JP4318512B2 - J-aggregate thin film formed body and optical information recording medium - Google Patents
J-aggregate thin film formed body and optical information recording medium Download PDFInfo
- Publication number
- JP4318512B2 JP4318512B2 JP2003309674A JP2003309674A JP4318512B2 JP 4318512 B2 JP4318512 B2 JP 4318512B2 JP 2003309674 A JP2003309674 A JP 2003309674A JP 2003309674 A JP2003309674 A JP 2003309674A JP 4318512 B2 JP4318512 B2 JP 4318512B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- dye
- film
- aggregate
- recording medium
- 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.)
- Expired - Fee Related
Links
- 239000010409 thin film Substances 0.000 title claims description 79
- 230000003287 optical effect Effects 0.000 title claims description 24
- 239000010408 film Substances 0.000 claims description 33
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 26
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 20
- 238000004528 spin coating Methods 0.000 claims description 14
- 229920006254 polymer film Polymers 0.000 claims description 6
- 239000002861 polymer material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 74
- 238000000034 method Methods 0.000 description 31
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
本発明は、光学素子に応用できるＪ会合体薄膜形成体、及びこれを利用したＣＤ−Ｒ、ＤＶＤ−Ｒ等のレーザー光により記録及び再生が可能なヒートモードによる追記型の光情報記録媒体であって、記録層にシアニン色素からなる色素膜とその上に設けた高分子材料膜からなる記録材料薄膜をＪ会合体薄膜に形成し、高屈折率を示すとともに、高速記録化、高密度記録化を可能とした光情報記録媒体に関する。 The present invention relates to a J aggregate thin film forming body applicable to an optical element, and a write-once type optical information recording medium by a heat mode capable of recording and reproducing by a laser beam such as CD-R and DVD-R using the same. In addition, a recording material thin film made of a cyanine dye and a polymer material film provided thereon is formed on the recording layer as a J-aggregate thin film, and exhibits a high refractive index, high speed recording, and high density recording. The present invention relates to an optical information recording medium that can be realized.
文字、図形等の画像や映像あるいは音声等のデータを記録し、再生する手段としては、波長７７０〜８３０ｎｍのレーザー光に対応した記録及び再生が可能な記録材料として例えばペンタメチン系シアニン色素を含有する記録層を有する光ディスクがＣＤ−Ｒとして知られているが、このレーザー光より短波長の例えば６２０〜６９０ｎｍの赤色レーザー光により高密度記録及び再生が可能なＤＶＤ−Ｒ（デジタル・ビデオ・ディスク−レコーダブル又はデジタルバーサタイル・ディスク−レコーダブル）等がＣＤ−Ｒに代わるこれからの時代を担うメディア（光情報記録媒体）として用いられるようになってきた。
このようなＣＤ−ＲやＤＶＤ−Ｒ等においては、現在、波長６００〜８００ｎｍの半導体レーザーに反応して、記録しようとする情報の信号に従って熱分解等によりピットを形成し、これにより記録することができる有機色素化合物を記録層に用い、記録の性能を向上させることが行われている。
As a means for recording and reproducing data such as images, images such as characters and graphics, video, or sound, a recording material capable of recording and reproducing corresponding to laser light with a wavelength of 770 to 830 nm, for example, contains a pentamethine cyanine dye. An optical disc having a recording layer is known as a CD-R. A DVD-R (digital video disc) capable of high-density recording and reproduction with a red laser beam having a shorter wavelength than this laser beam, for example, 620 to 690 nm. Recordable or digital versatile disc-recordable) has come to be used as a medium (optical information recording medium) that bears the future era replacing CD-R.
In such CD-R, DVD-R, etc., pits are formed by thermal decomposition in accordance with a signal of information to be recorded in response to a semiconductor laser having a wavelength of 600 to 800 nm, and recording is thereby performed. An organic dye compound that can be used for the recording layer is used to improve recording performance.
