JP2009080424A - Optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical member having a low birefringence and excellent transparency, such as a lens by using a specific polycarbonate resin having a very low birefringence, high heat resistance and excellent transparency as a molding material. <P>SOLUTION: The optical member comprises the polycarbonate copolymer comprising essentially of a constitutional unit (A) derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and a constitutional unit (B) derived from 1,1-bis (4-hydroxyphenyl) decane or 4,4'- (m-phenylenediisopropylidene) diphenol, wherein the constitutional unit (A) occupies 50-100 mol% of all the constitutional units. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical member made of polycarbonate resin and an optical unit in which a plurality of optical members are integrated with a holder. Specifically, the present invention relates to an optical member and an optical unit that do not have a resolution or image quality deterioration caused by birefringence or chromatic aberration by using a polycarbonate resin having extremely small birefringence and excellent transparency.

  Conventionally, polymethyl methacrylate resin has been used as an optical material for lenses, light guide plates and the like because it has good transparency and low birefringence. However, in recent years, the demand for improving the heat resistance of resins from the viewpoint of increasing the density and safety of electronic devices has increased, and it is difficult to say that polymethyl methacrylate resins have sufficient heat resistance. On the other hand, polycarbonate resins obtained by reacting bisphenol A with a carbonate precursor are excellent in transparency, heat resistance, mechanical properties, and dimensional stability, and thus are used in various applications including optical materials. However, the polycarbonate resin has a large birefringence caused by the orientation of the molecular chain, and the residual stress during molding, for the characteristics required for optical members such as lenses, prisms, light guide plates, and optical waveguides that require optical accuracy. Due to the large optical distortion caused by the above, it has been difficult to develop the optical element.

  As a method for improving the birefringence of such PC-A, a method of graft copolymerization with a styrene resin has been proposed. (For example, see Patent Documents 1 and 2) However, the graft copolymer of PC-A and styrene resin has low mechanical strength, is extremely brittle, and is difficult to be molded due to poor thermal stability. In order to increase the strength, it is necessary to increase the molecular weight. However, if the molecular weight is increased, the moldability and surface accuracy deteriorate, and a practical lens cannot be obtained.

  As an improvement of this point, a method of mixing a polycarbonate resin composed of an aromatic dihydroxy component such as bis (4-hydroxy-3,5-dimethylphenyl) propane and an acrylonitrile-styrene copolymer has been proposed. (For example, refer to Patent Document 3) However, although the transparency and birefringence are improved, this resin composition has a drawback that it has low thermal stability and is very difficult to mold.

  Further, polycarbonate resins derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane are known as polycarbonate resins having improved birefringence, and are being studied for use as optical disk substrates. In particular, since it is possible to adjust the oxygen transmission rate by copolymerization or blending with PC-A, it is adapted as a substrate material for a limited reproduction type optical medium in which a dye layer that changes color by oxygen is laminated on a recording layer. Yes. However, it has not been confirmed whether these resins can sufficiently satisfy the required characteristics as a plastic lens. (For example, Patent Documents 4, 5, 6, and 7)

In addition, as an optical unit composed of lenses made of multiple different materials, chromatic aberration is corrected by combining a plastic lens made of alicyclic polyolefin resin with a high Abbe number and a plastic lens made of polycarbonate resin with a low Abbe number. It has been reported to do. (For example, see Patent Document 8)
Thus, when used in an optical unit, there is a demand for improvement in heat resistance and birefringence of a polycarbonate resin exhibiting a low Abbe number.

Japanese Patent Laid-Open No. 61-19630 JP 63-15822 A JP-A-5-27101 Special Table 2002-539323 Special table 2003-535948 gazette JP 2005-538483 A Special table 2007-504580 gazette Japanese Patent Laying-Open No. 2005-309109

  An object of the present invention is to provide an optical member that can correct chromatic aberration and realize high resolution and an optical unit in which a plurality of optical members are integrated with a holder. And as a result of intensive studies to achieve the above object, the present inventor has obtained an optical member comprising a polycarbonate resin exhibiting low birefringence and high heat resistance, including cyclohexyl group-containing dihydric phenol, and at least one or more It has been found that an optical unit in which these members are integrated with a holder using the optical member is excellent in resolution due to birefringence and chromatic aberration and chromatic aberration / resolution without deterioration in image quality.

（式中、Ｒ^１〜Ｒ^２は夫々独立して水素原子、芳香族基を含んでもよい炭素原子数１〜９の炭化水素基、またはハロゲン原子である。）
で表される構成単位（Ａ）と
（Ｂ）下記式［２］

