JPH02115222A - Material for optical instrument - Google Patents
Material for optical instrumentInfo
- Publication number
- JPH02115222A JPH02115222A JP26812888A JP26812888A JPH02115222A JP H02115222 A JPH02115222 A JP H02115222A JP 26812888 A JP26812888 A JP 26812888A JP 26812888 A JP26812888 A JP 26812888A JP H02115222 A JPH02115222 A JP H02115222A
- Authority
- JP
- Japan
- Prior art keywords
- phenyl
- group
- formula
- hydroxyphenyl
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 17
- 230000003287 optical effect Effects 0.000 title claims description 25
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- -1 biphenylyl Chemical group 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- BKTRENAPTCBBFA-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-phenylphenyl)propan-2-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 BKTRENAPTCBBFA-UHFFFAOYSA-N 0.000 abstract description 3
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- GZEBECRWRATTQK-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-phenylphenyl)-1-phenylethyl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C=1C=C(C(O)=CC=1)C=1C=CC=CC=1)(C)C1=CC=CC=C1 GZEBECRWRATTQK-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- DNCLEPRFPJLBTQ-UHFFFAOYSA-N 2-cyclohexyl-4-[1-(3-cyclohexyl-4-hydroxyphenyl)cyclohexyl]phenol Chemical compound OC1=CC=C(C2(CCCCC2)C=2C=C(C(O)=CC=2)C2CCCCC2)C=C1C1CCCCC1 DNCLEPRFPJLBTQ-UHFFFAOYSA-N 0.000 description 1
- WKVWOPDUENJKAR-UHFFFAOYSA-N 2-cyclohexyl-4-[2-(3-cyclohexyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(C2CCCCC2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1CCCCC1 WKVWOPDUENJKAR-UHFFFAOYSA-N 0.000 description 1
- XPJHDKGPMKPLRW-UHFFFAOYSA-N 3-[1-(3-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=CC(O)=CC=1C(C)C1=CC=CC(O)=C1 XPJHDKGPMKPLRW-UHFFFAOYSA-N 0.000 description 1
- OTSCPDDAOASPMM-UHFFFAOYSA-N 4-(4-hydroxy-3-phenylphenyl)-2-phenylphenol Chemical group OC1=CC=C(C=2C=C(C(O)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 OTSCPDDAOASPMM-UHFFFAOYSA-N 0.000 description 1
- DFAXBVOHLIMORA-UHFFFAOYSA-N 4-[(4-hydroxy-3-phenylphenyl)methyl]-2-phenylphenol Chemical compound C1=C(C=2C=CC=CC=2)C(O)=CC=C1CC(C=1)=CC=C(O)C=1C1=CC=CC=C1 DFAXBVOHLIMORA-UHFFFAOYSA-N 0.000 description 1
- JRMCUXIQWVQWPZ-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-phenylphenyl)-1-(2-phenylphenyl)ethyl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C=1C(=CC=CC=1)C=1C=CC=CC=1)(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 JRMCUXIQWVQWPZ-UHFFFAOYSA-N 0.000 description 1
- DTZMXGCBQJBCGV-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-phenylphenyl)-1-(4-phenoxyphenyl)ethyl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C=1C=C(C(O)=CC=1)C=1C=CC=CC=1)(C)C(C=C1)=CC=C1OC1=CC=CC=C1 DTZMXGCBQJBCGV-UHFFFAOYSA-N 0.000 description 1
- GKMIYDCPSZVJFY-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-phenylphenyl)-2-phenylethyl]-2-phenylphenol Chemical compound OC1=CC=C(C(CC=2C=CC=CC=2)C=2C=C(C(O)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 GKMIYDCPSZVJFY-UHFFFAOYSA-N 0.000 description 1
- VQCOOYBPEMJQBN-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-phenylphenyl)cyclohexyl]-2-phenylphenol Chemical compound OC1=CC=C(C2(CCCCC2)C=2C=C(C(O)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 VQCOOYBPEMJQBN-UHFFFAOYSA-N 0.000 description 1
- BNGGVJXIUPQHJA-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-phenylphenyl)ethyl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 BNGGVJXIUPQHJA-UHFFFAOYSA-N 0.000 description 1
- VMCGGTQGFTZWCU-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-phenylphenyl)octan-2-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(CCCCCC)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 VMCGGTQGFTZWCU-UHFFFAOYSA-N 0.000 description 1
- JJIAQFSVASVDNQ-UHFFFAOYSA-N 4-[3-(4-hydroxy-3-phenylphenyl)pentan-3-yl]-2-phenylphenol Chemical compound C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(CC)(CC)C(C=1)=CC=C(O)C=1C1=CC=CC=C1 JJIAQFSVASVDNQ-UHFFFAOYSA-N 0.000 description 1
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 208000014380 ornithine aminotransferase deficiency Diseases 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は光学機器用素材に関し、ディジタルオーディオ
ディスク、ディジタルビデオディスク、光メモリ−ディ
スクなどのディスク基板、光学レンズ、プリズム、光フ
ァイバー等に適した素材に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to materials for optical equipment, and materials suitable for disc substrates such as digital audio discs, digital video discs, and optical memory discs, optical lenses, prisms, optical fibers, etc. Regarding.