シアニン色素は様々な会合体を形成することが知られている。その会合状態を薄膜上で制御することは困難である。その中に、比較的シャープな吸収を有するＪ会合体薄膜がある。そのＪ会合体薄膜の製法としては、（ｉ）ＬＢ膜法、（ｉｉ）スピンコート法、（ｉｉｉ）デップ（Ｄｉｐ）法が挙げられる。
ＬＢ膜法（Ｌａｎｇｍｕｉｒ−Ｂｌｏｄｇｅｔｔ法：親水基と疎水基の両方を持つ分子を適当な溶媒に溶かして水面上に展開させると気−液界面に吸着されて、単分子膜を水面上に形成する。これに基板等をゆっくり浸漬させる等で均一な薄膜を形成させる方法。）は、精密・均一な薄膜形成が可能であり、優れた光学特性をもつ色素薄膜が得られるが、成膜時に高度な制御が必要であることから、時間、コスト面で問題がある。スピンコート法（色素溶液を回転する基板の上に滴下し薄膜状に広げる方法）は、容易に色素薄膜形成が可能であるが、単純なコート条件下では色素の分子が様々な状態で存在するため会合状態を制御することが困難であるという問題がある。デップ法（色素溶液に基板を浸漬したの後取り出して乾燥し、その表面に色素膜を形成する方法）は、容易に色素分子の会合状態を制御することが可能であるが、均一な薄膜形成やその薄膜を安定に保持させることに困難がある。
It is known that cyanine dyes form various aggregates. It is difficult to control the association state on the thin film. Among them is a J-aggregate thin film having a relatively sharp absorption. Examples of the method for producing the J aggregate thin film include (i) an LB film method, (ii) a spin coating method, and (iii) a dip method.
LB membrane method (Langmuir-Blodgett method: When a molecule having both a hydrophilic group and a hydrophobic group is dissolved in an appropriate solvent and developed on the water surface, it is adsorbed at the gas-liquid interface to form a monomolecular film on the water surface. The method of forming a uniform thin film by slowly immersing the substrate etc. in this is capable of forming a precise and uniform thin film, and a dye thin film having excellent optical properties can be obtained. There is a problem in terms of time and cost because it needs to be controlled. The spin coating method (a method in which a dye solution is dropped onto a rotating substrate and spreads in a thin film form) can easily form a dye thin film, but dye molecules exist in various states under simple coating conditions. Therefore, there is a problem that it is difficult to control the meeting state. The dipping method (a method in which a substrate is immersed in a dye solution and then taken out and dried to form a dye film on the surface) can easily control the association state of dye molecules, but it can form a uniform thin film. In addition, it is difficult to stably hold the thin film.
上記の各方法の内、スピンコート法は、通常の色素膜形成法として、工程上の簡便さ、操作の容易さの面で他の手法より優れており、ＣＤ−ＲやＤＶＤ−Ｒなどの光情報記録媒体製造工程に広く使われている。スピンコート法あるいはこれに類似する薄膜形成法で、Ｊ会合体薄膜を形成しているものとして、例えば以下の３件を挙げることができる。
すなわち、有機色素（シアニン色素）のＪ会合体薄膜を形成するものとして、（１）シアニン色素／シリカゲル溶液を用いるもの、また、（２）シアニン色素／高分子材料の高粘度溶液をラビング処理して用いるもの、そして（３）Ｊ会合体を形成し易いスクエアリリウム色素を用いるものである。
That is, as a material for forming a J-aggregate thin film of an organic dye (cyanine dye), (1) using a cyanine dye / silica gel solution, and (2) rubbing a high viscosity solution of cyanine dye / polymer material. And (3) a squarylium dye that easily forms a J-aggregate.
