JPH04151287A - Two-layer organic optical recording medium having polycarbonate crosslinking body as record retaining layer and manufacture thereof - Google Patents
Two-layer organic optical recording medium having polycarbonate crosslinking body as record retaining layer and manufacture thereofInfo
- Publication number
- JPH04151287A JPH04151287A JP2139935A JP13993590A JPH04151287A JP H04151287 A JPH04151287 A JP H04151287A JP 2139935 A JP2139935 A JP 2139935A JP 13993590 A JP13993590 A JP 13993590A JP H04151287 A JPH04151287 A JP H04151287A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- group
- recording medium
- resin
- optical recording
- 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
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 26
- 230000003287 optical effect Effects 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000004132 cross linking Methods 0.000 title abstract description 12
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- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 10
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- 238000010438 heat treatment Methods 0.000 claims abstract description 8
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
主１」二＠土」Ｌ１野
本発明は熱時の形状変化を利用した消去可能な光記録媒
体およびその製造法に関する。さらに詳しくは、有機ポ
リマー／色素からなる記録層の一部に架橋性ポリマーを
用いることを特徴とする光記録媒体およびその製造法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an erasable optical recording medium that utilizes shape change upon heating and a method for manufacturing the same. More specifically, the present invention relates to an optical recording medium characterized in that a crosslinkable polymer is used as a part of a recording layer made of an organic polymer/dye, and a method for producing the same.
背景 術とその間超克
従来、有機色素を用いた光記録媒体は多数提案されてい
る（例えば、特開昭６１−１６３８９１６１−２６８４
８７ ６２−５６１９１ ６２−１２２７８７ 、６２
−３９２８６．６３−７２５９４号各公報＃照〉、、ｔ
た、有機色素と有機ポリマーとを組み合わせて用いた光
記録媒体も多数提案されている（例えば、特開昭６２−
９０２９１６３−６２７９４．６３−１９１６９１号各
公報参照）、シかしながら、これらの記録媒体における
記録原理は、色素が光（多くはレーザー光）を吸収して
生じる熱による記録媒体の非可逆的な形状変化（多くの
場合、ピット形成）に基づいているため、記録の消去が
きわめて困難であるか不可能であった。すなわち、色素
単独媒体の場合は、色素の気化、離散を伴うビット形成
により記録を行なうため、いったん形成したピントを消
去することは不可能であった。また、ポリマーと色素の
混合系の場合は、ポリマーの流動変形を伴うビット形成
によって記録を行なうため、いったん形成した記録ピッ
トを効率的に消去することは困難であった。また、別の
従来技術（特開昭６０−６９８４６．６３−１３６３３
７６３−１３６３３８ 、６３−１６４０４２号各公報
参照）によれば、レーザー光照射により加熱・膨張しド
ーム状突起部（ハンダ）を形成する膨張層、およびこの
形状を保持する保持層とから成る記録・消去の可能な媒
体が提案されている。この媒体に記録を行なう場合は、
あらかじめ膨張層に混合された色素の吸収波長（λ１）
でレーザー光照射を行い、該膨張層がバンブを形成し、
保持層がこの形状を維持できるようにする。また、記録
されたバングの消去を行なう場合は、予め保持層に混合
された色素の吸収波長（λ２）でレーザー光照射を行い
、保持層をそのＴｇ以上に加熱してバンブ形状の維持が
困難となるようにする。Background Techniques and Overcoming Them In the past, many optical recording media using organic dyes have been proposed (for example, Japanese Patent Laid-Open No. 61-16389161-2684).
87 62-56191 62-122787, 62
-39286.63-72594 Publications #teru〉,,t
In addition, many optical recording media using a combination of organic dyes and organic polymers have been proposed (for example, Japanese Patent Application Laid-Open No. 1983-1999).
9029163-62794.63-191691) However, the recording principle of these recording media is that the recording medium is irreversible due to the heat generated when the dye absorbs light (often laser light). Because they are based on shape changes (often pit formation), erasing the records has been extremely difficult or impossible. That is, in the case of a dye-only medium, since recording is performed by forming bits accompanied by vaporization and scattering of the dye, it is impossible to erase the focus once formed. Furthermore, in the case of a mixed system of a polymer and a dye, recording is performed by bit formation accompanied by flow deformation of the polymer, so it is difficult to efficiently erase the recording pits once formed. In addition, another prior art (Japanese Patent Application Laid-Open No. 60-69846.63-13633
No. 763-136338 and No. 63-164042), there is a recording medium comprising an expansion layer that is heated and expanded by laser beam irradiation to form a dome-shaped protrusion (solder), and a retention layer that maintains this shape. Erasable media have been proposed. When recording on this medium,
Absorption wavelength (λ1) of the dye mixed in the expansion layer in advance
irradiation with laser light, the expanded layer forms bumps,
Allow the retaining layer to maintain this shape. In addition, when erasing recorded bangs, laser light is irradiated at the absorption wavelength (λ2) of the dye mixed in the retention layer in advance, and the retention layer is heated above its Tg, making it difficult to maintain the bump shape. Make it so that
色素／′ポリマーからなるこの二層媒体の場合、記録を
効率よく行なう、言い替えればバンブを出来るだけ高く
するには保持層のポリマーの■ｑを出来るだけ高くすれ
ばよい、そうすれば、熱膨張の程度が高い状態で保持層
がガラス状態になるからである。その反面、消去を効率
よく行なうためには逆に保持層の１０が低い方がよい、
しかも、消去可能な媒体を得るためには、保持層にレー
ザー光照射による非可逆的な変形、すなわちポリマーの
流動変形が起こることは好ましくない、このような、観
点から保持層用樹脂としては、三次元架橋ポリマーが好
ましい、しかしながら、架橋ポリマーを積層するために
は一般に塗工後硬化過程が必要となり、工業的にはこの
硬化を、短時間で行なう必要が生じる。これは、フィル
ム基板上に連続コーティングする場合には、必須の要件
になる。In the case of this two-layer medium consisting of a dye/'polymer, in order to perform recording efficiently, in other words, to make the bump as high as possible, the q of the polymer in the retention layer should be made as high as possible. This is because the holding layer becomes a glass state when the degree of . On the other hand, in order to erase efficiently, it is better for the retention layer to have a lower 10.
Moreover, in order to obtain an erasable medium, it is undesirable for the holding layer to undergo irreversible deformation due to laser beam irradiation, that is, flow deformation of the polymer.From this viewpoint, as a resin for the holding layer, Three-dimensionally crosslinked polymers are preferred; however, in order to laminate crosslinked polymers, a post-coating curing process is generally required, and industrially it is necessary to perform this curing in a short period of time. This becomes an essential requirement for continuous coating on film substrates.
ｉ匪立旦躬
本発明は上述の課題を解決し、すぐれた保持層用樹脂を
有する光記録媒体及びその製造法を提供することを目的
とする。An object of the present invention is to solve the above-mentioned problems and provide an optical recording medium having an excellent resin for a retention layer and a method for manufacturing the same.
良朋！ソ１威
本発明者らは上述の相矛盾する要件を満足する保持層用
樹脂を得るべく鋭意検討の結果、特定の構造を有するポ
リカーボネート架橋体が所望の熱的特性を有し、かつ紫
外線照射または熱処理により短時間で硬化することを見
いだし本発明に刺違した。Good friend! As a result of intensive studies to obtain a resin for the retaining layer that satisfies the above-mentioned contradictory requirements, the inventors have found that a polycarbonate crosslinked product with a specific structure has the desired thermal properties and is resistant to ultraviolet irradiation. Alternatively, it was found that it could be cured in a short time by heat treatment, and was incorporated into the present invention.
