JPH02294306A - Resin for optical disk substrate - Google Patents
Resin for optical disk substrateInfo
- Publication number
- JPH02294306A JPH02294306A JP1114694A JP11469489A JPH02294306A JP H02294306 A JPH02294306 A JP H02294306A JP 1114694 A JP1114694 A JP 1114694A JP 11469489 A JP11469489 A JP 11469489A JP H02294306 A JPH02294306 A JP H02294306A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- parts
- weight
- formula
- oxymethyl
- 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.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000003440 styrenes Chemical class 0.000 abstract description 15
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 abstract description 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 abstract 2
- 230000001850 reproductive effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 7
- OJAHGXITBYVUEO-UHFFFAOYSA-N decane 2-methylprop-2-enoic acid prop-2-enoic acid Chemical compound C(C(=C)C)(=O)O.C(C=C)(=O)O.CCCCCCCCCC OJAHGXITBYVUEO-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- WWIRABUTUYUIAT-UHFFFAOYSA-N 2-methylprop-2-enoic acid;pentadecane Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CCCCCCCCCCCCCCC WWIRABUTUYUIAT-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- -1 methacrylic acid ester compound Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- DOTSLXAPJSPHJZ-UHFFFAOYSA-N 1,2,3-tribromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C(Br)=C1Br DOTSLXAPJSPHJZ-UHFFFAOYSA-N 0.000 description 1
- DXXGWBOAAMSTFR-UHFFFAOYSA-N 1,2,5-tribromo-3-ethenylbenzene Chemical compound BrC1=C(C=C)C=C(C=C1Br)Br DXXGWBOAAMSTFR-UHFFFAOYSA-N 0.000 description 1
- HJSWOSQTWGDDLQ-UHFFFAOYSA-N 1,2-dibromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1Br HJSWOSQTWGDDLQ-UHFFFAOYSA-N 0.000 description 1
- KWVKCGGJLLNVSC-UHFFFAOYSA-N 1,4-dibromo-2-ethenylbenzene Chemical compound BrC1=CC=C(Br)C(C=C)=C1 KWVKCGGJLLNVSC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- BRTHMFXKGHIZAM-UHFFFAOYSA-N 2-hydroxy-1-phenylheptan-1-one Chemical compound CCCCCC(O)C(=O)C1=CC=CC=C1 BRTHMFXKGHIZAM-UHFFFAOYSA-N 0.000 description 1
- HGEAJQRQJIHKKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;pentadecane;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O.CCCCCCCCCCCCCCC HGEAJQRQJIHKKQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- COYPJOXAWCRUGJ-UHFFFAOYSA-N C(C=C)(=O)O.CCCCCCCCCCCCCCC.C(C=C)(=O)O Chemical compound C(C=C)(=O)O.CCCCCCCCCCCCCCC.C(C=C)(=O)O COYPJOXAWCRUGJ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical class C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- VBJHDYCFGAXWDN-UHFFFAOYSA-N decane prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCCCCCCCCC VBJHDYCFGAXWDN-UHFFFAOYSA-N 0.000 description 1
- FEKRGEXVMOWHGD-UHFFFAOYSA-N decane;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CCCCCCCCCC FEKRGEXVMOWHGD-UHFFFAOYSA-N 0.000 description 1
- KWWBHCXWSVLTBF-UHFFFAOYSA-N decane;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCC KWWBHCXWSVLTBF-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- AVGYVDOSBJFXFR-UHFFFAOYSA-N diphenyl sulfite Chemical compound C=1C=CC=CC=1OS(=O)OC1=CC=CC=C1 AVGYVDOSBJFXFR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/21—Bromine
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の背景〕
く産業上の利用分野〉
本発明は、再生専用型、書き込み型及び書き込み／消去
可能型の光ディスクに使用される基板用樹脂に関するも
のであり、更に詳しくは、複屈折、耐熱性に優れている
ことに加えて、吸水性が小さく、光ディスクの信頼性を
極めて高くすることができる光ディスク基板用樹脂に関
するものである。[Detailed Description of the Invention] (Background of the Invention) Industrial Application Fields The present invention relates to a substrate resin used for read-only, writable, and writable/erasable optical discs; Specifically, the present invention relates to a resin for optical disc substrates that has excellent birefringence and heat resistance, has low water absorption, and can extremely increase the reliability of optical discs.