しかしながら、上記（１）の方法（特許文献１）は、薄膜中のシアニン色素濃度がシリカによって薄められることで、色素薄膜としてはレーザーで識別できるのに十分なピットを形成する機能を有することができず、この技術を光情報記録媒体に応用することは困難である。また、上記（２）の方法（特許文献２）は、同様に薄膜中のシアニン色素濃度が高分子材料によって薄められることで、満足なピットを形成することかてきない上に、ラビング処理に必要な熱（１３０℃）を基板（ポリカーボネート）に加えてしまい、基板の変形をもたらし、この技術も光情報記録媒体に応用することは困難である。そして上記（３）の方法（特許文献３）は、スクエアリリウム色素は有機溶剤に対する溶解性が乏しく、光情報記録媒体の基板であるポリカーボネートを侵食しない溶剤に対しての溶解性を確保し難く、その色素溶液のスピンコート法により得られる色素薄膜は十分な膜厚を得られないという問題がある。また、溶解性を確保するために、スクエアリリウム色素分子に適当な置換基を導入して化学修飾すると、Ｊ会合体の形成に悪影響を及ぼし、そのため、設計する上で、「溶解性」、「会合性」を考慮しなければならない複雑さがあり、この技術も光情報記録媒体に応用することは適切ではない。 However, the above method (1) (Patent Document 1) has a function of forming pits sufficient to be identified by a laser as a dye thin film because the cyanine dye concentration in the thin film is diluted with silica. Therefore, it is difficult to apply this technique to an optical information recording medium. In addition, the method (2) described above (Patent Document 2) is not necessary for forming a satisfactory pit because the cyanine dye concentration in the thin film is also thinned by the polymer material, and is necessary for the rubbing treatment. Heat (130 ° C.) is applied to the substrate (polycarbonate) to cause deformation of the substrate, and this technique is also difficult to apply to the optical information recording medium. In the method (3) described above (Patent Document 3), squarylium dye has poor solubility in an organic solvent, and it is difficult to ensure solubility in a solvent that does not erode polycarbonate as a substrate of an optical information recording medium. The dye thin film obtained by the spin coating method of the dye solution has a problem that a sufficient film thickness cannot be obtained. In addition, in order to ensure the solubility, when a suitable substituent is introduced into the squarylium dye molecule and chemically modified, it adversely affects the formation of the J-aggregate. Therefore, in designing, “solubility”, “ There is a complexity that must consider “association”, and it is not appropriate to apply this technique to an optical information recording medium.
優れた光記録媒体を得るには、記録層としての記録材料薄膜としては、均一な薄膜を形成させること、良い光学特性（高屈折率）やシャープな吸収スペクトルをを持つ薄膜を形成させること、基板を侵すことが無い溶剤の色素溶液で塗布可能なこと、記録材料薄膜中の記録を行う部分の構成成分が色素材料のみか、あるいは色素材料の方が多い割合であること、これらを簡易な方法で実現できることであるが、上記した従来の方法によるＪ会合体薄膜によってはこれら全てを満足できるものがないという問題点がある。また、従来のＪ会合体薄膜では、熱安定性が低く、短い輻射寿命を持つため、量子収率が低くなるという問題もある。 In order to obtain an excellent optical recording medium, as a recording material thin film as a recording layer, a uniform thin film should be formed, a thin film having good optical properties (high refractive index) and a sharp absorption spectrum, It can be applied with a dye solution of a solvent that does not attack the substrate, and the constituent component of the recording portion in the recording material thin film is only the dye material, or the proportion of the dye material is larger. However, there is a problem that none of the J-aggregate thin films obtained by the conventional methods described above can satisfy all of these. In addition, the conventional J-aggregate thin film has a problem in that the quantum yield is low because the thermal stability is low and the radiation lifetime is short.
本発明者らは、上記課題を解決するために鋭意研究した結果、シアニン色素の色素膜とその上に設ける高分子材料膜をスピンコート法により形成することより、その両層からなる記録材料薄膜を少なくとも色素膜についてＪ会合体薄膜とすることができることを見い出し、本発明をするに至った。
したがって、本発明は、（１）、基板上にシアニン色素を含有する色素溶液をスピンコートすることにより得られる色素膜と、該色素膜の上に高分子材料液としてポリ（ジアリルジメチルアンモニウム−クロライド）液をスピンコートすることにより得られる高分子膜を有し、少なくとも色素膜をＪ会合体薄膜とするＪ会合体薄膜形成体を提供するものである。
また、本発明は、（２）、シアニン色素がチオシアニン色素である上記（１）のＪ会合体薄膜形成体、（３）、基板上に色素膜を含む光干渉層を有する光情報記録媒体において、該基板上に色素膜を形成する色素膜形成体が上記（１）又は（２）のＪ会合体薄膜形成体である光情報記録媒体を提供するものである。
As a result of diligent research to solve the above-mentioned problems, the present inventors have formed a recording material thin film comprising both layers by forming a dye film of a cyanine dye and a polymer material film provided thereon by a spin coating method. Has been found to be a J-aggregate thin film at least with respect to the dye film, leading to the present invention.
Accordingly, the present invention provides (1) a dye film obtained by spin-coating a dye solution containing a cyanine dye on a substrate, and poly (diallyldimethylammonium chloride) as a polymer material solution on the dye film. ) A J-aggregate thin film forming body having a polymer film obtained by spin-coating a liquid and having at least a dye film as a J-aggregate thin film.