従来、光学機器用素材としては透明性の点からアクリル
樹脂、ポリカーボネート樹脂等が用いられている。アク
リル樹脂は光学的均一性には優れているが吸湿による変
形があり、光ディスク等の精密成形品には使用できない
という問題がある。Conventionally, acrylic resins, polycarbonate resins, and the like have been used as materials for optical devices due to their transparency. Although acrylic resin has excellent optical uniformity, it suffers from deformation due to moisture absorption, making it unusable for precision molded products such as optical discs.
また、ポリカーボネート樹脂は透明性、機械的強度、耐
熱性に優れてはいるものの、流動性が低いことから成形
品の光学的均一性がなくなり、複屈折が生じるという問
題がある。Furthermore, although polycarbonate resins have excellent transparency, mechanical strength, and heat resistance, their low fluidity causes optical uniformity of molded products, resulting in birefringence.
［発明が解決しようとする課題］
本発明の目的は、このような事情のもとで、光学機器用
素材として要求されている透明性、耐熱性、機械的強度
、耐水性を全て満足する光学的に均一な光学機器用素材
を提供することにある。[Problems to be Solved by the Invention] Under these circumstances, the purpose of the present invention is to develop an optical material that satisfies all of the transparency, heat resistance, mechanical strength, and water resistance required of materials for optical equipment. The objective is to provide a material for optical equipment that is uniform in terms of quality.
本発明者らは、前記目的を達成するために鋭意研究を重
ねた結果、特定の構造を有するポリホルマール樹脂から
なる素材が光学機器用素材として前記目的に適した素材
であることを見い出し、この知見に基づいて本発明を完
成するに至った。As a result of extensive research in order to achieve the above object, the present inventors discovered that a material made of polyformal resin having a specific structure is a material suitable for the above object as a material for optical equipment. The present invention was completed based on the findings.
すなわち、本発明は、−形式
〔ここで、式（１）中の×はフェニル基又はシクロヘキ
シル基を示し、Ｙは単結合、
−Ｃ−（但し、Ｒ１及びＲ２は水素原子、炭素数１〜６
Ｒ２のアルキル基、フェニル基、ビフェニリルル基又は
フェノキシフェニル基を示す。）又は＼ｌ
示す。〕で表される繰り返し単位を有し、かつ極限粘度
〔η〕が０．２〜５．０ ａ／ ｇであるポリホルマー
ル樹脂からなることを特徴とする光学機器用素材を提供
するものである。That is, the present invention provides a -format [wherein x in formula (1) represents a phenyl group or a cyclohexyl group, Y represents a single bond, -C- (however, R1 and R2 are hydrogen atoms, carbon atoms 1 to 6
R2 represents an alkyl group, phenyl group, biphenylyl group or phenoxyphenyl group. ) or \l Show. ] and has a limiting viscosity [η] of 0.2 to 5.0 a/g. .
前記Ｒ１及びＲ２のアルキル基の具体例としては、例え
ば、メチル基、エチル基、ｎ−プロピル基、イソプロピ
ル基、ｎ−ブチル基、１−メチルプロピル基、２−メチ
ルプロピル基、ｔｅｒｔ−７’チル基、ｎ−ペンチル基
、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基ぐ
イソヘキシル基等を挙げることができる。Specific examples of the alkyl groups for R1 and R2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-7' Examples include tyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group and isohexyl group.