（式中、Ｒ^３〜Ｒ^６は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよいアルキル基、炭素原子数６〜１０のアリール基、または炭素原子数１〜６のアルコキシ基を表す。Ｗは単結合、炭素原子数１〜１５のアルキレン基、または炭素原子数１〜２０の芳香族基を含んでもよいアルキレン基、または酸素原子を表す。）
で表される構成単位（Ａ）から構成され、全構成単位における構成単位（Ａ）の割合が５０〜１００モル％からなるポリカーボネート樹脂から構成されることを特徴とする光学部材。
（２）全構成単位における構成単位（Ａ）の割合が７０〜１００モル％からなる前項１記載の光学部材。
（３）構成単位（Ａ）が１，１−ビス（４−ヒドロキシ−３−メチルフェニル）シクロヘキサンから誘導される構成単位である前項１または前項２のいずれか１項に記載の光学部材。
（４）構成単位（Ｂ）が２，２−ビス（４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）デカン、および４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノールからなる群より選ばれる少なくとも一種の化合物から誘導された構成単位である前項１〜３のいずれか１項に記載の光学部材。
（５）該光学部材の表面全面に反射防止膜及び防湿皮膜を有する前項１〜４のいずれか１項に記載の光学部材。
（６）前記反射防止膜及び防湿皮膜がスパッタリングによって形成され、且つシリコン系材質を含む膜である前項１〜５のいずれか１項に記載の光学部材。
（７）該光学部材を構成するポリカーボネート樹脂の波長５８９ｎｍ（Ｎａ−Ｄ線）における屈折率が１．５５０〜１．６００であり、且つアッベ数が２０〜３５であることを特徴とする前項１〜６のいずれか１項に記載の光学部材。
（８）前記光学部材が射出成形法あるいは射出圧縮成形法により形成された前項１〜７のいずれか１項に記載の光学部材。
（９）該光学部材が、ピックアップレンズ、カメラレンズ、マイクロアレーレンズ、プロジェクターレンズ及びフレネルレンズからなる群より選ばれた少なくとも一種の光路変換部品、プリズム、光ファイバー、リフローハンダ付け部品、プラスチックミラー、導光板、光導波路である前項１〜８のいずれか１項に記載の光学部材。
（１０）前項１〜９のいずれか１項に記載の光学部材を少なくとも１以上含み、該１以上の光学部材をホルダで一体化した光学ユニット。
が提供される。 In order to solve the above problems, according to the present invention,
(1) (A) The following formula [1]

(In the formula, R ^{1 and} R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)
Structural units (A) and (B) represented by the following formula [2]

(Wherein R ^{3 to} R ⁶ are each independently a hydrogen atom, an alkyl group that may contain an aromatic group having 1 to 9 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 1 to 1 carbon atom) Represents an alkoxy group of 6. W represents a single bond, an alkylene group having 1 to 15 carbon atoms, an alkylene group which may contain an aromatic group having 1 to 20 carbon atoms, or an oxygen atom.)
An optical member comprising a polycarbonate resin composed of a structural unit (A) represented by the formula (A), wherein the proportion of the structural unit (A) in all the structural units is 50 to 100 mol%.
(2) The optical member according to item 1, wherein the proportion of the structural unit (A) in all the structural units is 70 to 100 mol%.
(3) The optical member according to any one of (1) or (2), wherein the structural unit (A) is a structural unit derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane.
(4) The structural unit (B) is 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, and 4,4 ′-(m-phenylenediisopropylidene) di 4. The optical member according to any one of items 1 to 3, which is a structural unit derived from at least one compound selected from the group consisting of phenol.
(5) The optical member according to any one of items 1 to 4, which has an antireflection film and a moisture-proof coating on the entire surface of the optical member.
(6) The optical member according to any one of items 1 to 5, wherein the antireflection film and the moisture-proof film are formed by sputtering and include a silicon-based material.
(7) The above-mentioned item 1, wherein the polycarbonate resin constituting the optical member has a refractive index of 1.550 to 1.600 at a wavelength of 589 nm (Na-D line) and an Abbe number of 20 to 35. The optical member of any one of -6.
(8) The optical member according to any one of items 1 to 7, wherein the optical member is formed by an injection molding method or an injection compression molding method.
(9) The optical member is at least one optical path conversion component selected from the group consisting of a pickup lens, a camera lens, a microarray lens, a projector lens and a Fresnel lens, a prism, an optical fiber, a reflow soldering component, a plastic mirror, a conductive mirror 9. The optical member according to any one of items 1 to 8, which is an optical plate or an optical waveguide.
(10) An optical unit comprising at least one optical member according to any one of items 1 to 9 and integrating the one or more optical members with a holder.
Is provided.

The present invention is described in detail below.
An optical unit in which a plurality of lenses are integrated with a holder is required to be reduced in size and weight and / or reduced in cost, and a plastic lens is preferably used. In particular, an alicyclic polyolefin resin having good optical properties is used. However, when an optical unit is formed using a plastic lens made of an alicyclic polyolefin resin, it is necessary to perform an optical design for correcting chromatic aberration in combination with a lens made of a material having a significantly different Abbe number. Since the alicyclic polyolefin resin has an Abbe number of about 45 to 60, a lens made of a polycarbonate resin having a low Abbe number can be suitably used. A plastic lens made of a polycarbonate resin is generally manufactured by injection molding and / or injection compression molding. At this time, orientation birefringence caused by orientation of the molecular chain of the polycarbonate resin by the action of strong shearing force and stress birefringence caused by thermal stress are generated. When the present inventor examined birefringence in detail, it is possible to make the birefringence lower than that of the conventional PC-A by using the structural unit represented by the above formula [1]. found. Further, it was found that by using the structural unit represented by the above formula [1], it has almost the same refractive index as PC-A and has a low water absorption rate. This can be used without changing the design of the optical unit that currently uses the PC-A, and an optical member having small dimensional stability due to water absorption and small chromatic aberration due to birefringence can be obtained.

  That is, according to the study of the present inventor, the structural unit (A) derived from the cyclohexyl group-containing dihydric phenol represented by the above formula [1] and the divalent phenol represented by [2] It was found that by using the structural unit (B), the lower birefringence and the higher heat resistance can be exhibited simultaneously than the conventional PC-A.