く従来の技術〉
光ディスク基板用樹脂として、無機ガラス、ポリメチル
メタクリレート及びポリカーボネート等の樹脂が実用化
されている。しかしながら、無機ガラスの場合には、光
学特性、耐熱性も良く、吸湿することもなく、基板の変
形及び記録層の保護の役割を十分に果すものの、割れや
すくて重い上に精密加工が高価であるので、広《利用さ
れるに至っていないのが現状である。BACKGROUND ART Resins such as inorganic glass, polymethyl methacrylate, and polycarbonate have been put into practical use as resins for optical disk substrates. However, inorganic glass has good optical properties and heat resistance, does not absorb moisture, and plays the role of preventing deformation of the substrate and protecting the recording layer, but it is easy to break, is heavy, and requires expensive precision processing. Currently, it is not widely used.
一方、ポリメチルメタクリレート及びポリカーボネート
に代表される樹脂を使用ｌ−だ基板は、前者が複屈折等
の光学特性に優れている反面、吸水性等の耐環境性に劣
り、後者がそれと相反する特性を有しているが、これら
の樹脂はいずれにあっても書き込み／消去可能な光ディ
スクへの応用には多くの解決すべき問題点があるのが実
状である。On the other hand, L-type substrates using resins such as polymethyl methacrylate and polycarbonate have excellent optical properties such as birefringence, but are inferior in environmental resistance such as water absorption, and the latter have contradictory properties. However, the reality is that there are many problems that need to be solved when applying any of these resins to writable/erasable optical discs.
これらの問題点に対して、多官能性のとニルモノマーを
使用した注型重合法による光ディスク基板が提案されて
きている。すなわち、たとえば、多価アルコールのアク
リル酸又はメタクリル酸のエステルを主とする組成物を
ラジカル共重合して得られる重合体（特開昭５８−１２
９００８号、特開昭６０−２５８２１９号、特開昭６１
−９８７１０号、特開昭６１−２２１２１０号、特開昭
６２−２３２４１４号、特開昭６３−６６２１３号各公
報等）により、耐熱性、吸水性、複屈折等の品質の向上
がみられると主張されている。また、スチレン等の芳香
族ビニル化合物を使用した重合体（特開昭６０−１１８
７０５号、特開昭６１−１１５９１３号、特開昭６１２
４６２１０号、特開昭６３−２１０１１１号、特開昭６
３−１６５４２１号各公報等）により、吸水性の改良及
び吸水による寸法変化の低減がみられると主張されてい
る。さらに、又、カーボネート基を有する架橋性のジア
リルカーボネート化合物（特開昭５９−１９３９２４号
、特開昭６０−２３５８０８号、特開昭６ １． −
２ ３ １． ０ １ ０号、特開昭６１−２５０００
７号各公報等）により透明性、複屈折、吸水変形が向上
すると主張されている。In order to solve these problems, an optical disk substrate has been proposed using a cast polymerization method using a polyfunctional monomer. That is, for example, a polymer obtained by radical copolymerization of a composition mainly containing an ester of acrylic acid or methacrylic acid of a polyhydric alcohol (Japanese Unexamined Patent Publication No. 58-12
No. 9008, JP-A-60-258219, JP-A-61
-98710, JP-A No. 61-221210, JP-A No. 62-232414, JP-A No. 63-66213, etc.), improvements in quality such as heat resistance, water absorption, and birefringence can be seen. It is claimed. In addition, polymers using aromatic vinyl compounds such as styrene (Japanese Unexamined Patent Publication No. 60-118
No. 705, JP-A-61-115913, JP-A-612
No. 46210, JP-A-63-210111, JP-A-6
No. 3-165421, etc.), it is claimed that water absorption is improved and dimensional changes due to water absorption are reduced. Furthermore, crosslinkable diallyl carbonate compounds having a carbonate group (JP-A-59-193924, JP-A-60-235808, JP-A-60-6 1. -
2 3 1. No. 0 1 0, JP-A-61-25000
No. 7 publications, etc.), it is claimed that transparency, birefringence, and water absorption deformation are improved.
しかしながら、ポリメチルメタクリレート及びボリカー
ボネートに対するこれらの提案は、注型重合法による生
産性の低下を招き、工業的に実施する際の大きな障害と
なっている。However, these proposals for polymethyl methacrylate and polycarbonate lead to a decrease in the productivity of the cast polymerization method, which is a major obstacle to industrial implementation.