なお、Ｒ′とＲ２とは、互いに同一の基であってもよく
、異なった基であってもよい。Note that R' and R2 may be the same group or different groups.
シクロペンチリデン基、１，１−シクロへキシリデン基
、１．１−シクロオクチリデン基等を挙げることができ
る。これらの中でも、特に１．１−シクロへキシリデン
基等が好ましい。Examples include a cyclopentylidene group, a 1,1-cyclohexylidene group, and a 1,1-cyclooctylidene group. Among these, 1,1-cyclohexylidene group and the like are particularly preferred.
前記−形式（１）で表される繰り返し単位からなるポリ
ホルマール樹脂は、例えば、１種または２種以上の次の
一般式
で表される二価フェノール類〔但し、Ｘ及びＹは前記と
同じ意味を有する。〕とメチレンシバライドとを、溶媒
中で、アルカリ金属水酸化物の存在下に反応させること
によって得ることができる。The polyformal resin consisting of the repeating unit represented by the above-mentioned format (1) is, for example, one or more dihydric phenols represented by the following general formula [where X and Y are the same as above] have meaning. ] and methylene cybaride in a solvent in the presence of an alkali metal hydroxide.
前記二価フェノール［［Ｍ）の具体例としては、例えば
、３．３′−ジフェニル−４，４′ジヒドロキシビフエ
ニル、３３′−ジシクロへキシル−４，４′−ジヒドロ
キシビフェニル、ビス（３−フェニル−４−ヒドロキシ
フェニル）メタン、１．１−ビス（３−フェニル−４−
ヒドロキシフェニル）エタン、２，２−ビス（３−フェ
ニル−４−ヒドロキシフェニル）プロパン、２゜２−ビ
ス（３−シクロへキシル−４−ヒドロキシフェニル）プ
ロパン、２．２−ビス（３−フェニル−４−ヒドロキシ
フェニル）メタン、２，２ビス（３−フェニル−４−ヒ
ドロキシフェニル）オクタン、１−フェニル−１，１−
ビス（３−フェニル−４−ヒドロキシフェニル）エタン
、１フェニル−１，１−ビス（３−シクロヘキシル４−
ヒドロキシフェニル）エタン、１−フェニル−２，２−
ビス（３−フェニル−４−ヒドロキシフェニル）エタン
、１−ビフェニリル−１，１ビス（３−フェニル−４−
ヒドロキシフェニル）エタン、１−ビフェニリル−１，
１−ビス（３フェニル−４−ヒドロキシフェニル）プロ
パン、ｌ−ビフェ・ニリルー１−フェニル−１，１−ビ
ス（３−フェニル−４−ヒドロキシフェニル）メタン、
１−（４−フェノキシフェニル）−１，１−ビス（３−
フェニル−４−ヒドロキシフェニル）エタン、３．３′
−ジシクロへキシル−４，４′−ジヒドロキシテトラフ
ェニルメタン、３．３−ビス（３−フェニル−４−ヒド
ロキシフェニル）ペンタン、１−フェニル−１，１−ビ
ス（３−フェニル−４−ヒドロキシフェニル）メタン、
１゜１−ビス（３−フェニル−４−ヒドロキシフェニル
）−１−フェニルブタン、１．１−ビス（３−フェニル
−４−ヒドロキシフェニル）シクロベンクン、１．１−
ビス（３−フェニル−４−ヒドロキシフェニル）シクロ
ヘキサン、１．１−ビス（３−シクロへキシル−４−ヒ
ドロキシフェニル）シクロヘキサン等を挙げることがで
きる。Specific examples of the dihydric phenol [[M] include 3,3'-diphenyl-4,4'dihydroxybiphenyl, 33'-dicyclohexyl-4,4'-dihydroxybiphenyl, bis(3- Phenyl-4-hydroxyphenyl)methane, 1,1-bis(3-phenyl-4-
hydroxyphenyl)ethane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2゜2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl) -4-hydroxyphenyl)methane, 2,2bis(3-phenyl-4-hydroxyphenyl)octane, 1-phenyl-1,1-
Bis(3-phenyl-4-hydroxyphenyl)ethane, 1phenyl-1,1-bis(3-cyclohexyl 4-
hydroxyphenyl)ethane, 1-phenyl-2,2-
Bis(3-phenyl-4-hydroxyphenyl)ethane, 1-biphenylyl-1,1bis(3-phenyl-4-
hydroxyphenyl)ethane, 1-biphenylyl-1,
1-bis(3phenyl-4-hydroxyphenyl)propane, 1-bife-nilyru-1-phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl)methane,
1-(4-phenoxyphenyl)-1,1-bis(3-
Phenyl-4-hydroxyphenyl)ethane, 3.3'
-dicyclohexyl-4,4'-dihydroxytetraphenylmethane, 3,3-bis(3-phenyl-4-hydroxyphenyl)pentane, 1-phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl) )methane,
1゜1-bis(3-phenyl-4-hydroxyphenyl)-1-phenylbutane, 1.1-bis(3-phenyl-4-hydroxyphenyl)cyclobencune, 1.1-
Bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, and the like can be mentioned.