  From the above knowledge, the polycarbonate resin in which the proportion of the structural unit (A) in all the structural units is 50 to 100 mol% satisfies the above problem, that is, is a polycarbonate resin having both low birefringence and high heat resistance, In addition, since the polycarbonate resin has a low Abbe number, it can be combined with a plastic lens made of an alicyclic polyolefin resin having a different Abbe number. As an optical unit in which a plurality of plastic lenses are integrated with a holder, the resolution is high. The chromatic aberration was found to be small.

As the structural unit (A), in the following formula [1], R ^{1 and} R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom. . More preferably, a compound which is the same or different and is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group is preferable. Specific examples of the preferable structural unit (A) include a structural unit having a carbonate bond derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane or the like.

As the structural unit (B), in the following formula [2], R ^{3 to} R ⁶ are each independently a hydrogen atom, an alkyl group that may contain an aromatic group having 1 to 9 carbon atoms, or a carbon number of 6 to 10 An aryl group or an alkoxy group having 1 to 6 carbon atoms. W represents a single bond, an alkylene group having 1 to 15 carbon atoms, or an alkylene group which may contain an aromatic group having 1 to 20 carbon atoms, or an oxygen atom. Specific examples of the preferable structural unit (B) include 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 4,4 ′-(m-phenylenediene). Isopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (3-methyl-4-hydroxyphenyl) decane, and 1,1-bis (2,3-dimethyl-4-) Hydroxyphenyl) decane and the like. Is mentioned.

  Among these, the structural unit (A) component is preferably a structural unit having a carbonate bond derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, and the structural unit (B) is 2 , 2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, and 4,4 ′-(m-phenylenediisopropylidene) diphenol It is preferably a structural unit having a carbonate bond derived from a compound, and derived from 1,1-bis (4-hydroxyphenyl) decane or 4,4 ′-(m-phenylenediisopropylidene) diphenol A structural unit having a carbonate bond is particularly preferable.

  Moreover, 50-100 mol% is preferable, as for the ratio of the structural unit (A) in all the structural units, 60-100 mol% is more preferable, and 70-100 mol% is still more preferable. When the molar ratio of the structural unit (A) is less than 50 mol%, the birefringence increases, the glass transition temperature decreases, and the heat resistance is inferior.

<Production method of polycarbonate resin>
The polycarbonate resin can be produced by reacting a dihydric phenol for deriving the structural unit (A) and a dihydric phenol for deriving the structural unit (B) with a carbonate precursor by a solution polymerization method or a melt polymerization method. More preferred polycarbonates are those produced by solution polymerization, that is, interfacial polymerization. These two types of dihydric phenols may be reacted simultaneously with the carbonate precursor or sequentially for each type.

  Further, carbonate-bonded structural units derived from other dihydric phenols may be copolymerized at a ratio of 10 mol% or less, preferably 5 mol% or less, as long as the object and characteristics of the present invention are not impaired. Representative examples of such other dihydric phenols include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl}. Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3,5 -Dibromo-4-hydroxy) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-H Roxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1′-bis- (4-hydroxyphenyl) -o-diisopropylbenzene, 1,1′-bis- (4-hydroxyphenyl) m-diisopropylbenzene, 1,1′-bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenyl Sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ester, 1,1- Bis (4-hydroxyphenyl) -2-methylpropane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane and the like can be mentioned, and these can be used alone or in admixture of two or more.

  Examples of the carbonate precursor include carbonyl halide, carbonate ester, and haloformate. Specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like, and phosgene or diphenyl carbonate is preferable. In producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polymerization method or melt polymerization method, oxidation of catalyst, terminal stopper and dihydric phenol is prevented as necessary. An antioxidant or the like may be used.

  The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

<End terminator>
In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such end terminators. Monofunctional phenols are commonly used as end terminators for molecular weight control, and the resulting polycarbonate resins are compared to those that do not because the ends are blocked by groups based on monofunctional phenols. Excellent thermal stability. Such monofunctional phenols may be those used as a terminal terminator for polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, and indicate monofunctional phenols represented by the following general formula. Can do.

［式中、Ａは水素原子または炭素数１〜９の直鎖または分岐のアルキル基あるいはアリールアルキル基を示し、ｒは１〜５、好ましくは１〜３の整数を示す。］

[Wherein, A represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or an arylalkyl group, and r represents an integer of 1 to 5, preferably 1 to 3. ]

  Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

  Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic ester group as a substituent, or long chain alkyl carboxylic acid chlorides can be used, When these are used to block the end of the aromatic polycarbonate resin, they not only function as a terminal terminator or molecular weight modifier, but also improve the melt fluidity of the resin and facilitate molding, as well as the substrate. The physical properties are improved. In particular, it has the effect of reducing the water absorption rate of the resin and is preferably used. These are represented by the following general formulas [Ia] to [Ih].

