JP2011236336A - Polycarbonate resin having low photoelastic constant and optical molded article - Google Patents

Abstract

【選択図】なしDisclosed is a polycarbonate resin and an optically molded product having a good balance between refractive index and Abbe number, low photoelastic constant, good heat resistance and moldability.
The main repeating unit is composed of a carbonate precursor (A) composed of a specific fluorbisphenol compound having a fluorene structure and a repeating unit (B), and the molar ratio of (A / B) is 1/99 or more. Polycarbonate resin characterized by being 30/70 or less. And an optical molded body using this polycarbonate resin.

[Selection figure] None

Description

  The present invention relates to a polycarbonate resin and an optical molded body having a good balance between a refractive index and an Abbe number, a low photoelastic constant, and excellent heat resistance and moldability.

  Polycarbonate resin (hereinafter sometimes referred to as PC) is a polymer in which bisphenol is linked by a carbonate ester, and among them, a polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A). (BPA-PC) is used in many fields because it has excellent properties such as transparency and heat resistance, and excellent mechanical properties such as impact resistance. In the optical field such as various lenses and optical discs, their characteristics such as impact resistance and transparency are attracting attention and occupy an important position as an optical application material.

Especially in the lens field, PC, which is a thermoplastic resin, is attracting attention because of its productivity and processability, and is representative of CR-39 (diethylene glycol bisallyl carbonate), which has been the mainstream material for plastic lenses. For example, in spectacle lenses, the superior toughness of BPA-PC is widely used as a substitute for other materials to provide higher safety.
However, although BPA-PC has a high refractive index of 1.585 but an Abbe number as low as 30, the problem of chromatic aberration is likely to occur, and there is a problem that the balance between the refractive index and Abbe number is poor. Further, there is a problem that the photoelastic constant is high and the optical distortion of the molded product is large.

  In order to solve such a problem of the polycarbonate resin, a copolymer polycarbonate resin of an aromatic diol and an aliphatic diol has been proposed. For example, a polycarbonate resin using spiroglycol as an aliphatic diol has a reduced photoelastic constant. However, there is a problem that the balance between the refractive index and the Abbe number is poor (see Patent Document 1). Polycarbonate resin using tricyclodecane dimethanol as an aliphatic diol has an excellent balance between refractive index and Abbe number, but its glass transition temperature is low, resulting in poor heat resistance and insufficient reduction in photoelastic constant. (See Patent Documents 2 and 3). The polycarbonate resin using cyclohexanedimethanol as the aliphatic diol also has an excellent balance between the refractive index and the Abbe number. However, the glass transition temperature is low, so the heat resistance is poor, and the photoelastic constant cannot be sufficiently reduced. There is a problem of not (see Patent Document 4). Furthermore, the polycarbonate resin using isosorbide as the aliphatic diol and bisphenol A as the aromatic diol has a good balance between refractive index and Abbe number and excellent heat resistance, but has a problem of high photoelastic constant. (See Patent Document 5).

On the other hand, a polycarbonate resin copolymerized with an aliphatic diol using 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as an aromatic diol has a low photoelastic constant and excellent heat resistance. (See Patent Document 6). However, Patent Document 6 does not describe the balance between the refractive index and the Abbe number, and further does not describe the use of isosorbide or the like at a specific ratio in the aliphatic diol.
For this reason, a polycarbonate resin and an optical molded body having a good balance between the refractive index and the Abbe number, a low photoelastic constant, excellent heat resistance and moldability have not yet been provided.

JP-A-10-120777 Japanese Unexamined Patent Publication No. 01-066234 JP-A-11-228683 JP 2003-90901 A JP 2009-62501 A JP 2004-67990 A

  An object of the present invention is to provide a polycarbonate resin and an optical molded article having a good balance between the refractive index and the Abbe number, a low photoelastic constant, and good heat resistance and moldability.

  As a result of intensive studies, the present inventors have found that a repeating unit (A) derived from a specific fluorbisphenol compound having a fluorene structure (the following formula (A)) and a repeating unit derived from a specific ether diol ( B) A polycarbonate resin and an optical material having a good balance between the refractive index and the Abbe number, a low photoelastic constant, good heat resistance, and moldability by constituting a specific ratio of (the following formula (B)) The inventors have determined that a molded body can be obtained, and have reached the present invention.

