JP2011183580A - Pigment for optical information recording medium and optical information recording medium using the same - Google Patents
Pigment for optical information recording medium and optical information recording medium using the same Download PDFInfo
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- 239000000049 pigment Substances 0.000 title abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 82
- 239000000758 substrate Substances 0.000 claims description 21
- 230000005540 biological transmission Effects 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000011241 protective layer Substances 0.000 claims description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
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- 238000002835 absorbance Methods 0.000 description 4
- -1 azo metal complex Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- MBXOOYPCIDHXGH-UHFFFAOYSA-N 3-butylpentane-2,4-dione Chemical compound CCCCC(C(C)=O)C(C)=O MBXOOYPCIDHXGH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000182022 Salvia sclarea Species 0.000 description 1
- 235000002911 Salvia sclarea Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 244000154870 Viola adunca Species 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 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
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 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
- 239000010931 gold Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
本発明は、光情報記録媒体用色素に関し、より詳しくは、半導体レーザによる波長が３６０〜４５０ｎｍのレーザ光（ブルーレーザ光、青紫レーザ光）による記録を行う光情報記録媒体用色素及びそれを用いた光情報記録媒体に関する。 The present invention relates to a dye for optical information recording media, and more specifically, to a dye for optical information recording media for recording with a laser beam (blue laser light, blue violet laser light) having a wavelength of 360 to 450 nm by a semiconductor laser. The present invention relates to an optical information recording medium.
有機色素を記録材料として用いた追記型光記録メディアは、波長７８０ｎｍのレーザ光を用いて記録再生を行う記録容量６５０ＭＢあるいは７００ＭＢのＣＤ−Ｒや、波長６５０ｎｍのレーザ光を用いて記録再生を行う単層ディスクで記録容量４．７ＧＢのＤＶＤ−Ｒ／＋Ｒが既に広く普及している。これらは未記録での反射率が高く、記録後は反射率が低くなることにより信号として情報を記録するＨｉｇｈ ｔｏ Ｌｏｗ型記録である。 A write-once optical recording medium using an organic dye as a recording material performs recording / reproduction using a CD-R having a recording capacity of 650 MB or 700 MB for recording / reproducing using a laser beam having a wavelength of 780 nm, or a laser beam having a wavelength of 650 nm. Single-layer DVD-R / + R with a recording capacity of 4.7 GB is already widely used. These are high-to-low type recordings in which information is recorded as a signal by having a high reflectivity when not recorded and a low reflectivity after recording.
更なる大容量メディアとして、２００６年には波長４０５ｎｍのレーザで記録再生を行い単層での記録容量が１５ＧＢのＨＤ（Ｈｉｇｈ Ｄｅｆｉｎｉｔｉｏｎ） ＤＶＤ−Ｒが商品化された。ＨＤ ＤＶＤ−Ｒでは、記録極性は、未記録での反射率が低く、記録後は反射率が高くなるＬｏｗ ｔｏ Ｈｉｇｈである。現在開発が進められている有機色素を記録層に用いたＢｌｕ−ｒａｙ Ｄｉｓｃ−Ｒ（以下、「有機ＢＤ−Ｒ」という。）は、波長４０５ｎｍのレーザで記録再生を行い単層での記録容量が２５ＧＢの追記型光記録メディアである。この有機ＢＤ−Ｒ記録極性は、ＨＤ ＤＶＤ−Ｒと同様、Ｌｏｗ ｔｏ Ｈｉｇｈである。 As a further large-capacity medium, in 2006, a high definition (HD) DVD-R with a recording capacity of 15 GB in a single layer was recorded and reproduced with a laser having a wavelength of 405 nm. In the HD DVD-R, the recording polarity is Low to High, where the reflectance when not recorded is low and the reflectance becomes high after recording. Blu-ray Disc-R (hereinafter referred to as “Organic BD-R”) using an organic dye as a recording layer, which is currently being developed, performs recording / reproduction with a laser having a wavelength of 405 nm and has a recording capacity of a single layer. Is a 25 GB recordable optical recording medium. The organic BD-R recording polarity is Low to High, similar to HD DVD-R.
