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Optical Component and Spirobiindan Polymer Therefor

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Optical Component and Spirobiindan Polymer Therefor Europaisches Patentamt European Patent Office Office europeen des brevets (11) EP 0 822 545 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) |nt CI * G1 1 B 7/24, C08G 64/06, 04.02.1998 Bulletin 1998/06 C08G 63/193, C08G 18/32, C08G 59/24, C08G 73/1 0, (21)rai.... Application t. number:i 97305763.1QTOncTCO, C08G 69/26, C08F~nnr- 20/30,nninn (22) Date of filing: 31.07.1997 C08F 16/32 (84) Designated Contracting States: • Yamashita, Watura AT BE CH DE DK ES Fl FR GB GR IE IT LI LU MC Omuta-shi, Fukuoka (JP) NL PT SE • Yoshimura, Tomomi Yokohama-shi, Kanagawa (JP) (30) Priority: 31.07.1996 JP 201825/96 • Shibuya, Atsushi 02.08.1996 J P 204614/96 Yokohama-shi, Kanagawa (JP) 02.08.1996 JP 204615/96 • Sakata, Yoshihiro 12.12.1996 JP 331831/96 Kamakura-shi, Kanagawa (JP) 12.12.1996 JP 331832/96 • Oikawa, Hideaki 12.12.1996 JP 331833/96 Yokohama-shi, Kanagawa (JP) • Ohta, Masahiro (71) Applicant: MITSUI TOATSU CHEMICALS, Kamakura-shi, Kanagawa (JP) INCORPORATED • Ajioka, Masanobu Tokyo (JP) Yokohama-shi, Kanagawa (JP) • Takagi, Masatoshi (72) Inventors: Yokohama-shi, Kanagawa (JP) • Otsuji, Atsuo • Karasawa, Akio Yokohama-shi, Kanagawa (JP) Yokohama-shi, Kanagawa (JP) • Takuma, Keisuke Yokohama-shi, Kanagawa (JP) (74) Representative: Stuart, Ian Alexander et al • Suzuki, Rihoko MEWBURN ELLIS Yokohama-shi, Kanagawa (JP) York House • Urakami, Tatsuhiro 23 Kingsway Yokohama-shi, Kanagawa (JP) London WC2B 6HP (GB) • Motoshima, Toshihiro Yokohama-shi, Kanagawa (JP) (54) Optical component and spirobiindan polymer therefor (57) There is provided a low-birefringent organic optical component comprising a polymer prepared by polymerizing a racemic mixture of the monomer with an asymmetric spiro ring represented by general formula (1) as an essential ingredient; Z,— X, ( 1 ) CM < ^- LO wherein ring A represents a monocyclic or polycyclic organic group, wherein two ring As are mutually bound each CM other via a spiro bond to form a spiro ring which has a molecular asymmetric structure; n is an integer of 0 to 10; X-, CM and Yi are binding Z-, is a polymerization-active CO groups; group. The component has excellent transparency, mechanical strength and heat resistance, as well as a low birefrin- o gence. a. LU Printed by Jouve, 75001 PARIS (FR) EP 0 822 545 A2 Description This invention relates to an organic optical component and a polymer with a spirobiindan structure, A preferred organic optical component of this invention has excellent transparency, mechanical strength and heat resistance as 5 well as a low birefringence, and is useful as, for example, a substrate for an optical disk, a pick-up lens, a plastic substrate for a liquid cell and a prism. Inorganic glasses have a number of excellent physical properties such as excellent transparency and a reduced optical anisotropy, and thus has been used in various fields. The glasses, however, have problems such as fragility due to their heavy weight and a poor productivity, leading to recent intensive attempts for developing a transparent 10 polymer as a substitute for an inorganic glass. A transparent polymer such as poly(methyl methacrylate) and polycarbonate has excellent transparency, mechan- ical properties such as shock resistance, processability and moldability, which has been, therefore, used in various applications such as transparent components of a car and a lens, as an alternative to an inorganic glass. Meanwhile, an optical disk on which information such as sounds, images and texts is recorded and reproduced is using a laser beam, has been being rapidly extended in its use. In an optical disk used as an information recording medium, a laser beam passes on the disk body during its use. Thus, the disk is required to be optically transparent, and is strongly required to be optically homogenous for reducing reading errors of an information. When using a con- ventional polymer such as polycarbonate and poly(methyl methacrylate), there occurs a problem that a residual stress generated by some factors such as a temperature distribution, molecular orientation and volume variation near a glass- 20 transition temperature generated by cooling and fluidizing processes of a resin during casting a disk substrate, may cause a birefringence when a laser beam passes through the disk substrate. Large optical heterogeneity due to the birefringence may become a fatal defect for an optical component such as an optical disk substrate because it may cause significant problems such as reading errors of a recorded information. Hence, an optical component, typically an optical disk substrate, is required to be made from a material with better optical characteristics than any of conven- es tional polymers, e.g., a low birefringence and excellent transparency and heat resistance. For dealing with the above problems, JP-A 63-31 4235 has disclosed a low-biref ringent polycarbonate from a spiro compound such as a homopolymeric polycarbonate