JPH02209290A - Optical recording material - Google Patents
Optical recording materialInfo
- Publication number
- JPH02209290A JPH02209290A JP1030677A JP3067789A JPH02209290A JP H02209290 A JPH02209290 A JP H02209290A JP 1030677 A JP1030677 A JP 1030677A JP 3067789 A JP3067789 A JP 3067789A JP H02209290 A JPH02209290 A JP H02209290A
- Authority
- JP
- Japan
- Prior art keywords
- optical recording
- layer
- infrared absorber
- recording medium
- near infrared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000000981 basic dye Substances 0.000 claims abstract description 7
- 239000006096 absorbing agent Substances 0.000 claims description 59
- 238000004040 coloring Methods 0.000 claims description 41
- 230000031700 light absorption Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010410 layer Substances 0.000 abstract description 67
- 239000011241 protective layer Substances 0.000 abstract description 23
- 230000002745 absorbent Effects 0.000 abstract description 8
- 239000002250 absorbent Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003475 lamination Methods 0.000 abstract description 2
- 238000002310 reflectometry Methods 0.000 abstract 2
- 239000000975 dye Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- -1 thiol nickel complexes Chemical class 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000012463 white pigment Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000001454 recorded image Methods 0.000 description 3
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 3
- XURABDHWIADCPO-UHFFFAOYSA-N 4-prop-2-enylhepta-1,6-diene Chemical compound C=CCC(CC=C)CC=C XURABDHWIADCPO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- YTUMSQUHKFFPLZ-UHFFFAOYSA-N 2-[2-[3-[2-(2-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical class C=1C=CC=C(O)C=1C(C)(C)C(C=1)=CC=CC=1C(C)(C)C1=CC=CC=C1O YTUMSQUHKFFPLZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、照射したレーザー光を熱変換して記録を行な
う光記録体に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an optical recording medium that performs recording by thermally converting irradiated laser light.
（従来技術）
現像・定着のいらない直接記録方式のなかで、塩基性染
料と有機顕色剤とを発色剤とする感熱記録紙は、操作性
、保守性が優れていることからファクシミリやプリンタ
ーに広く利用されている。(Prior art) Among the direct recording methods that do not require development or fixing, thermal recording paper that uses basic dye and organic color developer as color formers is easy to operate and maintain, making it suitable for facsimiles and printers. Widely used.
しかしながら、この方式は、サーマルヘッドや発熱ＩＣ
ペンを感熱記録紙に直接接触させて加熱記録するために
、サーマルヘッドや発熱ＩＣペンに発色溶融物が付着し
て、カス付着やスティッキング等のトラブルを起こし、
記録障害や記録品質を損なう問題点が在った。However, this method cannot be used with thermal heads or heat-generating ICs.
Because the pen is brought into direct contact with thermal recording paper to heat and record, colored molten matter adheres to the thermal head and heat-generating IC pen, causing problems such as adhesion of residue and sticking.
There were problems with recording failures and recording quality.
特にプロッタープリンターのように記録の流れ方向に連
続して線画きする場合、カス付着のトラブルを引起こさ
ずに連続印字することは、不可能であった。Particularly in the case of continuous line drawing in the recording flow direction, such as with a plotter printer, it has been impossible to perform continuous printing without causing problems such as adhesion of residue.
又、サーマルヘッドによる記録方式では、画像解像度を
、８本／ｍｍ以上に上げることは難しいとされている。Furthermore, in the recording method using a thermal head, it is considered difficult to increase the image resolution to 8 lines/mm or more.
従ってカス付着、スティッキング等のトラブルを解消し
、解像度をさらに向上させる方法として光による無接触
の記録方式が提案されている。Therefore, a non-contact recording method using light has been proposed as a method of eliminating problems such as adhesion of residue and sticking and further improving resolution.
特開昭５４−４１４２号公報は、支持体に、ロイコ染料
を主体とする感熱記録層を塗布してなる感熱記録体にお
いて、格子欠陥を持たせた金属化合物を用いることによ
り、この金属化合物が可視、赤外領域の光を吸収し、熱
変換することにより感熱記録が可能であることを開示し
ている。JP-A No. 54-4142 discloses that in a heat-sensitive recording material in which a heat-sensitive recording layer containing leuco dye as a main component is coated on a support, a metal compound having lattice defects is used. It is disclosed that thermal recording is possible by absorbing light in the visible and infrared regions and converting it into heat.
