JPS58142931A - Optical resin composition and optical element - Google Patents
Optical resin composition and optical elementInfo
- Publication number
- JPS58142931A JPS58142931A JP2638082A JP2638082A JPS58142931A JP S58142931 A JPS58142931 A JP S58142931A JP 2638082 A JP2638082 A JP 2638082A JP 2638082 A JP2638082 A JP 2638082A JP S58142931 A JPS58142931 A JP S58142931A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- crosslinking agent
- polymer
- optical
- monomer
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 26
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 14
- -1 aromatic divinyl compound Chemical class 0.000 abstract description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012662 bulk polymerization Methods 0.000 abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 2
- 150000002825 nitriles Chemical class 0.000 abstract description 2
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CMHULLZFVLTEFN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)(F)F CMHULLZFVLTEFN-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 101150046432 Tril gene Proteins 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical class 0.000 description 1
- 238000001053 micromoulding Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は射出成層、圧縮成型等によって作られるプラス
チック光学素子及びこれに用いられる光学用樹脂組成物
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a plastic optical element made by injection layering, compression molding, etc., and an optical resin composition used therein.
プラスチック光学素子はガラス製のものに比べて軽い、
耐衝撃性が高い、研摩が不要で大量生産が容易である、
非球面レンズが量産できる等の利点を有しているため近
年その需要、が増大しつつある。しかLl一方プラスチ
ック光学素子はガラス製のものに比へII造上の画ある
いはプラスチック素材そのものの面から来る時性のため
に精度が悪く、又屈折率の選択の幅が小さい、複屈折が
大奮い、熱安定性が悪い岬の欠点を有しておりこれまで
、これらの点がプラスチック光学素子の使用を阻書する
要因となっていた。時に、プラスチック光学素子はガラ
ス製のものに比べて線膨張係数が1オーダー太き(、結
果として温度変化による面精度の悪化や、屈折率の温度
依存性が大きいことによる光学素子設計上の制約等大き
な問題があり、より熱安定性の良好な線膨張係数の小さ
いプラスチック光学素子の開発が望まれてきた。Plastic optical elements are lighter than glass ones.
High impact resistance, no polishing required, easy mass production.
Demand for aspherical lenses has been increasing in recent years because they have advantages such as being able to be mass-produced. However, compared to glass optical elements, plastic optical elements have poor precision due to the temporal characteristics of the image on the structure or the plastic material itself, and also have a small range of refractive index selection and large birefringence. However, these problems have been factors that have hindered the use of plastic optical elements until now. Plastic optical elements sometimes have linear expansion coefficients that are one order of magnitude larger than those made of glass (as a result, surface precision deteriorates due to temperature changes, and optical element design is constrained by the large temperature dependence of the refractive index). There have been major problems such as the development of plastic optical elements with better thermal stability and a smaller coefficient of linear expansion.
そこで本発明の目的は、熱安定性の良好な光学用樹脂組
成物及び光学用素子tm供することにある。Therefore, an object of the present invention is to provide an optical resin composition and an optical element TM having good thermal stability.
本発明の他の目的は屈折率の温度依存性が小さい光学用
樹脂組成物及び光学用素子を提供することにある。Another object of the present invention is to provide an optical resin composition and an optical element whose refractive index has low temperature dependence.
本発明のさらに他の目的は温度変化による面精度の悪化
の少ない光学層IIIIi111[酸物及び光学用素子
を提供することにある。Still another object of the present invention is to provide an optical layer IIIi111 (acid and optical element) in which the surface precision is less deteriorated due to temperature changes.
本発明の目的は1単量体に対し、o、ooi〜2L)重
量−の少なくとも一種の架橋剤を加えて反応させてなる
ビニル系重合体(以下本発明の重合体という)を主成分
として食む光学用樹脂組成物、及び該樹脂組成物を成型
して得られる光学用素子によって達成される。The object of the present invention is to use as a main component a vinyl polymer (hereinafter referred to as the polymer of the present invention) obtained by adding and reacting at least one crosslinking agent of o, ooi to 2 L) by weight to one monomer. This is achieved by an edible optical resin composition and an optical element obtained by molding the resin composition.