[式中、Ｒ_１およびＲ_２は夫々独立して、水素原子、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基またはハロゲン原子を示し、Ｒ_３およびＲ_４は夫々独立して、炭素原子数１〜１０の芳香族基を含んでもよい炭化水素基を示し、ｍおよびｎは夫々独立して１〜４の整数を示し、ｐおよびｑは、夫々独立して１以上の整数を示す。]
で表される繰り返し単位（Ａ）と下記式

で表される繰り返し単位（Ｂ）であり、それら繰り返し単位（Ａ）と繰り返し単位（Ｂ）とのモル比（Ａ／Ｂ）が１／９９以上３０／７０以下のポリカーボネート樹脂。 That is, the present invention is as follows.
1. The main repeating unit is the following formula

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom, and R ₃ and R ₄ each independently represent A hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, m and n each independently represent an integer of 1 to 4, and p and q each independently represent 1 or more. Indicates an integer. ]
The repeating unit (A) represented by the following formula

A polycarbonate resin in which the molar ratio (A / B) between the repeating unit (A) and the repeating unit (B) is 1/99 or more and 30/70 or less.

で表される繰り返し単位（Ａ１）であり、および繰り返し単位（Ｂ）が下記式

で表される繰り返し単位（Ｂ１）である上記１記載のポリカーボネート樹脂。 2. The repeating unit (A) is represented by the following formula

And the repeating unit (B) is represented by the following formula:

2. The polycarbonate resin according to 1 above, which is a repeating unit (B1) represented by

3. 2. The polycarbonate resin according to 1 above, wherein the refractive index is in the range of 1.510 to 1.580 and the Abbe number is in the range of 32 to 60.
4). 2. An optical molded body using the polycarbonate resin described in 1 above.
5). An optical lens using the polycarbonate resin described in 1 above.

The polycarbonate resin of the present invention has a good balance between the refractive index and the Abbe number by reacting a specific fluorbisphenol compound having a fluorene structure and a specific ether diol with a carbonate precursor at a specific ratio. It became possible to have the characteristics that the constant is low and the heat resistance is good.
Furthermore, by using the polycarbonate resin of the present invention, it has become possible to provide an optical molded body having a good balance between the refractive index and the Abbe number, a low photoelastic constant, and good heat resistance. . Therefore, the industrial effect that it produces is exceptional.

Hereinafter, the present invention will be described in detail.
<Polycarbonate resin>
In the polycarbonate resin of the present invention, the main repeating unit is composed of a unit (A) and a repeating unit (B).

(Repeating unit (A))
The repeating unit (A) according to the present invention is derived from a fluorbisphenol compound having a fluorene structure as shown in the formula (A). In the formula (A), R ₁ and R ₂ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, or halogen groups (fluorine atoms, chlorine atoms, Bromine atom and the like). More preferably, they are a hydrogen atom, a C1-C6 alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or a halogen group (a fluorine atom, a chlorine atom, a bromine atom, etc.). R ₃ and R ₄ are preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an ethylene group. R ₃ and R ₄ are the same or different alkylene groups. Moreover, p and q represent the number of repetition of-(R < ₃ > -O)-and-(O-R < ₄ >)-, respectively. p and q are the same or different and are integers of 1 or more, for example, 1 to 5, preferably 1 to 3, particularly preferably 1. When p and q are 0, the glass transition temperature becomes high when the repeating unit (A), the repeating unit (B) and a specific ratio are used, and there is a problem in formability. Specifically, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- ( 4-hydroxybutoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [2- (2-hydroxyethoxy) -5-methylphenyl ] Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-ethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-propylphenyl] fluorene, 9,9 -Bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-n-butyl Ruphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3- (1-methylpropyl) phenyl Fluorene, 9,9-bis [4- (3-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (4-hydroxybutoxy) -3-methylphenyl] fluorene, 9,9 -Bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5- Propylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-di- n-butylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diisobutylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5- Bis (1-methylpropyl) phenyl] fluorene, 9,9-bis [4- (3-hydroxypropoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (4-hydroxybutoxy)- 3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl] fluorene, 9,9-bi [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-diphenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-benzylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dibenzylphenyl] fluorene, 9,9-bis [4- (2- Hydroxyethoxy) -3-propenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-fluorophenyl] fluorene, and their 9,9-bis (hydroxyalkoxyphenyl) fluorenes, p And recursions derived from 9,9-bis [hydroxypoly (alkyleneoxy) phenyl] fluorenes and the like in which q is 2 or more Is a unit is illustrated. Among these, repeating units derived from 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene are It is preferable because of its high refractive index and excellent fluidity. Among them, a repeating unit derived from 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) (formula (A1)) is particularly preferable because of its high refractive index and low photoelastic constant. .