特開昭５８−２０９５９４号公報は、０．８〜２μｍの
近赤外領域に吸収波長を持つ近赤外吸収剤と感熱発色材
料を少なくとも１組以上基板上に積層する光学的記録媒
体を、特開昭５８−９４４９４号公報は、１種又は２種
以上の感熱発色材料と、０．７〜３μｍの近赤外光に最
大吸収波長をもつ化合物からなる１種又は２種以上の近
赤外吸収剤とを基材上に被覆してなる記録媒体を開示し
ており、これらの記録媒体への記録は、熱板及び近赤外
付近の波長のレーザー光によって行なうことができるこ
とを開示している。JP-A-58-209594 discloses an optical recording medium in which at least one set of a near-infrared absorber and a heat-sensitive coloring material having an absorption wavelength in the near-infrared region of 0.8 to 2 μm are laminated on a substrate. JP-A-58-94494 discloses that one or more heat-sensitive coloring materials and one or more near-infrared compounds consisting of a compound having a maximum absorption wavelength in near-infrared light of 0.7 to 3 μm. The present invention discloses a recording medium formed by coating a base material with an external absorbent, and discloses that recording on these recording media can be performed using a hot plate and a laser beam having a wavelength around near infrared. ing.
（発明が解決しようとする課題）
上記公報には、プラスチック板やフィルムなど非親水性
の材料を基材とする光記録体と、親水性材料である紙を
基材とする光記録体について記載されているが、実用的
な光記録体とするための、レーザー光との関係で光記録
体が保持すべき条件は何等明らかにされていない。(Problem to be Solved by the Invention) The above publication describes an optical recording medium whose base material is a non-hydrophilic material such as a plastic plate or film, and an optical recording medium whose base material is paper, which is a hydrophilic material. However, the conditions that an optical recording medium should maintain in relation to laser light in order to make it a practical optical recording medium have not been clarified.
光ディスクが機械的読み取りであるため、読み取り波長
における光学的コントラストが得られれば良いのに対し
、本発明の記録体は、記録された情報を、直接人間が肉
眼により読みとるため、肉眼で判読できるコントラスト
が要求される。Since optical discs are mechanically readable, it is sufficient to obtain optical contrast at the reading wavelength, whereas the recording medium of the present invention has a contrast that can be read with the naked eye because the recorded information can be directly read by humans with the naked eye. is required.
又、事務処理や、通常の測定に使用し得る汎用の光記録
装置を考えると、使用し得るレーザーの出力は低出力の
ものにならざるを得ない。このような装置に使用し得る
小型のレーザーは、主波長が６５０〜１５００ｍμ近赤
外付近のものである。Furthermore, considering a general-purpose optical recording device that can be used for office processing and ordinary measurements, the output of the laser that can be used must be low. A small laser that can be used in such a device has a dominant wavelength in the vicinity of near infrared rays of 650 to 1500 mμ.
このような状況に鑑みて、近赤外付近に主波長を有する
低出力のレーザー光によっても、肉眼で直接判読可能な
画像を記録可能とする光記録体を提供することを本発明
の課題とした。In view of this situation, it is an object of the present invention to provide an optical recording medium that can record images that can be directly read with the naked eye even with a low-power laser beam having a dominant wavelength in the near-infrared region. did.
（課題を解決するための手段）
上記課題は、近赤外付近に主波長を有するレーザー光に
よって記録する、基材上に、塩基性染料と有機顕色剤と
を含有する感熱発色層と近赤外吸収剤を含有する光吸収
層を積層した光記録体において、該記録体表面のレーザ
ー光主波長における反射率が、１５〜８０％である光記
録体とすることによって解決された。(Means for Solving the Problem) The above problem is to create a heat-sensitive color forming layer containing a basic dye and an organic color developer on a base material, which is recorded using a laser beam having a main wavelength in the vicinity of near-infrared. The problem was solved by creating an optical recording medium in which a light absorption layer containing an infrared absorbing agent is laminated, and the reflectance of the surface of the recording medium at the dominant wavelength of the laser beam is 15 to 80%.