[In each formula, X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5. A divalent aliphatic hydrocarbon group, T represents a single bond or a bond similar to the above X, and n represents an integer of 10 to 50.
Q represents a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, p represents an integer of 0 to 4, Y represents 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. 5 is a divalent aliphatic hydrocarbon group, and W ¹ is a hydrogen atom, —CO—R ¹³ , —CO—O—R ¹⁴ or R ¹⁵ , wherein R ¹³ , R ¹⁴ and R ¹⁵ are 1 to 10 carbon atoms, preferably 1 to 5 monovalent aliphatic hydrocarbon groups, 4 to 8 carbon atoms, preferably 5 to 6 monovalent alicyclic hydrocarbon groups or 6 to 15 carbon atoms, respectively. Preferably 6-12 monovalent | monohydric aromatic hydrocarbon group is shown.
l represents an integer of 4 to 20, preferably 5 to 10, m represents an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, Z represents a single bond or a carbon number of 1 to 10, preferably an 1-5 divalent aliphatic hydrocarbon group, ^{W 2} is a hydrogen atom, C1-10, preferably 1 to 5 monovalent aliphatic hydrocarbon group, having 4 to 8 carbon atoms, Preferably, it represents a monovalent alicyclic hydrocarbon group having 5 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms. ]

  Of these, the substituted phenols of [Ia] and [Ib] are preferable. As the substituted phenols of [Ia], those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, and octadecyl. Phenol, eicosylphenol, docosylphenol and triacontylphenol can be mentioned.

  Further, as the substituted phenols of [Ib], compounds in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

  In the substituted phenols or substituted benzoic acid chlorides represented by the above general formulas [Ia] to [Ig], the position of the substituent is generally preferably a para-position or an ortho-position, and a mixture of both is preferred.

  The monofunctional phenols are desirably introduced at the end of at least 5 mol%, preferably at least 10 mol%, based on the total terminal of the obtained aromatic polycarbonate, and the monofunctional phenols may be used alone or in combination of two kinds. You may mix and use above.

  The reaction by the melt polymerization method is typically a transesterification reaction between a dihydric phenol and a carbonate ester. The alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Or it is performed by the method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 1,300 Pa to 13 Pa (10 to 0.1 Torr) to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Is preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, alkali metal salts, alkaline earth metal salts, and quaternary ammonium salts. Alkoxides of alkali metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds And catalysts usually used in esterification reactions and transesterification reactions of zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. Selected by range.

  Further, in this polymerization reaction, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are added at the later stage or after completion of the polycondensation reaction in order to reduce the phenolic end groups. In particular, 2-methoxycarbonylphenyl phenyl carbonate is preferably used.

Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate resin after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
Details of other reaction formats are well known in various documents and patent publications.

<Production method of resin pellet>
The polycarbonate resin of the present invention is produced by a conventionally known conventional method (solution polymerization method, melt polymerization method, etc.) after considering that the purpose of use is the production of optical members such as lenses, followed by filtration in a solution state. It is preferable to remove impurities such as unreacted components and foreign matters. Furthermore, in the extrusion process (pelletizing process) for obtaining a pellet-like polycarbonate resin for use in injection molding (including injection compression molding), foreign substances are removed by passing a sintered metal filter or the like in the molten state. Is desirable. As the filter, those having a filtration accuracy of 10 μm or less are preferably used. In any case, it is necessary that the raw material resin before injection molding (including injection compression molding) has a low content of foreign matters, impurities, solvents and the like as much as possible.

  Furthermore, in order to produce such low foreign matter pellets, in addition to the above, a manufacturing device such as an extruder or pelletizer should be installed in a clean air atmosphere, and the cooling water for the cooling bath should have a small amount of foreign matter. It is preferable that the raw material supply hopper, the supply flow path, the storage tank for the obtained pellets, and the like be filled with cleaner air or the like. For example, it is appropriate to adopt a method similar to that proposed in JP-A-11-21357. Further, a method of pouring an inert gas typified by nitrogen gas into the extruder and shielding oxygen can be suitably used as a means for improving hue.

  Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical molding materials are used to narrow the shape distribution of pellets, further reduce miscuts, and generate minute amounts during transportation or transportation. Further reduction of powder and reduction of bubbles (vacuum bubbles) generated in the strands and pellets can be appropriately performed. These prescriptions can further increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder (including an elliptical column) more preferably. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. In the elliptic cylinder, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

<Phosphorus stabilizer>
In the present invention, the polycarbonate resin contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof with respect to the polycarbonate resin. It can mix | blend in the ratio of -0.05weight%. By blending this phosphorus compound, the thermal stability of the aromatic polycarbonate resin is improved, and a decrease in molecular weight and a deterioration in hue during molding are prevented.

  The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof, and preferably the following general formulas (1) to (4) At least one phosphorus compound selected from the group consisting of:

Here, R ^{1 to} R ¹² are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, It represents an alkyl group having 1 to 20 carbon atoms such as octadecyl, an aryl group having 6 to 15 carbon atoms such as phenyl, tolyl and naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl. When two alkyl groups are present in one compound, the two alkyl groups may be bonded to each other to form a ring.

  Examples of the phosphorus compound represented by the above formula (1) include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentae Thritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc. Examples of the phosphorus compound represented by the formula (2) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. Examples of the phosphorus compound represented by the above formula (3) include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite. ) The compounds of formula, dimethylbenzene phosphonate, benzene phosphonic acid diethyl, and the like dipropyl benzene phosphonate. Of these, distearyl pentaerythritol diphosphite, triethyl phosphate, dimethyl benzenephosphonate, and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferably used.