で表される繰り返し単位（Ｂ１）、（Ｂ２）および（Ｂ３）が例示される。これらは、糖質由来のエーテルジオールであり、自然界のバイオマスからも得られる物質で、再生可能資源と呼ばれるものの１つである。繰り返し単位（Ｂ１）、（Ｂ２）および（Ｂ３）は、それぞれイソソルビド、イソマンニド、イソイディッドと呼ばれる。イソソルビドは、でんぷんから得られるＤーグルコースに水添した後、脱水を受けさせることにより得られる。その他のエーテルジオールについても、出発物質を除いて同様の反応により得られる。 (Repeating unit (B))
The repeating unit (B) according to the present invention is derived from an aliphatic diol having an ether group, as shown in the formula (B). The above formula (B) is a stereoisomer related formula

The repeating units (B1), (B2) and (B3) represented by 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)
As for the polycarbonate resin of this invention, the main repeating unit consists of a repeating unit (A) and a repeating unit (B), and those molar ratio (A / B) is 1/99 or more and 30/70 or less. A molar ratio (A / B) of 1/99 or more is preferable because the refractive index increases. A molar ratio (A / B) of 30/70 or less is preferable because the photoelastic constant is low and the Abbe number is 32 or more. An Abbe number equal to or higher than the lower limit is preferable because chromatic aberration is reduced when used as a lens. Preferably, the molar ratio (A / B) of the main repeating unit (A) to the repeating unit (B) is 5/95 or more and 24/76 or less, more preferably the main repeating unit (A) and the repeating unit. The molar ratio (A / B) with (B) is 10/90 or more and 23/77 or less. The molar ratio (A / B) is measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL. The main repeating unit in the present invention is a total of the repeating units (A) and (B) of 90 mol% or more, preferably 95 mol% or more, more preferably 100 mol%, based on all repeating units. is there.

(Specific viscosity: η _SP )
The specific viscosity (η _SP ) of the polycarbonate resin of the present invention is 0.15 or more and 1.50 or less. 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. Preferably, it is 0.20 or more and 1.20 or less, and particularly preferably 0.20 or more and 1.00 or less. You may use together with other resin 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 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 of this invention, it can carry out in the following way. That is, the polycarbonate resin is dissolved in 20 to 30 times the 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 solid component soluble in methylene chloride. 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.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin of the present invention is preferably 140 to 170 ° C., more preferably 140 to 160 ° C. 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.

(Photoelastic constant)
The absolute value of the photoelastic constant of the polycarbonate resin of the present invention is 25 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 23 × 10 ⁻¹² Pa ⁻¹ or less, and even more preferably 22 × 10 ⁻¹² Pa ⁻¹ or less. is there. When the absolute value is 25 × 10 ⁻¹² Pa ⁻¹ or less, birefringence due to stress hardly occurs and optical distortion is reduced when used as an optical molded body. The photoelastic constant can be reduced by increasing the composition of the repeating unit (B) based on all repeating units. The photoelastic constant is measured using a spectroellipometer M-220 manufactured by JASCO Corporation for an unstretched film.