本発明は近赤外領域付近に主波長を有するレーザーを使
用するものであり、現在汎用の記録システムに使用でき
る低価格のレーザーとしては、おおよそ６５０ｍμ〜１
５００ｍμのものである。The present invention uses a laser with a dominant wavelength near the near-infrared region, and currently low-cost lasers that can be used in general-purpose recording systems have wavelengths of approximately 650 mμ to 1
It has a diameter of 500 mμ.
一方、本発明の有機近赤外吸収剤も、水溶性の有無に係
わらず多少とも７００〜９００ｍμ付近に吸収を有し、
その塗布層も明らかに着色している。On the other hand, the organic near-infrared absorber of the present invention also has absorption in the vicinity of 700 to 900 mμ, regardless of whether it is water-soluble or not.
The coating layer is also clearly colored.
光記録紙にレーザー光照射により光記録画像を描いて肉
眼で読み取る場合、機械的読取りと異なる点が幾つかあ
り、重要である。即ち、機械的読取りの場合この着色は
全く問題に成らないのに対し、肉眼で読み取る場合は肉
眼で判別可能な画像と地色のコントラストが一定以上無
ければならないＯ
本発明者らは、肉眼的コントラストと光エネルギーに実
用上の制約を設けたとき、レーザー光波長に対して光記
録体面の反射率に必要不可欠な領域がある事を見出だし
た。When an optically recorded image is drawn on optical recording paper by laser beam irradiation and read with the naked eye, there are several important differences from mechanical reading. That is, in the case of mechanical reading, this coloring is not a problem at all, whereas in the case of reading with the naked eye, there must be a certain level of contrast between the image and the background color that can be discerned with the naked eye. When we set practical constraints on contrast and light energy, we discovered that there is an essential region for the reflectance of the optical recording surface relative to the wavelength of the laser light.
レーザー主波長に対する光記録体表面の反射率が１５％
未満の場合、光吸収は十分になされるから、画像濃度は
十分高濃度であるが、地色との関係で肉眼的コントラス
トが小さく肉眼での読取りが難しく成る。また、レーザ
ー主波長に対する光記録体表面の反射率が８０％を超え
る場合は、半導体の低出力のレーザー光では光吸収が弱
く発生する熱量が不十分で、画像が全く記録できないか
、記録できてもきわめて低濃度であって、やはり地色と
の関係で肉眼的コントラストが小さく肉眼テの読み取り
が難しい。The reflectance of the surface of the optical recording medium for the laser main wavelength is 15%
When the density is less than 1, light absorption is sufficient and the image density is sufficiently high, but the visual contrast with the ground color is small and it becomes difficult to read with the naked eye. In addition, if the reflectance of the surface of the optical recording medium with respect to the laser main wavelength exceeds 80%, the low-output semiconductor laser light will have weak light absorption and the amount of heat generated will be insufficient, resulting in either no image being recorded or no image being recorded. However, the density is extremely low, and the visual contrast with the ground color is small, making it difficult to read with the naked eye.
本発明の光記録体は、基材上に、感熱発色層と光吸収層
を積層したものであるが、積層の順序は特に限定するも
のではなく、基材・感熱発色層・光吸収層の順でも、基
材・光吸収層・感熱発色層の順でもよい。又、最上層の
上に外部からの影響を少な（するための保護層を設けて
もよく、特に、感熱発色層が最上層である場合は好まし
い結果をもたらす。The optical recording medium of the present invention has a thermosensitive coloring layer and a light absorption layer laminated on a base material, but the order of lamination is not particularly limited. The order may be the base material, the light absorbing layer, and the thermosensitive coloring layer. Further, a protective layer may be provided on the top layer to reduce external influences, and particularly when the heat-sensitive coloring layer is the top layer, favorable results are brought about.
感熱発色層の下に設ける光吸収層は、−船釣に近赤外吸
収剤と、バインダー及び白色顔料からなる塗料を基材上
に塗布して得られる。白色顔料は可視光とともに近赤外
光を効率よく反射し、白色顔料周囲の近赤外吸収剤に効
率よく近赤外光を供給する。The light-absorbing layer provided under the heat-sensitive coloring layer is obtained by applying a paint consisting of a near-infrared absorber, a binder, and a white pigment onto a substrate. The white pigment efficiently reflects near-infrared light as well as visible light, and efficiently supplies near-infrared light to the near-infrared absorber surrounding the white pigment.