これらの中でも、特に２．２−ビス（３−フェニル−４
−ヒドロキシフェニル）フロパン、２゜２−ビス（３−
シクロヘキシル−４−ヒドロキシフェニル）プロパン、
１−フェニル−１，１−ビス（３−フェニル−４−ヒド
ロキシフェニル）エタン、１−（４−フェノキシフェニ
ル）−１，１＝ヒス（３−フェニル−４ヒドロキシフエ
ニル）エタン、３，３′−ジシクロへキシル−４，４′
−ジヒドロキシテトラフェニルメタン、ｌ−フェニル−
１，１−ビス（３−シクロへキシル−４−ヒドロキシフ
ェニル）エタン、１．１−ビス（３−フェニル−４−ヒ
ドロキシフェニル）シクロヘキサン、１，１−ビス（３
−シクロへキシル−４ヒドロキシフヱニル）シクロヘキ
サン等が好適に用いられる。Among these, 2,2-bis(3-phenyl-4
-hydroxyphenyl)furopane, 2゜2-bis(3-
cyclohexyl-4-hydroxyphenyl)propane,
1-phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl)ethane, 1-(4-phenoxyphenyl)-1,1=his(3-phenyl-4hydroxyphenyl)ethane, 3,3 '-dicyclohexyl-4,4'
-dihydroxytetraphenylmethane, l-phenyl-
1,1-bis(3-cyclohexyl-4-hydroxyphenyl)ethane, 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-hydroxyphenyl)ethane
-cyclohexyl-4hydroxyphenyl)cyclohexane and the like are preferably used.
メチレンシバライドとしては、塩化メチレン、臭化メチ
レンが用いられるが、好ましくは塩化メチレンが用いら
れる。As methylene cybaride, methylene chloride and methylene bromide are used, and methylene chloride is preferably used.
マタ、アルカリ金属水酸化物としては、水酸化ナトリウ
ム、水酸化カリウム等が用いられるが、好ましくは水酸
化ナトリウムが用いられる。As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide, etc. are used, and sodium hydroxide is preferably used.
また、溶媒としては、例えばＮ−メチルピロリドン、Ｎ
、Ｎ−ジメチルホルムアミド、ジメチルアセトアミド、
ジメチルイミダゾリジノン、スルホラン、ジメチルスル
ホキシドが用いられる。Further, as a solvent, for example, N-methylpyrrolidone, N-methylpyrrolidone,
, N-dimethylformamide, dimethylacetamide,
Dimethylimidazolidinone, sulfolane, and dimethylsulfoxide are used.
各反応物の使用量は、二価フェノール１に対して重量比
でメチレンシバライドが好ましくは１．０５〜５となる
ように、アルカリ金属水酸化物が好ましくは２．１〜３
．０、さらに好ましくは２．２〜２゜８となるように用
いられ、溶媒は二価フェノールの濃度が好ましくは０．
１〜３モル／！、さらに好ましくは０．５〜２モル／ｌ
となるように用いられる。The amount of each reactant to be used is such that methylene cybaride is preferably used in a weight ratio of 1.05 to 5, and alkali metal hydroxide is preferably used in a weight ratio of 2.1 to 3.