すなわち、本発明は、
（１）基板上に、少なくとも室温でゴム弾性を示す樹脂
（Ｐ２）と色素（Ｄ２）とからなる膨張層（Ａ＞と、室
温でガラス状態、それより高い温度でゴム状態に可逆的
に変化し得る樹脂（Ｐ２）と色素（Ｄ２）とからなる保
持層（Ｂ）とを支持してなる光記録媒体において、該保
持層樹脂Ｐ２が
（ａ）室温での弾性率が５０ｋｇ／ｍｍ２以上であり、
（ｂ）ガラス転移温度か６０〜１５０℃であって、ｆｃ
）架橋構造を有するポリカーボネート樹脂であることを
特徴とする消去可能な二層型有機光記録媒体である。That is, the present invention provides: (1) An expansion layer (A>) consisting of a resin (P2) exhibiting rubber elasticity at least at room temperature and a dye (D2) on a substrate; In an optical recording medium that supports a retention layer (B) consisting of a resin (P2) that can reversibly change its state and a dye (D2), the retention layer resin P2 has (a) an elastic modulus at room temperature; is 50 kg/mm2 or more,
(b) The glass transition temperature is 60 to 150°C, and fc
) An erasable two-layer organic optical recording medium characterized by being made of a polycarbonate resin having a crosslinked structure.
また本発明は、ポリカーボネートをラジカル開始剤およ
び必要に応じて架橋剤の共存下、膨張層（Ａ）上に塗工
した後、紫外光照射または熱処理することを特徴とする
上記の光記ｉａ体の製造法を包含する。Further, the present invention provides the above-mentioned optical recording material, which is characterized in that polycarbonate is coated on the expansion layer (A) in the coexistence of a radical initiator and, if necessary, a crosslinking agent, and then subjected to ultraviolet light irradiation or heat treatment. It includes the manufacturing method of
本発明における光記録媒体は、少なくとも室温でゴム弾
性を示す樹脂（Ｐ２）と色素（ＤＩ）とからなる膨張層
（Ａ）と、室温でガラス状態、それより高い温度でゴム
状態に可逆的に変化し得るｉ脂（Ｐ２）と色素（Ｄ２）
とからなる保持層（Ｂ）を基板で支持してなる。なお、
基板に対するｍ膜層（Ａ）と保持層（Ｂ）との関係は、
レーザー入射方向に対応して適宜変更できる。The optical recording medium of the present invention comprises an expandable layer (A) consisting of a resin (P2) exhibiting rubber elasticity at least at room temperature and a dye (DI), and a reversible layer (A) that is in a glass state at room temperature and in a rubber state at a higher temperature. Changeable fat (P2) and pigment (D2)
A holding layer (B) consisting of is supported by a substrate. In addition,
The relationship between the m-film layer (A) and the holding layer (B) with respect to the substrate is as follows:
It can be changed as appropriate depending on the direction of laser incidence.
膨張層（Ａ）はレーザー照射により加熱した際に効果的
に膨張することが記録特性を高める上で必要である。そ
して、記録により生成したバングを効率的に消去して元
の状態に戻すためには高いゴム弾性が消去時には要求さ
れる。したがって、樹脂（Ｐ２）は高いゴム弾性を示し
、且っレーザー光照射により流Ｉ！Ｉｌｆ形を起こさな
いことが必要である。好適に用いられる樹脂としては、
天然ゴム：スチレン−ブタジェンゴム、ブタジェンゴム
、イングレンゴム、ニトリルゴム、クロロズレンゴム、
ブチルゴム、エチレン−プロピレンゴム、ウレタンゴム
、シリコーンゴムなどの合成ゴム：スチレン系、オレフ
ィン系、ウレタン系の熱可塑性エラストマー：アミン架
橋型、イソシアネート架橋型、紫外線架橋型のエラスト
マーが挙げられる。In order to improve the recording properties, it is necessary for the expansion layer (A) to expand effectively when heated by laser irradiation. In order to efficiently erase the bangs generated by recording and restore the original state, high rubber elasticity is required during erasing. Therefore, the resin (P2) exhibits high rubber elasticity, and when irradiated with laser light, the resin (P2) exhibits high rubber elasticity. It is necessary not to cause the Ilf form. Preferred resins include:
Natural rubber: styrene-butadiene rubber, butadiene rubber, Inglene rubber, nitrile rubber, chlorozurene rubber,
Synthetic rubbers such as butyl rubber, ethylene-propylene rubber, urethane rubber, and silicone rubber; Styrene-based, olefin-based, and urethane-based thermoplastic elastomers; Examples include amine-crosslinked, isocyanate-crosslinked, and UV-crosslinked elastomers.
色素Ｄ１およびＤ２は、それぞれ記録過程および消去過
程においてレーザー光を効率よく吸収して熱に変換する
役割をする。従って、記録用レーザーおよび消去用レー
ザーの発振波長域に合致している色素が選ばれる。そし
て、両レーザー光を選択的に吸収出来るように、それぞ
れの発振波長域での吸収強度が過度に重ならないことが
好ましい、また、現状の光記録分野で使用されるレーザ
ーが半導体レーザーであることがら近赤外に吸収ピーク
を有する色素が好ましい、また、読み取りは媒体表面の
光反射を利用するために、保持層での光反射率が高いこ
とが要求される。この観点から、色素Ｄ２は高反射率を
有することが好ましい。The dyes D1 and D2 play the role of efficiently absorbing laser light and converting it into heat during the recording and erasing processes, respectively. Therefore, a dye is selected that matches the oscillation wavelength range of the recording laser and the erasing laser. In order to selectively absorb both laser beams, it is preferable that the absorption intensities in each oscillation wavelength range do not overlap excessively, and that the lasers currently used in the optical recording field are semiconductor lasers. A dye having an absorption peak in the near-infrared region is preferable, and since reading utilizes light reflection on the medium surface, the retention layer is required to have a high light reflectance. From this point of view, it is preferable that the dye D2 has a high reflectance.
もちろん吸収特性を効率的に行なうために、色素はそれ
ぞれの樹脂に均一分散するように選択すべきである。好
適な色素Ｄ１およびＤ２としては、ポリメチン系色素、
ビリリウム系色素、チアピリリウム系色素、スクワリリ
ウム系色素、クロコニウム系色素、アズレニウム系色素
などのシアニン系色素：フタロシアニンやナフタロシア
ニンなどのフタロシアニン系色素ニジチオール金属錯体
；ナフトキノン、アントラキノン系色素；トリフェニル
メタン系色素：アミニウム、ジインモニウム系色素か挙
げられる。Of course, for efficient absorption properties, the dyes should be selected to be uniformly dispersed in the respective resin. Suitable dyes D1 and D2 include polymethine dyes,
Cyanine dyes such as biryllium dyes, thiapyrylium dyes, squalirium dyes, croconium dyes, and azulenium dyes: Phthalocyanine dyes such as phthalocyanine and naphthalocyanine Nidithiol metal complexes; Naphthoquinone and anthraquinone dyes; Triphenylmethane dyes: Examples include aminium and diimmonium dyes.