(Refractive index and Abbe number)
The polycarbonate resin of the present invention preferably has a refractive index in the range of 1.510 to 1.580 and an Abbe number in the range of 32 to 60, more preferably a refractive index of 1.520 to 1. .570 or less, Abbe number is in the range of 34 or more and 60 or less, more preferably the refractive index is in the range of 1.530 or more and 1.570 or less, and Abbe number is in the range of 35 or more and 55 or less. It is. The refractive index can be increased by increasing the composition of the repeating unit (A) based on all repeating units. On the other hand, the Abbe number can be increased by increasing the composition of the repeating unit (B) based on all repeating units. The excellent balance between the refractive index and the Abbe number in the present invention specifically means that the refractive index is 1.51 or more and the Abbe number is 32 or more, and the composition of the repeating unit (A) and the repeating unit (B). It can be achieved by controlling.

(Pencil hardness)
The polycarbonate resin of the present invention preferably has a pencil hardness of HB or higher. From the viewpoint of excellent scratch resistance, it is preferably HB or more, and more preferably F or more. 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 is measured according to JIS K-5600. It is preferable to use the pencil hardness used for the surface hardness test of the paint film that can be used as an index. The pencil hardness becomes 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B in this order, and the hardest is 9H, The soft one is 6B.

(Production method of polycarbonate resin)
The polycarbonate resin 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.

<Optical molding>
An optical molded body using the polycarbonate resin 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 of the present invention is excellent in moldability and heat resistance, it can be used as various molded products. In particular, it is advantageously used as an optical molding suitable for structural materials or functional 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. be able to. Among these, it can be used particularly advantageously as an optical lens.

<Optical film>
Specifically, the optical film using the polycarbonate resin of the present invention may be used for a retardation film, a plastic substrate film, a polarizing plate protective film, an antireflection film, a brightness enhancement film, an optical disk protective film, a diffusion film, and the like. Especially, it can use suitably for a phase difference film, a polarizing plate protective film, and an antireflection film.
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, but is in the range of 180 to 350 ° C, 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 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.

  The thickness of the unstretched film using the polycarbonate of the present invention is preferably in the range of 30 to 400 μm, more preferably in the range of 40 to 300 μm. 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.

<Optical lens>
The optical lens using the polycarbonate resin of the present invention is a spectacle lens, a camera lens, a binocular lens, a microscope lens, a projector lens, a cell phone lens, a Fresnel lens, a lenticular lens, an fθ lens, a headlamp lens, a pickup lens, or the like. Applications are listed.

As a method for molding an optical lens from a molding material such as pellets, powders, and flakes made of the polycarbonate resin of the present invention, a method known per se can be employed. Specifically, it is molded by various molding methods such as injection molding, compression molding, extrusion molding or injection compression molding. As an optical lens molding method, injection compression molding is the most preferable method because a lens with little optical distortion can be molded.
In the injection compression molding, the cylinder temperature is preferably 200 to 300 ° C, and the mold temperature is preferably 40 to 120 ° C. In molding, a release agent can be blended as necessary.

  As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

  Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, and stearyl stearate is preferable.

  Specific examples of partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra All esters or parts of dipentaerythritol, such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include esters. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.

  The optical lens using the polycarbonate resin having the characteristics satisfying the above-mentioned specific viscosity, glass transition temperature, photoelastic constant, pencil hardness, refractive index, and Abbe number is excellent in optical characteristics and physical characteristics. This is also preferable.

The optical lens of the present invention can be used by subjecting the surface thereof to a post-processing treatment such as a hard coat (cured) layer, an antireflection coating layer or an antifogging coating layer as necessary.
As the hard coat layer formed on the surface of the lens substrate of the present invention, either thermosetting or active energy curable is preferably used. Examples of the thermosetting hard coat material include silicone resins such as organopolysiloxane and melamine resins. As such silicone resins, resins described in JP-A-48-056230, JP-A-49-014535, JP-A-08-054501, JP-A-08-198985 and the like can be used.

  As the melamine-based resin, a coating composition comprising a crosslinking agent, a curing agent, etc. is dried and / or heat-cured on a melamine resin such as methylated methylol melamine, propylated methylol melamine, butylated methylol melamine or isobutylated methylol melamine. This is a hard coat layer obtained.

