or more and 0.50 or less. Moreover, you may use together with other resin for the polycarbonate resin copolymer of this invention in the range which does not impair the effect of this invention.
The specific viscosity referred to in the present invention was determined using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin copolymer in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

  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, a polycarbonate resin copolymer is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a methylene chloride soluble component solid. obtain. Using a Ostwald viscometer, the specific viscosity at 20 ° C. is determined from a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride.

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

(purity)
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 preferably 90% or more, and 95% or more. More preferred. If it is less than 90%, the weather resistance may deteriorate. The method for setting the monomer purity to 90% or higher is not particularly limited, and examples thereof include a method of performing repulp washing with a solvent (washing with a solvent and repeating filtration several times), and a technique such as distillation and recrystallization. .

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

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, you may add a terminal stopper, antioxidant, etc. as needed.

  Examples of the carbonic acid diester used in the transesterification include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, 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 of the total of dihydroxy compounds.

In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.
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. It can be used alone or in combination.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium 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 include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt and the like.

  Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetate Barium and the like are exemplified.

  Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl groups, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Can be mentioned. Further, tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole can be used. Moreover, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like are exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, and the like. 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 equivalent, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ equivalent, more preferably 1 × with ^respect to 1 mol of the diol component. It is selected in the range of 10 ⁻⁷ to 1 × 10 ⁻³ equivalents.

  In addition, a catalyst deactivator can be added at a later stage of the reaction. As the catalyst deactivator to be used, a known catalyst deactivator is effectively used. Among them, sulfonic acid ammonium salt and phosphonium salt are preferable. Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

  Further, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Among these, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

The amount of the catalyst deactivator used is preferably 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used. 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, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, release agents, etc. Additives can be blended.

<Molded body>
A molded article using the polycarbonate resin copolymer of the present invention is molded by an arbitrary method such as an injection molding method, a compression molding method, an extrusion molding method, or 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, optical lenses, optical discs, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, structural materials for optical components such as displays, electrical and electronic parts such as exteriors and front panels of personal computers and mobile phones. In addition, 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 formed using the polycarbonate resin copolymer of the present invention is a surface protective film, a decorative film, a front plate, a retardation film, a plastic substrate film, a polarizing plate protective film, an antireflection film, and a luminance. Uses such as a rising film, a protective film for an optical disk, and a diffusion film can be mentioned.
Examples of the method for producing the optical film include known methods such as a solution casting method, a melt extrusion method, a hot press method, and a calendar method. Of these, the solution casting method and the melt extrusion method are preferable, and the melt extrusion method is particularly preferable from the viewpoint of productivity.

  In the melt extrusion method, a method in which a resin is extruded using a T die and sent to a cooling roll is preferably used. The temperature at this time is determined from the molecular weight, Tg, melt flow characteristics and the like of the polycarbonate resin copolymer, but is in the range of 180 to 350 ° C, and more preferably in the range of 200 to 320 ° C. When the temperature is lower than 180 ° C., the viscosity is increased, and the orientation and stress strain of the polymer tend to remain, which is not preferable. On the other hand, when the temperature is higher than 350 ° C., problems such as thermal deterioration, coloring, and die line (stripe) from the T-die are likely to occur.

  Further, since the polycarbonate resin copolymer of the present invention has good solubility in an organic solvent, 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 preferably 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 residual solvent amount exceeds 2% by weight, the glass transition temperature of the film is remarkably lowered, which is not preferable from the viewpoint of heat resistance.

  As a thickness of the unstretched film using 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 product is further stretched to obtain a retardation film, it may be appropriately determined within the above range in consideration of a desired retardation value and thickness of the optical film.

  Hereinafter, 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 resins used and the evaluation methods used in the examples are as follows.

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

2. Specific Viscosity Measurement A specific viscosity was measured using an Ostwald viscometer from a solution of 0.7 g of a polycarbonate resin copolymer in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

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

4). Water absorption rate The water absorption rate was determined by dissolving a polycarbonate resin copolymer pellet in methylene chloride, evaporating the methylene chloride, using a cast film with a thickness of 200 μm, drying at 100 ° C. for 12 hours, and then immersed in water at 25 ° C. for 48 hours. The weight increase after the measurement was measured, and the water absorption was determined by the following formula.
Water absorption rate (%) = {(resin weight after water absorption−resin weight before water absorption) / resin weight before water absorption} × 100

5). Weathering discoloration In accordance with JIS B7753, a sunshine weatherometer S80 manufactured by Suga Test Instruments Co., Ltd. was used to 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. Irradiation treatment was performed for 500 hours on a flat surface (width 60 mm x length 60 mm x thickness 3 mm) of an injection-molded piece under the conditions of a black panel temperature of 63 ° C and a relative humidity of 50%. It was. The surface spray (rainfall) time was 12 minutes / 1 hour. A type glass filter was used. For the test pieces before and after the test, a color difference ΔE was measured using a spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller ΔE, the smaller the discoloration.