本発明において、保持層（Ｂ）に用いられる樹脂（Ｐ２
）は、記録時に熱膨張により生成したバンプを固定し、
消去時にはバンプの固定の解除を許容する機能を担って
いる。従って、内作用を効率的に行なうために、高温で
はゴム状態になり膨張層（Ａ）の熱膨張に伴うバンプを
形成しやすくするために、弾性率か低いことが必要であ
る。高温での弾性率は室温での値の１／１０以下、好ま
しくは！’２０以下であることかよい。常温では膨張層
（Ａ）の収縮力に抗してバンプを固定するために高い引
っ張り弾性率が必要であり、５０嘘／ｍｍ２以上、好ま
しくは８０ｋｇ ／ｍｍ２以上であることが必要である
が８００ｋｇ ／−を越えると高温での弾性率が高い値
となり消去しにくくなる。引っ張り弾性率が低いとバン
プの形状を十分に保持できなくなり、記録特性および記
録安定性が低下する。また、効率的な記録および消去の
ためには、ガラス状態からゴム状態に変化する温度（ガ
ラス転移温度Ｔｇ）も重要になる。その意味から、転移
温度は６０〜１５０°Ｃ１好ましくは７０〜１２０℃が
挙げられる。これ以下であれば形成したバンプの窩さか
低く記録特性において好ましくなく、また記録安定性に
おいても好ましくない、またこれ以上では、消去時に消
去残が残り好ましくない。In the present invention, the resin (P2
) fixes the bumps generated by thermal expansion during recording,
It has a function of allowing release of bump fixation during erasing. Therefore, in order to efficiently perform the internal action, it is necessary to have a low elastic modulus in order to become rubbery at high temperatures and to facilitate the formation of bumps due to thermal expansion of the expansion layer (A). The elastic modulus at high temperature is preferably 1/10 or less of the value at room temperature, preferably! Must be 20 or below. At room temperature, a high tensile modulus is required to fix the bump against the shrinkage force of the expansion layer (A), and it needs to be 50 kg/mm2 or more, preferably 80 kg/mm2 or more, but 800 kg If it exceeds /-, the elastic modulus at high temperature becomes a high value and becomes difficult to erase. If the tensile modulus is low, the shape of the bump cannot be maintained sufficiently, resulting in a decrease in recording characteristics and recording stability. Furthermore, for efficient recording and erasing, the temperature at which the glass state changes to the rubber state (glass transition temperature Tg) is also important. In this sense, the transition temperature is 60 to 150°C, preferably 70 to 120°C. If it is less than this, the voids of the formed bumps will be low, which is not desirable in terms of recording properties, and if it is not desirable in terms of recording stability, and if it is more than this, erased residue will remain during erasing, which is not desirable.
本発明において用いられる樹脂Ｐ２としては、脂肪族不
飽和炭化水素基を分子内に含むポリカーボネートを光ま
たは熱反応により架橋してなるポリカーボネート架Ｗ＃
木である。かかるポリカーボネートはそれ自体該記録媒
体保持層に適する■９を有するばかりでなく、丈夫で均
一な塗膜を形成することができる。そればかりでなく、
架橋して不溶化することも可能である。不溶化の程度は
、ジクロルメタンなどの良溶剤に対する溶解部分が１０
ｗｔ％以下であることが好ましく、更に好ましくは５１
％以下である０本発明に使用されるポリカーボネート樹
脂としては、下記式［Ｉ］〜［ＩＶ］から選ばれる少な
くとも１種の単位を少なくとも１０モル％以上含むポリ
カーボネートを架橋したものが挙げられる。The resin P2 used in the present invention is a polycarbonate crosslinked W# obtained by crosslinking polycarbonate containing an aliphatic unsaturated hydrocarbon group in the molecule by photo or thermal reaction.
It's a tree. Such polycarbonate itself not only has (9) suitable for the recording medium holding layer, but also can form a durable and uniform coating film. Not only that, but
It is also possible to insolubilize by crosslinking. The degree of insolubilization is as follows: 10% of the amount dissolved in a good solvent such as dichloromethane
It is preferably 51% by weight or less, more preferably 51% by weight or less.
% or less. Examples of the polycarbonate resin used in the present invention include those obtained by crosslinking polycarbonate containing at least 10 mol % or more of at least one type of unit selected from the following formulas [I] to [IV].
または下記−数式［■］：
または下記−数式［■］：
ポリカーボネート［Ｉ］、［ｎ］、［１１１］および［
ＩＶ］中のそれぞれＲｔ、 Ｒ２，Ｒ３，ＲＡ、 Ｒ
う、ＲＢおよびＲ７に用いられる脂肪族不飽和炭化水素
基の好適例としてはビニル基、アリル基、プロペニル基
、インプロペニル基、１．４−ブタジェニル基、１．３
−ペンタジェニル基などが挙げられる。また、Ｒａ、
Ｒｂに用いられる飽和炭化水素基の好適例としてはメチ
ル基、エチル基、プロピル基、イソブチル基、イソブチ
ル基などが挙げられる。また、ポリカーボネート［ＩＩ
］中のＲｃの好適例を、結合している炭素数を含めた環
状二価基として示すと、シクロペンチリデン基、シクロ
へキシリデン基、ビシクロ［２，２，１１へブチリデン
基などが挙げられる。ｔた、ポリカーボネート［ＩＶｒ
中のＸの好適例としては、フェニレン基、シクロアルキ
レン基、アラルキレン基、−０−１−Ｓ−１−ＳＯ２Ｃ
Ｈ３ＣＨ。Or the following formula [■]: Or the following formula [■]: Polycarbonate [I], [n], [111] and [
IV] respectively Rt, R2, R3, RA, R
Preferable examples of the aliphatic unsaturated hydrocarbon group used for RB and R7 include vinyl group, allyl group, propenyl group, impropenyl group, 1.4-butadienyl group, 1.3
-pentagenyl group and the like. Also, Ra,
Suitable examples of the saturated hydrocarbon group used for Rb include methyl group, ethyl group, propyl group, isobutyl group, and isobutyl group. In addition, polycarbonate [II
] Preferable examples of Rc as a cyclic divalent group including the number of bonded carbon atoms include a cyclopentylidene group, a cyclohexylidene group, a bicyclo[2,2,11butylidene group, etc. . Polycarbonate [IVr
Preferable examples of X in the group include phenylene group, cycloalkylene group, aralkylene group, -0-1-S-1-SO2C
H3CH.
Ｃ−Ａｒ−Ｃ−、−３Ｏ２−Ａｒ−３Ｏ２ＣＨ３ＣＨ３
０（ｃＨ２）２ ０−５ Ｏ（ｃＨ２）−〇−基な
どが挙げられる。これらの不飽和基を含む単位［Ｉ］、
［Ｉ［］、［ＩＩＩ］および［ＩＶ］から選ばれる少な
くとも１種の繰返し単位はポリカーボネート中に少なく
とも１０モル％、好ましくは２０モル％以上含まれる。Examples include C-Ar-C-, -3O2-Ar-3O2CH3CH30(cH2)20-5O(cH2)-〇-, and the like. Units [I] containing these unsaturated groups,
At least one type of repeating unit selected from [I[], [III] and [IV] is contained in the polycarbonate in an amount of at least 10 mol%, preferably 20 mol% or more.
不飽和基を含む単位の占める割合が１０モル％未満であ
ると架橋度が十分でなくなるために好ましくない。これ
らの、構造の選択ならびに割合は、Ｔ（ｌを含む熱的性
質、力学的性質、色素との相溶性、架橋剤との相溶性、
溶媒に対する溶解性、光架橋性などを勘案して選択すべ
きである０本発明においてはこれらの単位を単独で用い
ても良いし、複数種を混合として用いてもよい。If the proportion of units containing unsaturated groups is less than 10 mol %, the degree of crosslinking will not be sufficient, which is not preferable. The selection and ratio of these structures are determined based on T (including thermal properties, mechanical properties, compatibility with dyes, compatibility with crosslinking agents,
These units should be selected in consideration of solubility in solvents, photocrosslinking properties, etc. In the present invention, these units may be used alone, or a plurality of these units may be used as a mixture.