  The amount of the phosphorus compound is 0.0001 to 0.05% by weight, preferably 0.0005 to 0.02% by weight, particularly preferably 0.001 to 0.01% by weight, based on the polycarbonate resin. . If the blending amount is less than 0.0001% by weight, it is difficult to obtain the above effect, and if it exceeds 0.05% by weight, the heat stability of the polycarbonate resin is adversely affected, and the hydrolysis resistance is also decreased. Absent.

<Antioxidant>
To the polycarbonate resin of the present invention, an antioxidant generally known for the purpose of antioxidant can be added. Examples thereof include phenolic antioxidants and lactone antioxidants. Specific examples of the phenolic antioxidant include triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediol-bis ( 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocin Mido), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1 , 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, etc. Is mentioned. Specific examples of the lactone antioxidant include, for example, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, 5,7-di- and t-butyl-3- (2,3-dimethylphenyl) -3H-benzofuran-2-one. The range of the preferable addition amount of these antioxidants is 0.0001 to 0.05% by weight with respect to the polycarbonate resin.

<Release agent>
Furthermore, higher fatty acid esters of monohydric or polyhydric alcohols can be added to the polycarbonate resin of the present invention as necessary. By compounding this higher fatty acid ester of monohydric or polyhydric alcohol, the mold releasability from the mold during the molding of the polycarbonate resin is improved, and in the molding of optical parts, the mold release load is small and the mold release is poor. It is possible to prevent deformation of the molded product due to. There is also an advantage that the melt flowability of the polycarbonate resin is improved.

  The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

  Further, partial esters or total esters of such monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol. Examples include monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used. It is done.

  The blending amount of the alcohol and higher fatty acid ester is 0.01 to 2% by weight, preferably 0.015 to 0.5% by weight, and 0.02 to 0.2% by weight based on the polycarbonate resin. Is more preferable. If the blending amount is less than 0.01% by weight, the above effect cannot be obtained, and if it exceeds 2% by weight, the mold surface may become dirty during molding.

  To the polycarbonate resin of the present invention, additives such as a light stabilizer, a colorant, an antistatic agent, and a lubricant can be added as long as the heat resistance and transparency are not impaired. In order to mix the said additive with the aromatic polycarbonate resin of this invention, it can implement by arbitrary methods. For example, a method of mixing with a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like is appropriately used.

<Specific viscosity>
The polycarbonate resin of the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity in the range of 0.17 to 0.55 measured at 20 ° C. A range is more preferable. If the specific viscosity is less than 0.17, the molded product becomes brittle, and if it is higher than 0.55, the melt viscosity and the solution viscosity become high and the handling becomes difficult.

<Glass transition temperature>
The polycarbonate resin used as the first lens of the present invention preferably has a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min of 125 ° C. or higher and lower than 250 ° C. Furthermore, it is preferable that it is 130 degreeC or more and less than 245 degreeC. When Tg is less than 125 ° C., the heat resistance is not sufficient depending on the use of the optical component formed using the resin. On the other hand, when Tg is 250 ° C. or more, the melt viscosity becomes high and the moldability is inferior.

<Photoelastic coefficient>
The polycarbonate resin of the present invention preferably has a photoelastic constant of 45 × 10 ¹² Pa ⁻¹ or less. Furthermore, it is preferable that it is 40 * 10 < ¹² > Pa <^-1> or less. When the photoelastic constant is larger than 45 × 10 ¹² Pa ⁻¹ , molding distortion generated during molding becomes large, and it is difficult to use as an optical member, which is not preferable.

<Water absorption rate>
According to ASTM D-570, the polycarbonate resin of the present invention preferably has a water absorption rate of 0.25% or less after 24 hours, which is obtained by immersing a φ45 mm molded plate in water and determined by weight change rate (% by weight). If the ratio is larger than 0.25%, image deterioration occurs due to a change in lens dimensions due to water absorption, which is not preferable.

<Abbe number>
According to JIS-K7142, the polycarbonate copolymer of the present invention uses an Abbe refractometer having a wavelength selection filter as a light source, and the wavelength is set to C line (656 nm), D line (589 nm), and F line (486 nm). The refractive index is measured by changing the refractive index, and the refractive index measured at 589 nm is preferably 1.550 to 1.600, and the Abbe number is preferably 20 to 35.

<Optical member>
The optical member in the present invention is at least one optical path conversion component selected from the group consisting of a pickup lens, a camera lens, a microarray lens, a projector lens, and a Fresnel lens, which are optical elements that are components for optical equipment, a prism, Optical fiber, reflow soldering parts, plastic mirror, light guide plate, optical waveguide, etc.

  Specifically, the lens has two spherical or aspherical refractive surfaces and can transmit light, and is not particularly limited as long as it satisfies this. For example, a spherical lens, Examples include aspherical lenses, pickup lenses, camera lenses, microarray lenses, projector lenses, and Fresnel lenses. In addition, the prism refers to a molded body having two or more polished surfaces that are not parallel but at an angle, and is not particularly limited as long as it satisfies this, but an example is given. For example, a right-angle prism, a porro prism, an amis prism, a pentagon prism, a doubless prism, a Hensolt prism, a Spreng prism, a mailer prism, a Wollaston prism, an inclined prism, and an Abbe prism.

  The optical member may have an antireflection film and / or a moisture barrier film on the entire surface of the optical member. The antireflection film and / or moisture barrier film is mainly formed by sputtering. Examples of these films include films containing titanium-based or silicon-based materials. For example, titanium oxide and silicon oxide are applicable. These films are formed of at least one layer and two to several tens of layers. For example, titanium oxide and silicon oxide films are preferably formed alternately.