．． The concentration of dihydric phenol in the solvent is preferably 0.0, more preferably 2.2 to 2.8.
1-3 moles/! , more preferably 0.5 to 2 mol/l
It is used as follows.
反応は通常２０〜１００°Ｃ１好ましくは５０〜８０°
Ｃの範囲の温度で行われる。反応時間は反応温度によっ
て左右されるが、通常１〜２０時間、好ましくは２〜５
時間である。The reaction is usually 20-100°C, preferably 50-80°C.
It is carried out at a temperature in the range of C. The reaction time depends on the reaction temperature, but is usually 1 to 20 hours, preferably 2 to 5 hours.
It's time.
本発明の光学機器用素材として用いられる前記ポリホル
マール樹脂は、極限粘度〔η〕が０．２〜５．０ａ／ｇ
のものが用いられる。極限粘度〔η〕が０．２ａ／ｇ未
満では機械的強度が十分でなく、５．０ｄｌ／ｇを超え
ると流動性が低く、成形品の残留応力にもとづ（複屈折
が大きくなり、光学機器用素材に適さなくなる。The polyformal resin used as the material for optical equipment of the present invention has an intrinsic viscosity [η] of 0.2 to 5.0 a/g.
are used. If the intrinsic viscosity [η] is less than 0.2 a/g, the mechanical strength is insufficient, and if it exceeds 5.0 dl/g, the fluidity is low, and due to the residual stress of the molded product (birefringence increases, It becomes unsuitable as a material for optical equipment.
また、このポリホルマール樹脂は、任意の割合の２種以
上の前記繰り返し単位からなる共重合体であってもよい
。これらは、１種単独で用いてもよくあるいは、２種以
上を任意の割合で混合物等として併用することもできる
。Moreover, this polyformal resin may be a copolymer consisting of two or more types of repeating units in arbitrary proportions. These may be used alone or in combination of two or more in any proportion, such as a mixture.
〔実施例〕
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。[Examples] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited thereto.
実施例１
反応器に、２．２−ビス（３−フェニル−４−ヒドロキ
シフェニル）プロパン１９０ｇ（０，５モル）、水酸化
ナトリウム４４ｇ（１，１モル）、塩化メチレン５１ｇ
（０，６モル）及び溶媒のＮ−メチルピロリドン５００
−を入れ、攪拌下に塩化メチレンの還流温度で４時間反
応させた。反応終了後、生成物を冷却して塩化メチレン
２１を加えて希釈し、０．０１規定の塩酸及び水でそれ
ぞれ洗浄し、有機層を分離しメタノール中に注入してポ
リホルマール樹脂を析出回収した。得られたポリホルマ
ール樹脂の収量は１８３ｇであり、このものの塩化メチ
レンを溶媒とする０、５ｇ／ａ、０゜４ｇ／Ｌｉ１．０
．３ｇ／ｄｉ濃度の溶液の２０°Ｃにおける還元粘度〔
ηｓｐ／ｃ）より求めた極限粘度〔η〕は０゜４７ｄｌ
／ｇであった。また、ガラス転移温度は１２０°Ｃであ
った。さらに、プロトン核磁気共鳴スペクトルから、こ
のポリホルマール樹脂は次の繰り返し単位からなること
が判明した。Example 1 In a reactor, 190 g (0.5 mol) of 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 44 g (1.1 mol) of sodium hydroxide, and 51 g of methylene chloride
(0.6 mol) and solvent N-methylpyrrolidone 500
- and reacted for 4 hours at the reflux temperature of methylene chloride while stirring. After the reaction was completed, the product was cooled, diluted with 21 methylene chloride, washed with 0.01N hydrochloric acid and water, and the organic layer was separated and poured into methanol to precipitate and recover the polyformal resin. . The yield of the obtained polyformal resin was 183 g, and the yield of this polyformal resin was 0.5 g/a, 0°4 g/Li1.0 using methylene chloride as a solvent.
．． Reduced viscosity at 20°C of a solution with a concentration of 3 g/di [
The intrinsic viscosity [η] calculated from ηsp/c) is 0°47dl
/g. Further, the glass transition temperature was 120°C. Furthermore, proton nuclear magnetic resonance spectroscopy revealed that this polyformal resin consisted of the following repeating units.