of spirobiindanol or a copolymeric polycarbonate of spirobiindanol and bisphenol-A. However, the former polycarbonate has a low birefringence, but is practically problematic due to its poor transparency and mechanical strength, while in the latter polycarbonate, increase of bisphenol-A improves trans- 30 parency and mechanical strength, but increases the birefringence, leading to limiting its applications as an optical component. Thus, it has been strongly desired to solve these conflicting problems. JP-A 3-1 6241 3 has suggested a polymer such as a polycarbonate having a spirobichroman structure as a material with a low birefringence. However, the polymer is also practically problematic due to its poor transparency and me- chanical strength, although a homopolymeric polycarbonate of a spirobichroman derivative has a low birefringence. 35 Furthermore, for a copolymeric polycarbonate of a spirobichroman derivative and bisphenol A, increase of bisphenol A causes increase of a birefringence although it improves transparency and mechanical strength. Thus, it has been desired to solve these conflicting problems. Polyimides are well known as an engineering plastic with a high heat resistance. Polyimides, however, have good heat resistance, but a high birefringence. For example, the polyimide described in JP-A 8-504967 may be used as an 40 optical material, but has a birefringence of at least 0.01 level which is not adequately low. Furthermore, according to "PHOTOSENSITIVE POLYIMIDE -Fundamentals and Applications", edited by KAZUYUKI HORIE and TAKASHI YA- MASHITA TECHNOMIC PUBLISHING COMP, p. 300 (1995), commercially available polyimides have a birefringence of at least 0. 1 ; even a special fluorinated polyimide indicates a birefringence of 0.01 level. Thus, these may significantly improve heat resistance, but considerably limit their use as an optical component. 45 Aromatic polyimides are also known as an engineering plastic. However, optical properties, particularly a refractive index and a birefringence, have not been described very much for aromatic polyimides, and thus, substantially no data on the properties are available. A polyimide can be prepared by reaction of a diamine with a tetracarboxylic dianhydride, and is excellent in some properties such as heat resistance, mechanical strength, chemical resistance, dimensional stability, incombustibility so and electric insulation. Hence, polyimides have been extensively used in the fields of electric and electronic devices. In particular, they are anticipated to be more extensively and more largely used, in the fields requiring good heat resistance and electric insulation. Polyimides have a high heat resistance and a high chemical resistance. It is advantageous in terms of its application to an optical component, while it is not necessarily advantageous in terms of processability. For example, Kapton or 55 Vespel (DuPont) and Upilex (Ube Industries Ltd.), represented by formulas (A) and (B), are well-known polyimides. Since these polyimides are insoluble, infusible and less processable, special and inefficient molding techniques such as compression and cutting or solution film casting of a polyamide acid as a precursor for a polyimide, have been used to prepare a molding or film. 2 EP 0 822 545 A2 O O To solve the above problems, Ultem (G.E.; USPs 3847867 and 3847869), a polyetherimide represented by formula (C) has been developed. This polyetherimide can be subject to melt process, and is soluble in a general solvent such as amides, phenols and halogenated hydrocarbons and thus has excellent processability as a solution. The polyeth- erimide, however, has a glass-transition temperature of about 215 °C, indicating an inadequate heat resistance. O Q The polyimides represented by formulas (D) and (E) (both are manufactured by Mitsui Toatsu Chemicals Inc.; JP- As 62-205124 and 2-18419) are known as those which has high heat resistance and can be subject to melt process. These polyimides have a glass-transition temperature of 250 °C level, indicating a better heat resistance than the above polyetherimide (C) and can be subject to melt process, but has a poor solubility in a solvent and thus is difficult to be processed as a solution. o o (D) EP 0 822 545 A2 O 0 II II c c / f■N c c II II o o (E) The heat-resistant adhesive polyimide represented by formula (F) is also known (JP-B 5-74637). The polyimide has the same level of heat resistance and thermal plasticity as those of formulas (D) and (E), as well as exhibits sufficient solubility in a solvent to be processable by melt process and solution molding depending on selection of the group R; wherein Ft' represents a particular tetravalent aromatic group. However, as aircraft and space instruments as well as electric and electronic devices will be advanced, higher heat resistance, i.e., a high glass-transition temperature, will be desired. The above polyetherimide of formula (C) and the polyimide of formula (D) have a number of bending groups in their principal chain for improving melt fluidity and solubility.
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