The present invention also relates to (2 ) an optical information recording medium having a J-aggregate thin film forming body according to (1 ), wherein the cyanine dye is a thiocyanine dye, ( 3 ), and an optical interference recording layer including a dye film on the substrate. The present invention provides an optical information recording medium in which the dye film forming body for forming a dye film on the substrate is the J aggregate thin film forming body of (1) or (2 ).
本発明において、スピンコート法を用いたことにより均一な薄膜を形成させることができ、記録材料薄膜を少なくとも色素膜についてＪ会合体とすることにより、良い光学特性（高屈折率）を持つ薄膜として、色素薄膜の吸収スペクトルを先鋭化（シャープ）させることができる。溶解性の良いシアニン色素を用いることにより溶剤の選択幅が広がり、基板を侵すことがない溶剤を用いてその色素溶液を塗布することができ、色素膜の上に高分子膜を設け、色素膜は色素材料のみで構成して記録材料薄膜中の構成成分に占める色素材料をある一定以上確保することができる（色素膜の膜厚が大きいほど特に表面の色素は剥落し（崩れ）易いがその上に高分子膜を設けるとその剥落を防止でき色素膜の膜厚を大きくできる）。これらのことを簡便なスピンコート法を用いることにより簡易に行うことができる。 In the present invention, a uniform thin film can be formed by using a spin coating method, and a thin film having good optical characteristics (high refractive index) can be obtained by using a recording material thin film as a J aggregate for at least a dye film. The absorption spectrum of the dye thin film can be sharpened. By using a highly soluble cyanine dye, the range of solvent choices can be expanded, and the dye solution can be applied using a solvent that does not attack the substrate. A polymer film is provided on the dye film, and the dye film is formed. Makes it possible to secure a certain amount or more of the dye material occupying the constituents of the recording material thin film only with the dye material (the larger the dye film thickness, the more easily the surface dye is peeled off) If a polymer film is provided on the top, peeling of the polymer film can be prevented and the film thickness of the dye film can be increased). These can be easily performed by using a simple spin coating method.
本発明によれば、優れた光学特性（高屈折率）やシャープな吸収スペクトルを持つことができる、色素膜と高分子膜としてポリ（ジアリルジメチルアンモニウム−クロライド）膜からなる記録材料薄膜をスピンコート法により形成するようにしたので、高速記録化、高密度記録化を行うことができ、しかも汎用されているスピンコート法を用いるので、従来の工程を大きな変更をすることなく用いることができ、優れた特性を持つＪ会合体薄膜形成体及びこれを用いた光情報記録媒体を簡便に提供することができる。
According to the present invention, a recording material thin film comprising a dye film and a poly (diallyldimethylammonium chloride) film as a polymer film, which can have excellent optical characteristics (high refractive index) and a sharp absorption spectrum, is spin-coated. Since it was formed by the method, high-speed recording, high-density recording can be performed, and since a widely used spin coating method is used, the conventional process can be used without major changes, It is possible to easily provide a J aggregate thin film forming body having excellent characteristics and an optical information recording medium using the same.
上記の各性能を持つことができるＪ会合体薄膜形成体及びこれを用いた光情報記録媒体を簡便に提供するという本発明の目的を、スピンコート法を用いてシアニン色素の色素膜と高分子膜を形成することにより実現した。 The object of the present invention to simply provide a J-aggregate thin film forming body capable of having each of the above-mentioned performances and an optical information recording medium using the same is as follows. This was realized by forming a film.
Ｊ会合体薄膜の形成法は以下のとおりである。
（１） 下記〔化１〕のシアニン色素（チオシアニン色素）を１．５ｇはかりとり、２，２，３，３−テトラフルオロ−１−プロパノール１００ｍＬに溶解させ、１５ｇ／Ｌの溶液を調製した。
The method for forming the J-aggregate thin film is as follows.
(1) 1.5 g of the cyanine dye (thiocyanine dye) of the following [Chemical Formula 1] was weighed and dissolved in 100 mL of 2,2,3,3-tetrafluoro-1-propanol to prepare a 15 g / L solution.