次に、このポリホルマール樹脂につき、光線透過率、ガ
ラス状態の光弾性係数、ゴム状態の光弾性係数、射出成
形品の複屈折及び屈折率を次の方法で測定した。Next, for this polyformal resin, the light transmittance, the photoelastic coefficient in the glass state, the photoelastic coefficient in the rubber state, and the birefringence and refractive index of the injection molded product were measured by the following methods.
（１）光線透過率
日立製作所製自記分光光度計で波長６３３ｎｍの光線透
過率を測定した。(1) Light transmittance The light transmittance at a wavelength of 633 nm was measured using a self-recording spectrophotometer manufactured by Hitachi.
（２）ガラス状態の光弾性係数
樹脂を熱プレスし、厚み０．２〜０．３１１１１Ｉ＋の
フィルムを作製し、この試料に加えた応力と複屈折より
算出した。(2) Photoelastic coefficient in a glass state was heat-pressed to produce a film with a thickness of 0.2 to 0.31111I+, and the photoelastic coefficient was calculated from the stress and birefringence applied to this sample.
（３）ゴム状態の光弾性係数
樹脂をキャピラリーレオメータ−より押し出し、それを
巻き取り機で巻き取り、溶融紡糸し、糸に加えられた応
力と複屈折より算出した。(3) Photoelastic coefficient in a rubber state was extruded from a capillary rheometer, wound up with a winder, melt-spun, and calculated from the stress and birefringence applied to the yarn.
（４）成形品の複屈折
住友重機製ミニマント成形機により厚み１．２ ｍｍの
平板を成形し、その成形品の中心の複屈折をエリプソメ
ーターにより測定した。(4) Birefringence of molded product A flat plate with a thickness of 1.2 mm was molded using a minimant molding machine manufactured by Sumitomo Heavy Industries, and the birefringence at the center of the molded product was measured using an ellipsometer.
（５）屈折率 アツベの屈折率計により測定した。(5) Refractive index Measured using an Atsube refractometer.
以上の結果をまとめて第１表に示す。The above results are summarized in Table 1.
実施例２
二価フェノールとして、■−フェニルー１．１ビス（３
−フェニル−４−ヒドロキシフェニル）エタン２２１ｇ
（０，５モル）を用いたほかは実施例１と同様の操作を
して、ポリホルマール樹脂２１５ｇを得た。このものの
極限粘度〔η〕は０．４９ａ／ｇであり、ガラス転移温
度は１４９°Ｃであった。また、プロトン核磁気共鳴ス
ペクトルから、このポリホルマール樹脂は次の繰り返し
単位からなることが判明した。このものの光学的性質は
第１表に示すとおりであった。Example 2 ■-Phenyl-1.1bis(3
-Phenyl-4-hydroxyphenyl)ethane 221g
(0.5 mol) was used, but the same operation as in Example 1 was carried out to obtain 215 g of polyformal resin. The intrinsic viscosity [η] of this product was 0.49 a/g, and the glass transition temperature was 149°C. Further, from proton nuclear magnetic resonance spectroscopy, it was found that this polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
リホルマール樹脂２５２ｇを得た。このものの極限粘度
〔η〕は０．４２社／ｇであり、ガラス転移温度は１３
９°Ｃであった。また、プロトン核磁気共鳴スペクトル
から、このポリホルマール樹脂は次の繰り返し単位から
なることが判明した。このものの光学的性質は第１表に
示すとおりであった。252 g of reformal resin was obtained. The intrinsic viscosity [η] of this material is 0.42/g, and the glass transition temperature is 13
It was 9°C. Further, from proton nuclear magnetic resonance spectroscopy, it was found that this polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
実施例３
二価フェノールとして１−（４−フヱノキシフェニル）
−１，１−ビス（３−フェニル−４−ヒドロキシフェニ
ル）エタン２６７ｇ（０，５モル）を用いたほかは実施
例１と同様の操作をして、ポ実施例４
二価フェノールとして、１，１−ビス（３−フェニル−
４−ヒドロキシフェニル）シクロヘキサン２１１ｇ（０
，５モル）を用いたほかは実施例１と同様の操作をして
、ポリホルマール樹脂２０３ｇを得た。・このものの極
限粘度〔η〕は０．４７ｄＪｌ７ｇであり、ガラス転移
温度は１３９°Ｃであった。Example 3 1-(4-phenoxyphenyl) as dihydric phenol
-1,1-Bis(3-phenyl-4-hydroxyphenyl)ethane 267 g (0.5 mol) was used, but the same procedure as in Example 1 was carried out to prepare 1 as dihydric phenol. ,1-bis(3-phenyl-
211 g (4-hydroxyphenyl)cyclohexane (0
, 5 mol) was used, and the same operation as in Example 1 was carried out to obtain 203 g of polyformal resin. - The intrinsic viscosity [η] of this product was 0.47 dJl7g, and the glass transition temperature was 139°C.