ところで、本発明者等によって紫外線等を照射すること
により高速に重合可能な多官能性のビニルモノマーが既
に提案されており、このモノマーによる技術は優れた品
質及び生産性を満足させることが明らかとなっている（
特開昭６１−１７４２０８号、特開昭６１−２７５３１
２号、特開昭６１−２８７９１３号、特開昭６２２２５
５０８号各公報等）。By the way, the present inventors have already proposed a polyfunctional vinyl monomer that can be rapidly polymerized by irradiation with ultraviolet rays, etc., and it is clear that the technology using this monomer satisfies excellent quality and productivity. It has become (
JP-A-61-174208, JP-A-61-27531
No. 2, JP-A-61-287913, JP-A-62225
508 publications, etc.).
光基板用樹脂としては、重合体の品質の中でも、とりわ
け、更に優れた低吸水性の向上が強く望まれるところで
ある。As a resin for optical substrates, among other polymer qualities, it is strongly desired to have further excellent low water absorption.
［発明の概要〕
く発明が解決しようとする課題〉
本発明は、光ディスク基板用樹脂として、レーザー光に
よる書き込み、読取り及び消去に際して誤作を与えない
優れた複屈折、集光により発生する熱で基板表面の溝及
び信号の変形が生じない耐熱性を有し、更に吸水時の寸
法変化及び高湿度環境下での記録膜保護を十分に果すた
めの低い吸水性を有し、しかも速い重合速度で製造する
ことができる樹脂を提供することを目的とするものであ
る。[Summary of the Invention] Problems to be Solved by the Invention> The present invention provides a resin for optical disc substrates that has excellent birefringence that prevents errors during writing, reading, and erasing with laser light, and that has excellent heat generated by condensing light. It has heat resistance that does not cause grooves on the substrate surface and deformation of signals, and also has low water absorption to sufficiently protect the recording film from dimensional changes during water absorption and in high humidity environments, and has a fast polymerization rate. The purpose of this invention is to provide a resin that can be manufactured using
く課題を解決しようとする手段〉
一般にスチレン誘導体は、吸水性の極めて低い重合体を
与えることが知られているが、その紫外線によって開始
される重合については、アクリル酸及びメタクリル酸エ
ステル誘導体に比較して重合速度が遅くて、本発明が目
的とする高速注型重合には不適であった。ところが、臭
素化スチレンは、驚くべきことに、極めて速い重合速度
をもつ組成物を与えることが見出された。Styrene derivatives are generally known to produce polymers with extremely low water absorption, but their polymerization initiated by ultraviolet rays is inferior to acrylic acid and methacrylic acid ester derivatives. As a result, the polymerization rate was slow, making it unsuitable for the high-speed cast polymerization aimed at in the present invention. However, it has been surprisingly found that brominated styrene provides compositions with extremely fast polymerization rates.
すなわち、本発明による光ディスク基板用樹脂は、下式
（Ｉ）で示されるラジカル重合性単量体２０〜８０重量
％と下式（ＩＩ）で示される臭素化スチレン８０〜２０
重量％とから主として成る単量体組成物を紫外線を使用
してラジカル共重合して得られたものであること、を特
徴とするものである。That is, the resin for optical disk substrates according to the present invention contains 20 to 80% by weight of the radically polymerizable monomer represented by the following formula (I) and 80 to 20% by weight of the brominated styrene represented by the following formula (II).
It is characterized in that it is obtained by radical copolymerization of a monomer composition mainly consisting of % by weight using ultraviolet rays.
（Ｒ およびＲ２は、同一でも異なってもよくて、それ
ぞれ水素又はメチル基を示す。ｎは、１又は２の整数を
表わす）
（ｍは、１〜３の整数を表わす）
く効果〉
上記の目的が達成される。(R and R2 may be the same or different and each represents hydrogen or a methyl group. n represents an integer of 1 or 2) (m represents an integer of 1 to 3) Effect> The above The purpose is achieved.
このようにして得られた本発明の光ディスク基板用樹脂
は、６０℃での飽和吸水率０，８重ｍ％以下、耐熱性１
５０℃以上、硬化時間４０秒以下の光学特性、機械特性
等に優れたものである。The thus obtained resin for optical disk substrates of the present invention has a saturated water absorption rate of 0.8% by weight or less at 60°C and a heat resistance of 1.