Other components can be added to the coating composition as long as the properties of the cured film obtained are not impaired. For example, a curing agent for accelerating the reaction, a particulate inorganic material for matching the refractive index with various base materials, and various surfactants for the purpose of improving wettability during coating and smoothness of the cured film. It can be included.
Moreover, it is possible to disperse a coloring agent (dye and pigment) and a filler, or dissolve an organic polymer to color a coating film. Furthermore, an ultraviolet absorber and an antioxidant can be added.

  The means for applying the coating composition to the substrate (plastic lens) is not particularly limited, and known methods such as a dip method, a spray method, a spin coating method, a bar coating method, a flow coating method, and a roll coating method can be used. Can be adopted. From the viewpoint of surface accuracy, a dip method and a spin coating method are preferably used.

  A single layer or a multilayer antireflection layer may be formed on the cured layer as necessary. As constituent components of the antireflection layer, conventionally known ones such as inorganic oxides, fluorides and nitrides are used. Specific examples include silicon dioxide, silicon monoxide, zirconium oxide, tantalum oxide, yttrium oxide, aluminum oxide, titanium oxide, magnesium fluoride, and silicon nitride. Examples of the forming method include a vacuum deposition method, a sputtering method, an ion plating method, and an ion beam assist method. By providing this antireflection layer, the antireflection performance is improved. Furthermore, an antifogging layer may be further formed on the cured layer or the antireflection layer.

  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 The viscosity was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin 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 / min) according to JIS K7121, using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. using 8 mg of polycarbonate resin The temperature elevation rate was measured under the condition of 20 ° C./min.

4). Refractive index and Abbe number It measured with the multi-wavelength Abbe refractometer DR-M2 made from an Atago Co., Ltd. using the 100-micrometer-thick unstretched film.

5). Measurement of photoelastic constant An unstretched film was cut into a size of 50 mm in the film forming direction and 10 mm in the width direction perpendicular thereto, and the photoelastic constant was measured using the sample. The photoelastic constant was measured using Spectroellipometer M-220 manufactured by JASCO Corporation.

6). Pencil hardness Measured by a base plate test method of JIS K5600 using a molded specimen having a thickness of 2 mm.

7). Biological material content (Degree of plant origin)
In accordance with ASTM D6866 05, the concentration of radioactive carbon (percent model)
The content of the biogenic substance was determined from the biogenic substance content test by n carbon; C14).

8). Optical distortion Using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a lens having a thickness of 0.3 mm, a convex curvature radius of 5 mm, a concave curvature radius of 4 mm, and φ5 mm is injection molded, and the lens is sandwiched between two polarizing plates. Optical distortion was evaluated by visually observing light leakage from behind using the Nicol method. The evaluation was as follows: A: Almost no light leakage, B: Slight light leakage was observed, X: Light leakage was remarkable.

[Example 1]
<Manufacture of polycarbonate resin>
361 parts of isosorbide (hereinafter abbreviated as ISS), 421 parts of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter abbreviated as BPEF), 749.7 parts of diphenyl carbonate, and tetramethylammonium hydroxy as a catalyst 0.8 × 10 ⁻² parts and 0.6 × 10 ⁻⁴ parts of sodium hydroxide 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 is carried out with stirring for a total of 6 hours. After completion of the reaction, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid twice the amount of the catalyst is added to deactivate the catalyst, and then discharged from the bottom of the reaction tank under nitrogen pressure. The pellet was obtained by cutting with a pelletizer while cooling in a water bath. The specific viscosity and glass transition temperature of the pellets were measured and listed in Table 1.

<Manufacture of optical film>
Next, a T-die having a width of 150 mm and a lip width of 500 μm and a film take-up device were attached to a 15 mmφ twin screw extrusion kneader manufactured by Technobel Co., Ltd. An unstretched film was obtained. A sample of 50 mm × 10 mm size was cut out from the obtained film, and the photoelastic constant, refractive index, Abbe number, and pencil hardness were measured using the sample and listed in Table 1.

<Manufacture of optical lenses>
Using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a lens having a thickness of 0.3 mm, a convex curvature radius of 5 mm, a concave curvature radius of 4 mm, and a diameter of 5 mm is injected under conditions of a cylinder temperature of 270 ° C. and a mold temperature of 90 ° C. Molded and evaluated for optical distortion and listed in Table 1.