本発明の重合体の製造に使用される架橋剤は、重合性の
二重結合を二個以上もつ化合物であり、例えばジビニル
ベンゼン、ジビニルナフタレン、およびそれらの誘導体
のような芳香族ジビニル化合物、例えばエチレングリコ
ールジメタクリレート、エチレングリコールジアクリレ
ート、トリエチレングリコールジメタクリレート、トリ
エチレングリコールジアクリレー)、トリメチ四−ルプ
ロパンシアクリレージ、アリルメタクリレージ1、・1
″□ ・。The crosslinking agent used in the production of the polymer of the present invention is a compound having two or more polymerizable double bonds, such as aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof, e.g. ethylene glycol dimethacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate), trimethy4-propane cyacrylate, allyl methacrylate 1, 1
″□・.
?)ラエチレングリコールジメ□タクリレート、1゜3
−ブタンジオールジメタクリレートなどの知音ジエチレ
ン性カルボン酸エステル、ジビニルエーテルなど全ての
ジビニル化合物および)リメチ田−ルプνバンドリアク
リレーFのような3個以上のビニル基をもつ化合物が挙
げられる。架橋剤は、一種または二種以上の併用の何れ
の態様でも差支えない0架橋剤の量は全単量体重量を基
礎にして0.001〜a)重量−の範囲が適当である。? ) Laethylene glycol dimethacrylate, 1゜3
Examples include all divinyl compounds such as diethylenic carboxylic acid esters such as -butanediol dimethacrylate, divinyl ether, and compounds having three or more vinyl groups such as divinyl acrylate F. The crosslinking agent may be used alone or in combination of two or more types. The amount of the crosslinking agent is suitably in the range of 0.001 to a) weight based on the total monomer weight.
添加量がこの範囲より多過ぎると不溶不融となり、成型
上好ましくない結果を与え、逆に少なくすぎると効果が
薄れる傾向を有する。架橋剤の量は分子量関節剤との兼
ね会いもあるが更に好ましくは0.5〜lO重量襲の範
囲である。If the amount added is too large than this range, it becomes insoluble and infusible, giving unfavorable results in terms of molding.On the other hand, if the amount added is too small, the effect tends to be weakened. The amount of crosslinking agent is more preferably in the range of 0.5 to 10% by weight, although there is a trade-off with the molecular weight of the articulating agent.
架橋剤を加えると、重合体は高分子量化し、極端に増量
させると網目構造が発達し、成型不能となる慣れがある
。これを抑sttするために分子量調節剤即ち、一般的
に連鎖移動剤と呼ばれ、生長途中の連鎖を捕獲せしめ、
分子量の増加を止め同時にm*された連鎖種は再び連鎖
反応を開始させるものを用いるζ七ができる。When a crosslinking agent is added, the polymer has a high molecular weight, and if the amount is increased excessively, a network structure develops, making it impossible to mold. In order to suppress this, molecular weight regulators, generally called chain transfer agents, are used to capture chains in the process of growth.
At the same time, the chain species that has been subjected to m* can be converted to ζ7 using a species that stops the increase in molecular weight and starts the chain reaction again.
分子量調節の度合により分子量調節剤の種類および量が
選ばれるが、極く少量で効果のあるものとしては、ラウ
リルメルカプタン、フェニルメルカプタン、ブチルメル
カプタン、ドデシルメルカプタンなどのメルカブタ、ン
訓、四塩化jll素、四臭化炭素などのハpゲン化炭素
などがあり、また比較的多量に加えて効果のあるものと
してシルエン、イソプロピルベンゼンなどの置換芳香族
化合物、トリクロル酢酸、トリブリム酢讃などの置換脂
肪酸などがある。會た単量体として重合体中に重合され
て含有されるべくして加えられ、しかも分子量調節剤と
しても効果のあるものとして、プソビレン、インブチレ
ン、α−メチルスチレン、アリルベンゼン、酢酸アリル
、アリデンク田リド、などのアリル化合物などが挙げら
れる。分子量関節剤は一種または二種以上併用の何れで
もよい。The type and amount of the molecular weight modifier are selected depending on the degree of molecular weight control, but examples of those that are effective in extremely small amounts include mercaptans such as lauryl mercaptan, phenyl mercaptan, butyl mercaptan, and dodecyl mercaptan; , carbon tetrabromide and other halogenated carbons, and those that are effective in relatively large amounts include substituted aromatic compounds such as silene and isopropylbenzene, and substituted fatty acids such as trichloroacetic acid and tribulium acetate. There is. Examples of monomers that are added as polymerized monomers and are also effective as molecular weight regulators include psobylene, imbutylene, α-methylstyrene, allylbenzene, allyl acetate, Examples include allyl compounds such as aryl chloride. The molecular weight joint agents may be used alone or in combination of two or more.