It has excellent optical properties, mechanical properties, etc. with a temperature of 50° C. or higher and a curing time of 40 seconds or less.
く単量体〉
本発明に使用する前記式（Ｉ）で示されるアクリル酸及
び／又はメタクリル酸エステル化合物の具体例としては
、ビス（オキシメチル）トリシクロ［５．２．１．０２
゜６）デカンージアクリレート、ビス（オキシメチル）
トリシクロ［５． ２．１．０２″６〕デカンージメ
タクリレート、ビス（オキシメチル）トリシクロ（５．
２．１．０２゜Ｂ〕デカンーアクリレートメタクリレー
ト及びこれらの混合物、ビス（オキシメチル）ペンタ３
，６ ２．７ ９．１３
シクロ（６．５．１．１ ．０ ．０ ）
ペンタデカンージアクリレート、ビス（オキシメチル）
ペンタシクロ（６．５．１．１３゜Ｂ０２゜７．０９゜
１３）ペンタデカンージメタクリレート、ビス（オキシ
メチル）ペンタシクロ〔６、５．８．６ ２，７
９．１３
１．１ ．０ ．０ ）ペンタデカンーア
クリレートメタクリレート及びこれらの混合物がある。Monomer> Specific examples of the acrylic acid and/or methacrylic acid ester compound represented by the formula (I) used in the present invention include bis(oxymethyl)tricyclo[5.2.1.02
゜6) Decane-diacrylate, bis(oxymethyl)
Tricyclo[5. 2.1.02″6] Decane dimethacrylate, bis(oxymethyl)tricyclo(5.
2.1.02゜B] Decane-acrylate methacrylate and mixtures thereof, bis(oxymethyl)penta3
,6 2.7 9.13 cyclo(6.5.1.1 .0 .0 )
Pentadecane-diacrylate, bis(oxymethyl)
Pentacyclo (6.5.1.13゜B02゜7.09゜13) Pentadecane dimethacrylate, bis(oxymethyl)pentacyclo [6, 5.8.6 2,7
9.13 1.1. 0. 0) Pentadecane-acrylate methacrylate and mixtures thereof.
これらのトリシクロデカン化合物及びペンタシクロペン
タデカン化合物は、群内および（または）群間で２種以
上併用しても良い。Two or more of these tricyclodecane compounds and pentacyclopentadecane compounds may be used in combination within a group and/or between groups.
一方、前記式（ＩＩ）で示される臭素化スチレンの具体
例としては、２−ブロモスチレン、３−プロモスチレン
、４−プロモスチレン、２．３−ジブロモスチレン、２
．４−ジブロモスチレン、２．５−ジブロモスチレン、
２．６−ジブロモスチレン、３．４−ジブロモスチレン
、３．５−ジブロモスチレン、２，３．４−トリブロモ
スチレン、２，３．５−トリブロモスチレン、２，３．
６−トリブロモスチレン、３，４．５−｝リブロモスチ
レン等がある。これらは、２種以上併用することができ
る。本発明の目的を達成するためにはこの臭素化スチレ
ンは臭素化の程度が高くなることが望ましいが、臭素化
の程度が高くにつれて臭素化スチレンは融点が高くなっ
て、常温で固体の化合物となる。従って、好ましく使用
される臭素化スチレンは、ジブロモスチレン（各異性体
を含む）、またはもしくは、モノブロモスチレン、ジブ
ロモスチレンおよびトリブロモスチレン（各異性体を含
む）の混合物である。On the other hand, specific examples of the brominated styrene represented by the formula (II) include 2-bromostyrene, 3-promostyrene, 4-promostyrene, 2,3-dibromostyrene, 2-bromostyrene,
．． 4-dibromostyrene, 2,5-dibromostyrene,
2.6-dibromostyrene, 3.4-dibromostyrene, 3.5-dibromostyrene, 2,3.4-tribromostyrene, 2,3.5-tribromostyrene, 2,3.
Examples include 6-tribromostyrene, 3,4.5-}ribromostyrene, and the like. Two or more of these can be used in combination. In order to achieve the purpose of the present invention, it is desirable that the brominated styrene has a high degree of bromination, but as the degree of bromination increases, the melting point of the brominated styrene increases and it becomes a solid compound at room temperature. Become. The brominated styrene preferably used is therefore dibromostyrene (including each isomer) or a mixture of monobromostyrene, dibromostyrene and tribromostyrene (including each isomer).