6). High-speed surface impact test Using a high-speed impact tester Shimadzu HYDROSHOTHITS-P10 (Shimadzu Corporation) with a 2 mm thick square plate, 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 the brittle fracture at that time and the maximum impact energy (average value) were evaluated.

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

8). Monomer purity 100 mg of a sample was dissolved in 1 ml of chloroform, methylated with 4 volumes of tetramethylammonium hydroxide, and subjected to reaction pyrolysis 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]
<Manufacture 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 catalyst Tetramethylammonium hydroxide 0.8 × 10 ⁻² parts and sodium hydroxide 0.6 × 10 ⁻⁴ parts were heated to 180 ° C. in a nitrogen atmosphere and melted. Thereafter, the degree of vacuum 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 maintained at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. The reaction was carried out with stirring for a total of 6 hours, discharged from the bottom of the reaction tank under nitrogen pressure, and cut with a pelletizer while cooling in a water tank to obtain a pellet. Various evaluation results are shown in Table 1.

[Example 2]
<Manufacture of polycarbonate resin copolymer>
The same evaluation as in Example 1 was performed except that 358 parts of ISS, 344 parts of HBPE having a purity of 97.1%, and 750 parts of DPC were used as raw materials. The results are shown in Table 1.

[Example 3]
<Manufacture of polycarbonate resin copolymer>
Except for using 460 parts of ISS, 115 parts of HBPE having a purity of 97.1%, and 750 parts of DPC as raw materials, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Example 4]
<Manufacture of polycarbonate resin copolymer>
The same evaluation as in Example 1 was conducted except that 358 parts of ISS, 172 parts of HBPE having a purity of 97.1%, 76 parts of 1,4-cyclohexanedimethanol (hereinafter CHDM) and 750 parts of DPC were used as raw materials. Went. The results are shown in Table 1.

[Example 5]
<Manufacture of polycarbonate resin copolymer>
Except for changing to 678 parts of bisphenol A instead of ISS, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Example 6]
<Manufacture of polycarbonate resin copolymer>
Except for using 172 parts of 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane (hereinafter abbreviated as HBPE) having a purity of 89.8%, the same operation as in Example 1 was carried out. Evaluation was performed. The results are shown in Table 1.

[Comparative Example 1]
<Manufacture of polycarbonate resin copolymer>
Except for using 501 parts of ISS and 750 parts of DPC as raw materials, the same operation as in Example 1 was performed and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 2]
<Manufacture of polycarbonate resin copolymer>
Except that ISS 435 parts, hexanediol (hereinafter referred to as HD) 60 parts, and DPC 750 parts were used as raw materials, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 3]
<Manufacture of polycarbonate resin copolymer>
Except that ISS 358 parts, CHDM 151 parts, and DPC 750 parts were used as raw materials, the same operation as in Example 1 was performed, and the same evaluation was performed. The results are shown in Table 1.

[Comparative Example 4]
Various evaluation results are shown in Table 1 using bisphenol A type polycarbonate resin (Panlite L1225 manufactured by Teijin Chemicals Ltd.).

[Comparative Example 5]
Various evaluation results are shown in Table 1 using polyacrylic resin (Acrypet MF manufactured by Mitsubishi Rayon).

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

Claims (10)

A polycarbonate resin copolymer containing 1 to 50 mol% of the repeating unit (A) represented by the following formula (A) in all 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 substituted group. Or an unsubstituted aryl group having 6 to 20 carbon atoms, and 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, and m and n each independently represents an integer of 0 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 are each 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 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. R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring. R ₃ and R ₄ are each 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 an integer of 0 to 20, and b represents an integer of 1 to 500. )   The polycarbonate resin copolymer according to claim 1, which has a glass transition temperature of 80C to 145C.   The polycarbonate resin copolymer according to claim 1, which has a specific viscosity of 0.15 to 1.5 measured with a 20 ° C methylene chloride solution. 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 in accordance with JIS K5600-5-4 is F or more.   2. The polycarbonate resin copolymer according to claim 1, wherein the saturated water absorption is 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.   A molded article made of the polycarbonate resin copolymer according to claim 1.   A film comprising the polycarbonate resin copolymer according to claim 1 as a raw material.