分子量調節剤は本発明の重合体の重合反応時に単量体に
対してθ〜20重量−の範囲で添加することが本発明の
目的に対して有利である。For the purpose of the present invention, it is advantageous for the molecular weight regulator to be added in an amount of θ to 20% by weight relative to the monomer during the polymerization reaction of the polymer of the present invention.
本発明の重合体すなわち光学用樹脂の大部分を占めるビ
ニル系重合体としてはビニル系単量体の単独重合体でも
、2つまたはそれ以上の共重合体でも良い。本発明の重
合体を1lJRするために使用される代表的な単量体と
しては、スチレン、り費pスチレン、プνムスチレン、
冒−ドスチレン、及びベンゼン禎に複数個のへ四ゲン置
換基を有するハロゲン化スチレン類、ターシャリブチル
スチレン、ターシャリ74ルスチレン、ビニルトルエン
等のアル中ルスチレン調、ベンゼン禎にフェノキシ基、
ペンジ−キシ基等のアル中ルオキシ基を1個以上有する
アルキルオキシスチレン類、ベンゼン禎に7凰品ルチオ
基、メルカプト基等のアルキルチオ基を1個以上有する
アルキルチオスチレン調、メチルメタクリレート、シク
ロへキシルメタクリレート、了ダ!ンチルメタクリレー
ト、2メチルシクレヘキシルメタタリレート、イソボ冒
二ルメタタリレート、ダリシジルメタクリレーシ及び勢
盆II !$1−2519号矢報記戦のぼりマー合成に
用いられる一連のメタクリル酸エステル系単量体、アタ
リ四1トリル、メタクリレートリル等の共役ニトリル贋
、ビ1ルナ7タレン、N−ビニルカルバソール等が挙げ
られる。The polymer of the present invention, that is, the vinyl polymer that makes up the majority of the optical resin, may be a homopolymer of vinyl monomers or a copolymer of two or more vinyl monomers. Typical monomers used to prepare the polymers of the present invention include styrene, p-styrene, p-styrene,
atomized styrene, and halogenated styrenes having a plurality of tetragene substituents on benzene, tert-butylstyrene, tert-74 styrene, alkyl-based styrene such as vinyltoluene, phenoxy group on benzene,
Alkyloxystyrenes having one or more alkyloxy groups such as pendoxy groups, alkylthiostyrenes having one or more alkylthio groups such as benzene and ruthio groups, mercapto groups, methyl methacrylate, cyclohexyl methacrylate , Ryoda! methyl methacrylate, 2-methyl cyclohexyl methacrylate, isobobenyl methacrylate, dalicidyl methacrylate, and Seibon II! $1-2519 Yahoki A series of methacrylic acid ester monomers used in the synthesis of streamers, conjugated nitrile counterfeits such as atari tetra-tolyl and methacrylate tril, bi-1-luna-7-talene, N-vinylcarbasol, etc. can be mentioned.
本発明の重合体管製造する処方としては例えば等が挙げ
られるが、これらに限定されるものではない。Examples of the formulation for producing the polymer tube of the present invention include, but are not limited to, the following.
重合体の重量平均分子量としては5oooo〜3000
000のものが用いられ、特に好ましくは、10000
0〜1000000のものが用いられる。The weight average molecular weight of the polymer is 5oooo~3000
000 is used, particularly preferably 10,000
0 to 1,000,000 is used.
本発明の重合体を製造するのに用いられる重合反応装置
は、一般に用いられる反応装置【そのまま転用すること
ができ、重合法としては塊状重合、1l1111重合、
溶液重合、披射纏重合などのような重合法tIl用して
差支えないが、塊状重合、懸濁重合が好ましい。The polymerization reaction equipment used to produce the polymer of the present invention is a generally used reaction equipment [can be used as is, and polymerization methods include bulk polymerization, 1l1111 polymerization,
Polymerization methods such as solution polymerization and enveloping polymerization may be used, but bulk polymerization and suspension polymerization are preferred.
本発明に係る樹脂組成物−は耐光性向上のために、紫外
纏吸収剤管書有しても良い。紫外線吸収剤としては、可
視領域の透過率まで滅、少させるものは好ましくないが
、特に他の樹脂時性を、そこなわずに有効に紫外線を吸
収するものならどんなものでも構わない。具体例として
は、オルトヒ、ド騨キシサリチル拳7晶ニル系化会物、
オM)とド田キシベンゾ7基ノン系化合物、2−(e−
ヒト田キシ7凰エル)ベンゾトリアゾール系化合物、シ
アノアタリレー)系化合物等費用いることができる。The resin composition according to the present invention may contain an ultraviolet absorber in order to improve light resistance. As the ultraviolet absorber, it is not preferable to use one that reduces the transmittance in the visible region, but any ultraviolet absorber may be used as long as it effectively absorbs ultraviolet light without damaging the properties of other resins. Specific examples include Orthohi, Dokisalicil 7-crystalline chemical compound,
2-(e-
Benzotriazole compounds, cyanoalaryl compounds, etc. can be used.
本発明において、本発明の重合体e主成分として食むと
は、本発明に係る樹脂組成物の約95重1憾ないし10
0重量重量率発明の重合体であることをいう。In the present invention, the term "polymer e of the present invention as a main component" refers to approximately 95% of the resin composition of the present invention.
It means that it is a polymer of the invention with a weight ratio of 0.
本発明に係る樹脂組成物な成層して、光学用素子な作る
場合の威蓋決は射出威源法のほか、圧縮成層法あるいは
射出威崖と圧縮成型の折衷法である四−リンナス法やマ
イクロモールディング法等およそ一担樹脂rt′fII
I融あるいは牛溶融させたIl威瓢させる方法はどれで
も適用することができる。In addition to the injection method, the method for manufacturing optical elements by layering the resin composition according to the present invention is the compression layering method or the four-linas method, which is a compromise between injection method and compression molding. Micromolding method, etc. Approximately one resin rt'fII
Any method of melting or melting may be applied.
また、或蓋品の熱安定性には成蓋品の吸湿が大きな影響
を及ぼすこともあるので、成置品の寸法安定性向上のた
めに、威厘品表面に樹脂及び無機物によ、るコーティン
グをほどこすことによって吸湿費防ぎ結Jl−に寸法安
定性を向上させる手段を揮つてもよいっ表面の樹脂コー
ティング法としては、例えばモノ!−あるいはプレポリ
!−を塗布した後、熱意合歓射纏重会、電子線重合等に
よって重合硬化させる方法、プリマー溶液f:@きつけ
る方法、プラズマ重合による方法等が挙げられる。In addition, since moisture absorption of a closed product can have a large effect on the thermal stability of a closed product, in order to improve the dimensional stability of the closed product, the surface of the capped product should be coated with resin and inorganic substances. Applying a coating may be used to prevent moisture absorption costs and improve dimensional stability. Examples of surface resin coating methods include mono! -Or prepoli! Examples include a method of applying a primer solution and then curing it by polymerization and curing by enthusiastic combination, electron beam polymerization, etc., a method of applying a primer solution, and a method of plasma polymerization.
表面コーティング用の樹脂としては、四7ツ化エチレン
等のフルオ霞アルキレン類、テシツメチルシラン等のオ
ルガノシラン類、テトラエチルオルソシリナート等のオ
ルソシリケー)−、ペンタフルオルエチルメタクリレ−
F等のフルオ田アルキルメタクリレート額、アクリロニ
トリル等の共役ニトリル類、スチレン、りpルスチレン
等のスチレン類を七ツマー成分として含む重合体が挙げ
られる。Resins for surface coating include fluoro-alkylenes such as tetra7tethylene, organosilanes such as teshitsumethylsilane, orthosilicates such as tetraethyl orthosilinate, and pentafluoroethyl methacrylate.
Examples include polymers containing fluorocarbon alkyl methacrylates such as F, conjugated nitrites such as acrylonitrile, and styrenes such as styrene and polystyrene as a heptamer component.
又無機物をコーティングする方法としては蒸着、スパッ
タリング、イオンブレーティング等が挙げられ、用いら
れる無機物としては、フッ化力〜シウム、ツク化マグネ
シウム、シリコン等が挙げられる。Methods for coating with an inorganic substance include vapor deposition, sputtering, ion blating, etc., and examples of the inorganic substance used include fluoride, silium, magnesium oxide, and silicon.
本発明の樹脂組成物を成製することによって得られる光
学用素子とは、例えば、スチールカメラ用、ビデオカメ
ラ用、望遠鏡用、眼鏡用、コンタクトレンズ用、太陽集
光用等のいわゆるレンズ類、ペンタプリズム等のプリズ
ム類、凹面鏡、ブリボン啼の鏡類、オプティカルファイ
バー、光導波路等の光導性素子類、ビデオディスク、オ
ーディオディスク岬のディスク碩等光を透過又は戻射す
ることによって機能管発揮する素子【言う。Optical elements obtained by producing the resin composition of the present invention include so-called lenses for still cameras, video cameras, telescopes, eyeglasses, contact lenses, solar concentrators, etc. Prisms such as pentaprisms, concave mirrors, glass mirrors, optical fibers, light guide elements such as optical waveguides, video discs, audio discs, etc., perform functions by transmitting or returning light. Motoko [says]
以下、実施l1rt挙げて本発明を具体的に説明するO
実施例−1
上記組成物を連続的に重合できるように配置した重合釜
、押出機及びモノマー除去装置の連結した一連の工程の
中に投入し、重合釜の温度t 130℃〜140℃の間
の制御された温度に設定し、樹脂組成物を得た。Hereinafter, the present invention will be specifically explained with reference to Example 1. Example 1 In a series of steps in which a polymerization pot, an extruder, and a monomer removal device are connected so that the above composition can be continuously polymerized. The temperature t of the polymerization kettle was set at a controlled temperature between 130°C and 140°C to obtain a resin composition.
この重合体の重量平均分子量は30万でガラス転移温度
は110℃であった。This polymer had a weight average molecular weight of 300,000 and a glass transition temperature of 110°C.
この重合体を用い、熱安定剤、紫外Jl@収剤等の添加
剤を加えたJv!一度t220℃として射出威濠してレ
ンス成溜品を作成した。Jv! using this polymer and adding additives such as a heat stabilizer and ultraviolet Jl@absorbent! Once the temperature was set to 220°C, injection was carried out to produce a lens product.
これをレンズ−1とする。This will be referred to as lens-1.
比較例−1
α−メチルスチレン、ジビニ七ルベンゼンを用いない以
外は実施例−1と同様にして、レンス成蓋品を作−した
。これを比較レンズ−1とする。Comparative Example 1 A lens-covered product was produced in the same manner as in Example 1 except that α-methylstyrene and divinylbenzene were not used. This will be referred to as comparative lens-1.
上記組成物を実施例−1と同様に重会し、樹脂組成物を
得た。The above composition was superimposed in the same manner as in Example-1 to obtain a resin composition.
この樹脂の重量平均分子量は35万で、ガラス転移点は
112℃であっto
この樹脂組成物を用い、樹脂組成物の温度を230℃と
して射出成渥してレンズ*iig品管作成した0
これをレンズ−2とする。The weight average molecular weight of this resin was 350,000, and the glass transition point was 112°C.Using this resin composition, injection molding was performed at a temperature of the resin composition of 230°C to create a lens. Let be lens-2.
比較例−2
エチレングリコールジメタタリレートを層いない以外は
実施H−2とrR#Aにして、レンズ成型品管作成した
。これを比較レンズ−2とする。Comparative Example 2 A lens molded product tube was prepared using Example H-2 and rR#A except that ethylene glycol dimethacrylate was not layered. This will be referred to as comparison lens-2.
実施例−3
冷却管、窒素導入菅、攪拌俸、温度針の装着された反応
釜にリン酸カルシウム1部、ドデシルベンゼンスルホン
酸ソーダ001部、蒸留水200部を準備し、これに上
記組成物を加え、80℃で3時間重合させた。重合完了
後、塩酸処理、水洗、濾過乾燥させ、樹脂組成物管得た
。この樹脂組成物の重量平均分子量は50万で、ガラス
転移温度は90℃であった。Example 3 1 part of calcium phosphate, 0.01 part of sodium dodecylbenzenesulfonate, and 200 parts of distilled water were prepared in a reaction pot equipped with a cooling tube, nitrogen introduction tube, stirring bale, and temperature needle, and the above composition was added thereto. , polymerization was carried out at 80° C. for 3 hours. After the polymerization was completed, the resin composition was treated with hydrochloric acid, washed with water, filtered and dried to obtain a resin composition tube. The weight average molecular weight of this resin composition was 500,000, and the glass transition temperature was 90°C.
この樹脂組成物な用い、樹脂の温度t220’cとして
圧縮虞麿してレンズ成型品を作成した。Using this resin composition, a lens molded product was prepared by subjecting it to compression at a resin temperature of t220'c.
これをレンズ−3とする。This will be referred to as lens-3.
以肇鍵杓
比較例−3
α−メチルスチレン、Fリメチロールプロパントリアク
リレートを用いない以外は、実施例−3と同様にしてレ
ンス處漏品を作製した。Comparative Example 3 A lens leakage product was prepared in the same manner as in Example 3 except that α-methylstyrene and F-limethylolpropane triacrylate were not used.
これを比較レンズ−3とする。This will be referred to as Comparison Lens-3.
比較例−4
トリメチロールプロパトリアクリレ−)t2111用い
た以外は実施例−3と同様にして、樹脂組成物な得た。Comparative Example 4 A resin composition was obtained in the same manner as in Example 3, except that trimethylolpropatriacrylate (T2111) was used.
この樹脂組成物t280℃盲で加熱して圧縮酸11を試
みたが、不溶不融で成層不能であった。This resin composition was heated blindly at 280°C to form a compression acid 11, but it was insoluble and infusible and could not be layered.
これらのレンズすンプルの比較試験結果を表−1にまと
めて記す。The comparative test results of these lens samples are summarized in Table-1.
表 −1 注 (1) if折率変化は最小偏角法で測定した。Table-1 Note (1) If the refractive index change was measured by the minimum deviation angle method.
(2)纏廖張係款はプラスチックマイクルメーターで測
定した。(2) The binding tension was measured using a plastic micrometer.
以上の結果から、本発明にょるsrs組威物を用いて作
製したレンズサンプルは屈折率の温度依存性及びms張
係歇が小さく熱安定性の良好なレンズであることがわか
る。From the above results, it can be seen that the lens sample produced using the SRS compound according to the present invention has a small temperature dependence of refractive index and a small MS tension coefficient, and is a lens with good thermal stability.
代履人 桑原義員Substitute Yoshikazu Kuwabara
Claims (1)
の少なくとも一種の架橋剤な加えて反応させてなるビニ
ル系重合体な主成分として含む光学用樹脂I11威物◎
(2) 単量体に対し、0.001〜加重量慢の少な
くとも一種の架橋剤を加えて反応させてなるビニル系重
合体を主成分として含む樹脂組成物を成蓋して得られる
光学用素子。(1) Optical resin I11, which contains as a main component a vinyl polymer made by reacting monomers with at least one crosslinking agent of 0.001 N2L1 weight ratio◎
(2) An optical product obtained by laminating a resin composition containing a vinyl polymer as a main component, which is obtained by adding and reacting at least one type of crosslinking agent with a weight of 0.001 to 100% to a monomer. element.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2638082A JPS58142931A (en) | 1982-02-19 | 1982-02-19 | Optical resin composition and optical element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2638082A JPS58142931A (en) | 1982-02-19 | 1982-02-19 | Optical resin composition and optical element |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS58142931A true JPS58142931A (en) | 1983-08-25 |
Family
ID=12191911
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2638082A Pending JPS58142931A (en) | 1982-02-19 | 1982-02-19 | Optical resin composition and optical element |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58142931A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58162614A (en) * | 1982-03-20 | 1983-09-27 | Konishiroku Photo Ind Co Ltd | Optical resin composition and optical element |
JPH01199981A (en) * | 1985-04-08 | 1989-08-11 | Wisconsin Alumni Res Found | Alpha, omega-bis(trivinylsilyl)alkane |
DE4319435A1 (en) * | 1993-06-11 | 1994-12-15 | Buna Gmbh | Process for the preparation of substantially uncrosslinked styrene copolymers |
EP0783958A3 (en) * | 1986-07-08 | 1998-04-01 | Lumenyte International Corporation | Cylindrical fiber optic conduit |
US6207747B1 (en) | 1996-12-17 | 2001-03-27 | Fiberstors Incorporated | Acrylic flexible light pipe of improved photo-thermal stability |
US8648160B2 (en) | 2004-11-09 | 2014-02-11 | Idemitsu Kosan Co., Ltd. | Optical semiconductor sealing material |
-
1982
- 1982-02-19 JP JP2638082A patent/JPS58142931A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58162614A (en) * | 1982-03-20 | 1983-09-27 | Konishiroku Photo Ind Co Ltd | Optical resin composition and optical element |
JPH01199981A (en) * | 1985-04-08 | 1989-08-11 | Wisconsin Alumni Res Found | Alpha, omega-bis(trivinylsilyl)alkane |
EP0783958A3 (en) * | 1986-07-08 | 1998-04-01 | Lumenyte International Corporation | Cylindrical fiber optic conduit |
DE4319435A1 (en) * | 1993-06-11 | 1994-12-15 | Buna Gmbh | Process for the preparation of substantially uncrosslinked styrene copolymers |
US6207747B1 (en) | 1996-12-17 | 2001-03-27 | Fiberstors Incorporated | Acrylic flexible light pipe of improved photo-thermal stability |
US8648160B2 (en) | 2004-11-09 | 2014-02-11 | Idemitsu Kosan Co., Ltd. | Optical semiconductor sealing material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS62138514A (en) | Resin material for optical use | |
EP1907432A1 (en) | Copolymer and polymerizable composition | |
JPS58142931A (en) | Optical resin composition and optical element | |
JP2546887B2 (en) | Thiocarboxylic acid ester compound and method for producing the same | |
JPH02150410A (en) | Resin material having high refractive index | |
JPH01197528A (en) | Composition for lens of high refractive index | |
JPH05303003A (en) | Composition for optical material and optical material | |
JP2707653B2 (en) | High Abbe number lens | |
JPH01182314A (en) | Composition for lens having high abbe's number | |
JPS58162617A (en) | Optical resin composition and optical element | |
JPH04366115A (en) | Optical plastic having low refractive index and enhanced dispersion | |
JPH0445401A (en) | Lens having high abbe's number | |
JP2564273B2 (en) | Casting optical resin material | |
JPH0229408A (en) | Lowly water-absorbing and transparent plastic | |
JPS6329701A (en) | Resin lens having high refractive index | |
JPH04225007A (en) | Optical resin having high refractive index and high strength | |
JPS59197412A (en) | Optical material | |
JPH0431082B2 (en) | ||
JPH065322B2 (en) | Method of manufacturing optical material | |
JPH0386712A (en) | Methacrylic resin with low birefringence and low hygroscopicity | |
JPH05301930A (en) | Transparent heat-resistant resin | |
JPH02289605A (en) | Low hygroscopic methacrylic resin | |
JPS6324201A (en) | Resin lens having high refractive index | |
JPH0616732A (en) | Transparent heat-resistant resin | |
JPS63248811A (en) | Composition for transparent resin having high refractive index |