（２） この溶液を厚さ１．２ｍｍ、４ｃｍ四方のポリカーボネート単板の基板に、１ｍ滴下した後、３０００ｒｐｍ（毎分の回転数）の回転数で３０秒間スピンコートした。 このようにして得られた色素薄膜について吸収スペクトルを測定した結果を図１に「ＰＤＤＡ処理前」として示す。 (2) After dropping 1 m of this solution onto a polycarbonate single plate having a thickness of 1.2 mm and 4 cm square, spin coating was performed for 30 seconds at a rotational speed of 3000 rpm (rotational speed per minute). The result of measuring the absorption spectrum of the dye thin film thus obtained is shown as “before PDDA treatment” in FIG.
（３） 次いで、下記〔化２〕のポリ（ジアリルジメチルアンモニウム−クロライド）（以下「ＰＤＤＡ」と略称する。）（平均分子量は４００，０００〜５００，０００、ｎ＝２，４８０〜３，１１０、Ａｌｄｒｉｃｈ社製）の１ｇ／Ｌの濃度の水溶液を用意し、前項（２）で得られた色素薄膜の上に２ｍＬ滴下した後、３０００ｒｐｍの回転数で３０秒間スピンコートし、ＰＤＤＡ薄膜をその色素薄膜上に形成した。
このようにして得られた均一な色素薄膜について吸収スペクトルを測定した結果を図１に「ＰＤＤＡ処理後」として示す。
(3) Next, poly (diallyldimethylammonium chloride) of the following [Chemical Formula 2] (hereinafter abbreviated as “PDDA”) (average molecular weight is 400,000 to 500,000, n = 2, 480 to 3,110). 1 g / L of an aqueous solution prepared by Aldrich), 2 mL was dropped on the dye thin film obtained in the previous item (2), spin-coated at 3000 rpm for 30 seconds, and the PDDA thin film was It was formed on a dye thin film.
The results of measuring the absorption spectrum of the uniform dye thin film thus obtained are shown as “after PDDA treatment” in FIG.
図１から、スペクトルは「ＰＤＤＡ処理後」のものが「ＰＤＤＡ処理前」のものより明らかに先鋭化していることがわかる。「ＰＤＤＡ処理前」の色素薄膜は様々な会合状態が混在しているためブロードな吸収を持つが、「ＰＤＤＡ処理後」の記録材料薄膜のＪ会合体は単量体の長波長側にシャープな吸収を示した。
これらの薄膜について色素分子の会合状態を調べるために以下の光物理的性質を測定した。
（Ａ） 蛍光寿命
日立Ｆ４５００蛍光分光光度計を用いて、単一光子計算法で測定した。その結果は以下のとおりであった。
「ＰＤＤＡ処理前」の薄膜：３（ｎｓ）
「ＰＤＤＡ処理後」の薄膜：２９（ｐｓ）
文献値（Ｊ会合体薄膜）：５１（ｐｓ）
（Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．，２０００，１０４，９６３０（Ｎ．Ｋｏｍｅｔａｎｉ ，Ｈ．Ｎａｋａｚｉｍａ，Ｋ．Ａｓａｍｉ，Ｙ．Ｙｏｎｅｚａｗａ，Ｏ．Ｋａｚｉｍ ｏｔｏ）
From FIG. 1, it can be seen that the spectrum “after PDDA processing” is clearly sharper than that “before PDDA processing”. The dye thin film “before PDDA treatment” has a broad absorption because various association states are mixed, but the J aggregate of the recording material thin film “after PDDA treatment” is sharp on the long wavelength side of the monomer. Absorption was shown.
The following photophysical properties were measured in order to investigate the association state of the dye molecules for these thin films.
(A) Fluorescence lifetime It measured by the single photon calculation method using the Hitachi F4500 fluorescence spectrophotometer. The results were as follows.