前記式（Ｉ）で示されるラジカル重合性単量体の使用さ
れる割合は、臭素化スチレンとの合計量に対して２０〜
８０重二％であり、従って前記式（ｎ）で示される臭素
化スチレンの使用される割合は、８０〜２Ｏｉｉ量％で
ある。The ratio of the radically polymerizable monomer represented by formula (I) to the total amount of brominated styrene is 20 to 20.
Therefore, the proportion of the brominated styrene represented by the formula (n) used is 80 to 2 Oii weight %.
臭素化スチレンの割合が８０重二％を越えると、ラジカ
ル重合体中の架橋構造が減少し、耐熱性の低下が著しく
なり、又重合速度が遅くなるので不都合である。一方、
２０重量％未満では、本発明の目的とする吸水性の低減
が望めない。If the proportion of brominated styrene exceeds 80% by weight, the crosslinked structure in the radical polymer decreases, the heat resistance decreases significantly, and the polymerization rate slows down, which is disadvantageous. on the other hand,
If it is less than 20% by weight, the reduction in water absorption that is the objective of the present invention cannot be expected.
前記式（Ｉ）で示されるラジカル重合性単瓜体の使用さ
れる割合は、好ましくは、４０〜６０重量％及び前記式
（ＩＩ）で示される臭素化スチレンの使用される割合は
、好ましくは、６０〜４０重量％である。The proportion of the radically polymerizable monomer represented by the formula (I) used is preferably 40 to 60% by weight, and the proportion of the brominated styrene represented by the formula (II) used is preferably 40 to 60% by weight. , 60-40% by weight.
本発明において重合させるべき単量体組成物は、単量体
（Ｉ）および（ＩＩ）から主としてなるものである。従
って、この組成物は、本発明の趣旨に沿う限り【単量体
（Ｉ） ＋ （ＩＩ） ］の２０重量％までのこれらの
共重合可能なエチレン性不飽和単量体を含んでいてもよ
い。そのような単量体としては（メタ）アクリル酸エス
テル（一価または多価アルコールとのエステル、ハロゲ
ン含有アルコールでもよい）、核および（または）側鎖
ノ＼ロゲン化スチレン（式（ＩＩ）以外のもの）、ジビ
ニルベンゼン（核および（または）側鎖ノ１ロゲン置換
体でもよい）、アリルエステル（酸側にノ１ロゲンなる
を有していてもよい）、その他がある。The monomer composition to be polymerized in the present invention mainly consists of monomers (I) and (II). Therefore, this composition may contain up to 20% by weight of [monomers (I) + (II)] of these copolymerizable ethylenically unsaturated monomers as long as the spirit of the present invention is met. good. Such monomers include (meth)acrylic acid esters (esters with monohydric or polyhydric alcohols, which may also be halogen-containing alcohols), core and/or side chain \ halogenated styrenes (other than formula (II)). ), divinylbenzene (which may be substituted with halogen in the core and/or side chain), allyl ester (which may have halogen on the acid side), and others.
く重合〉
本発明のラジカル重合性単量体及び臭素化スチレンより
主として成る組成物に紫外線を照射してラジカル共重合
を行なう際には、公知の光増感剤が使用されることがふ
つうである。光増感剤の具体例としては、ペンゾフエノ
ン、ベンゾインエチルエーテル、ベンジル、アセトフエ
ノン、アントラキノン等がある「光増感剤」は、光によ
ってラジカルを発生させる開始剤であっても良く、具体
的には、ジフエニルサルファイト、チオカ一／くメート
等の硫黄化合物などがある。これらの光増感剤の使用量
は、前記組成物１００部に対して０．０１〜２０部、゛
好ましくは０．１〜１０部の範囲である。Polymerization> When carrying out radical copolymerization by irradiating ultraviolet rays to a composition mainly consisting of the radically polymerizable monomer of the present invention and brominated styrene, a known photosensitizer is usually used. be. Specific examples of photosensitizers include penzophenone, benzoin ethyl ether, benzyl, acetophenone, anthraquinone, etc. The "photosensitizer" may be an initiator that generates radicals by light, and specifically, , diphenyl sulfite, thiocamono/cumate, and other sulfur compounds. The amount of these photosensitizers used is in the range of 0.01 to 20 parts, preferably 0.1 to 10 parts, per 100 parts of the composition.