<Optical member molding method>
The optical member constituting the optical unit formed from the polycarbonate resin in the present invention is molded by any method such as an injection molding method, a compression molding method, an injection compression molding method, an extrusion molding method, or a solution casting method. In view of ease of molding and cost, it is particularly preferable to mold by an injection molding method or an injection compression molding method.

<Light transmittance of optical member>
As for the optical member which comprises the optical unit of this invention, it is preferable that the transmittance | permeability in 550 nm of a shaping | molding board is 80% or more. Further, it is preferably 85% or more. If the transmittance is lower than 80%, it is difficult to use as an optical member.

<Birefringence of optical member>
The optical member constituting the optical unit of the present invention has a retardation at ₅₅₀ nm of the molded plate as Re ₅₅₀ (nm), and the thickness of the measurement site of transmittance and retardation is d (mm).
It is preferable that Re ₅₅₀ / d (mm) ≦ 10 × 10 ⁻⁶ is satisfied. An optical element made of a general bisphenol A type polycarbonate resin usually has a large retardation, and it may be possible to reduce the value depending on molding conditions, but the condition width is usually very small. It becomes very difficult and in many cases the above equation cannot be satisfied. Since the polycarbonate resin of the present invention has a small retardation caused by the orientation of the resin and a small molding distortion, a good optical element can be obtained without strictly setting molding conditions.

<Optical unit>
The optical unit of the present invention has a configuration in which at least one optical member is integrated with a holder. For example, in an optical unit composed of two optical members, when the lens made of the polycarbonate resin of the present invention is used as the first lens, the second lens has a different Abbe number and low birefringence. By using, an effect of correcting chromatic aberration can be obtained. As a material used, it is preferable that Abbe number is 45-60. In addition, the birefringence preferably has a phase difference of 100 nm or less due to normal incidence of a 2.5 mm thick molded plate. As such a material, alicyclic polyolefin resin, polymethyl methacrylate, olefin / maleimide resin, and poly (1,3-cyclohexanediene) are preferable, and alicyclic polyolefin resin is more preferable. Moreover, you may use mold glass besides a plastic lens.

<Manufacturing method of optical unit>
For example, the optical unit of the present invention includes a method in which the optical unit of the present invention is assembled into a cylindrical holder in a state in which a combination direction of a plurality of lenses is set in order to cancel birefringence due to orientation during injection molding. In addition, when a lens is assembled into a holder, a new stress is added, for example, stress due to curing shrinkage of the adhesive if it is adhesively fixed, or tightening stress due to the holder if it is fixedly fitted. Since birefringence occurs, a holder in which the first lens is arranged and a holder in which the second lens is arranged are formed separately, one holder is brought into contact with the other holder, and then one optical axis of the holder Can also be used in which both holders are connected and fixed after rotating around the rotation axis to cancel the orientation birefringence.

  As described above, the optical member and the optical unit formed of the polycarbonate resin having excellent heat resistance and thermal stability, extremely low birefringence, and excellent transparency in the present invention have good optical characteristics. Therefore, it is suitable as a digital still camera camera, a liquid crystal display, a liquid crystal projector, a copying machine, an optical unit of an electric / electronic device such as an optical disk device, and an optical unit such as a demultiplexer or a multiplexer in an optical communication device. Can be used.

  Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. In the examples and comparative examples, “parts” is parts by weight. Evaluation was according to the following method.

(1) Specific viscosity 0.7 g of polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.

(2) Glass transition point (Tg)
A 2910 type DSC manufactured by TS Instruments Japan Co., Ltd. was used, and the temperature was increased at a rate of 20 ° C./min.

(3) Water absorption rate 4.0 g of polycarbonate resin was put into a 45 mmφ mold, held in a compression molding machine at a temperature of 280 ° C. for 1 minute, and then cooled to room temperature in a pressurized state to obtain a 45 mmφ compression molding plate. . Thereafter, in accordance with ASTM D-570, a φ45 mm compression molded plate was immersed in water at a temperature of 23 ° C. for 24 hours, and the water absorption was measured by the weight change rate (% by weight) before and after.

(4) Photoelastic constant 5 g of polycarbonate resin composition pellets were dissolved in 100 ml of methylene chloride, and the solution was cast on a flat glass plate and allowed to stand overnight to prepare a cast film. After the film was dried at 60 ° C. for 2 hours, a film having a length of 50 mm, a width of 20 mm, and an average thickness of 150 μm was prepared, and measurement was performed by setting a photoelastic stage on an ellipsometer M-220 manufactured by JASCO Corporation. It was. As the measurement conditions, a load of 1 N or less was applied to the film, and the phase difference at that time was measured. Measurement was performed at five points, and the photoelastic coefficient was calculated according to the following formula.
Re = F × c × d
Re: phase difference [nm], F: stress [N / m ² ], c: photoelastic constant [Pa ⁻¹ ],
d: Thickness [nm]

(5) Abbe number Using the cast film prepared above, in accordance with JIS-K7142, an Abbe refractometer having a wavelength selection filter as a light source is used, and the wavelength is C line (656 nm), D line (589 nm), F line The refractive index was measured by changing to (486 nm), and the Abbe number was measured using the obtained refractive index.