Thin film before PDDA treatment: 3 (ns)
Thin film after “PDDA treatment”: 29 (ps)
Literature value (J-aggregate thin film): 51 (ps)
(J. Phys. Chem., 2000, 104, 9630 (N. Kometani, H. Nakajima, K. Asami, Y. Yonezawa, O. Kazim auto)
（Ｂ） りん光
日立Ｆ４５００蛍光分光光度計を用いて、時間変化測定モードの方法で測定した。その結果は以下のとおりであった。
「ＰＤＤＡ処理前」の薄膜：観測された
「ＰＤＤＡ処理後」の薄膜：観測されず
以上より、「ＰＤＤＡ処理前」のシアニン色素薄膜ではＪ会合体を形成されていないのに対し、「ＰＤＤＡ処理後」のシアニン色素薄膜ではＪ会合体が形成されていることがわかる。なお、励起スペクトルと吸収スペクトルの比較より、りん光にはＨ会合体・単量体が関与していることがわかった。これよりＪ会合体は三重項状態を生成しないと考えられる。
（Ｃ） 光学特性の測定
日立Ｕ−４０００分光光度計を用いて、反射率及び透過率を測定し、屈折率・消衰係数を計算から求めた。その結果は下記〔表１〕のとおりであった。
(B) Phosphorescence Using a Hitachi F4500 fluorescence spectrophotometer, measurement was performed by the method of the time change measurement mode. The results were as follows.
Thin film before “PDDA treatment”: observed Thin film after “PDDA treatment”: not observed As described above, the cyanine dye thin film “before PDDA treatment” did not form J aggregates, whereas “PDDA treatment” It can be seen that J aggregates are formed in the “after” cyanine dye thin film. From comparison between the excitation spectrum and the absorption spectrum, it was found that H aggregates and monomers were involved in phosphorescence. From this, it is considered that the J aggregate does not generate a triplet state.
(C) Measurement of optical characteristics Reflectance and transmittance were measured using a Hitachi U-4000 spectrophotometer, and the refractive index and extinction coefficient were obtained from the calculation. The results were as shown in [Table 1] below.
表１より、「ＰＤＤＡ処理後」の薄膜はＪ会合体を形成されていることにより、屈折率の向上が見られる。
なお、「ＰＤＤＡ処理後」のシアニン色素薄膜の熱安定性を吸収スペクトルにより観測したところ、文献では３日間であったのに対し、８日間安定に保持された（日本化学会大８３春季年会 ２００３年 講演予稿集Ｉ、２ＰＡ−０９３中の図２）。
As can be seen from Table 1, the thin film after “PDDA treatment” has an improved refractive index due to the formation of J aggregates.
In addition, when the thermal stability of the cyanine dye thin film “after PDDA treatment” was observed by the absorption spectrum, it was stable for 8 days, compared with 3 days in the literature (The 83rd Annual Meeting of the Chemical Society of Japan, 83) 2003 Lecture Proceedings I, Fig. 2 in 2PA-093).
実施例１の「ＰＤＤＡ処理後」の薄膜と同様に、ＰＤＤＡ処理後のシアニン色素薄膜（Ｊ会合体シアニン色素薄膜）を形成し、これを光情報記録媒体であるＤＶＤ−Ｒに応用した実施例を以下に示す。
（１） 上記〔化１〕のシアニン色素を１．５ｇはかりとり、２，２，３，３−テトラフルオロ−１−プロパノール１００ｍＬに溶解させ、１５ｇ／Ｌの溶液を調製した。
（２） この溶液を厚さ０．６ｍｍ、グルーブ溝が０．７４μｍの間隔で刻んである１２０ｍｍφ（直径）のポリカーボネート基板に１ｍＬ滴下し、３０００ｒｐｍでスピンコートした。
（３） 次いで、上記〔化２〕のＰＤＤＡの１ｇ／Ｌの濃度の水溶液を用意し、前項（２）で得られた色素薄膜の上に２ｍＬ滴下した後、３０００ｒｐｍの回転数で３０秒間スピンコートし、ＰＤＤＡ薄膜をその色素薄膜上に形成した。このようにして、均一なＪ会合体薄膜を得た。
（４） そのＪ会合体薄膜を形成した基板（ＤＶＤ−Ｒ基板）を８０℃、３０分間熱処理し、残留している余分な溶剤、水分を揮発処理した。
（５） その後、ＰＤＤＡ薄膜上に１００ｎｍの厚さのＡｕ（金）をスパッタリングして、反射膜を形成した。
（６） ＤＶＤ−Ｒ基板の周縁部や内周部分に飛び散った色素をメタノールで洗浄した。
（７） 前記反射膜上に紫外線硬化型の接着剤（大日本インキ化学工業社製ＳＤ−３１８）をスピンコートし、続いて厚さ０．６ｍｍの１２０ｍｍφ（直径）のポリカーボネート基板を載せて、貼り合わせを行い、その基板側から紫外線を照射して硬化させた。
（８） このようにして、均一なシアニン色素Ｊ会合体薄膜（色素膜と高分子薄膜からなる記録材料薄膜）を記録層に持つＤＶＤ−Ｒディスクを得た。
得られたＤＶＤ−Ｒディスクの電気特性評価結果を表２に示す。表中、「記録感度（１ｘ）／ｍＷ」は等倍速（１倍速）で記録したときの最適条件における記録パワーを示し、その他の類する表記はこれに準じる。また、「ＤＣジッター（１ｘ）／％」は等倍速（１倍速）で記録したときの最適条件におけるＤａｔｅ ｔｏ Ｃｌｏｃｋ ジッターを示し、その他の類する表記はこれに準じる。
［比較例１］
In the same manner as the thin film after “PDDA treatment” in Example 1, a cyanine dye thin film (J-aggregate cyanine dye thin film) after PDDA treatment was formed and applied to DVD-R as an optical information recording medium. Is shown below.