更に本発明において、紫外線を照射してラジカル共重合
を行なった後、加熱することによって重合反応の完結及
び重合時に発生する歪を除去することも可能である。Furthermore, in the present invention, it is also possible to complete the polymerization reaction and remove distortion generated during polymerization by heating after radical copolymerization by irradiating ultraviolet rays.
なお、この目的のために上記の光増感剤に加えて公知の
ラジカル開始剤、具体的１こは、過酸化ベンゾイル、ジ
イソブロビルバーオキシカーボネート、ラウロイルバー
オキサイド、ターシャリープチルバーオキシビパレート
、ジクミルパーオキサイド、アゾイソブチロニトリル等
を予め当該組成物に添加することができる。これらのラ
ジカル開始剤の使用量は、前記組成物１００部に対して
、０．０１〜２０部、好ましくは０． １〜１０部、
の範囲である。For this purpose, in addition to the above-mentioned photosensitizers, known radical initiators, specifically benzoyl peroxide, diisobrobyl peroxycarbonate, lauroyl peroxide, tertiary butyl peroxybiparate, are used. , dicumyl peroxide, azoisobutyronitrile, etc. can be added to the composition in advance. The amount of these radical initiators used is 0.01 to 20 parts, preferably 0.01 parts to 100 parts of the composition. 1 to 10 copies,
is within the range of
本発明の組成物の紫外線及び加熱によるラジカル共重合
の方法は、大気中もしくは不活性ガス中で、１０〜２０
０℃の温度で行なうのが好ましい。The method of radical copolymerization of the composition of the present invention by ultraviolet rays and heating is carried out in air or in an inert gas for 10 to 20
Preferably it is carried out at a temperature of 0°C.
く生成樹脂〉
本発明の特色をなす単量体より生成する小合体は、架橋
していて融解を伴う手段によって成形することはできな
い。従って、いわゆる注型重合によって板状で得るか、
あるいは他の形状で得てから所望形状に機械加工するこ
とがふつうである。Resin produced by resin> The small aggregate produced from monomers, which is a feature of the present invention, is crosslinked and cannot be molded by means involving melting. Therefore, it can be obtained in the form of a plate by so-called cast polymerization, or
Alternatively, it is common to obtain it in another shape and then machine it into the desired shape.
く実験例〉
以下に実験例および比較例は、本発明をさらに具体的に
説明するためのものである。なお実験例中の部は重量部
を、％は重量％を、示す。Experimental Examples> The following experimental examples and comparative examples are for explaining the present invention more specifically. In addition, parts in the experimental examples indicate parts by weight, and % indicates weight %.
実験例において得られた諸物性は、下記の試験法により
１１Ｎ定したものである。The various physical properties obtained in the experimental examples were determined at 11N by the following test method.
（Ｉ） ｍ屈折：東芝歪測定機（東芝硝子社製）にて測
定したものである。(I) m refraction: Measured using a Toshiba strain meter (manufactured by Toshiba Glass Co., Ltd.).
（２）吸水率；６０℃温水中に試験片（横２ｃ１１１，
縦５ｃｌＩ１１厚さ１ｍｍ）を浸漬し、重量増が一定に
達するまで経時変化をｎ１定
し、一定に達したときの重量より初
期のｍ量に対する増加率を求めた。(2) Water absorption rate; test piece (horizontal 2c111,
5 clI (longitudinal), 11 mm (thickness: 1 mm) was immersed, the change over time was determined by n1 until the weight increase reached a constant level, and the rate of increase with respect to the initial m amount was determined from the weight when the weight increase reached a constant level.
（３）耐熱性： ＤＭＡ試験機（デュポン社製）にて測
定し、損失弾性率が極大を示す温
度を求めた。(3) Heat resistance: Measured using a DMA tester (manufactured by DuPont) to determine the temperature at which the loss modulus reaches its maximum.
（４）弾性率： ＤＭＡ試験機（同上）にて測定し、５
０℃における貯蔵弾性率を求めた。(4) Elastic modulus: Measured with a DMA tester (same as above), 5
The storage modulus at 0°C was determined.
実施例１
ビス（オキシメチル）トリシクロ（５． ２． １
．０２″Ｂ〕デカンーアクリレートメタクリレート（ジ
アクリレート体１６％、ジメタクリレート体３６％及び
アクリレート／メタクリレート交叉体４８％とから成る
混合物）８０部、ジブロモスチレン（モノ〜トリブロモ
スチレン、各種異性体混合物、製鉄化学社品）２０部に
対して、１−ヒドロキシシク口へキシルフエニルケトン
（「イノレガキュア−１８４」チバガイギー社品）及び
ペンゾイルパーオキサイド０． ５部を加えて均一に
攪拌混合した後、脱泡し、この液を直径１３ｃ＋ｎ，厚
さ１．５論朧のガラス板とシリコーンゴムとで構成され
た鋳型の中へ注入した。次いで、ガラス板面より出力８
０Ｗ／ｃｍの高圧水銀灯で２０秒間紫外線を照射したと
ころ、液状部分のない硬化物が得られた。更に、この硬
化物をエアーオーブン中１５０℃で２時間加熱して重合
反応を完結させて無色透明の光ディスク基板状の硬化物
を得た。物性測定結果は表−１に示す通りであった。Example 1 Bis(oxymethyl)tricyclo(5.2.1
．． 02″B] Decane-acrylate methacrylate (mixture consisting of 16% diacrylate, 36% dimethacrylate and 48% acrylate/methacrylate cross-body), 80 parts dibromostyrene (mono-tribromostyrene, various isomer mixtures, 20 parts of 1-hydroxyhexyl phenyl ketone ("INOREGACURE-184", a Ciba Geigy product) and 0.0 parts of penzoyl peroxide. After adding 5 parts and stirring and mixing uniformly, the liquid was defoamed and poured into a mold made of a glass plate with a diameter of 13cm+n and a thickness of 1.5cm and silicone rubber. Next, output 8 from the glass plate surface.
When irradiated with ultraviolet rays for 20 seconds using a high-pressure mercury lamp of 0 W/cm, a cured product without a liquid portion was obtained. Further, this cured product was heated in an air oven at 150° C. for 2 hours to complete the polymerization reaction, thereby obtaining a colorless and transparent cured product in the form of an optical disc substrate. The physical property measurement results were as shown in Table-1.
実施例２及び３
実施例１中のビス（オキシメチル）トリシクロ（５．２
．１．０２゜６〕デカンーアクリレートメタクリレート
８０部及びジブロモスチレン２０部の割合及び紫外線照
射時間を表−１に記載する通りに代える以外は、実施例
１と同様の操作を行なって、重合体を得た。Examples 2 and 3 Bis(oxymethyl)tricyclo(5.2
．． 1.02゜6] The same procedure as in Example 1 was performed except that the proportions of 80 parts of decane-acrylate methacrylate and 20 parts of dibromostyrene and the ultraviolet irradiation time were changed as shown in Table 1 to prepare a polymer. Obtained.
実施例４
実施例１中のビス（オキシメチル）トリシクロ［５．
２． １． ０２゜８］デカンーアクリレートメ
タクリレートの代りにビス（オキシメチル）ペンタシク
ロ（６．５．１．１３′６．０２゜７．０９゜１３〕ペ
ンタデカンージメタクリレートを用い、紫外線照射時間
を１５秒間とする以外は、実施例１と同様の操作を行な
って、重合体を得た。物性測定結果は、表−１に示す通
りであった。Example 4 Bis(oxymethyl)tricyclo[5.
2. 1. 02゜8] Decane-acrylate Instead of methacrylate, bis(oxymethyl)pentacyclo(6.5.1.13'6.02゜7.09゜13) Pentadecane-dimethacrylate was used, and the UV irradiation time was 15 seconds. A polymer was obtained by performing the same operations as in Example 1 except for the following.The physical property measurement results were as shown in Table-1.
比較例１
実施例１のビス（オキシメチル）トリシクロ（５．２．
１．０２゜６〕デカンーアクリレートメタクリレート８
０部及びジブロモスチレン２０部の代りに、ビス（オキ
シメチル）トリシクロ〔５．２． １． ０２゜６
〕デカンーアクリレートメタクリレート１００部を用い
、紫外線照射時間を１５秒間とする以外は、実施例１と
同様の操作を行なって、重合体を得た。物性測定結果は
、表−１に示す通りであった。Comparative Example 1 Bis(oxymethyl)tricyclo (5.2.