こうした、Ｌｏｗ ｔｏ Ｈｉｇｈ記録によって高密度の光情報の記録再生が可能な光情報記録媒体に適した新たな有機色素が提案されている。
例えば、特許文献１では、カチオン部がモノメチンシアニン色素であり、アニオン部がアゾ金属錯体である有機色素を用いることにより、ＨＤ ＤＶＤ−Ｒ構造でＬｏｗ ｔｏ Ｈｉｇｈ型記録の４０５ｎｍのレーザを用いた記録再生を行えることを示している。しかし、有機ＢＤ−Ｒとしてのディスクの特性の評価結果は記載されていない。また、この特許においては、アニオン部とカチオン部とからなる色素が、青色レーザ光等のような短波長レーザ光に対しては、有機色素におけるカチオン部が実質的な吸光能を発揮する原子団として機能することを述べている。
また、特許文献２および特許文献３では、特定のアゾ金属錯体が、Ｌｏｗ ｔｏ Ｈｉｇｈ記録の４０５ｎｍのレーザ光用いた記録再生を行うメヂィアに好適であるとしているが、有機ＢＤ−Ｒ特有の課題については記載されていない。
There has been proposed a new organic dye suitable for an optical information recording medium capable of recording / reproducing high-density optical information by Low to High recording.
For example, in Patent Document 1, a low-to-high type 405 nm laser with an HD DVD-R structure was used by using an organic dye whose cation portion is a monomethine cyanine dye and whose anion portion is an azo metal complex. It shows that recording and playback can be performed. However, the evaluation results of the characteristics of the disc as the organic BD-R are not described. Further, in this patent, the dye composed of an anion portion and a cation portion is an atomic group in which the cation portion in the organic dye exhibits a substantial light absorption ability for a short wavelength laser beam such as a blue laser beam. As it works.
Further, in Patent Document 2 and Patent Document 3, a specific azo metal complex is said to be suitable for a medium that performs recording / reproduction using a 405 nm laser beam for Low to High recording. Is not listed.
上記の特許文献に開示された色素は、基本的には、Ｌｏｗ ｔｏ Ｈｉｇｈ記録に適したものであり、ＨＤ ＤＶＤ−Ｒと有機ＢＤ−Ｒの両方に使用できる色素である。
しかし、発明者らが鋭意検討した結果、実際には、Ｏｎ−Ｇｒｏｏｖｅ記録とＩｎ−Ｇｒｏｏｖｅ記録の違いにより、色素の最適な特性が異なることがわかってきた。
The dyes disclosed in the above patent documents are basically suitable for Low to High recording and can be used for both HD DVD-R and organic BD-R.
However, as a result of intensive studies by the inventors, it has been found that the optimum characteristics of the dye actually differ depending on the difference between the On-Groove recording and the In-Groove recording.
すなわち、ＨＤ ＤＶＤ−Ｒは、トラックピッチ０．４０μｍの案内溝が形成された光透過性材料からなる第１の基板上に、色素含有記録層、反射層をこの順に有し、さらに保護層及び／又は接着層を介して或いは介さずに、第２の基板を設け、必要に応じてその上に反射層を形成したいわゆるダミーディスクを設けた積層構造であり、第１の基板を通して片面側からレーザ光にて記録・再生を行なうものである。そして、照射されるレーザ光のスポット径が０．５４μｍである。 That is, the HD DVD-R has a dye-containing recording layer and a reflective layer in this order on a first substrate made of a light transmissive material in which guide grooves having a track pitch of 0.40 μm are formed. It is a laminated structure in which a second substrate is provided with or without an adhesive layer, and a so-called dummy disk having a reflective layer formed thereon if necessary, and from one side through the first substrate. Recording / reproduction is performed with a laser beam. The spot diameter of the irradiated laser beam is 0.54 μm.
一方、有機ＢＤ−Ｒは、トラックピッチ０．３２μｍの案内溝が形成された光透過性材料からなる基板上に、反射層、色素含有記録層をこの順に有し、さらに保護層介して光透過層（カバー層）を設けた積層構造であり（特許文献４、５参照）、光透過層（カバー層）側から照射されるレーザ光により記録再生を行うものである。そして、照射されるレーザ光のスポット径が０．４１μｍである。したがって、有機ＢＤ−ＲはＨＤ＿ＤＶＤ−Ｒに比べてスポット径が小さいので、同じ記録パワーの場合エネルギー密度が大きくなる。ここで、有機ＢＤ−ＲはＨＤ＿ＤＶＤ−Ｒに比べてトラックピッチが狭いので、隣接する案内溝への熱干渉が発生しやすくなる。
このような熱干渉が発生すると、ジッタが高くなり、記録特性が低下してしまう。そのため良好な記録が難しくなるという問題がある。
On the other hand, the organic BD-R has a reflective layer and a dye-containing recording layer in this order on a substrate made of a light transmissive material in which guide grooves having a track pitch of 0.32 μm are formed. It has a laminated structure provided with a layer (cover layer) (see Patent Documents 4 and 5), and performs recording and reproduction by laser light irradiated from the light transmission layer (cover layer) side. The spot diameter of the irradiated laser beam is 0.41 μm. Therefore, since the organic BD-R has a smaller spot diameter than the HD_DVD-R, the energy density is increased with the same recording power. Here, since the organic BD-R has a narrower track pitch than the HD_DVD-R, thermal interference with an adjacent guide groove is likely to occur.