また、プロトン核磁気共鳴スペクトルから、このポリホ
ルマール樹脂は次の繰り返し単位からなることが判明し
た。このものの光学的性質は第１表に示すとおりであっ
た。Further, from proton nuclear magnetic resonance spectroscopy, it was found that this polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
ことが判明した。このものの光学的性質は第１表に示す
とおりであった。It has been found. The optical properties of this product were as shown in Table 1.
実施例５
二価フェノールとして、２．２−ビス（３−シクロヘキ
シル−４−ヒドロキシフェニル）プロパン１９２ｇ（０
，５モル）を用いたほかは実施例１と同様の操作をして
、ポリホルマール樹脂１８４ｇを得た。このものの極限
粘度〔η〕は０．４４ｃ＋Ｊ！／ｇであり、ガラス転移
温度は１１２°Ｃであった。Example 5 As a dihydric phenol, 192 g of 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane (0
, 5 mol) was used, and the same operation as in Example 1 was carried out to obtain 184 g of polyformal resin. The intrinsic viscosity [η] of this product is 0.44c+J! /g, and the glass transition temperature was 112°C.
また、プロトン核磁気共鳴スペクトルから、このポリホ
ルマール樹脂は次の繰り返し単位からなる実施例６
二価フェノールとして、１．１−ビス（３−シクロへキ
シル−４−ヒドロキシフェニル）シフ、ロヘキサン２１
６ｇ（０，５モル）を用いたほかは実施例１と同様の操
作をして、ポリホルマール樹脂１９８ｇを得た。このも
のの極限粘度［η］は０゜４７ｄ／ｇであり、ガラス転
移温度は１２８°Ｃであった。また、プロトン核磁気共
鳴スペクトルから、このポリホルマール樹脂は次の繰り
返し単位からなることが判明した。このものの光学的性
質は第１表に示すとおりであった。Moreover, from the proton nuclear magnetic resonance spectrum, this polyformal resin is composed of the following repeating units Example 6 Dihydric phenol: 1,1-bis(3-cyclohexyl-4-hydroxyphenyl) Schiff, lohexane 21
198 g of polyformal resin was obtained by carrying out the same operation as in Example 1 except that 6 g (0.5 mol) was used. The intrinsic viscosity [η] of this product was 0°47 d/g, and the glass transition temperature was 128°C. Further, from proton nuclear magnetic resonance spectroscopy, it was found that this polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
実施例７
二価フェノールとして、１−フェニル−１，１−ヒス（
３−シクロヘキシル−４−ヒドロキシフェニル）エタン
２２７ｇ（０，５モル）を用いたほかは実施例１と同様
の操作をして、ポリホルマール樹脂１９６ｇを得た。こ
のものの極限粘度〔η〕は０．４２ａ／ｇであり、ガラ
ス転移温度は１４０℃であった。また、プロトン核磁気
共鳴スペクトルから、このポリホルマール樹脂は次の繰
り返し単位からなることが判明した。このものの光学的
性質は第１表に示すとおりであった。Example 7 As a dihydric phenol, 1-phenyl-1,1-his (
The same procedure as in Example 1 was carried out except that 227 g (0.5 mol) of 3-cyclohexyl-4-hydroxyphenyl)ethane was used to obtain 196 g of a polyformal resin. The intrinsic viscosity [η] of this product was 0.42 a/g, and the glass transition temperature was 140°C. Further, from proton nuclear magnetic resonance spectroscopy, it was found that this polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
実施例８
二価フェノールとして、３．３’ −ジシクロへキシル
−４，４′−ジヒドロキシ−テトラフェニルメタン２５
９ｇ（０，５モル）を用いたほがは実施例１と同様の操
作をして、ポリホルマール樹脂２５１ｇを得た。このも
のの極限粘度〔η〕は０゜４１ｄＪｌ／ｇであり、ガラ
ス転移温度は１５３°Ｃであった。また、プロトン核磁
気共鳴スペクトルから、このポリホルマール樹脂は次の
繰り返し単位からなることが判明した。このものの光学
的性質は第１表に示すとおりであった。Example 8 As dihydric phenol, 3,3'-dicyclohexyl-4,4'-dihydroxy-tetraphenylmethane 25
Using 9 g (0.5 mol) of the hoga, the same operation as in Example 1 was carried out to obtain 251 g of polyformal resin. The intrinsic viscosity [η] of this product was 0°41 dJl/g, and the glass transition temperature was 153°C. Further, from proton nuclear magnetic resonance spectroscopy, it was found that this polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
比較例に
価フェノールとして、２，２−ビス（４−ヒドロキシフ
ェニル）プロパン〔ビスフェノールＡ） １１４ｇ （
０，５モル）を用いたほかは実施例１と同様の操作をし
て、ポリホルマール樹脂１１０ｇを得た。このものの極
限粘度〔η〕は０．５４ｃＵ／ｇであり、ガラス転移温
度は９０°Ｃであった。In a comparative example, 114 g of 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] was used as a phenol.
0.5 mol) was used, but the same operation as in Example 1 was carried out to obtain 110 g of polyformal resin. The intrinsic viscosity [η] of this product was 0.54 cU/g, and the glass transition temperature was 90°C.
このポリホルマール樹脂は次の繰り返し単位からなるも
のである。このものの光学的性質は第１表に示すとおり
であった。This polyformal resin consists of the following repeating units. The optical properties of this product were as shown in Table 1.
本発明により得られた光学機器用素材は、透明性、耐熱
性、機械的強度、耐水性に優れると共に光学的均一性に
も優れており、その工業的価値は極めて大である。The material for optical equipment obtained by the present invention has excellent transparency, heat resistance, mechanical strength, water resistance, and optical uniformity, and has extremely high industrial value.
Claims (1)
シル基を示し、Ｙは単結合、 ▲数式、化学式、表等があります▼（但し、Ｒ＾１及び
Ｒ＾２は水素原子、炭素数１〜６のアルキル基、フェニ
ル基、ビフ ェニリル基又はフェノキシフェニル基を示す。 ）又は ▲数式、化学式、表等があります▼（但し、ｎは４〜８
の整数を示す。 ）を示す。〕で表される繰り返し単位を有し、かつ極限
粘度〔η〕が０．２〜５．０ｄｌ／ｇであるポリホルマ
ール樹脂からなることを特徴とする光学機器用素材。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [Here, X in formula [I] represents a phenyl group or cyclohexyl group, Y is a single bond, ▲ Mathematical formula , chemical formulas, tables, etc. ▼ (However, R^1 and R^2 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a biphenylyl group, or a phenoxyphenyl group.) or ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (However, n is 4 to 8
indicates an integer. ) is shown. ] A material for optical equipment, characterized by being made of a polyformal resin having a repeating unit represented by the following formula and having an intrinsic viscosity [η] of 0.2 to 5.0 dl/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26812888A JPH02115222A (en) | 1988-10-26 | 1988-10-26 | Material for optical instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26812888A JPH02115222A (en) | 1988-10-26 | 1988-10-26 | Material for optical instrument |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02115222A true JPH02115222A (en) | 1990-04-27 |
Family
ID=17454273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26812888A Pending JPH02115222A (en) | 1988-10-26 | 1988-10-26 | Material for optical instrument |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02115222A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7691477B2 (en) * | 2003-07-25 | 2010-04-06 | Bayer Materialscience Ag | Polyformals as a coextrusion protective layer on polycarbonate |
-
1988
- 1988-10-26 JP JP26812888A patent/JPH02115222A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7691477B2 (en) * | 2003-07-25 | 2010-04-06 | Bayer Materialscience Ag | Polyformals as a coextrusion protective layer on polycarbonate |
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