1.02゜6] Decane-acrylate methacrylate 8
0 parts and 20 parts of dibromostyrene, bis(oxymethyl)tricyclo[5.2. 1. 02゜6
] A polymer was obtained in the same manner as in Example 1, except that 100 parts of decane-acrylate methacrylate was used and the ultraviolet irradiation time was changed to 15 seconds. The physical property measurement results were as shown in Table-1.
比較例２
実施例１のジブロモスチレン２０部の代りにスチレン２
０部を用い、紫外線照射時間を３０秒間とする以外は、
実施例１と同様の操作を行なって、重合体を得た。物性
測定結果は、表−１に示す通りであった。Comparative Example 2 Styrene 2 instead of 20 parts of dibromostyrene in Example 1
Except for using 0 parts and setting the ultraviolet irradiation time to 30 seconds,
The same operation as in Example 1 was performed to obtain a polymer. The physical property measurement results were as shown in Table-1.
比較例３
実施例１のビス（オキシメチル）トリシクロ［５．
２． １． ０”’）デカンーアクリレートメタク
リレート８０部及びジブロモスチレン２０部の代りに、
ビス（オキシメチル）トリシクロ〔５．２． １．
０２゜６〕デカンーアクリレートメタクリレート６０
部及びスチレン４０部を用い、紫外線照射時間を６０秒
間とする以外は、実施例１と同様の操作を行なって、重
合体を得た。物性測定結果は、表−１に示す通りであっ
た。Comparative Example 3 Bis(oxymethyl)tricyclo[5.
2. 1. 0"') Decane-acrylate methacrylate 80 parts and dibromostyrene 20 parts,
Bis(oxymethyl)tricyclo [5.2. 1.
02゜6] Decane-acrylate methacrylate 60
A polymer was obtained by carrying out the same operation as in Example 1 except that 40 parts of styrene and 40 parts of styrene were used and the ultraviolet irradiation time was 60 seconds. The physical property measurement results were as shown in Table-1.
Claims (1)
重量％と下式（ＩＩ）で示される臭素化スチレン８０〜
２０重量％とから主として成る単量体組成物を紫外線を
使用してラジカル共重合して得られたものであることを
特徴とする、光ディスク基板用樹脂。 ▲数式、化学式、表等があります▼（Ｉ） （Ｒ＿１およびＲ＿２は、同一でも異なってもよくて、
それぞれ水素又はメチル基を示す。ｎは、１又は２の整
数を表わす） ▲数式、化学式、表等があります▼（ＩＩ） （ｍは１〜３の整数を表わす）[Claims] Radically polymerizable monomers 20 to 80 represented by the following formula (I)
Brominated styrene represented by weight% and formula (II) below: 80~
A resin for optical disk substrates, characterized in that it is obtained by radical copolymerization of a monomer composition mainly consisting of 20% by weight using ultraviolet rays. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R_1 and R_2 may be the same or different,
Each represents hydrogen or methyl group. n represents an integer of 1 or 2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (m represents an integer of 1 to 3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1114694A JP2983226B2 (en) | 1989-05-08 | 1989-05-08 | Transparent resin material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1114694A JP2983226B2 (en) | 1989-05-08 | 1989-05-08 | Transparent resin material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02294306A true JPH02294306A (en) | 1990-12-05 |
| JP2983226B2 JP2983226B2 (en) | 1999-11-29 |
Family
ID=14644293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1114694A Expired - Fee Related JP2983226B2 (en) | 1989-05-08 | 1989-05-08 | Transparent resin material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2983226B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10144469A (en) * | 1996-09-12 | 1998-05-29 | Mitsubishi Chem Corp | Organic electroluminescent element and manufacture thereof |
| JP2008218421A (en) * | 1996-09-12 | 2008-09-18 | Mitsubishi Chemicals Corp | Organic electroluminescent element and its manufacturing method |
-
1989
- 1989-05-08 JP JP1114694A patent/JP2983226B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10144469A (en) * | 1996-09-12 | 1998-05-29 | Mitsubishi Chem Corp | Organic electroluminescent element and manufacture thereof |
| JP2008218421A (en) * | 1996-09-12 | 2008-09-18 | Mitsubishi Chemicals Corp | Organic electroluminescent element and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2983226B2 (en) | 1999-11-29 |
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