(6) Light transmittance (T ₅₅₀ )
A molded piece having a thickness of 1.0 mm, a width of 1.0 mm, and a length of 2.0 mm was injection molded using an injection molding machine N-20C manufactured by Nippon Steel. The transmittance at 550 nm of the produced molded body was measured with a U-4001 spectrophotometer manufactured by Hitachi, Ltd.

(7) Phase difference (Re ₅₅₀ )
The normal incidence birefringence at 550 nm of the prepared test piece and the molded body was measured with an M-220 ellipsometer manufactured by JASCO Corporation.

(8) Birefringence evaluation of plano-convex lens A plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.80 mm, and a focal length of 2.0 mm under the molding conditions shown in Table 2 using an injection molding machine N-20C manufactured by Nippon Steel Works. Was injection molded. For those that can be molded, place a polarizing plate with a phase difference of 90 ° before and after the plano-convex lens, enter white light from one polarizing plate side, and visually observe the interference color appearing on the plano-convex lens Thus, the degree of birefringence was evaluated. The evaluation was performed as follows: ◎: no interference fringe pattern, ○: one interference fringe, ×: two or more interference fringes. Table 3 shows the molding results and the evaluation results.

(9) Production of Lens Unit The optical unit shown in FIG. 1 was produced by injection molding using a polycarbonate resin for the first lens (1) and an amorphous polyolefin resin for the second lens (2). The holder (3) is divided, and the plastic lenses (1) and (2) are incorporated into the divided holders (4) and (5), and (4) and (5) are joined. The combination of the two plastic lenses (1) and (2) and the optical characteristics were optimized by rotating the optical axis (6) as the central axis, and then connected and fixed with an adhesive to be integrated. The specifications of the obtained lens unit are a focal length of 5.8 mm, an F value of 2.0, a light receiving size diameter of 7.2 mm, a total lens length of 15.4 mm, and a lens diameter of 14 mm.

(10) Evaluation of lens unit In the evaluation system shown in FIG. 2, the lens unit (7) is incorporated into a 1/3 inch C-MOS sensor (8), and an ITE standard resolution chart (11) is used. The image data (10) captured from the 1/3 inch C-MOS sensor at the same magnification was subjected to image processing by the computer (9), and the resolution was evaluated from the difference image from the original image.
○: There is almost no difference image.
(Triangle | delta): A difference image is recognized slightly.
X: The difference image is clearly recognized.

[Example 1]
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 5553 parts of a 48% aqueous sodium hydroxide solution and 23376 parts of ion-exchanged water, and 1,1-bis (4-hydroxy-3-methylphenyl) was added thereto. After dissolving 3844 parts of cyclohexane, 499 parts of 4,4 ′-(m-phenylenediisopropylidene) diphenol and 8.69 parts of hydrosulfite, 15945 parts of methylene chloride was added, and phosgene was added at 15 to 25 ° C. with stirring. 2000 parts were blown in over 60 minutes. After completion of the phosgene blowing, 595 parts of 48% aqueous sodium hydroxide and 97.40 parts of p-tert-butylphenol were added, stirring was resumed, 6.89 parts of triethylamine was added after emulsification, and the mixture was further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having a mesh opening of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Thereafter, tris (2,4-di-tert-butylphenyl) phosphite is added to the powder so as to be 0.0025% by weight and stearic acid monoglyceride to be 0.05% by weight. The powder was melt-kneaded while degassing with a vent type twin screw extruder [KTX-46, manufactured by Kobe Steel, Ltd.] to obtain polycarbonate resin composition pellets. The physical property values of this polycarbonate resin (BISOC-Z: BISP-M = 90 mol%: 10 mol%) were measured as follows.