When such thermal interference occurs, jitter increases and recording characteristics deteriorate. Therefore, there is a problem that good recording becomes difficult.
本発明は、以上のような事情に鑑みてなされたものであって、有機ＢＤ−Ｒのような短波長レーザ（４０５ｎｍ）を用いて、Ｉｎ−Ｇｒｏｏｖｅ記録を行う光情報記録媒体において、高感度で、かつ、良好な記録特性を得ることができる光情報記録媒体用色素及びそれを用いた光情報記録媒体を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is an optical information recording medium that performs In-Groove recording using a short wavelength laser (405 nm) such as an organic BD-R. In addition, an object of the present invention is to provide a dye for an optical information recording medium capable of obtaining good recording characteristics and an optical information recording medium using the same.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、鋭意検討を重ねた結果、特定の構造のアゾ金属錯体色素を記録層材料として用いることで上記目的が達成できることを見出した。
本発明は、これらの知見に基づいて完成に至ったものであり、以下のとおりのものである。
［１］波長が３６０〜４５０ｎｍのレーザ光により記録再生を行う追記型光情報記録媒体の記録層用の有機色素であって、下記の一般式で示されることを特徴とする光情報記録媒体用色素。
［２］螺旋状の案内溝を一方の面に有する基板と、前記基板の一方の面上に形成された反射層と、前記反射層上に形成された記録層と、前記記録層上に形成された保護層と、前記保護層上に形成された光透過層とを少なくとも有する、波長が３６０〜４５０ｎｍのレーザ光により記録再生を行う追記型光情報記録媒体において、
前記記録層に用いる有機色素が、下記一般式で表されることを特徴とする光情報記録媒体。
The present invention has been completed based on these findings, and is as follows.
[1] An organic dye for a recording layer of a write-once optical information recording medium that performs recording and reproduction with a laser beam having a wavelength of 360 to 450 nm, and is represented by the following general formula: Pigment.
[2] A substrate having a spiral guide groove on one surface, a reflective layer formed on one surface of the substrate, a recording layer formed on the reflective layer, and formed on the recording layer In a write-once type optical information recording medium that has at least a protective layer and a light transmission layer formed on the protective layer, and performs recording and reproduction with a laser beam having a wavelength of 360 to 450 nm,
An optical information recording medium, wherein the organic dye used in the recording layer is represented by the following general formula:
本発明によれば、有機ＢＤ−Ｒのような短波長レーザ（４０５ｎｍ）で記録再生を行う光記録メディアにおいて、高感度であり、すなわち、記録でのレーザ光の照射パワーが小さく、変調が大きく、ジッタが低い、良好な記録特性を得ることができる。 According to the present invention, an optical recording medium for recording / reproducing with a short wavelength laser (405 nm) such as an organic BD-R has high sensitivity, that is, the irradiation power of laser light in recording is small and the modulation is large. Good recording characteristics with low jitter can be obtained.
図１は、本発明の一実施の形態であるブルーレーザ光を用いる光情報記録媒体の断面図である。図１に示すとおり、本発明の光情報記録媒体１１は、基板２と、この基板２上に形成した光反射層３と、この光反射層３の上に形成した光吸収層すなわち光記録層４と、この光記録層４の上に形成した保護層５と、この保護層５の上に形成されたカバー層すなわち光透過層６とを有する。 FIG. 1 is a cross-sectional view of an optical information recording medium using a blue laser beam according to an embodiment of the present invention. As shown in FIG. 1, an optical information recording medium 11 of the present invention includes a substrate 2, a light reflecting layer 3 formed on the substrate 2, and a light absorbing layer, that is, an optical recording layer, formed on the light reflecting layer 3. 4, a protective layer 5 formed on the optical recording layer 4, and a cover layer, that is, a light transmission layer 6 formed on the protective layer 5.
こうした構成の光情報記録媒体においては、光透過層６を通してレーザ光７を照射し、照射された光記録層４がそのレーザ光を吸収して光エネルギーを熱エネルギーに変換し、光記録層４の分解あるいは変性などを生じさせ、記録ピットを形成し、記録部分および未記録部分の光反射率などによるコントラストを電気信号（変調度）として読み取っている。 In the optical information recording medium having such a configuration, the laser light 7 is irradiated through the light transmission layer 6, and the irradiated optical recording layer 4 absorbs the laser light and converts the light energy into heat energy. The recording pits are formed, and the contrast due to the light reflectance of the recorded portion and the unrecorded portion is read as an electric signal (degree of modulation).