(1) 1.5 g of the cyanine dye of the above [Chemical Formula 1] was weighed and dissolved in 100 mL of 2,2,3,3-tetrafluoro-1-propanol to prepare a 15 g / L solution.
(2) 1 mL of this solution was dropped on a 120 mmφ (diameter) polycarbonate substrate having a thickness of 0.6 mm and groove grooves cut at an interval of 0.74 μm, and spin-coated at 3000 rpm.
(3) Next, prepare a 1 g / L aqueous solution of PDDA in the above [Chemical Formula 2], drop 2 mL onto the dye thin film obtained in (2) above, and spin for 30 seconds at a rotation speed of 3000 rpm. A PDDA thin film was formed on the dye thin film. In this way, a uniform J aggregate thin film was obtained.
(4) The substrate (DVD-R substrate) on which the J-aggregate thin film was formed was heat-treated at 80 ° C. for 30 minutes, and the remaining excess solvent and moisture were volatilized.
(5) Thereafter, Au (gold) with a thickness of 100 nm was sputtered on the PDDA thin film to form a reflective film.
(6) Dye scattered on the peripheral edge and inner peripheral part of the DVD-R substrate was washed with methanol.
(7) A UV curable adhesive (SD-318 manufactured by Dainippon Ink & Chemicals, Inc.) is spin-coated on the reflective film, and then a 0.6 mm thick 120 mmφ (diameter) polycarbonate substrate is placed. Bonding was performed, and ultraviolet rays were irradiated from the substrate side to be cured.
(8) In this way, a DVD-R disc having a uniform cyanine dye J aggregate thin film (a recording material thin film comprising a dye film and a polymer thin film) as a recording layer was obtained.
Table 2 shows the electrical property evaluation results of the obtained DVD-R disc. In the table, “recording sensitivity (1 ×) / mW” indicates recording power under optimum conditions when recording is performed at the same speed (1 × speed), and other similar notations are based on this. “DC jitter (1 ×) /%” indicates Date to Clock jitter under optimum conditions when recording is performed at the same speed (1 × speed), and other similar notations are based on this.
[Comparative Example 1]
実施例２において、ＰＤＤＡ水溶液を塗布せず、その薄膜を設けることをしなかった以外は同様にしてＤＶＤ−Ｒディスクを得た。 得られたＤＶＤ−Ｒディスクの電気特性評価結果を表２に示す。 In Example 2, a DVD-R disc was obtained in the same manner except that the PDDA aqueous solution was not applied and the thin film was not provided. Table 2 shows the electrical property evaluation results of the obtained DVD-R disc.
表２より、均一なシアニン色素Ｊ会合体薄膜を記録層に用いることで、高速記録時のジッターが低く抑えられ、また、感度向上も認められた。 From Table 2, by using a uniform cyanine dye J aggregate thin film for the recording layer, jitter during high-speed recording can be suppressed to a low level, and an improvement in sensitivity was recognized.