  Using the obtained pellets, specific viscosity, glass transition temperature, water absorption, photoelastic constant, and Abbe number were measured and listed in Table 1. Then, after drying at 120 ° C. for 5 hours, a molding plate having a thickness of 1.0 mm, a width of 1.0 mm, and a length of 2.0 mm was formed under the molding conditions shown in Table 2 using an injection molding machine N-20C manufactured by Nippon Steel Works. And molded. The light transmittance and birefringence of the molded plate were measured and listed in Table 2. Using the molding machine N-20C, a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.80 mm, and a focal length of 2.0 mm was injection molded under the molding conditions shown in Table 3. After that, a polarizing plate with a phase difference of 90 ° is arranged before and after the plano-convex lens, white light is incident from one side of the polarizing plate, and the interference color appearing on the plano-convex lens is visually observed. The degree was evaluated and the results are shown in Table 3. Further, using the molding machine N-20C, the plastic lens used in the optical unit shown in FIG. 1 is made of polycarbonate resin using the first lens (1), amorphous polyolefin resin (ZEONEX 480R, manufactured by Nippon Zeon Co., Ltd.). ) Was used to mold the second lens (2). The holder was divided, and the plastic lenses (1) and (2) were incorporated for each of the divided holders (3) and (4), and (3) and (4) were joined. The optical characteristics of the two plastic lenses (1) and (2) were optimized by rotating about the optical axis (6) as a central axis, and then connected and fixed with an adhesive to be integrated. The specifications of the obtained optical unit were a focal length of 5.8 mm, an F value of 2.0, a light receiving size diameter of 7.2 mm, a total lens length of 15.4 mm, and a lens diameter of 14 mm. The above optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and magnification using an ITE standard resolution chart is processed by a computer. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Example 2]
Table 1 shows all the same procedures as in Example 1 except that 2989 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 1497 parts of 4,4 ′-(m-phenylenediisopropylidene) diphenol were used. Polycarbonate resin pellets having the characteristics described in 1) were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Example 3]
Table 1 shows all the same procedures as in Example 1 except that 2135 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 2496 parts of 4,4 ′-(m-phenylenediisopropylidene) diphenol were used. Polycarbonate resin pellets having the characteristics described in 1) were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Example 4]
Table 1 shows all the same procedures as in Example 1 except that 3844 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 329 parts of 2,2′-bis (4-hydroxyphenyl) propane were used. Polycarbonate resin pellets having the following characteristics were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Example 5]
Table 1 shows all the same procedures as in Example 1 except that 3844 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 470 parts of 1,1′-bis (4-hydroxyphenyl) decane were used. Polycarbonate resin pellets having the following characteristics were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Example 6]
Except for 4271 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, the same procedure as in Example 1 was carried out to obtain polycarbonate resin pellets having the characteristics shown in Table 1. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Comparative Example 1]
Table 1 shows all the same procedures as in Example 1 except that 1708 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 2995 parts of 4,4 ′-(m-phenylenediisopropylidene) diphenol were used. Polycarbonate resin pellets having the characteristics described in 1) were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Comparative Example 2]
Table 1 shows all the same procedures as in Example 1 except that 1708 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 1974 parts of 2,2′-bis (4-hydroxyphenyl) propane were used. Polycarbonate resin pellets having the following characteristics were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Comparative Example 3]
Table 1 shows all the same procedures as in Example 1 except that 1708 parts of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 2822 parts of 1,1′-bis (4-hydroxyphenyl) decane were used. Polycarbonate resin pellets having the following characteristics were obtained. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

[Comparative Example 4]
Except for using 3290 parts of 2,2′-bis (4-hydroxyphenyl) propane, the same procedure as in Example 1 was performed to obtain polycarbonate resin pellets having the characteristics shown in Table 1. Furthermore, evaluation was performed in the same manner as in Example 1 except that the molded plate and the plano-convex lens were molded under the molding conditions described in Tables 2 and 3, and the results are shown in Tables 2 and 3. The optical unit shown in FIG. 1 was prepared by injection molding using the above polycarbonate resin for the first lens (1) and the amorphous polyolefin resin for the second lens (2). The created optical unit is incorporated into a 1/3 inch C-MOS sensor, and image data captured from the 1/3 inch C-MOS sensor at the same distance and at the same magnification using an ITE standard resolution chart. The resolution was evaluated from the difference image from the original image, and the results are shown in Table 4.

* 1 BisOC-Z
: 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane * 2 BisP-M
: 4,4 '-(m-phenylenediisopropylidene) diphenol * 3 BisP-A
: 2,2'-bis (4-hydroxyphenyl) propane * 4 BisP-DED
: 1,1′-bis (4-hydroxyphenyl) decane

It is the schematic which shows the optical unit which integrated the optical member with the holder. It is the evaluation system of the resolution in an optical unit.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st lens 2 2nd lens 3 1st holder 4 2nd holder 5 Joint surface 6 Optical axis 7 Lens unit 8 CMOS sensor 9 Computer 10 Video output 11 Evaluation image

Claims (10)

(A) The following formula [1]

(In the formula, R ^{1 and} R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)
Structural units (A) and (B) represented by the following formula [2]

(Wherein R ^{3 to} R ⁶ are each independently a hydrogen atom, an alkyl group that may contain an aromatic group having 1 to 9 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 1 to 1 carbon atom) Represents an alkoxy group of 6. W represents a single bond, an alkylene group having 1 to 15 carbon atoms, an alkylene group which may contain an aromatic group having 1 to 20 carbon atoms, or an oxygen atom.)
An optical member comprising a polycarbonate resin composed of a structural unit (B) represented by formula (B), wherein the proportion of the structural unit (A) in all the structural units is 50 to 100 mol%.   The optical member according to claim 1, wherein the proportion of the structural unit (A) in all the structural units is 70 to 100 mol%.   The optical member according to claim 1, wherein the structural unit (A) is a structural unit derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane.   The structural unit (B) comprises 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, and 4,4 ′-(m-phenylenediisopropylidene) diphenol. The optical member according to claim 1, which is a structural unit derived from at least one compound selected from the group.   The optical member according to claim 1, further comprising an antireflection film and / or a moisture-proof coating on the entire surface of the optical member.   The optical optical member according to claim 1, wherein the antireflection film and / or the moisture-proof film is a film formed by sputtering.   The polycarbonate resin constituting the optical member has a refractive index at a wavelength of 589 nm (Na-D line) of 1.550 to 1.600 and an Abbe number of 20 to 35. The optical member according to any one of the above.   The optical member according to claim 1, wherein the optical member is formed by an injection molding method or an injection compression molding method.   The optical member is at least one optical path conversion component selected from the group consisting of a pickup lens, a camera lens, a microarray lens, a projector lens, and a Fresnel lens, a prism, an optical fiber, a reflow soldering component, a plastic mirror, a light guide plate, or It is an optical waveguide, The optical member of any one of Claims 1-8.   An optical unit comprising at least one or more optical members according to any one of claims 1 to 9, wherein the one or more optical members are integrated with a holder.

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