前記光記録層４は、レーザ光を照射することにより、発熱、吸熱、溶融、昇華、変形または変性をともなう層であるが、本発明においては、該光記録層４が、下記の一般式で示されるアゾ金属錯体色素により構成されている。
式中のＲ１１、Ｒ１２、Ｒ１３、Ｒ１４で表されるアルキル基としては、特に限定されないが、好ましくは、炭素数１〜６のアルキル基が好ましく用いられ、特に、炭素数２〜４の直鎖のアルキル基が好ましく用いられる。
なお、上記アゾ金属錯体の合成方法は特に限定されるものではなく、例えば、細田豊著『理論製造染料化学』（昭和３２年１１月２５日、株式会社技報堂発行、５９５〜６０１頁）等に記載された公知のアゾ金属錯体の製造方法を用いて製造される。
Although it does not specifically limit as an alkyl group represented by R < 11 >, R < 12 >, R <13> , R < 14 > in a formula, Preferably, a C1-C6 alkyl group is used preferably, Especially, C2-C2 4 linear alkyl groups are preferably used.
The method for synthesizing the azo metal complex is not particularly limited. For example, it is described in Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry” (November 25, 1957, published by Gihodo Co., Ltd., pages 595-601) Manufactured using the known methods for producing azo metal complexes described.
光記録層４は、前記一般式で表される色素を、例えば、２，２，３，３−テトラフルオロ−１−プロパノール（ＴＦＰ）等の有機溶剤に溶かした色素溶液を、ＤＣジッタ値が最も低くなるときの光学密度（Ｏｐｔｉｃａｌ Ｄｅｎｓｉｔｙ：以下、「ＯＤ値」とする。）になるように、スピンコート法等の手段により、光反射層３の表面に一様にコーティングすることによってこれを形成される。
ここでＯＤ値とは、色素の最大吸収波長における吸光度を示すものである。測定方法は、図１の基板２の上に、直接色素溶液を塗布して、各々の色素の最大吸収波長の光を用いて吸光度を測定することで行われる。ＯＤ値は成膜条件（回転数、時間等）によって調整される。ＤＣジッタが最も低くなるＯＤ値は、光記録層４の成膜条件を変えてＯＤ値を変えたサンプルディスクを複数点用意し、市販の記録再生装置（例えばパルステック社製 ＯＤＵ−１０００）で記録を行い、それぞれのＤＣジッタ値を求め、その結果から決定する。
The optical recording layer 4 has a DC jitter value of a dye solution obtained by dissolving the dye represented by the general formula in an organic solvent such as 2,2,3,3-tetrafluoro-1-propanol (TFP). By coating the surface of the light reflecting layer 3 uniformly by means such as a spin coating method so as to obtain the optical density at the lowest (Optical Density: hereinafter referred to as “OD value”). It is formed.
Here, the OD value indicates the absorbance at the maximum absorption wavelength of the dye. The measurement method is performed by applying a dye solution directly on the substrate 2 of FIG. 1 and measuring the absorbance using light of the maximum absorption wavelength of each dye. The OD value is adjusted according to the film forming conditions (rotation speed, time, etc.). For the OD value at which the DC jitter is lowest, a plurality of sample disks having different OD values by changing the film formation conditions of the optical recording layer 4 are prepared, and a commercially available recording / reproducing apparatus (for example, ODU-1000 manufactured by Pulstec) is used. Recording is performed to determine each DC jitter value, and the result is determined.
以下、本発明の光情報記録媒体１１における、前記光記録層４以外の構成層について説明する。
（基板）
基板２は、レーザ光に対する屈折率がたとえば１．５〜１．７程度の範囲内の透明度の高い材料で、耐衝撃性に優れた主として樹脂により形成したもの、たとえばポリカーボネート、ガラス板、アクリル板、エポキシ板等を用いる。
基板２には、ピッチ０．３２μｍからなるスパイラル状の案内溝が形成される。トラッキングの誘導をするソフト等の変更を伴えば、溝はリング状の溝でも使用が可能となる。この案内溝の溝幅Ｗ１は１６０ｎｍ〜２００ｎｍが好ましく、溝深さＤ１は３２ｎｍ〜４５ｎｍが好ましい。ここで溝幅Ｗ１は、図１に示すように溝深さＤ１の半分の深さの位置での幅すなわち半値幅で測定される。この案内溝上に光反射層３が構成される。
Hereinafter, constituent layers other than the optical recording layer 4 in the optical information recording medium 11 of the present invention will be described.
(substrate)
The substrate 2 is a highly transparent material having a refractive index with respect to laser light in the range of, for example, about 1.5 to 1.7, and is formed mainly of a resin excellent in impact resistance, such as a polycarbonate, a glass plate, an acrylic plate. An epoxy board is used.
A spiral guide groove having a pitch of 0.32 μm is formed on the substrate 2. The groove can be used as a ring-shaped groove if the software for guiding the tracking is changed. The groove width W1 of the guide groove is preferably 160 nm to 200 nm, and the groove depth D1 is preferably 32 nm to 45 nm. Here, the groove width W1 is measured by a width at a half depth of the groove depth D1, that is, a half-value width as shown in FIG. A light reflecting layer 3 is formed on the guide groove.
（光反射層）
光反射層３は、熱伝導率および光反射性の高い金属膜であり、たとえば、金、銀、銅、アルミニウム、あるいはこれらを含む合金を、蒸着法、スパッタ法等の手段により形成する。
光反射層３の厚さは４０ｎｍ〜６５ｎｍが好ましい。なお、光反射層３は案内溝内にも形成されるため、案内溝の寸法は光射層３の厚さ分変化する。光反射層３を形成後の溝３’の溝幅Ｗ２は１５０ｎｍ〜１９０ｎｍが好ましく、溝深さＤ２は３２ｎｍ〜４５ｎｍが好ましい。
(Light reflection layer)
The light reflecting layer 3 is a metal film having a high thermal conductivity and high light reflectivity. For example, gold, silver, copper, aluminum, or an alloy containing these is formed by means such as vapor deposition or sputtering.
The thickness of the light reflecting layer 3 is preferably 40 nm to 65 nm. Since the light reflecting layer 3 is also formed in the guide groove, the size of the guide groove changes by the thickness of the light emitting layer 3. The groove width W2 of the groove 3 ′ after forming the light reflecting layer 3 is preferably 150 nm to 190 nm, and the groove depth D2 is preferably 32 nm to 45 nm.
（保護層）
保護層５は、カバー層６の成膜時における光記録層４に含まれる色素のカバー層６への拡散や、カバー層６の形成用の硬化樹脂の溶剤等の光記録層４への浸透などの混和現象を防止するためのものである。この保護層５を構成する材料は、酸化珪素、特に二酸化珪素や、酸化亜鉛、酸化セリウム、酸化イットリウム等の酸化物；硫化亜鉛、硫化イットリウムなどの硫化物；窒化珪素などの窒化物、炭化珪素；酸化物と硫黄化合物との混合物などが挙げられる。この保護層５はスパッタリング等の方法で形成される。
(Protective layer)
The protective layer 5 diffuses the dye contained in the optical recording layer 4 into the cover layer 6 when the cover layer 6 is formed, and penetrates the optical recording layer 4 with a solvent of a cured resin for forming the cover layer 6. This is to prevent the mixing phenomenon. The material constituting the protective layer 5 is silicon oxide, particularly silicon dioxide, oxides such as zinc oxide, cerium oxide and yttrium oxide; sulfides such as zinc sulfide and yttrium sulfide; nitrides such as silicon nitride; silicon carbide A mixture of an oxide and a sulfur compound. The protective layer 5 is formed by a method such as sputtering.
（光透過層）
本発明の光情報記録媒体１１においては、光透過層６を通してレーザ光７を照射し、照射された光記録層４がそのレーザ光を吸収して光エネルギーを熱エネルギーに変換し、光記録層４の分解あるいは変性などを生じさせ、記録ピットを形成し、記録部分および未記録部分の光反射率などによるコントラストを電気信号（変調度）として読み取っている。
したがって、光透過層６は、レーザ光を透過する材料、例えばポリカーボネート樹脂、アクリル系樹脂，ポリオレフィン系樹脂等の樹脂で形成されている。
また、光透過層６は、光反射層３や光記録層４を外部の衝撃から保護するとともに、これら各層３、４が湿気等の腐食因子と接触するのを防止する保護層としても機能する。
この光透過層６は、紫外線または放射線によって硬化する硬化性樹脂をスピンコート法等によって厚さ０．１ｍｍに形成される。この光透過層６の光透過性は、効果後の厚み０．１ｍｍで、４０５ｎｍの波長の光にて分光光度計で測定したときに７０％以上好ましくは８０％以上である。
なお、光透過層６は比較的柔らかく傷つきやすいので、アクリル系樹脂などで構成されたハードコート層（図示せず）を形成してもよい。
(Light transmission layer)
In the optical information recording medium 11 of the present invention, the laser beam 7 is irradiated through the light transmission layer 6, and the irradiated optical recording layer 4 absorbs the laser beam and converts the light energy into heat energy. 4 is generated, recording pits are formed, and the contrast due to the light reflectance of the recorded portion and the unrecorded portion is read as an electric signal (degree of modulation).