本発明において使用できるシアニン色素は、上記〔化１〕のチオシアニンのみならず、同式において置換基Ｃｌを他のハロゲン原子に置換したもの、これらの代わりに又はこれらとともに他の置換基を単数又は複数導入したもの、また、これらにおいて「Ｃ3 Ｈ6 」の一方又は両方を他のアルキレン基、アルキル基（Ｎ+ の対イオンの陰イオンは各種が挙げられる）に置換したもの、また、これらにおいて「Ｋ+ 」の代わりに他のアルカリ金属イオン（物質名を「クロリド」の代わりに「ハライド」とする）、アンモニウムイオンを用いたもの、さらにはこれらにおいてメチン鎖はモノメチン、トリメチン、ペンタメチン等のものでもよく、その置換基もなくてもよく他のアルキル基等の置換基であってもよい。さらに、これらにおいて、両方の「Ｓ」が共に「Ｃ」であり、これに例えばメチル基が２個置換したシアニン色素であってもよい。
また、上記〔化２〕の高分子（ポリマー）は、「Ｃｌ- 」の代わりに他のハロゲンイオンでもよい。
The cyanine dye that can be used in the present invention is not limited to the thiocyanine of the above [Chemical Formula 1], but the one in which the substituent Cl is substituted with another halogen atom in the same formula, Introduced in plural, in which one or both of “C 3 H 6 ” is substituted with another alkylene group or alkyl group (various anions of N + counter ions are included) In which other alkali metal ions (substance name is “halide” instead of “chloride”) and ammonium ions are used instead of “K + ”, and in these, the methine chain is monomethine, trimethine, pentamethine, etc. Or may be a substituent such as another alkyl group. Further, in these, both “S” are both “C”, and for example, a cyanine dye in which two methyl groups are substituted may be used.
Further, the polymer (polymer) of [Chemical Formula 2] may be other halogen ions instead of “Cl − ”.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003309674A JP4318512B2 (en) | 2003-09-02 | 2003-09-02 | J-aggregate thin film formed body and optical information recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003309674A JP4318512B2 (en) | 2003-09-02 | 2003-09-02 | J-aggregate thin film formed body and optical information recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005074872A JP2005074872A (en) | 2005-03-24 |
| JP4318512B2 true JP4318512B2 (en) | 2009-08-26 |
Family
ID=34411756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003309674A Expired - Fee Related JP4318512B2 (en) | 2003-09-02 | 2003-09-02 | J-aggregate thin film formed body and optical information recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4318512B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008010100A (en) * | 2006-06-30 | 2008-01-17 | Nara Institute Of Science & Technology | Dye that forms dye aggregate, composition containing dye aggregate, and information recording / reproducing method using structural conversion of dye aggregate |
-
2003
- 2003-09-02 JP JP2003309674A patent/JP4318512B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005074872A (en) | 2005-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2000033775A (en) | Optical information recording medium | |
| JP3648823B2 (en) | Optical recording medium and information recording method | |
| JP4151399B2 (en) | Optical information recording medium | |
| JP4318512B2 (en) | J-aggregate thin film formed body and optical information recording medium | |
| JP3673963B2 (en) | Optical information recording medium | |
| US20080008850A1 (en) | Optical information recording medium and method for producing the same | |
| CN1211363C (en) | Novel Phenindole Styrene Salt Compound and Its Application in High Density Recording Media | |
| JPH07161069A (en) | Optical recording medium | |
| JP2897773B2 (en) | Optical recording / reproducing method | |
| JP3168469B2 (en) | Optical recording medium | |
| JP3543464B2 (en) | Optical recording medium and information recording method | |
| CN1201308C (en) | Optical recording medium | |
| JP3713622B2 (en) | Optical information recording medium | |
| JP3002209B2 (en) | Optical information recording medium | |
| JP3556564B2 (en) | Method of manufacturing optical recording medium and optical recording medium | |
| JPWO2005095521A1 (en) | Monomethine dye compound, optical information recording medium thereof, and production method thereof | |
| JPH08115538A (en) | Method for manufacturing organic optical recording disk | |
| JP2006123281A (en) | Optical recording medium and optical recording / reproducing method using the same | |
| JP2000289341A (en) | Optical information recording medium | |
| JP3002207B2 (en) | Optical information recording medium | |
| JP3713619B2 (en) | Optical information recording medium | |
| JPH0569673A (en) | Optical data recording medium and production thereof | |
| JPH0749529B2 (en) | Methine compound and optical recording medium containing the same | |
| JP2001171232A (en) | Optical recording medium | |
| JP2007066363A (en) | THIN FILM FORMED BODY, ITS MANUFACTURING METHOD, AND OPTICAL RECORDING MEDIUM USING THE THIN FILM FORMED BODY |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060719 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090317 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090417 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090519 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090526 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120605 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |