JPH0132794B2 - - Google Patents
Info
- Publication number
- JPH0132794B2 JPH0132794B2 JP56113749A JP11374981A JPH0132794B2 JP H0132794 B2 JPH0132794 B2 JP H0132794B2 JP 56113749 A JP56113749 A JP 56113749A JP 11374981 A JP11374981 A JP 11374981A JP H0132794 B2 JPH0132794 B2 JP H0132794B2
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor laser
- metal complex
- formula
- recording film
- nickel
- 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
Links
- 239000004065 semiconductor Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- -1 aliphatic diamine Chemical class 0.000 claims description 29
- 239000000020 Nitrocellulose Substances 0.000 claims description 28
- 229920001220 nitrocellulos Polymers 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Chemical group 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Chemical group 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004984 aromatic diamines Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 239000006096 absorbing agent Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 238000002144 chemical decomposition reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 101000863770 Homo sapiens DNA ligase 1 Proteins 0.000 description 2
- 101000619640 Homo sapiens Leucine-rich repeats and immunoglobulin-like domains protein 1 Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 102100022170 Leucine-rich repeats and immunoglobulin-like domains protein 1 Human genes 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000001883 metal evaporation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- QGKGHQPUCHEWMC-UHFFFAOYSA-N 1-sulfanylnaphthalen-2-ol Chemical compound C1=CC=CC2=C(S)C(O)=CC=C21 QGKGHQPUCHEWMC-UHFFFAOYSA-N 0.000 description 1
- RPKCLSMBVQLWIN-UHFFFAOYSA-N 2-n-methylbenzene-1,2-diamine Chemical compound CNC1=CC=CC=C1N RPKCLSMBVQLWIN-UHFFFAOYSA-N 0.000 description 1
- KHXKYJYWAPRBDH-UHFFFAOYSA-L 3h-dithiole-3-carboxylate;nickel(2+) Chemical compound [Ni+2].[O-]C(=O)C1SSC=C1.[O-]C(=O)C1SSC=C1 KHXKYJYWAPRBDH-UHFFFAOYSA-L 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- ZMUIGFHVLBHRMK-UHFFFAOYSA-N benzene-1,2-diamine;nickel Chemical compound [Ni].NC1=CC=CC=C1N ZMUIGFHVLBHRMK-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007738 vacuum evaporation 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
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
- G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Description
【発明の詳細な説明】
本発明は半導体レーザ記録フイルムに関する。
さらに詳しくは、半導体レーザ光の吸収能を有
し、かつレーザ光を照射された部位が半導体レー
ザ光の吸収能を失う新規な半導体レーザ記録フイ
ルムに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a semiconductor laser recording film.
More specifically, the present invention relates to a novel semiconductor laser recording film that has the ability to absorb semiconductor laser light and loses the ability to absorb semiconductor laser light in areas irradiated with laser light.
近年、画像、音響を始めとする情報の記録およ
び再生を高速度に高密度に、しかも簡便に行うこ
とがますます強く要望されており、各種の方法が
提案されまた一部実用化されている。 In recent years, there has been an increasing demand for recording and reproducing information such as images and sounds at high speed, high density, and easily, and various methods have been proposed and some have been put into practical use. .
その中で、レーザ光によつてフイルムに記録す
る方式はレンズによつて絞り込んだレーザ光の焦
点を基板上の記録層に当てて記録する、いわゆる
ヒートモード記録方式であり、従来の感熱記録方
式のように発熱体を感熱記録層に直接接触させず
に記録できるため、発熱体の熱容量や熱の拡散な
どの問題が起らず、高速度および高密度の記録が
可能となる。レーザによるヒートモード記録方式
はレーザ光を照射した部位の記録層にレーザ光の
熱的作用に基づく物理的または化学的変化を起さ
せることにより、照射されたスポツトと照射され
ていない領域との間に光学的な濃度差を生じさせ
る記録方式である。この記録方式に使用する記録
フイルムとしては、従来、ポリエステルなどの基
板上にモリブデン、インジウム、ビスマス、テル
ルなどの金属を真空蒸着やスパツタリングなどの
方法により薄膜状に結着させた記録フイルムが知
られており、これにレーザ光を照射して部分的に
金属を蒸発させて記録することができ、ビデオデ
イスクのマスターデイスクの作成用に一部実用化
されている。しかしながら、この記録フイルムは
使用する金属のレーザ光反射率が高く、したがつ
て、レーザ光の吸収効率が低いため、記録に要す
るレーザ光も大きな出力が要求され、レーザ発生
装置が大型となるので、必ずしも経済的に有利な
記録フイルムではない。この記録フイルムに対
し、熱を吸収するカーボンブラツクなどの微粒子
およびニトロセルロースなどの自己酸化結合物質
を結合する被覆物質とを包含した記録フイルムが
提案されている（特開昭48―43632号）。この記録
フイルムはレーザ光を照射してカーボンブラツク
などの微粒子を他の記録テープに移着させること
によりネガ、ポジの記録が可能となるものである
が、この記録方式はカーボンブラツクなどの微粒
子をレーザ光により記録フイルム上から逃散せし
めるという物質移動を必須とする。そのため、微
粒子の粒状性に基づき高密度の記録が得られにく
く、光学的に高い濃度差を得るにはやはり大きな
出力のレーザ光を要することになり、前述の金属
薄膜を用いた記録フイルムの問題点を解決するに
は到つていない。さらに、より低い出力のレーザ
光で記録が可能な記録フイルムとして、記録に用
いるレーザ光の波長領域で強い吸収特性を有し、
かつ光を吸収して発熱するメチレンブルー、ブリ
リアントグリーンなどの色素とニトロセルロース
などの低温度で気化する有機物質とを結合した記
録材料を塗布した記録フイルムが提案されている
（特開昭55―87595号）。 Among them, the method of recording on film with laser light is the so-called heat mode recording method, in which the laser light narrowed down by a lens is focused on the recording layer on the substrate, and is the so-called heat mode recording method, which is different from the conventional thermal recording method. Since recording can be performed without bringing the heating element into direct contact with the heat-sensitive recording layer, problems such as the heat capacity of the heating element and heat diffusion do not occur, and high-speed and high-density recording is possible. The heat mode recording method using a laser causes a physical or chemical change in the recording layer in the area irradiated with laser light based on the thermal effect of the laser light, thereby creating a gap between the irradiated spot and the non-irradiated area. This is a recording method that creates an optical density difference between the images. Recording films used in this recording method have conventionally been made by bonding metals such as molybdenum, indium, bismuth, tellurium, etc. in a thin film onto a substrate such as polyester using methods such as vacuum evaporation or sputtering. The metal can be irradiated with laser light to partially evaporate the metal for recording, and has been put into practical use in some cases for creating master discs for video discs. However, the metal used in this recording film has a high laser light reflectance, and therefore the laser light absorption efficiency is low, so the laser light required for recording requires a large output, which requires a large laser generator. However, it is not necessarily an economically advantageous recording film. In contrast to this recording film, a recording film that includes fine particles such as carbon black that absorbs heat and a coating material that binds an autooxidation binding substance such as nitrocellulose has been proposed (Japanese Patent Application Laid-open No. 43632/1983). This recording film enables negative and positive recording by irradiating laser light to transfer fine particles such as carbon black to other recording tapes. It is essential to transport the material by causing it to escape from the recording film using laser light. Therefore, it is difficult to obtain high-density recording due to the granularity of the fine particles, and a high output laser beam is still required to obtain a high optical density difference, which is the problem with recording films using metal thin films as mentioned above. The issue has not yet been resolved. Furthermore, as a recording film that can be recorded with a lower output laser beam, it has strong absorption characteristics in the wavelength range of the laser beam used for recording.
A recording film coated with a recording material that combines dyes such as methylene blue and brilliant green, which generate heat by absorbing light, and an organic substance that vaporizes at low temperatures, such as nitrocellulose, has been proposed (Japanese Patent Application Laid-Open No. 87595-1989). issue).
この記録フイルムはレーザ光を照射してニトロ
セルロースなどの気化性有機物質を気化させ、同
時に色素を分解させてしまうことにより記録が可
能となるものであるが、この記録方式もニトロセ
ルロースなどの気化性の有機物質を気化させると
いう物質移動を必須とする方式である。そのた
め、記録に用いるレーザ光の低出力化を十分に達
しているとはいいがたいばかりでなく、レーザ光
の照射されたスポツトの周辺に盛り上りを併うた
め記録フイルムの読取の際のノイズの原因になり
易く、また使用するレーザ光の波長領域が可視光
領域に限られてしまい、半導体レーザのような近
赤外域の光を用いることができない欠点がある。 This recording film is capable of recording by irradiating laser light to vaporize volatile organic substances such as nitrocellulose and at the same time decompose the dye. This method requires mass transfer by vaporizing organic substances. Therefore, not only is it difficult to say that the output of the laser beam used for recording has been sufficiently reduced, but also noise is generated when reading the recording film due to the bulge around the spot irradiated with the laser beam. Moreover, the wavelength range of the laser light used is limited to the visible light range, and there is a drawback that light in the near-infrared range cannot be used like a semiconductor laser.
このような状況に鑑み、本発明者らは低出力の
半導体レーザ光で光学的に高い濃度差を得ること
ができる記録フイルムとして、上述のような熱を
吸収する微粒子や有機物質の物質移動を利用した
記録方式に対して、レーザ光の熱的作用による化
学的変化を利用する方式について研究を行つた。
その結果、種々の光吸収剤の中にはそれ単独では
半導体レーザ光に対して化学的に安定でありなが
ら、ニトロセルロースと共存させた状態で半導体
レーザ光を受けると、そのの熱的作用により極め
て容易に化学的分解を起こし、その吸収能を喪失
する化合物が存在することを見出した。ついで、
これを用いて記録フイルムを作成し、半導体レー
ザ光を照射したところ、従来の記録方式と較べ、
低出力の半導体レーザ光により光学的に高い濃度
差を得ることができるばかりでなく、レーザ光の
照射されたスポツトの周辺の盛り上がりを極めて
小さくすることが可能となることを見出し、本発
明に到つた。 In view of this situation, the present inventors have developed a recording film that can obtain a high optical density difference using low-power semiconductor laser light by utilizing the mass transfer of heat-absorbing fine particles and organic substances as described above. Regarding the recording method used, we conducted research on a method that utilizes chemical changes caused by the thermal action of laser light.
As a result, some light absorbers are chemically stable against semiconductor laser light when used alone, but when they are exposed to semiconductor laser light in the presence of nitrocellulose, they become unstable due to the thermal effects of the semiconductor laser light. It has been found that there are compounds that undergo chemical decomposition extremely easily and lose their absorption ability. Then,
When we created a recording film using this and irradiated it with semiconductor laser light, we found that compared to conventional recording methods,
The present inventors have discovered that it is not only possible to obtain a high optical density difference using a low-power semiconductor laser beam, but also that it is possible to extremely minimize the swelling around the spot irradiated with the laser beam, and have thus arrived at the present invention. Ivy.
本発明の記録フイルムは、光吸収剤の選択によ
り半導体レーザを用いて記録することができるば
かりか、銀塩写真のような現像処理が全く不要
で、かつ記録に用いる半導体レーザ光をそのまま
出力を低下させて読取光として用いることのでき
る実時間レーザ記録が可能である。 The recording film of the present invention not only allows recording using a semiconductor laser by selecting a light absorbing agent, but also does not require any development processing like silver halide photography, and can directly output the semiconductor laser light used for recording. Real-time laser recording is possible, which can be lowered and used as a reading light.
すなわち、本発明は基板上に、記録に用いる
半導体レーザ光の波長領域で、強い吸収能を有し
かつニトロセルロースの共存下で分解してその吸
収能を失う光吸収剤と、ニトロセルロースを含
有する記録媒体を塗布したことを特徴とする半導
体レーザ記録フイルムを提供するものである。本
発明に用いる光吸収剤は、記録に用いる半導体レ
ーザ光の波長領域で強い吸収能を有し、かつニト
ロセルロースの共存下に、熱的作用により容易に
分解してその吸収能を失う物質である。本発明者
らの研究により種々の金属錯体やアミニウム塩類
がこの性質を有することが判つた。これらの金属
錯体やアミニウム塩類は単独で加熱またはレーザ
光を受けた場合は化学的に安定であるにもかかわ
らずニトロセルロースと共存した状態で加熱また
は半導体レーザ光を受けた場合、それ自体の分解
温度と較べはるかに低温度で容易に化学的分解を
起こし、吸収能を失う性質を有するものである。
その化学的分解の機構は必ずしも明確ではない
が、ニトロセルロースが加熱されて出現する強力
な酸化作用により金属錯体やアミニウム塩類の化
学的分解が促進され、吸収能を失わしめるものと
推定される。すなわち、本発明に用いる光吸収剤
は半導体レーザ光を吸収して発熱し、吸収剤近傍
のニトロセルロースに熱を伝達し、ニトロセルロ
ースの酸化作用を惹起するとともに、その酸化作
用により化学的分解を起こし、吸収能を喪失する
性質を兼ね備えた吸収能である。このような吸収
剤として大別して６種、すなわち、芳香族ジアミ
ン系金属錯体、脂肪族ジアミン系金属錯体、芳香
族ジチオール系金属錯体、脂肪族ジチオール系金
属錯体、メルカプトフエノール系金属錯体および
アリールアミニウム塩類があげられる。 That is, the present invention provides a substrate containing a light absorbing agent that has a strong absorption ability in the wavelength range of semiconductor laser light used for recording and that decomposes and loses its absorption ability in the coexistence of nitrocellulose, and nitrocellulose. The present invention provides a semiconductor laser recording film coated with a recording medium of the type. The light absorbent used in the present invention is a substance that has strong absorption ability in the wavelength range of the semiconductor laser light used for recording, and that easily decomposes and loses its absorption ability due to thermal action in the coexistence of nitrocellulose. be. Through research conducted by the present inventors, it has been found that various metal complexes and aminium salts have this property. Although these metal complexes and aminium salts are chemically stable when heated or exposed to laser light alone, they decompose themselves when heated or exposed to semiconductor laser light in the presence of nitrocellulose. It has the property of easily causing chemical decomposition and losing its absorption ability at a much lower temperature.
Although the mechanism of chemical decomposition is not necessarily clear, it is presumed that the strong oxidation that appears when nitrocellulose is heated accelerates the chemical decomposition of metal complexes and aminium salts, causing them to lose their absorption capacity. That is, the light absorber used in the present invention absorbs semiconductor laser light, generates heat, transfers the heat to nitrocellulose near the absorber, causes oxidation of nitrocellulose, and causes chemical decomposition due to the oxidation. It has the property of causing absorption and loss of absorption capacity. There are six types of such absorbents: aromatic diamine metal complexes, aliphatic diamine metal complexes, aromatic dithiol metal complexes, aliphatic dithiol metal complexes, mercaptophenol metal complexes, and arylaminium. Salts can be given.
(1)芳香族ジアミン系金属錯体としては、
一般式（）
（式中、Ｘは水素、アルキル基、置換アルキル
基、ハロゲン基、ニトロ基、ｎは１〜４の整数値
を、Ｍはニツケル、コバルト、パラジウム、白金
を示す）で表わされる化合物であり、そのうち特
にビス（４―クロロ―ｏ―フエニレンジアミン）
ニツケル（吸収極大波長λnax800nm、モル比吸光
係数ε66600）およびビス（４―メチル―ｏ―フエ
ニレンジアミン）ニツケル（λnax795nm、
ε55100）が合成が容易でニトロセルロースとの相
溶性にすぐれているため好ましい。 (1) The aromatic diamine metal complex has the general formula () (In the formula, X is hydrogen, an alkyl group, a substituted alkyl group, a halogen group, a nitro group, n is an integer value of 1 to 4, and M is nickel, cobalt, palladium, or platinum). Especially bis(4-chloro-o-phenylenediamine)
Nickel (maximum absorption wavelength λ nax 800 nm, molar extinction coefficient ε66600) and bis(4-methyl-o-phenylenediamine) nickel (λ nax 795 nm,
ε55100) is preferred because it is easy to synthesize and has excellent compatibility with nitrocellulose.
また(2)脂肪族ジアミン系金属錯体としては、
一般式（）
（式中、Ｙは水素、アルキル基、フエニル基、シ
アノ基を、Ｍはニツケル、コバルト、パラジウ
ム、白金を示す）で表わされる化合物であり、そ
のうち特にビス（ジイミノサクシノニトリロ）ニ
ツケル（λnax700nm、ε23500）およびビス（ジイ
ミノサクシノニトリロ）パラジウム（λnax
705nm、ε8300）が合成が容易でニトロセルロー
スとの相溶性にすぐれているため好ましい。 In addition, (2) the aliphatic diamine metal complex has the general formula () (In the formula, Y represents hydrogen, an alkyl group, a phenyl group, or a cyano group, and M represents nickel, cobalt, palladium, or platinum.) Among them, bis(diiminosuccinonitrilo)nickel (λ nax 700nm, ε23500) and bis(diiminosuccinonitrilo)palladium (λ nax
705 nm, ε8300) is preferred because it is easy to synthesize and has excellent compatibility with nitrocellulose.
また(3)芳香族ジチオール系金属錯体としては、
一般式（）
（式中、Ｚは水素、アルキル基、ハロゲン基を、
ｎは１〜４の整数値を、Ｍはニツケル、コバル
ト、パラジウム、白金を、ｍは−１または−２の
整数を、Ａはｍが−１のとき１価のカチオンであ
り、またｍは−２のとき２価のカチオンを示す）
で表わされる化合物であり、そのうち特にビス
（１―メチル―３，４―ジチオフエノレート）ニ
ツケル（）テトラ―ｎ―ブチルアンモニウム
（λnax890nm、ε16270）およびビス（１，２，３，
４―テトラクロロ―５，６―ジチオフエノレー
ト）ニツケル（）テトラ―ｎ―ブチルアンモニ
ウム（λnax885nm、ε15700）が合成が容易でニト
ロセルロースとの相溶性にすぐれているため好ま
しい。 In addition, (3) the aromatic dithiol metal complex has the general formula () (In the formula, Z is hydrogen, an alkyl group, a halogen group,
n is an integer value of 1 to 4, M is nickel, cobalt, palladium, platinum, m is an integer of -1 or -2, A is a monovalent cation when m is -1, and m is -2 indicates a divalent cation)
It is a compound represented by bis(1-methyl-3,4-dithiophenolate)nickel()tetra-n-butylammonium (λ nax 890nm, ε16270) and bis(1,2,3,
4-Tetrachloro-5,6-dithiophenolate) nickel()tetra-n-butylammonium (λ nax 885 nm, ε15700) is preferred because it is easy to synthesize and has excellent compatibility with nitrocellulose.
また(4)脂肪族ジチオール系金属錯体としては、
一般式（）
（式中、Ｅは水素、アルキル基、フエニル基を、
ｐは２または３の整数値を、Ｍはｐが２のときニ
ツケル、コバルト、パラジウム、白金を、ｐが３
のときバナジウム、クロム、モリブデンを示す）
で表わされる化合物であり、そのうち特にビス
〔シス―１，２―ビス（ｐ―メトキシフエニル）
エチレン―１，２―ジチオレート〕ニツケル
（λnax920nm、ε35000）およびビス（シス―１，
２―ビスフエニルエチレン―１，２―ジチオレー
ト）白金（λnax800nm、ε51600）およびトリス
（シス―１，２―ビスフエニルエチレン―１，２
―ジチオレート）バナジウム（λnax750nm、
ε27000）が合成が容易でニトロセルロースとの相
溶性にすぐれているため好ましい。 In addition, (4) the aliphatic dithiol metal complex has the general formula () (In the formula, E represents hydrogen, an alkyl group, a phenyl group,
p is an integer value of 2 or 3, M is nickel, cobalt, palladium, platinum when p is 2, and p is 3.
(indicates vanadium, chromium, molybdenum)
It is a compound represented by
Ethylene-1,2-dithiolate]nickel (λ nax 920nm, ε35000) and bis(cis-1,
2-bisphenylethylene-1,2-dithiolate) platinum (λ nax 800nm, ε51600) and tris(cis-1,2-bisphenylethylene-1,2
-dithiolate) vanadium (λ nax 750nm,
ε27000) is preferred because it is easy to synthesize and has excellent compatibility with nitrocellulose.
また(5)５メルトカプトフエノール系金属錯体と
しては一般式（）または（）
（式中、Ｇは水素、アルキル基、ハロゲン基を、
Ｍはニツケル、コバルト、パラジウム、白金を、
ｍは−１または−２の整数を、Ａはｍが−１のと
き１価のカチオンであり、またｍが−２のとき２
価のカチオンを示す）で表わされる化合物であ
り、そのうち特にビス（１―メルカプト―２―ナ
フトレート）ニツケル（）テトラ―ｎ―ブチル
アンモニウム（λnax1100nm、ε12290）およびビ
ス（１―メルカプト―２―フエノレート）ニツケ
ル（）テトラ―ｎ―ブチルアンモニウム（λnax
1025nm、ε12700）が合成が容易でニトロセルロ
ースとの相溶性にすぐれているため好ましい。 In addition, (5) 5-meltocaptophenol metal complex has the general formula () or () (In the formula, G represents hydrogen, an alkyl group, a halogen group,
M stands for nickel, cobalt, palladium, platinum,
m is an integer of -1 or -2, A is a monovalent cation when m is -1, and 2 when m is -2.
It is a compound represented by bis(1-mercapto-2-naphthorate)nickel()tetra-n-butylammonium (λ nax 1100 nm, ε12290) and bis(1-mercapto-2-naphtholate) (indicating a valent cation). phenolate) nickel () tetra-n-butylammonium (λ nax
1025 nm, ε12700) is preferred because it is easy to synthesize and has excellent compatibility with nitrocellulose.
さらに(6)アリールアミニウム塩類としては、一
般式（）または（）
（式中、R1およびR2は同じかまたは異なるアル
キル基を、R3は水素、アルキル基、フエニル基、
ベンジル基をｍは＋１または＋２の整数を、Ｌは
ｍが＋１のとき１価のアニオンであり、またｍが
＋２のとき２価のアニオンを示す）で表わされる
化合物であり、４，4′―ビス（ｐ―ジメチルアミ
ノフエニル）アミニウムアイオダイド（λnax740
にε12880、λnax1000にε32890）、４，4′―ビス
（ｐ―ジエチルアミノフエニル）アミニウムフル
オロボレート（λnax730にε18800、λnax995に
ε38690）およびビス（ｐ―ジエチルアミノフエニ
ル）〔Ｎ，Ｎ―ビス（ｐ―ジエチルアミノフエニ
ル）―4′―アミノビフエニル〕アミニウムヘキサ
フルオロアンチモネート（λnax600にε2600、λnax
1055にε24300）が合成が容易でニトロセルロース
との相溶性にすぐれているため好ましい。上記し
たこれらの光吸収剤は、ニトロセルロース共存下
で熱的作用により分解して光吸収能を失う、たと
えば加熱すると200℃以下で光吸収剤が分解を起
こし吸収能を失い、また加熱する代わりに光吸収
剤の有する極大吸収波長に近い波長の半導体レー
ザ光を照射することにより吸収能を喪失する。 Furthermore, (6) arylaminium salts include the general formula () or () (In the formula, R 1 and R 2 are the same or different alkyl groups, R 3 is hydrogen, an alkyl group, a phenyl group,
A compound represented by a benzyl group, m is an integer of +1 or +2, L is a monovalent anion when m is +1, and a divalent anion when m is +2), -Bis(p-dimethylaminophenyl)aminium iodide (λ nax 740
ε12880 for λ nax 1000, ε32890 for λ nax 1000), 4,4'-bis(p-diethylaminophenyl) aminium fluoroborate (ε18800 for λ nax 730, ε38690 for λ nax 995) and bis(p-diethylaminophenyl) [ N,N-bis(p-diethylaminophenyl)-4'-aminobiphenyl] aminium hexafluoroantimonate (λ nax 600 to ε2600, λ nax
1055 and ε24300) is preferred because it is easy to synthesize and has excellent compatibility with nitrocellulose. These light absorbers described above decompose due to thermal action in the coexistence of nitrocellulose and lose their light absorbing ability. The absorption ability is lost by irradiating the material with semiconductor laser light having a wavelength close to the maximum absorption wavelength of the light absorbent.
本発明の半導体レーザ記録フイルムは、上記の
光吸収能およびニトロセルロースならびに必要に
応じその他の媒体を適当な溶剤に混合溶解させて
調製したような、光吸収剤およびニトロセルロー
スを含有する記録媒体を半導体レーザ光を透過
し、耐熱性を有したポリエチレンテレフタレー
ト、ポリカーボネートなどのプラスチツクフイル
ムやガラスなどの透明な基板上に塗布して得られ
る。レーザ光で記録された情報の読取に際し、読
取用のレーザ光の透過量を検出する場合と異な
り、読取用のレーザ光の反射光量で読取る場合
は、基板上に金属蒸着を行つたのち金属蒸着層の
上に、上記の光吸収剤とニトロセルロースとを含
有する記録媒体を塗布して本発明の半導体レーザ
記録フイルムを得ることができる。また、基板上
に塗布する記録媒体において、光吸収剤のニトロ
セルロースに対する添加割合は１〜50重量％であ
るが、通常、３〜30重量％が好ましい。添加割合
が大きいと塗膜と基板との密着性が悪化し、添加
割合が小さいと光学的濃度差が十分に得にくくな
る。また、記録媒体には形成される塗膜と基板と
の密着性および塗膜の経済的な安定性を改善する
ために適宜ポリアクリル酸メチル、ポリメタクリ
ル酸メチルなどのアクリル樹脂、セルロースアセ
テートなどのニトロセルロース以外のセルロース
誘導体、ポリ塩化ビニル、ポリ塩化ビニル―ポリ
酢酸ビニル共重合体などのビニル系樹脂などの有
機高分子化合物を加えてもよい。また、光吸収剤
とニトロセルロースを溶解せしめる溶剤としては
アセトン、メチルエチルケトンなどのケトン系溶
剤、エタノール、イソプロパノールなどのアルコ
ール系溶剤、メチルセロソルブ、エチルセロソル
ブなどのセロソルブ系溶剤、エチレングリコール
モノメチルエーテル、ジエチレングリコールモノ
メチルエーテルアセテートなどのグリコールエー
テルエステル系溶剤、ジクロルメタン、クロロホ
ルムなどの塩素系炭化水素溶剤のうちいずれか１
種以上の溶剤を用いることが可能である。 The semiconductor laser recording film of the present invention has the above-mentioned light absorption ability and a recording medium containing a light absorbing agent and nitrocellulose, such as one prepared by mixing and dissolving nitrocellulose and other media as necessary in a suitable solvent. It is obtained by coating on a transparent substrate such as glass or plastic film such as polyethylene terephthalate or polycarbonate, which transmits semiconductor laser light and has heat resistance. When reading information recorded with a laser beam, unlike the case where the amount of transmission of the reading laser beam is detected, when reading by the amount of reflected light of the reading laser beam, metal evaporation is performed on the substrate and then metal evaporation is performed. The semiconductor laser recording film of the present invention can be obtained by applying a recording medium containing the above-mentioned light absorbent and nitrocellulose onto the layer. Further, in a recording medium coated on a substrate, the addition ratio of the light absorbent to nitrocellulose is 1 to 50% by weight, but usually 3 to 30% by weight is preferable. If the addition ratio is large, the adhesion between the coating film and the substrate will deteriorate, and if the addition ratio is small, it will be difficult to obtain a sufficient optical density difference. In addition, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, cellulose acetate, etc. are appropriately added to the recording medium in order to improve the adhesion between the coating film and the substrate and the economic stability of the coating film. Organic polymer compounds such as cellulose derivatives other than nitrocellulose, vinyl resins such as polyvinyl chloride and polyvinyl chloride-polyvinyl acetate copolymers may be added. In addition, solvents for dissolving the light absorber and nitrocellulose include ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as ethanol and isopropanol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ethylene glycol monomethyl ether, diethylene glycol monomethyl Any one of glycol ether ester solvents such as ether acetate, chlorine hydrocarbon solvents such as dichloromethane, chloroform, etc.
It is possible to use more than one type of solvent.
本発明の半導体レーザ記録フイルムに半導体レ
ーザ光を照射してレーザ記録を行うためには、含
有する光吸収剤の吸収波長領域に波長を有するレ
ーザ光を各種の半導体レーザから選択して使用す
る、かつ使用する半導体レーザをレンズによつて
通常2μ以下のスポツトビームに集光して記録フ
イルムに照射すれば、高密度で低エネルギーのレ
ーザ光による光学的に高い濃度差を有する実時間
レーザ記録が可能となる。すなわち、本発明の半
導体レーザ記録フイルムは、低出力の半導体レー
ザ光により極めて高密度で光学的に高い濃度差が
得られること、光吸収剤の選択により近赤外領域
の各種半導体レーザ光も使用できること、記録に
用いたレーザ光をそのまま出力を低下させて読取
光として用いることが可能なこと、現象定着など
の後処理を必要としない実時間記録であること、
さらに室内光に感光することがないため暗室操作
が不要であることなどの利点を有しており、マイ
クロ画像、COM、マイクロフアクシミリ、写真
植字用原板、光学式ビデオデイスク、光学式オー
デイオデイスクなどに広く応用することが可能で
ある。 In order to perform laser recording by irradiating the semiconductor laser recording film of the present invention with semiconductor laser light, a laser light having a wavelength in the absorption wavelength region of the light absorbing agent contained is selected from various semiconductor lasers and used. In addition, if the semiconductor laser used is focused with a lens into a spot beam of usually 2μ or less and irradiated onto the recording film, real-time laser recording with a high optical density difference using high-density, low-energy laser light can be achieved. It becomes possible. That is, the semiconductor laser recording film of the present invention can obtain extremely high density and optically high density difference using low-power semiconductor laser light, and can also use various types of semiconductor laser light in the near-infrared region by selecting a light absorber. It is possible to directly reduce the output of the laser beam used for recording and use it as a reading beam, and it is a real-time recording that does not require post-processing such as phenomenon fixation.
Furthermore, it has the advantage of not being exposed to indoor light, so there is no need for darkroom operations. It can be widely applied to
以下、本発明を実施例をもつて説明する。 Hereinafter, the present invention will be explained using examples.
実施例中の部はすべて重量部を表わす。 All parts in the examples represent parts by weight.
実施例 １
エチルセロソルブアセテート200部にニトロセ
ルロース（旭化成製LIG1/2）10部、ビス（４―
メチル―ｏ―フエニレンジアミン）ニツケル２部
を加えて撹きまぜ、溶解させた組成物をスピンナ
ーを用いてポリエチレンテレフタレートフイルム
上に塗布し、所定の条件で乾燥して約0.5μmの赤
紫色の塗膜面を形成させた。次いで塗膜面へ集束
した半導体レーザ光線（GaAlAs系レーザ、
780nm、光出力5mW）を直線状に掃引照射した。
比較試験としてビス（４―メチル―ｏ―フエニレ
ンジアミン）ニツケルの代わりにカーボンブラツ
ク２部を用いて同様に行つた記録フイルムについ
てもレーザ光を直線状に掃引照射した。両者のレ
ーザ照射部を電子顕微鏡で観察した結果、カーボ
ンブラツクを用いた場合、レーザ光の軌跡がわず
かに確認できる程度に対し、ビス（４―メチル―
ｏ―フエニレン―ジアミン）ニツケルを用いた場
合の直線は極めて鮮明で、照射部近傍の盛り上が
りはほとんどみられず、光学顕微鏡による観察で
は、未照射部分が赤紫色を呈しているのに対して
照射部は黄色に変色していることが判つた。Example 1 200 parts of ethyl cellosolve acetate, 10 parts of nitrocellulose (LIG1/2 manufactured by Asahi Kasei), and bis(4-
Add 2 parts of methyl-o-phenylenediamine) nickel, stir, and dissolve the composition. The resulting composition is applied onto a polyethylene terephthalate film using a spinner, and dried under specified conditions to form a reddish-purple color of about 0.5 μm. A coating film surface was formed. Next, a semiconductor laser beam (GaAlAs laser,
780 nm, optical output 5 mW) was irradiated in a linear sweep.
As a comparative test, a similar recording film using two parts of carbon black instead of bis(4-methyl-o-phenylenediamine) nickel was irradiated with laser light in a linear sweep. As a result of observing the laser irradiated parts of both with an electron microscope, it was found that when carbon black was used, the trajectory of the laser beam could be seen slightly, but when carbon black was used, the trajectory of the laser beam was slightly visible, whereas
When using (o-phenylene-diamine) nickel, the straight line is extremely clear, and there is almost no swelling near the irradiated area, and when observed with an optical microscope, the unirradiated area has a reddish-purple color, whereas the irradiated area shows a reddish-purple color. It was found that the part had turned yellow.
また、本記録フイルムをミクロ融点測定器（東
京百本製作所製）の加熱板の上にのせて加熱する
と、約160℃に到達したところで赤紫色から黄色
に変色した。次いで、加熱前後の記録フイルムの
近赤外部の光線透過率を測定（島津製作所製マル
チパーパス自記分光光度計）した結果、780nmの
透過率は照射前を１として照射後に３となつた。 When this recording film was heated by placing it on the heating plate of a micro melting point meter (manufactured by Tokyo Hyakubon Seisakusho), the color changed from reddish-purple to yellow when it reached about 160°C. Next, the near-infrared light transmittance of the recording film before and after heating was measured (using a multipurpose self-recording spectrophotometer manufactured by Shimadzu Corporation). As a result, the transmittance at 780 nm was 1 before irradiation and 3 after irradiation.
実施例 ２
実施例１のエチルセロソルブアセテート200部
の代わりにメチルエチルケトン150部を、ビス
（４―メチル―ｏ―フエニレンジアミン）ニツケ
ル２部の代わりにビス（イミノサクシノニトリ
ロ）ニツケル１部を用いる以外実施例１と同様に
行つて緑色の記録フイルムを得た。このフイルム
をミクロ融点測定器の加熱板の上にのせ加熱する
と約150℃に到達したところで緑色から黄色に変
色した。次いで加熱前後の記録フイルムの近赤外
部の光線透過率を測定した結果、700nmの透過率
は照射前を１として照射後に４となつた。Example 2 150 parts of methyl ethyl ketone is used in place of 200 parts of ethyl cellosolve acetate in Example 1, and 1 part of bis(iminosuccinonitrile) nickel is used in place of 2 parts of bis(4-methyl-o-phenylenediamine) nickel. A green recording film was obtained in the same manner as in Example 1 except for this. When this film was placed on the heating plate of a micro melting point meter and heated, the color changed from green to yellow when the temperature reached approximately 150°C. Next, the near-infrared light transmittance of the recording film before and after heating was measured. As a result, the transmittance at 700 nm was 1 before irradiation and 4 after irradiation.
実施例 ３
エチルセロソルブアセテート200部にニトロセ
ルロース（旭化成製LIG1/2）10部、メタクリル
酸メチル・アクリル酸エチルの共重合体であるメ
タクリル酸樹脂７部、ビス（１―メチル―３，４
―ジチオフエノレート）ニツケル（）テトラ―
ｎ―ブチルアンモニウム２部を加えてかきまぜ、
以下実施例１と同様に行つて緑色の記録フイルム
を得た。次いで塗膜面へ集束した半導体レーザ光
線（GaAs系レーザ、905nm、光出力5mw）を直
線状に掃引照射し、電子顕微鏡で観察した結果、
極めて鮮明な直線が描かれ、照射部近傍の盛り上
がりはみとめられず、光学顕微鏡による観察で
は、照射部分は黄緑色に変色していることが判つ
た。Example 3 200 parts of ethyl cellosolve acetate, 10 parts of nitrocellulose (LIG1/2 manufactured by Asahi Kasei), 7 parts of methacrylic acid resin which is a copolymer of methyl methacrylate and ethyl acrylate, and bis(1-methyl-3,4
-dithiophenolate)nickel()tetra-
Add 2 parts of n-butylammonium and stir.
Thereafter, the same procedure as in Example 1 was carried out to obtain a green recording film. Next, a focused semiconductor laser beam (GaAs laser, 905 nm, optical output 5 mw) was swept linearly onto the coating surface, and the results were observed using an electron microscope.
An extremely clear straight line was drawn, no swelling was observed near the irradiated area, and observation with an optical microscope revealed that the irradiated area had changed color to yellow-green.
また、本記録フイルムをミクロ融点測定器の加
熱板の上にのせて加熱すると約170℃に到達した
ところで緑色から黄緑色に変色し、180℃で黄色
となることが判つた。次いで加熱前後の記録フイ
ルムの近赤外部の光線透過率を測定した結果、
905nmの透過率は照射前を１として照射後２とな
つた。 It was also found that when this recording film was placed on the heating plate of a micro melting point meter and heated, the color changed from green to yellow-green when it reached about 170°C, and turned yellow at 180°C. Next, we measured the near-infrared light transmittance of the recording film before and after heating, and found that
The transmittance at 905 nm was 1 before irradiation and 2 after irradiation.
実施例 ４
実施例３のビス（１―メチル―３，４―ジチオ
フエノレート）ニツケル（）テトラ―ｎ―ブチ
ルアンモニウム２部の代わりにビス〔シス―１，
２―ビス（ｐ―メトキシフエニル）エチレン―
１，２―ジチオレート〕ニツケル２部を用いる以
外、実施例３と同様に行つて緑色の記録フイルム
を得た。Example 4 Bis[cis-1,
2-bis(p-methoxyphenyl)ethylene-
A green recording film was obtained in the same manner as in Example 3 except that 2 parts of nickel 1,2-dithiolate was used.
また半導体レーザ光線（GaAs系レーザ、
905nm、光出力5mw）の軌跡は鮮明であり、ミ
クロ融点測定器による加熱により約160℃で黄色
に変色し加熱前後の905nmの光線透過率は照射前
を１として照射後３となつた。 In addition, semiconductor laser beams (GaAs lasers,
905 nm, light output 5 mw) was clear, and it turned yellow at about 160°C by heating with a micro melting point measuring device, and the light transmittance at 905 nm before and after heating was 1 before irradiation and 3 after irradiation.
実施例 ５
実施例１のビス（４―メチル―ｏ―フエニレン
ジアミン）ニツケル２部の代わりにビス（１―メ
チルカプトレート―２―ナフトレート）ニツケル
（）テトラ―ｎ―ブチルアンモニウム２部を用
いる以外実施例１と同様に行つて暗褐色の記録フ
イルムを得た。次いで塗膜面へ集束したYAGレ
ーザ光線（1060nm、光出力10mw））の軌跡は鮮
明であり、ミクロ融点測定器による加熱により約
160℃に黄色に変色し、加熱前後の1060nmの光線
透過率は照射前を１として照射後３となつた。Example 5 In place of 2 parts of bis(4-methyl-o-phenylenediamine) nickel in Example 1, 2 parts of bis(1-methylcaptorate-2-naphthlate) nickel()tetra-n-butylammonium is used. A dark brown recording film was obtained in the same manner as in Example 1 except for this. Next, the trajectory of the YAG laser beam (1060nm, optical output 10mw) focused on the coating surface was clear, and it was heated by a micro melting point measuring device.
It turned yellow at 160°C, and the light transmittance at 1060 nm before and after heating was 1 before irradiation and 3 after irradiation.
実施例 ６
実施例１のビス（４―メチル―ｏ―フエニレン
ジアミン）ニツケル２部の代わりに４，4′―ビス
（ｐ―ジメチルアミノフエニル）アミニウムアイ
オダイド２部を用いる以外、実施例１と同様に行
つて濃青色の記録フイルムを得た。次いで塗膜面
へ集束した半導体レーザ光線（GaAlAs系レー
ザ、780nm、光出力5mw）の軌跡は鮮明であり、
ミクロ融点測定器による加熱により約150℃で黄
色に変色し、加熱前後の780nmの光線透過率は照
射前を１として照射後４となつた。Example 6 The procedure was carried out except that 2 parts of 4,4'-bis(p-dimethylaminophenyl) aminium iodide were used in place of 2 parts of bis(4-methyl-o-phenylenediamine)nickel in Example 1. A dark blue recording film was obtained in the same manner as in Example 1. Next, the trajectory of the semiconductor laser beam (GaAlAs laser, 780 nm, optical output 5 mw) focused on the coating surface was clear.
It turned yellow at about 150°C by heating with a micro melting point measuring device, and the light transmittance at 780 nm before and after heating was 1 before irradiation and 4 after irradiation.
Claims (1)
波長領域で、強い吸収能を有しかつニトロセルロ
ースの共存下で分解してその吸収能を失う、芳香
族ジアミン系金属錯体、脂肪族ジアミン系金属錯
体、芳香族ジチオール系金属錯体、脂肪族ジチオ
ール系金属錯体、メルカプトフエノール系金属錯
体またはアリールアミニウム塩類から選ばれる光
吸収剤と、ニトロセルロースとを含有する記録
媒体を塗布したことを特徴とする半導体レーザ記
録フイルム。 ２ 芳香族ジアミン系金属錯体が一般式（） （式中、Ｘは水素、アルキル基、置換アルキル
基、ハロゲン基、ニトロ基、ｎは１〜４の整数値
を、Ｍはニツケル、コバルト、パラジウム、白金
を示す）で表わされる化合物である特許請求の範
囲第１項記載の半導体レーザ記録フイルム。 ３ 脂肪族ジアミン系金属錯体が一般式（） （式中、Ｙは水素、アルキル基、フエニル基、シ
アノ基を、Ｍはニツケル、コバルト、パラジウ
ム、白金を示す）で表わされる化合物である特許
請求の範囲第１項記載の半導体レーザ記録フイル
ム。 ４ 芳香族ジチオール系金属錯体が一般式（） （式中、Ｚは水素、アルキル基、ハロゲン基を、
ｎは１〜４の整数値を、Ｍはニツケル、コバル
ト、パラジウム、白金を、ｍは−１または−２の
整数を、Ａはｍが−１のとき１価のカチオンであ
り、またｍが−２のとき２価のカチオンを示す）
で表わされる化合物である特許請求の範囲第１項
記載の半導体レーザ記録フイルム。 ５ 脂肪族ジチオール系金属錯体が一般式（） （式中、Ｅは水素、アルキル基、フエニル基を、
ｐは２または３の整数値を、Ｍはｐが２のときニ
ツケル、コバルト、パラジウム、白金を、ｐが３
のときバナジウム、クロム、モリブデンを示す）
で表わされる化合物である特許請求の範囲第１項
記載の半導体レーザ記録フイルム。 ６ メルカプトフエノール系金属錯体が一般式
（）または（） （式中、Ｇは水素、アルキル基、ハロゲン基を、
Ｍはニツケル、コバルト、パラジウム、白金を、
ｍは−１または−２の整数を、Ａはｍが−１のと
き１価のカチオンであり、またｍが−２のとき２
価のカチオンを示す）で表わされる化合物である
特許請求の範囲第１項記載の半導体レーザ記録フ
イルム。 ７ アリールアミニウム塩類が一般式（）また
は（） （式中、R1およびR2は同じかまたは異なるアル
キル基を、R3は水素、アルキル基、フエニル基、
ベンジル基を、ｍは＋１または＋２の整数を、Ｌ
はｍが＋１のとき１価のアニオンであり、またｍ
が＋２のとき２価のアニオンを示す）で表わされ
る化合物である特許請求の範囲第１項記載の半導
体レーザ記録フイルム。[Scope of Claims] 1. An aromatic diamine-based metal complex that has a strong absorption ability in the wavelength region of the semiconductor laser light used for recording and that decomposes and loses its absorption ability in the coexistence of nitrocellulose is disposed on a substrate. , an aliphatic diamine-based metal complex, an aromatic dithiol-based metal complex, an aliphatic dithiol-based metal complex, a mercaptophenol-based metal complex, or an arylaminium salt, and a recording medium containing nitrocellulose. A semiconductor laser recording film characterized by: 2 The aromatic diamine metal complex has the general formula () (In the formula, X is hydrogen, an alkyl group, a substituted alkyl group, a halogen group, a nitro group, n is an integer value of 1 to 4, and M is nickel, cobalt, palladium, or platinum.) A semiconductor laser recording film according to claim 1. 3 The aliphatic diamine metal complex has the general formula () 2. The semiconductor laser recording film according to claim 1, which is a compound represented by the formula (in the formula, Y represents hydrogen, an alkyl group, a phenyl group, or a cyano group, and M represents nickel, cobalt, palladium, or platinum). 4 Aromatic dithiol metal complex has the general formula () (In the formula, Z is hydrogen, an alkyl group, a halogen group,
n is an integer value of 1 to 4, M is nickel, cobalt, palladium, platinum, m is an integer of -1 or -2, A is a monovalent cation when m is -1; -2 indicates a divalent cation)
A semiconductor laser recording film according to claim 1, which is a compound represented by: 5 The aliphatic dithiol metal complex has the general formula () (In the formula, E represents hydrogen, an alkyl group, a phenyl group,
p is an integer value of 2 or 3, M is nickel, cobalt, palladium, platinum when p is 2, and p is 3.
(indicates vanadium, chromium, molybdenum)
A semiconductor laser recording film according to claim 1, which is a compound represented by: 6 The mercaptophenol metal complex has the general formula () or () (In the formula, G represents hydrogen, an alkyl group, a halogen group,
M stands for nickel, cobalt, palladium, platinum,
m is an integer of -1 or -2, A is a monovalent cation when m is -1, and 2 when m is -2.
2. The semiconductor laser recording film according to claim 1, which is a compound represented by: 7 Aryl aminium salts have the general formula () or () (In the formula, R 1 and R 2 are the same or different alkyl groups, R 3 is hydrogen, an alkyl group, a phenyl group,
benzyl group, m is an integer of +1 or +2, L
is a monovalent anion when m is +1, and m
2. The semiconductor laser recording film according to claim 1, which is a compound represented by the formula (when +2 indicates a divalent anion).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56113749A JPS5816888A (en) | 1981-07-22 | 1981-07-22 | Lasers-recording film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56113749A JPS5816888A (en) | 1981-07-22 | 1981-07-22 | Lasers-recording film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5816888A JPS5816888A (en) | 1983-01-31 |
| JPH0132794B2 true JPH0132794B2 (en) | 1989-07-10 |
Family
ID=14620143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56113749A Granted JPS5816888A (en) | 1981-07-22 | 1981-07-22 | Lasers-recording film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5816888A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59177746A (en) * | 1983-03-26 | 1984-10-08 | Pioneer Electronic Corp | Production of disc |
| JPS6021294A (en) * | 1983-07-18 | 1985-02-02 | Mitsui Toatsu Chem Inc | Thermal recording material |
| JPS6036190A (en) * | 1983-08-09 | 1985-02-25 | Tdk Corp | Optical recording medium |
| JPS6083029A (en) * | 1983-10-13 | 1985-05-11 | Mitsui Toatsu Chem Inc | Optical recording medium |
| JPH0316642Y2 (en) * | 1985-02-18 | 1991-04-10 | ||
| JPS61139202U (en) * | 1985-02-18 | 1986-08-29 | ||
| JPS61284487A (en) * | 1985-06-12 | 1986-12-15 | Daicel Chem Ind Ltd | Film for laser recording |
| US5028708A (en) * | 1987-04-14 | 1991-07-02 | Sumitomo Chemical Company, Limited | Azamethinyl quinoline derivatives |
| US4952552A (en) * | 1989-06-20 | 1990-08-28 | Eastman Kodak Company | Infrared absorbing quinoid dyes for dye-donor element used in laser-induced thermal dye transfer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5135144A (en) * | 1974-09-19 | 1976-03-25 | Matsushita Electric Ind Co Ltd | Yuwakashiki |
| JPS5163622A (en) * | 1974-08-28 | 1976-06-02 | Philips Nv | |
| JPS5639580A (en) * | 1979-09-07 | 1981-04-15 | Nec Corp | Real-time acoustic-wave holography |
-
1981
- 1981-07-22 JP JP56113749A patent/JPS5816888A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163622A (en) * | 1974-08-28 | 1976-06-02 | Philips Nv | |
| JPS5135144A (en) * | 1974-09-19 | 1976-03-25 | Matsushita Electric Ind Co Ltd | Yuwakashiki |
| JPS5639580A (en) * | 1979-09-07 | 1981-04-15 | Nec Corp | Real-time acoustic-wave holography |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5816888A (en) | 1983-01-31 |
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