Therefore, the light transmission layer 6 is formed of a material that transmits laser light, for example, a resin such as a polycarbonate resin, an acrylic resin, or a polyolefin resin.
Further, the light transmission layer 6 protects the light reflection layer 3 and the optical recording layer 4 from external impacts, and also functions as a protection layer for preventing the layers 3 and 4 from coming into contact with corrosion factors such as moisture. .
This light transmission layer 6 is formed of a curable resin that is cured by ultraviolet rays or radiation to a thickness of 0.1 mm by spin coating or the like. The light transmittance of the light transmissive layer 6 is 70% or more, preferably 80% or more when measured with a spectrophotometer with light having a wavelength of 405 nm and a thickness of 0.1 mm after the effect.
Since the light transmission layer 6 is relatively soft and easily damaged, a hard coat layer (not shown) made of an acrylic resin or the like may be formed.
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
（実施例１）
図１に示す、外径１２０ｍｍ、厚さ１．１ｍｍの円盤状のポリカーボネート製の基板２にピッチ０．３２μｍからなるスパイラル状の案内溝を形成した。この基板２の案内溝が形成された側の上面に、Ａｇ合金からなる光反射層３をスパッタリングにより形成し、案内溝に対応するトラックを基板側からみて光反射層３上に深さ４５ｎｍ、幅１６０ｎｍに形成した。
Example 1
A spiral guide groove having a pitch of 0.32 μm was formed on a disc-shaped polycarbonate substrate 2 having an outer diameter of 120 mm and a thickness of 1.1 mm shown in FIG. A light reflecting layer 3 made of an Ag alloy is formed by sputtering on the upper surface of the substrate 2 on which the guide groove is formed, and the track corresponding to the guide groove is 45 nm deep on the light reflecting layer 3 when viewed from the substrate side. A width of 160 nm was formed.
上記光反射層３が形成されたその上面に、図２の吸収スペクトル（溶液および薄膜）を示す下記の式で示される色素（色素１）を２，２，３，３−テトラフルオロ−１−プロパノール（ＴＦＰ）に溶解した色素溶液をスピンコート法により塗布し、温度８０℃で１０分乾燥後、吸収最大波長（λｍａｘ＝４５０ｎｍ）での光学密度（ＯＤ値）が０．２２となるように形成した。ＯＤ値は、基板２のみの吸光度をベースライン（ＯＤ値がゼロ）として、基板２上に光反射層３を形成せずに、直接、光記録層４を形成したときの吸光度を指している。その同じスピンコートの回転パターンで基板２の案内溝が形成された側の上面に、Ａｇ合金からなる光反射層３を形成した。その後、更に光記録層４の上面にＺｎＳ−ＳｉＯ２材料からなる透明な保護層５を２０ｎｍの厚さになるようにスパッタリングした。それからＵＶ硬化樹脂をスピンコート法により塗布し、ＵＶ光照射により硬化させることにより厚さ０．１ｍｍのカバー層（光透過層）６を形成し、有機ＢＤ−Ｒ１１の追記型の光情報記録媒体の試料を得た。 On the upper surface on which the light reflecting layer 3 is formed, a dye (dye 1) represented by the following formula showing the absorption spectrum (solution and thin film) of FIG. 2 is added to 2,2,3,3-tetrafluoro-1- A dye solution dissolved in propanol (TFP) is applied by spin coating, dried at a temperature of 80 ° C. for 10 minutes, and the optical density (OD value) at the maximum absorption wavelength (λmax = 450 nm) is 0.22. Formed. The OD value refers to the absorbance when the optical recording layer 4 is directly formed without forming the light reflecting layer 3 on the substrate 2 with the absorbance of only the substrate 2 being the baseline (OD value is zero). . The light reflecting layer 3 made of an Ag alloy was formed on the upper surface of the substrate 2 on the side where the guide groove was formed with the same spin coat rotation pattern. Thereafter, a transparent protective layer 5 made of a ZnS—SiO 2 material was further sputtered on the upper surface of the optical recording layer 4 to a thickness of 20 nm. Then, a UV curable resin is applied by a spin coat method and cured by UV light irradiation to form a cover layer (light transmission layer) 6 having a thickness of 0.1 mm, and a write-once type optical information recording medium of organic BD-R11 Samples were obtained.
（色素１）
続いて、この有機ＢＤ−Ｒ１１を開口数ＮＡ０．８５、レーザ波長４０５ｎｍの市販の記録再生装置（パルステック社製ＯＤＵ−１０００）を用いて、線速９．８４ｍ／秒（２倍速記録）で記録し、再生特性を評価したところ、レーザパワーは４．９ｍＷであった。
その後、上記記録機を用いて、レーザ出力を０．３５ｍＷにし、記録信号を再生したところ、図５に示す明瞭なアイパターンが得られた。このときの変調度は４１％、ＤＣジッタは６．８％であった。
表１に最大吸収波長（λｍａｘ）、ＯＤ値、記録パワー、変調度、ＤＣジッタを測定した結果を示す。
Subsequently, the organic BD-R11 was recorded at a linear velocity of 9.84 m / sec (double speed recording) using a commercially available recording / reproducing apparatus (ODU-1000 manufactured by Pulstec Corp.) having a numerical aperture NA of 0.85 and a laser wavelength of 405 nm. When recording and reproducing characteristics were evaluated, the laser power was 4.9 mW.
Thereafter, when the laser output was set to 0.35 mW and the recorded signal was reproduced using the above-mentioned recorder, the clear eye pattern shown in FIG. 5 was obtained. At this time, the degree of modulation was 41% and the DC jitter was 6.8%.
Table 1 shows the results of measuring the maximum absorption wavelength (λmax), OD value, recording power, modulation degree, and DC jitter.
（実施例２〜７）
実施例１において、（色素１）の代わりに、それぞれ図３、図４に示す吸収スペクトル（溶液および薄膜）を示す下記の式で示される（色素２）、（色素３）、及び下記の式で示される（色素４）〜（色素７）を用いた以外は同様にして有機ＢＤ−Ｒ１１を得た。
実施例１に準じて最大吸収波長（λｍａｘ）、ＯＤ値、記録パワー、変調度、ＤＣジッタを測定した結果を表１に示す。
(Examples 2 to 7)
In Example 1, instead of (Dye 1), (Dye 2), (Dye 3), and the following formulas shown in the following formulas showing the absorption spectra (solution and thin film) shown in FIGS. 3 and 4, respectively. Organic BD-R11 was obtained in the same manner except that (Dye 4) to (Dye 7) represented by
Table 1 shows the results of measuring the maximum absorption wavelength (λmax), OD value, recording power, modulation degree, and DC jitter according to Example 1.
（色素２）
（比較例１）
実施例１において、（色素１）の代わりに、下記の式で示される色素（比較色素１）を用いたこと以外は同様にして、有機ＢＤ−Ｒ１１を得た。
実施例１に準じて最大吸収波長（λｍａｘ）、ＯＤ値、記録パワー、変調度、ＤＣジッタを測定した結果を表１に示す。
続いて、この有機ＢＤ−Ｒ１１を開口数ＮＡ０．８５、レーザ波長４０５ｎｍの市販の記録再生装置（パルステック社製ＯＤＵ−１０００）を用いて、線速９．８４ｍ／秒（２倍速記録）で記録し、再生特性を評価したところ、レーザパワーは７．２ｍＷであった。
その後、上記記録機を用いて、レーザ出力を０．３５ｍＷにし、記録信号を再生したところ、図６に示すアイパターンが得られたが波形は明瞭ではない。このときの変調度は４３％であり、ＤＣジッタは２Ｔ振幅不足により評価不能であった。
(Comparative Example 1)
In Example 1, organic BD-R11 was obtained in the same manner except that a dye represented by the following formula (Comparative Dye 1) was used instead of (Dye 1).
Table 1 shows the results of measuring the maximum absorption wavelength (λmax), OD value, recording power, modulation degree, and DC jitter according to Example 1.
Subsequently, the organic BD-R11 was recorded at a linear velocity of 9.84 m / sec (double speed recording) using a commercially available recording / reproducing apparatus (ODU-1000 manufactured by Pulstec Corp.) having a numerical aperture NA of 0.85 and a laser wavelength of 405 nm. When recording and reproducing characteristics were evaluated, the laser power was 7.2 mW.
Thereafter, using the above recorder, the laser output was set to 0.35 mW and the recorded signal was reproduced. As a result, the eye pattern shown in FIG. 6 was obtained, but the waveform was not clear. The degree of modulation at this time was 43%, and the DC jitter could not be evaluated due to insufficient 2T amplitude.
（比較色素１）
（比較例２、３）
比較例１において、（色素１）の代わりに、カチオン部に光吸収能を有さない下記の
式で示される（比較色素２）及び（比較色素３）の化合物を用いたこと以外は同様にして有機ＢＤ−Ｒ１１を得た。
実施例１に準じて最大吸収波長（λｍａｘ）、ＯＤ値、記録パワー、変調度、ＤＣジッタを測定した結果を表１に示す。
続いて、この有機ＢＤ−Ｒ１１を開口数ＮＡ０．８５、レーザ波長４０５ｎｍの市販の記録再生装置（パルステック社製ＯＤＵ−１０００）を用いて、線速９．８４ｍ／秒（２倍速記録）で記録し、再生特性を評価したところ、レーザパワーは８．３および９．５ｍＷであった。
その後、上記記録機を用いて、レーザ出力を０．３５ｍＷにし、記録信号を再生したところ、図７および８に示すアイパターンが得られたが波形は明瞭ではない。このときの変調度は、それぞれ３５％および３７％であり、ＤＣジッタは２Ｔ振幅不足により評価不能であった。
(Comparative Examples 2 and 3)
In Comparative Example 1, the same procedure was used except that instead of (Dye 1), the compounds of (Comparative Dye 2) and (Comparative Dye 3) represented by the following formulas having no light absorption ability in the cation moiety were used. Thus, organic BD-R11 was obtained.
Table 1 shows the results of measuring the maximum absorption wavelength (λmax), OD value, recording power, modulation degree, and DC jitter according to Example 1.
Subsequently, the organic BD-R11 was recorded at a linear velocity of 9.84 m / sec (double speed recording) using a commercially available recording / reproducing apparatus (ODU-1000 manufactured by Pulstec Corp.) having a numerical aperture NA of 0.85 and a laser wavelength of 405 nm. When recording and evaluating the reproduction characteristics, the laser power was 8.3 and 9.5 mW.
Thereafter, using the above recorder, the laser output was set to 0.35 mW and the recorded signal was reproduced. As a result, the eye pattern shown in FIGS. 7 and 8 was obtained, but the waveform was not clear. The modulation degrees at this time were 35% and 37%, respectively, and the DC jitter could not be evaluated due to insufficient 2T amplitude.
（比較色素２）
本発明の光情報記録媒体用色素は、ブルーレーザにより、Ｉｎ Ｇｒｏｏｖｅ記録のＬｏｗ ｔｏ Ｈｉｇｈ型記録を行う光記録メディアにおいて使用することができる。 The dye for an optical information recording medium of the present invention can be used in an optical recording medium for performing In Groove recording Low to High type recording with a blue laser.
２：基板
３：光反射層
４：光記録層（光吸収層）
５：保護層
６：光透過層（カバー層）
７：レーザ光（記録、再生）
１１：本発明の追記型光ディスク（有機ＢＤ―Ｒ）
2: Substrate 3: Light reflection layer 4: Optical recording layer (light absorption layer)
5: Protective layer 6: Light transmission layer (cover layer)
7: Laser light (recording, reproduction)
11: Write-once optical disc of the present invention (organic BD-R)
Claims (2)
前記記録層に用いる有機色素が、下記一般式で表されることを特徴とする光情報記録媒体。
An optical information recording medium, wherein the organic dye used in the recording layer is represented by the following general formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010048769A JP2011183580A (en) | 2010-03-05 | 2010-03-05 | Pigment for optical information recording medium and optical information recording medium using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010048769A JP2011183580A (en) | 2010-03-05 | 2010-03-05 | Pigment for optical information recording medium and optical information recording medium using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2011183580A true JP2011183580A (en) | 2011-09-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010048769A Withdrawn JP2011183580A (en) | 2010-03-05 | 2010-03-05 | Pigment for optical information recording medium and optical information recording medium using the same |
Country Status (1)
| Country | Link |
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| JP (1) | JP2011183580A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013161916A1 (en) * | 2012-04-26 | 2013-10-31 | ソニー株式会社 | Optical information recording medium |
-
2010
- 2010-03-05 JP JP2010048769A patent/JP2011183580A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013161916A1 (en) * | 2012-04-26 | 2013-10-31 | ソニー株式会社 | Optical information recording medium |
| JP2013242953A (en) * | 2012-04-26 | 2013-12-05 | Sony Corp | Optical information recording medium |
| US9082430B2 (en) | 2012-04-26 | 2015-07-14 | Sony Corporation | Optical information recording medium |
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