［Ｔコ、［Ｕ］、［Ｉｆ［コ及び「■コ以外の繰返し単
位は、不飽和基を含んでいない繰返し単位、例えば式［
Ｉ］、［■コ、［Ｉ［［］、［■］の繰返代表例として
下記式、
ＣＨ３
あるいは、
で表わされる単位を有するポリカーボネートが挙げられ
る。王叡−β７Ｌ二し一幕１２ａ和ｔ、Ｉ＼Ｏ〒Ｊｒ−
ｊ、２ｆｉ桑二６ヱい２もＪＬゝ。The repeating units other than [Tco, [U], [If[co and "■] are repeating units that do not contain an unsaturated group, such as those of the formula [
Typical repeating examples of I], [■co, [I[], [■] include polycarbonates having units represented by the following formula, CH3 or. Wang Rui-β7L 2nd act 12a sum t, I\O〒Jr-
j, 2fi Kuwaji 6ヱii 2 is also JLも.
本発明に用いられるポリカーボネート系樹脂は、従来よ
く知られている反応（日刊工業新聞社、プラスチック材
料講座［５１、ポリカーボネート樹脂、９頁〜１４頁参
照）によって得られる。その−例を下記に示す。The polycarbonate resin used in the present invention can be obtained by a conventionally well-known reaction (see Nikkan Kogyo Shimbun, Plastic Materials Course [51, Polycarbonate Resin, pages 9 to 14]). An example is shown below.
（１）ホスゲンを用いる次式で示される反応、（Ｒ１）
ｍ Ｒａ Ｒｂ （Ｒ２）ｎジオキシ化合物の
ビスクロロホルメートを用いる反応
炭酸ジエステルを用いる次式で表わされる反応
などが用いられる（上記式中、Ｒ１，Ｒ２、Ｒａ、 Ｒ
ｂ、Ｉおよびｎは前記式［Ｉ］と同じ定義のものである
。Ｒ８はアリーレン基を表す、Ｒ３はアルキル、シクロ
アルキル及びアリール基のいずれかを表わす、）ポリカ
ーボネートが透明性に優れ、かつ安価に製造できる点で
ホスゲンを用いる反応が最も好適に用いられる。(1) Reaction represented by the following formula using phosgene, (R1)
m Ra Rb (R2)n Reaction using bischloroformate of dioxy compound Reaction using carbonic diester expressed by the following formula (in the above formula, R1, R2, Ra, R
b, I and n have the same definitions as in formula [I] above. R8 represents an arylene group, R3 represents any one of an alkyl, cycloalkyl, and aryl group.) The reaction using phosgene is most preferably used because the polycarbonate has excellent transparency and can be produced at low cost.
ポリカーボネートの架橋反応は、熱的に行うこともでき
るし、光化学反応的に行うこともできる。The crosslinking reaction of polycarbonate can be carried out thermally or by photochemical reaction.
熱による架橋反応は、ラジカル開始剤の共存下で必要に
応じて架橋剤を加えて該ポリマーを加熱することにより
容易に達成される。ラジカル開始剤としては、５０〜１
００°Ｃでの半減期が１〜１０時間のものがアロセス上
から好ましい。具体例としてはベンゾイルパーオキサイ
ド、ジイソプロピルパーオキサイド、ｔ〜プチルパーオ
キシピパレート、オクタノイルパーオキサイド、ラウロ
イルパーオキサイド、アセチルパーオキサイド、シクロ
ヘキサンパーオキサイドなどのパーオキサイド類、アゾ
ビスイソブチロニトリルおよびアゾビスイソバレロニト
リルなどのアゾ化合物が挙げられる。また、架橋剤も用
いることができる。架橋剤としては、シアツルフタし一
ト、ジアリルアミン塩酸塩、ジアリルエーテルＥなどの
ジアリル化合物、トリメチロールプロパントリアクリレ
ート、エチレンジメタクリレート、ペンタエリスリトー
ルテトラアクリレートなどの多官能アクリレートが好適
に用いられる。Thermal crosslinking reaction is easily achieved by heating the polymer in the presence of a radical initiator, optionally adding a crosslinking agent. As a radical initiator, 50 to 1
Those having a half-life of 1 to 10 hours at 00°C are preferable from the standpoint of aromatherapy. Specific examples include peroxides such as benzoyl peroxide, diisopropyl peroxide, t-butyl peroxypiparate, octanoyl peroxide, lauroyl peroxide, acetyl peroxide, and cyclohexane peroxide, azobisisobutyronitrile, and azo Examples include azo compounds such as bisisovaleronitrile. Moreover, a crosslinking agent can also be used. As the crosslinking agent, diallyl compounds such as cyazulfate, diallylamine hydrochloride, and diallyl ether E, and polyfunctional acrylates such as trimethylolpropane triacrylate, ethylene dimethacrylate, and pentaerythritol tetraacrylate are preferably used.
ポリカーボネートを熱的に架橋反応する場合は、ｆｉ工
ｒ＆５０〜１５０℃、好４ Ｌ ＜ ハフ０〜１５０
℃”’Ｃ−行う。When thermally crosslinking polycarbonate, the temperature is 50 to 150°C, preferably 4 L < Huff 0 to 150
℃”'C-Do.
５０℃以下では熱硬化反応が十分に進行せず好ましくは
ない。また、１５０℃以上では基板や色素の劣化を来す
ために好ましくない、硬化時間は、一般に５分〜１０時
間、好ましくは１０分〜５時間の範囲で行なわれる。If the temperature is below 50°C, the thermosetting reaction will not proceed sufficiently, which is not preferable. Moreover, curing time is generally 5 minutes to 10 hours, preferably 10 minutes to 5 hours, since temperatures above 150 DEG C. cause deterioration of the substrate and dye, which is undesirable.
ポリカーボネートの架橋反応を紫外光線の照射により行
なう場合には、光ラジカル開始剤のほかに好ましくは架
橋剤の共存下で塗工ｆ＆紫外線照射することにより行な
われる。この場合に好適に用いられる架橋剤としては、
（１）ポリアリル化合物、（２１多官能アクリレート、
（３１ポリメルカアタンおよび（４）多官能アジド化合
物などが挙げられる。ポリアリル化合物としては、ジア
リルフタレート、ジアリルアミン塩酸塩、ジアリルエー
テルなどのジアリル化合物が好適例として挙げられる。When the crosslinking reaction of polycarbonate is carried out by irradiation with ultraviolet light, it is carried out by coating and irradiating with ultraviolet light, preferably in the coexistence of a crosslinking agent in addition to a photoradical initiator. The crosslinking agent suitably used in this case is:
(1) Polyallyl compound, (21 polyfunctional acrylate,
Examples include (31 polymerkaatane and (4) polyfunctional azide compounds. Preferred examples of the polyallyl compound include diallyl compounds such as diallyl phthalate, diallylamine hydrochloride, and diallyl ether.
多官能アクリレートとしては、トリメチロールプロパン
トリアクリレート、エチレングリコールジメタクリレー
ト、ペンタエリスリトールテトラアクリレートなどが代
表的な例として挙げられる。ポリメルカプタンとしては
、ペンタエリスリトールテトラ（３−メルカプトグロビ
オネート）や１，４−ジメルカプトヘキサンなどが挙げ
られる。多官能のアジド化合物としては、熱安定性が比
較的良好な芳香族系アジドが好ましく用いられる。好適
に用いられる多官能アジドとしては、４．４“−ジアジ
ドベンザルアセトン、２．６−ジ（４°−アジドベンザ
ル）シクロヘキサノン、２，６−ジ（４゛−アジドベン
ザル）−４−メチルシクロヘキサンノン、ジ［４−（４
°−アジドフェニル）ブタジェニル１ケトン、４．４°
−ジアジドカルコン、４．４°−ジアジドスチルベン−
２，２°−ジスルホン酸などが挙げられる。上記架橋剤
の内、ポリアリル化合物、多官能アクリレート、および
ポリメルカプタンを使用する光架橋反応においては光ラ
ジカル開始剤の共存が好ましい、好適な光ラジカル開始
剤としては、ベンゾフェノン、ミヒラーズゲトンなどの
ベンゾフェノン系化合物、ベンジル、フェニルメトキシ
ジケトンなどのジケトン系化合物、ベンゾインエチルエ
ーテル、ベンジルジメチルケタールなどのベンゾイン系
化合物、２，４−ジエチルチオキサントンなどのチオキ
サントン系化合物、２−メチルアントラキノン、カンフ
ァーキノンなどのキノン系化合物などが好ましく用いら
れる。また、必要に応じて上記開始剤以外の光架橋反応
促進剤（例えば、Ｎ、Ｎ−ジエチルアミンベンゼン誘導
体）を併用することも可能である。照射源としては水銀
灯、中圧水銀灯、高圧水銀灯、メチルハライドランプな
どが好適に用いられる。光源のパワーは、Ｉ ｌｌ１４
／−〜１ｋ１４／′−か用いられる。照射時間は光源の
パワーおよび光反応速度に依存するが、１秒〜１時間、
好ましくは１秒〜１０分間の間で行なわれる。Typical examples of polyfunctional acrylates include trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and pentaerythritol tetraacrylate. Examples of the polymercaptan include pentaerythritol tetra (3-mercaptoglobionate) and 1,4-dimercaptohexane. As the polyfunctional azide compound, aromatic azide having relatively good thermal stability is preferably used. Suitably used polyfunctional azides include 4,4"-diazidobenzalacetone, 2,6-di(4°-azidobenzal)cyclohexanone, and 2,6-di(4'-azidobenzal)-4-methylcyclohexane. Non, di[4-(4
°-azidophenyl)butadienyl 1 ketone, 4.4°
-Diazidochalcone, 4.4°-Diazidostilbene-
Examples include 2,2°-disulfonic acid. Among the crosslinking agents mentioned above, the coexistence of a photoradical initiator is preferable in the photocrosslinking reaction using polyallyl compounds, polyfunctional acrylates, and polymercaptans. As suitable photoradical initiators, benzophenone compounds such as benzophenone and Michler's getone are preferred. , diketone compounds such as benzyl and phenylmethoxydiketone, benzoin compounds such as benzoin ethyl ether and benzyl dimethyl ketal, thioxanthone compounds such as 2,4-diethylthioxanthone, quinone compounds such as 2-methylanthraquinone and camphorquinone, etc. is preferably used. Furthermore, it is also possible to use a photocrosslinking reaction promoter other than the above-mentioned initiator (for example, N,N-diethylamine benzene derivative) in combination, if necessary. As the irradiation source, a mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a methyl halide lamp, etc. are suitably used. The power of the light source is Ill14
/- to 1k14/'- is used. The irradiation time depends on the power of the light source and the photoreaction speed, but it ranges from 1 second to 1 hour.
It is preferably carried out for 1 second to 10 minutes.
本発明において用いられるこれらのポリカーボネート、
架橋剤および開始剤は、色素と混合した上で基板上に塗
工・硬化される。使用する基板は特に限定はないが、一
般にはポリカーボネート、ポリメチルメタクリレート、
ポリ−４−メチルペンテン−１、カラスなどのディスク
状基板やポリエステルなどのフィルム状基板が用いられ
る。色素／樹脂の比率（重量比）は、色素の吸光度、膜
厚にも依存するが一般には０．０５〜０．４、好ましく
は０．１〜０．３である。膨脹層の膜厚は一般には、０
．５〜１０μｍ、好ましくは１．０〜５．０μｍか用い
られ、保持層の膜厚は０．１〜３．０μｍ、好ましくは
０．３〜２０μｍが用いられる。塗工法は特に限定はな
いが、スピンコード法、流延法、バーコード法、ドクタ
ーナイフ法、グラビヤコート法などが用いられる。その
際使用される好適な溶媒としては、ヘキサン、ヘプタン
、シクロヘキサンなどの脂肪族炭化水素；ベンゼン、ト
ルエン、キシレンなどの芳香族炭化水素：メタノール、
エタノール、ブタノールなどのアルコール類；クロロホ
ルム、塩化メチレンなどのハロアルカン類；酢酸エチル
、酢酸ブチルなどのエステル類；アセトン、メチルエチ
ルゲトン、メチルイソブチルゲトン、シクロヘキサノン
などのゲトン類：エチレングリコールモノメチルエーテ
ル、エチレングリコールモノブチルエーテルなどのグラ
イム類：テトラヒドロフラン、ジオキンなどのエーテル
類、ニトロメタン、アセトニトリルおよびそれらの混合
物が挙げられる。These polycarbonates used in the present invention,
The crosslinking agent and initiator are mixed with the dye and then applied onto the substrate and cured. The substrate used is not particularly limited, but generally polycarbonate, polymethyl methacrylate,
A disk-shaped substrate such as poly-4-methylpentene-1 or glass, or a film-shaped substrate such as polyester is used. The dye/resin ratio (weight ratio) is generally 0.05 to 0.4, preferably 0.1 to 0.3, although it depends on the absorbance of the dye and the film thickness. The thickness of the expansion layer is generally 0.
．． The thickness of the holding layer is 5 to 10 μm, preferably 1.0 to 5.0 μm, and the thickness of the holding layer is 0.1 to 3.0 μm, preferably 0.3 to 20 μm. The coating method is not particularly limited, but a spin code method, a casting method, a bar code method, a doctor knife method, a gravure coating method, etc. are used. Suitable solvents used in this case include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; methanol,
Alcohols such as ethanol and butanol; Haloalkanes such as chloroform and methylene chloride; Esters such as ethyl acetate and butyl acetate; Getones such as acetone, methyl ethyl getone, methyl isobutyl getone, and cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol Examples include glymes such as monobutyl ether: ethers such as tetrahydrofuran and dioquine, nitromethane, acetonitrile, and mixtures thereof.
かくして得られた二層媒体の記録・再生・消去は二種類
のレーザー光を照射することにより行なう、その際使用
するレーザーとしては、ヘリウムネオンレーザ−、アル
ゴンレーザー、半導体レーザーなどが用いられるが、小
型で安価な半導体レーザーがより好ましい、以下、膨脹
層色素Ｄ１が８４０ ｒ＋ｎ近傍に吸収を示し、保持層
色素Ｄ２が７８０ｎｉ１近傍に吸収を示す媒体を例にと
って説明する。Recording, reproduction, and erasing of the thus obtained dual-layer medium is performed by irradiating it with two types of laser light. The lasers used at this time include helium neon lasers, argon lasers, and semiconductor lasers. A compact and inexpensive semiconductor laser is more preferable.A medium in which the expansion layer dye D1 exhibits absorption near 840r+n and the retention layer dye D2 exhibits absorption near 780ni1 will be described below as an example.
記録は、８４０ｎｎのレーサー光を照射することにより
行なう、この際、主として膨脹層が光を吸収してバング
を形成する。再生は、８４０ｎｎの弱いレーサー光を照
射し、記録部と未記録部との反射率の差を読みとること
により行なわれる。消去は、７８０ｎｎのレーザー光を
照射することにより行なわれる。一般的に、記録は、５
〜３０１１４、好ましくは７〜２０ｎ１４のパワーで２
０〜００１μ秒照射する。再生は０．５〜３ｎＷ、好ま
しくは０．７〜２．０＋ａ簀のパワーで行なわれる。消
去は、１〜２０ｎ１４．好ましくは３〜１２１のパワー
で０．１〜２０μ秒照射する。Recording is performed by irradiating a laser beam of 840 nn. At this time, the expansion layer mainly absorbs the light to form a bang. Reproduction is performed by irradiating a weak laser beam of 840 nn and reading the difference in reflectance between the recorded area and the unrecorded area. Erasing is performed by irradiating a 780 nn laser beam. Generally, the record is 5
~30114, preferably 2 with a power of 7-20n14
Irradiate for 0 to 001 microseconds. Reproduction is performed at a power of 0.5 to 3 nW, preferably 0.7 to 2.0+a. Erasing is 1 to 20n14. Preferably, irradiation is performed at a power of 3 to 121 for 0.1 to 20 μsec.
発明の効果
本発明の架橋ポリカーボネート樹脂を保持層とする二層
媒体は優れたバング形成性、言い替えれば記録特性を示
すだけでなく、優れた消去特性を示す、そして、媒体の
流動を伴う非可逆的な変形を生じないために記録、消去
の繰り返しに耐える。Effects of the Invention The two-layer medium having the crosslinked polycarbonate resin of the present invention as a holding layer not only exhibits excellent bang forming properties, in other words, recording properties, but also exhibits excellent erasing properties, and is irreversible with medium flow. It can withstand repeated recording and erasure without causing any physical deformation.
また、本発明によると、製膜が低温・高速で行なえるな
めに、基板や使用色素の劣化を来たすことなく塗工・硬
化が行なえ、かつａ＃コストが安価になると言う工業上
の利点も有している。Further, according to the present invention, since film formation can be performed at low temperatures and high speeds, coating and curing can be performed without deteriorating the substrate or the dye used, and the cost is low. have.
Ｋ１週
以下に、本発明を実論例に従ってさらに詳しく説明する
。In the following K1 week, the present invention will be explained in more detail according to a practical example.
参考例１
（３，３“−ジアリルビスフェノールＡ〜ビスフェノー
ルＺコポリカーボネートの製造法）
撹拌機、温度計、ガス導入管および還流冷却器を備え付
けた１リツトルの三つ口丸底フラスコに乾燥した窒素ガ
スを流しながら、４８．５％のカ性ソーダ水溶液５３．
７重量部、水２３０．８重量部、 ３．３’−ジアリル
ビスフェノールＡ３１．４重量部、ビスフェノール２２
７．３重量部を仕込んで溶解した。この溶液を水浴で２
０℃に冷却し撹拌しながらホスゲンガス２６．２重量部
を１時間かけて徐々に導入した。その後、４８．５％の
力性ソーダ水溶液８，４重量部を加え、さらに反応停止
剤としてρ−ｔ−ブチルフェノール０．６１重量部を加
えた後、３０℃で１時間重合反応を続けた０反応終了後
、塩化メチレン層を分離して塩酸酸性にしたのち、水洗
を繰り返し溶存塩類を除去した。その後、塩化メチレン
を蒸発して固体を得な（収＄９９％、）。かくして得ら
れた重合体の塩化メチレン中、２０℃で測定した比粘度
は０．２１であった。このものは、塩化メチレン、クロ
ロホルム、トルエン、テトラヒドロフラン、シクロヘキ
サノンなどに１０重量％可溶であった。また、水素核磁
気共鳴スペクトルによる測定の結果、このものは下記式
の２，２゛−ジアリルビスフェノールＡルビスフエノー
ルＺの１：１共重合ポリカーボネートであることが確認
された。Reference Example 1 (Production method of 3,3″-diallylbisphenol A to bisphenol Z copolycarbonate) Dry nitrogen was placed in a 1 liter three-necked round bottom flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser. While flowing gas, add 48.5% caustic soda aqueous solution 53.
7 parts by weight, 230.8 parts by weight of water, 31.4 parts by weight of 3.3'-diallylbisphenol A, 22 parts by weight of bisphenol.
7.3 parts by weight was charged and dissolved. Pour this solution in a water bath for 2
While cooling to 0°C and stirring, 26.2 parts by weight of phosgene gas was gradually introduced over 1 hour. Thereafter, 8.4 parts by weight of a 48.5% aqueous sodium hydroxide solution was added, and 0.61 parts by weight of ρ-t-butylphenol was added as a reaction terminator, and the polymerization reaction was continued at 30°C for 1 hour. After the reaction was completed, the methylene chloride layer was separated and acidified with hydrochloric acid, and then washed with water repeatedly to remove dissolved salts. The methylene chloride was then evaporated to obtain a solid (yield $99%). The specific viscosity of the thus obtained polymer measured in methylene chloride at 20°C was 0.21. This product was soluble at 10% by weight in methylene chloride, chloroform, toluene, tetrahydrofuran, cyclohexanone, and the like. Further, as a result of measurement by hydrogen nuclear magnetic resonance spectroscopy, it was confirmed that this product was a 1:1 copolymerized polycarbonate of 2,2'-diallylbisphenol A and rubisphenol Z of the following formula.
実施例１
膨脹層樹脂Ｐ】として、ウレタンアクリレートＵ−１２
２＾（新中村化学）１００重１部を用い、この樹脂に光
重合開始刑としてイルガキュアー９０７（ｃｈｉｂａ
Ｇｅｉｇｙ社）を３重量部、８３０ｎｉ半導体レーザ用
色素としてポリメチン色素ＩＲ−８２０（日本化薬）を
１０重量部添加し、溶媒としてメチルエチルゲトンを用
い、塗工溶液を作成した。得らた溶液をガラス基板に膜
厚３〜４μｍになるように塗工し乾燥した後、窒素雰囲
気下で８０ ｗ ｙ’ ｃｉの高圧水銀灯光を３０分間
照射することにより紫外光硬化を行なった。次に、参考
例１で得たアリル置換ポリカーボネート共重合体１００
重量部、シアニン色素（ＮＫ−１２５，日本感光色素）
１０重量部、ペンタエリスリトールテトラ（３−メルカ
プトプロピオネート）１０重量部およびイルガキュア９
０７．１重量部をクロロホルムに溶解して１０重量％の
均一溶液を得た。この溶液を厚み１μｍになるように上
記膨張層上に塗布したのち８０℃にて１０分間乾燥した
。しかる後、この皮膜を静置下、８０ｗ／ｉの照射エネ
ルギーを持つ高圧水銀灯により１０分間照射することに
より皮膜を硬化した。得られた二層構成媒体に、８３０
ｎＩｌの発振波長と先頭出力１０１１４の半導体レーザ
光を０２μ秒照射したところ、媒体表面に直径１．４μ
ｍの明瞭な***部（バンプ）の形成が認められた。引続
き、この記録スポット上に、ビーム径５μｍ、発振波長
７８０ｎｍの７１−半導体レーザ光を５μ秒間照射した
ところ、上記のバンプは８Ｎ鏡観察では確認できない程
度に消滅していた。この結果から、上記の記録媒体は記
録・消去の可能な光字情報記録媒体となりうろことが分
かった。Example 1 Urethane acrylate U-12 as expansion layer resin P
2^ (Shin Nakamura Chemical) 1 part 100 weight was used, and Irgacure 907 (chiba
A coating solution was prepared by adding 3 parts by weight of Polymethine dye IR-820 (Nippon Kayaku) as a dye for an 830 ni semiconductor laser, and using methyl ethyl getone as a solvent. The obtained solution was applied to a glass substrate to a film thickness of 3 to 4 μm, dried, and then cured with ultraviolet light by irradiating it with light from a high-pressure mercury lamp of 80 w y' ci for 30 minutes in a nitrogen atmosphere. . Next, allyl-substituted polycarbonate copolymer 100 obtained in Reference Example 1
Parts by weight, cyanine dye (NK-125, Nippon Kanko Dyes)
10 parts by weight, 10 parts by weight of pentaerythritol tetra(3-mercaptopropionate) and Irgacure 9
07.1 parts by weight was dissolved in chloroform to obtain a 10% by weight homogeneous solution. This solution was applied onto the expansion layer to a thickness of 1 μm, and then dried at 80° C. for 10 minutes. Thereafter, the film was cured by irradiating it for 10 minutes with a high-pressure mercury lamp having an irradiation energy of 80 w/i while the film was left standing. The resulting two-layer medium was given 830
When a semiconductor laser beam with an oscillation wavelength of nIl and a leading output of 10114 was irradiated for 02 μs, a diameter of 1.4 μ was formed on the medium surface.
Formation of a clear protuberance (bump) of m was observed. Subsequently, when this recording spot was irradiated with a 71-semiconductor laser beam having a beam diameter of 5 μm and an oscillation wavelength of 780 nm for 5 μs, the bumps mentioned above had disappeared to such an extent that they could not be confirmed by 8N mirror observation. From this result, it was found that the above-mentioned recording medium could be an optical information recording medium that can be recorded and erased.
実論例２
実株例１において保持層としてアリル置換ポリカーボネ
ート共重合体を用いる代わりに、下記のアリル置換ポリ
カーボネート単独重合体を用いて同様に二層媒体を得た
。Practical Example 2 Instead of using the allyl-substituted polycarbonate copolymer as the retention layer in Practical Example 1, the following allyl-substituted polycarbonate homopolymer was used to obtain a two-layer medium in the same manner.
かくして得られた二層構成ａ体に、８３０ｎ１１の発振
波長と先頭出力１０ｎ−の半導体レーザ光を０．１μ秒
照射したところ、媒体表面に直径１．４μｍの明譚な隆
起部（バンプ）の形成が認められた。引続き、この記録
スポット上に、ビーム径５μｍ、発振波長７８０ｎｌｌ
の７１半導体レーザ光を４．０μ秒間照射したところ、
上記のバンプは顕微鏡観察では確認できない程度に消滅
していた。When the thus obtained two-layer structure A body was irradiated with a semiconductor laser beam having an oscillation wavelength of 830n11 and a leading output of 10n- for 0.1 μs, a distinct bump with a diameter of 1.4 μm was observed on the medium surface. Formation was observed. Subsequently, a beam diameter of 5 μm and an oscillation wavelength of 780 nll was placed on this recording spot.
When irradiated with 71 semiconductor laser light for 4.0μ seconds,
The above bumps had disappeared to such an extent that they could not be confirmed by microscopic observation.
この結果から、上記の記録媒体は記録・消去の可能な光
学情報記録媒体となりうろことが分かった。From this result, it was found that the above-mentioned recording medium could be an optical information recording medium capable of recording and erasing information.
ＣＨ２ＣＨ２
実施例３
実施例１において膨張層として単独のウレタンアクリレ
ートＵ−１２２Ａを用いる代わりに、多官能架橋成分で
あるウレタンアクリレートオリゴマー（Ｕ−１２２６＾
、新中村化学）との４：６重量比混合物を用い、同様に
二層媒体を作成した。かくして得られた二層構成媒体に
８３Ｏｎ１Ｍの発振波長と先頭出力１０ｎ１４の半導体
レーザ光を０．２μ秒照射したところ、媒体表面に直径
１．６μｍの明瞭な***部（バンプ）の形成か認められ
た。引続き、この記録スポット上に、ビーム径５μｍ、
発振波長７８０ｎｉｍの７１−半導体レーザ光を５．０
μ秒間照射したところ、上記のバンプは蓼微鏡観察では
確認できない程度に消滅していた。この結果から、上記
の記録媒体は記録・消去の可能な光学情報記録媒体とな
りうろことが分かった。CH2CH2 Example 3 Instead of using urethane acrylate U-122A alone as the expansion layer in Example 1, urethane acrylate oligomer (U-1226^) which is a multifunctional crosslinking component was used.
A two-layer medium was prepared in the same manner using a 4:6 weight ratio mixture of 1. When the thus obtained two-layered medium was irradiated with a semiconductor laser beam with an oscillation wavelength of 83On1M and a leading output of 10N14 for 0.2μ seconds, the formation of clear bumps with a diameter of 1.6μm was observed on the medium surface. Ta. Subsequently, a beam diameter of 5 μm was placed on this recording spot.
71-semiconductor laser light with an oscillation wavelength of 780 nm at 5.0
When irradiated for μ seconds, the bumps mentioned above had disappeared to such an extent that they could not be confirmed by microscopic observation. From this result, it was found that the above-mentioned recording medium could be an optical information recording medium capable of recording and erasing information.
実施例４
実施例１において、ペンタエリスリトールテトラ（３−
メルカグトプロピオネート）を用いる代わりに、トリメ
チロールプロパントリアクリレートを用いて同様に二層
媒体を作成した。この媒体に実施例１と同様に発振波長
８３０ｎｎ 、強度１０ｎＷの記録用レーザ光を０．２
μ秒照射したところ、明瞭なバンプ形成が認められた。Example 4 In Example 1, pentaerythritol tetra(3-
A bilayer media was similarly made using trimethylolpropane triacrylate instead of using trimethylolpropane triacrylate (mercagtopropionate). As in Example 1, a recording laser beam with an oscillation wavelength of 830 nn and an intensity of 10 nW was applied to this medium for 0.2 min.
After microsecond irradiation, clear bump formation was observed.
引続き、こ記録スポット上に、ビーム径５μｍ、発振波
長７８０ｒ＋ｎの７１半導体レーザ光を６μ秒間照射し
たところ、上記のバンプは謬微鏡観察では確認できない
程度に消滅していた。この結果から、上記の記録媒体は
記録・消去の可能な光学情報記録媒体となりうろことが
分かった。Subsequently, when this recording spot was irradiated with 71 semiconductor laser light having a beam diameter of 5 μm and an oscillation wavelength of 780 r+n for 6 μ seconds, the bumps mentioned above had disappeared to such an extent that they could not be confirmed by microscopic observation. From this result, it was found that the above-mentioned recording medium could be an optical information recording medium capable of recording and erasing information.
実施例５
実施例３で得た二層媒体を、線速度２ｍ／秒で移動しな
がら発振波長８４０ｎｌ、強度１０ｎ−のレーザを５
ＭＨｚ （ｄｕｔｙ比５０）のサイクルで照射したと
ころ媒体上に直径１．２μｍの明瞭なバンプ列が形成し
、そのＣ／’ Ｎ比は５２ｄＢであった。引続き、この
記録バング列上に、発振波長７８０ｎｌの７１−半導体
レーザ光を連続照射したところ、上記のバンプは消滅し
た。この記録・消去テストを１０００回繰り返しな後Ｃ
／Ｎ比は５２ｄＢと全く変化しなかった。この結果から
、上記の記録媒体は高い繰り返し記録・消去特性を有す
る光学情報記録媒体となりうろことが分かった。Example 5 A laser with an oscillation wavelength of 840 nl and an intensity of 10 n- was applied to the two-layer medium obtained in Example 3 while moving at a linear velocity of 2 m/s.
When irradiated with a cycle of MHz (duty ratio 50), a clear bump row with a diameter of 1.2 μm was formed on the medium, and the C/'N ratio was 52 dB. Subsequently, when this recording bump array was continuously irradiated with 71-semiconductor laser light having an oscillation wavelength of 780 nl, the bumps disappeared. After repeating this recording/erasing test 1000 times,
/N ratio remained unchanged at 52 dB. From this result, it was found that the above recording medium could be an optical information recording medium having high repeated recording/erasing characteristics.