[Example 2]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 376 parts and BPEF 376 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 381 parts and BPEF 361 parts, the same operations as in Example 1 were carried out, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 426.1 parts and BPEF 226 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. In addition, a film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 444.2 parts and BPEF 180.6 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 451.2 parts and BPEF 150.5 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. An optical lens was prepared and evaluated in the same manner as in Example 1 except that the cylinder temperature was changed to 275 ° C. The results are shown in Table 1.

[Example 7]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 476.3 parts and BPEF 75.2 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. An optical lens was prepared and evaluated in the same manner as in Example 1 except that the cylinder temperature was changed to 275 ° C. The results are shown in Table 1.

[Comparative Example 1]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 250.6 parts and BPEF 752.3 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 326 parts and BPEF 527 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
<Manufacture of polycarbonate resin>
Except that the amounts of ISS and BPEF were changed to ISS 501.3 parts and BPEF 0 parts, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. An optical lens was prepared and evaluated in the same manner as in Example 1 except that the cylinder temperature was changed to 280 ° C. The results are shown in Table 1.

[Comparative Example 4]
<Manufacture of polycarbonate resin>
Except that bisphenol A (hereinafter abbreviated as BPA) was used in place of BPEF, and the amounts of ISS and BPA were changed to ISS 340.9 parts and BPA 250 parts, the same operation as in Example 1 was performed, and the specific viscosity of the pellets The glass transition temperature was measured. A film was prepared and evaluated in the same manner as in Example 1. Further, an optical lens was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 5]
<Manufacture of polycarbonate resin>
Example 9, except that 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as BCF) was used instead of BPEF, and the amounts of ISS and BCF were changed to ISS 441 parts and BCF 156 parts. The exact same operation was performed, and the specific viscosity and glass transition temperature of the pellet were measured. A film was prepared and evaluated in the same manner as in Example 1. In addition, an attempt was made to produce an optical lens in the same manner as in Example 1, but since the melt viscosity was high, the molding was performed at a cylinder temperature of 310 ° C. and a mold temperature of 100 ° C., bubbles were generated and a molded piece was obtained. There wasn't. The results are shown in Table 1.

[Comparative Example 6]
<Manufacture of polycarbonate resin>
Instead of ISS, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane (hereinafter abbreviated as SPG) is used, and SPG, Except that the amount of BPEF was changed to SPG782 parts and BPEF376 parts below, the same operations as in Example 1 were performed, and the specific viscosity and glass transition temperature of the pellets were measured. A film was prepared and evaluated in the same manner as in Example 1. An optical lens was prepared and evaluated in the same manner as in Example 1 except that the cylinder temperature was changed to 250 ° C. and the mold temperature was changed to 70 ° C. The results are shown in Table 1.

  In Table 1, BPEF is 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene derivative, BCF is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene derivative, BPA is 2,2 -Bis (4-hydroxyphenyl) propane derivative, ISS is an isosorbide derivative, SPG is a spiroglycol derivative, and is a diol component of a repeating unit.

Claims (5)

The main repeating unit is the following formula

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a hydrocarbon group that may contain an aromatic group having 1 to 10 carbon atoms, or a halogen atom, and R ₃ and R ₄ each independently represent A hydrocarbon group which may contain an aromatic group having 1 to 10 carbon atoms, m and n each independently represent an integer of 1 to 4, and p and q each independently represent 1 or more. Indicates an integer. ]
The repeating unit (A) represented by the following formula

A polycarbonate resin having a molar ratio (A / B) of the repeating unit (A) to the repeating unit (B) of from 1/99 to 30/70. The repeating unit (A) is represented by the following formula

And the repeating unit (B) is represented by the following formula:

The polycarbonate resin of Claim 1 which is a repeating unit (B1) represented by these.   The polycarbonate resin according to claim 1, wherein the refractive index is in the range of 1.510 to 1.580 and the Abbe number is in the range of 32 to 60.   An optical molded body formed using the polycarbonate resin according to claim 1.   An optical lens using the polycarbonate resin according to claim 1.