特許出願人 帝 人 株 式 会 社 帝人化成株式会社 代 理 人 弁理士 前 １）純 博Patent applicant Teijin Kaisha Ltd. Teijin Chemicals Ltd. Former Patent Attorney 1) Hiroshi Jun
Claims (4)
（Ｐ＿１）と色素（Ｄ＿１）とからなる膨脹層（Ａ）と
、室温でガラス状態、それより高い温度でゴム状態に可
逆的に変化し得る樹脂（Ｐ＿２）と色素（Ｄ＿２）とか
らなる保持層（Ｂ）とを支持してなる光記録媒体におい
て、該保持層樹脂Ｐ＿２が （ａ）室温での弾性率が５０ｋｇ／ｍｍ＾２以上であり
、 （ｂ）ガラス転移温度が６０〜１５０℃であって、 （ｃ）架橋構造を有するポリカーボネート樹脂であるこ
とを特徴とする消去可能な二層型有機光記録媒体。(1) On the substrate, there is an expansion layer (A) consisting of a resin (P_1) that exhibits rubber elasticity at least at room temperature and a dye (D_1), which changes reversibly into a glass state at room temperature and into a rubber state at higher temperatures. In an optical recording medium formed by supporting a holding layer (B) consisting of a resin (P_2) and a dye (D_2), the holding layer resin P_2 (a) has an elastic modulus of 50 kg/mm^2 at room temperature. An erasable two-layer organic optical recording medium, characterized in that (b) it has a glass transition temperature of 60 to 150°C, and (c) it is made of a polycarbonate resin having a crosslinked structure.
数式、化学式、表等があります▼［ I ］ または下記一般式［II］： ▲数式、化学式、表等があります▼［II］ 式［ I ］中、Ｒ＿１およびＲ＿２は同一または異なり
炭素数２〜８の一価の脂肪族不飽和炭化水素基であり、
Ｒ＿ａおよびＲ＿ｂは同一または異なり水素原子、ハロ
ゲン原子を有していてもよい炭素数１〜８の飽和炭化水
素基または芳香族炭化水素基である。 式［II］中、Ｒ＿３およびＲ＿４は同一または異なり炭
素数２〜８の一価の脂肪族不飽和炭化水素基であり、Ｒ
＿ｃは炭素数４〜１０の二価の飽和炭化水素基である、
式［ I ］、［II］中、ｍおよびｎはそれぞれ０．１又
は２であり、かつｍ＋ｎは１以上である。 または下記一般式［III］： ▲数式、化学式、表等があります▼［III］ 式［III］中、Ｒ＿５は炭素数２〜８の一価の脂肪族不
飽和炭化水素基である、また、１は１または２である。 からなる単位を少なくとも１０モル％以上含むポリカー
ボネートを架橋したものであることを特徴とする請求項
１記載の消去可能な二層型有機光記録媒体。(2) Polycarbonate resin has the following general formula [I]: ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] or the following general formula [II]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] In the formula [I], R_1 and R_2 are the same or different and have a carbon number of 2 to 8 monovalent aliphatic unsaturated hydrocarbon group,
R_a and R_b are the same or different and are a saturated hydrocarbon group or an aromatic hydrocarbon group having 1 to 8 carbon atoms, which may have a hydrogen atom or a halogen atom. In formula [II], R_3 and R_4 are the same or different and are monovalent aliphatic unsaturated hydrocarbon groups having 2 to 8 carbon atoms, and R
_c is a divalent saturated hydrocarbon group having 4 to 10 carbon atoms,
In formulas [I] and [II], m and n are each 0.1 or 2, and m+n is 1 or more. Or the following general formula [III]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] In formula [III], R_5 is a monovalent aliphatic unsaturated hydrocarbon group having 2 to 8 carbon atoms, and 1 is 1 or 2. 2. The erasable two-layer organic optical recording medium according to claim 1, wherein the erasable two-layer organic optical recording medium is a crosslinked polycarbonate containing at least 10 mol% or more of units consisting of.
式、化学式、表等があります▼［IV］ 式［IV］中、Ｘは炭素数２以上のアルキレ ン基、フェニレン基、シクロアルキレン基、アラルキレ
ン基、−Ｏ−、−Ｓ−、−ＳＯ＿２▲数式、化学式、表
等があります▼、−ＳＯ＿２−Ａｒ− ＳＯ＿２−、−Ｏ−Ｚ−Ｏ−基のいずれかを表わす、た
だし、Ａｒは核置換されていてもよい炭素数６〜１２の
アリーレン基である、またＺは炭素数２〜４のアルキレ
ン基、Ｒ＿６およびＲ＿７は同一または異なり炭素数２
〜８の一価の脂肪族不飽和炭化水素基である、また、１
およびｎはそれぞれ０、１または２でありかつｍ＋ｎは
１以上である。 で表わされる単位を少なくとも１０モル％以上含むポリ
カーボネートを架橋したものであることを特徴とすると
する請求項１記載の消去可能な二層型有機光記録媒体。(3) Polycarbonate resin has the following general formula [IV]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] In formula [IV], X is an alkylene group with 2 or more carbon atoms, a phenylene group, a cycloalkylene group, or an aralkylene group. group, -O-, -S-, -SO_2▲ Numerical formulas, chemical formulas, tables, etc.▼, -SO_2-Ar- Represents either SO_2-, -O-Z-O- group, provided that Ar is a nuclear is an optionally substituted arylene group having 6 to 12 carbon atoms, Z is an alkylene group having 2 to 4 carbon atoms, and R_6 and R_7 are the same or different;
~8 monovalent aliphatic unsaturated hydrocarbon groups, and 1
and n are 0, 1 or 2, respectively, and m+n is 1 or more. 2. The erasable two-layer organic optical recording medium according to claim 1, wherein the erasable two-layer organic optical recording medium is a crosslinked polycarbonate containing at least 10 mol % of units represented by the following.
応じて架橋剤の共存下、膨脹層（Ａ）上に塗工した後、
紫外光照射または熱処理することを特徴とする請求項１
〜３記載の消去可能な光記録媒体の製造法。(4) After coating polycarbonate on the expansion layer (A) in the coexistence of a radical initiator and, if necessary, a crosslinking agent,
Claim 1 characterized in that it is subjected to ultraviolet light irradiation or heat treatment.
3. The method for producing an erasable optical recording medium according to item 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2139935A JPH04151287A (en) | 1990-03-14 | 1990-05-31 | Two-layer organic optical recording medium having polycarbonate crosslinking body as record retaining layer and manufacture thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6126690 | 1990-03-14 | ||
| JP2-61266 | 1990-03-14 | ||
| JP2139935A JPH04151287A (en) | 1990-03-14 | 1990-05-31 | Two-layer organic optical recording medium having polycarbonate crosslinking body as record retaining layer and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04151287A true JPH04151287A (en) | 1992-05-25 |
Family
ID=26402311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2139935A Pending JPH04151287A (en) | 1990-03-14 | 1990-05-31 | Two-layer organic optical recording medium having polycarbonate crosslinking body as record retaining layer and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04151287A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10428190B2 (en) | 2014-06-20 | 2019-10-01 | Sabic Global Technologies B.V. | Processes for designing cross-linkable polycarbonates and articles formed therefrom |
-
1990
- 1990-05-31 JP JP2139935A patent/JPH04151287A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10428190B2 (en) | 2014-06-20 | 2019-10-01 | Sabic Global Technologies B.V. | Processes for designing cross-linkable polycarbonates and articles formed therefrom |
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