感熱発色層の上に設ける光吸収層は、透明である必要か
ら、通常バインダーと近赤外吸収剤からなる塗料を塗布
して得られる。従って、透明な保護層中に近赤外吸収剤
を含有せしめ、保護層と光吸収層の役割を合わせてもた
せる方法は好ましい方法である。The light-absorbing layer provided on the heat-sensitive coloring layer needs to be transparent, so it is usually obtained by applying a paint consisting of a binder and a near-infrared absorber. Therefore, a preferred method is to incorporate a near-infrared absorber into a transparent protective layer so that the transparent protective layer functions as both a protective layer and a light absorbing layer.
感熱発色層の下側に光吸収層を設けるとともに、上側に
近赤外吸収剤を含有する保護層を設けてもよい。この場
合、所定量の近赤外吸収剤を、下層と上層に分けること
により、光記録体の着色を改善することができる。A light absorption layer may be provided below the thermosensitive coloring layer, and a protective layer containing a near-infrared absorber may be provided above. In this case, coloring of the optical recording medium can be improved by dividing a predetermined amount of the near-infrared absorber into the lower layer and the upper layer.
近赤外吸収剤は特に限定するものではないが、基材に親
水性材料を使用した場合は、水溶性近赤外吸収剤あるい
は微粒化した分散性近赤外吸収剤を使用することが好ま
しく、特に水溶性近赤外吸収剤の使用が好ましい。The near-infrared absorber is not particularly limited, but if a hydrophilic material is used as the base material, it is preferable to use a water-soluble near-infrared absorber or a micronized dispersible near-infrared absorber. In particular, it is preferable to use water-soluble near-infrared absorbers.
近赤外吸収剤を利用した光記録体は従来からいくつか知
られていることは、上述した通りであるが、それらの中
に、水溶性近赤外吸収剤を使用した例はない。As mentioned above, some optical recording media using near-infrared absorbers have been known, but there is no example of using a water-soluble near-infrared absorber among them.
本発明は、人間が直接扱い且つ記録が目視できる光記録
体を得ることが１つの目的であるから、その取扱は安全
なものであることが好ましい。水溶性の化合物は蓄積性
が無く、この点で、水溶性近赤外吸収剤の使用は安全上
好ましい。親水性基村上を使用する場合、水溶性近赤外
吸収剤は水性塗料とすることができるので、従来の水性
塗料の塗工設備をそのまま使用できるから製造上有利で
ある。又、水溶性近赤外吸収剤は、塗料中に均一に存在
するから、近赤外光の吸収もいたるところ均一に行なわ
れ、解像力がよく、均一な画像を得ることができる。更
に、水溶性近赤外吸収剤は、単位重量あたりの近赤外吸
収力が大きく、分散性近赤外吸収剤に比べその使用量を
少なくすることができるから、近赤外吸収剤が着色して
いる場合でも、光記録体の地色を改善することができる
し、経済的にも有利である。Since one purpose of the present invention is to obtain an optical recording medium that can be directly handled by humans and whose records can be viewed, it is preferable that the handling thereof be safe. Water-soluble compounds do not accumulate, and in this respect, the use of water-soluble near-infrared absorbers is preferable from the viewpoint of safety. When using the hydrophilic group Murakami, the water-soluble near-infrared absorber can be made into a water-based paint, which is advantageous in production since conventional water-based paint coating equipment can be used as is. Furthermore, since the water-soluble near-infrared absorber is uniformly present in the paint, near-infrared light is absorbed uniformly everywhere, and a uniform image with good resolution can be obtained. Furthermore, water-soluble near-infrared absorbers have a large near-infrared absorbing power per unit weight, and can be used in a smaller amount than dispersible near-infrared absorbers. Even when the optical recording medium is used, the background color of the optical recording medium can be improved, and it is also economically advantageous.
本発明における水溶性近赤外吸収剤とは、近赤外光を吸
収して、所望の記録濃度を得るに必要な熱量を放出する
ことができる近赤外吸収剤の量が溶解できるものである
。その量は、近赤外吸収剤の近赤外吸収能や光記録体の
組成、あるいはレーザー光の出力、集光度あるいは記録
面との距離など光記録装置との関係で一概には決定でき
ないが、実験によれば、水に対する溶解度が５％以上あ
れば水溶性近赤外吸収剤となり得る場合が多い。好まし
くは、水に対する溶解度が１０％以上ものである。従っ
て、上記条件を満たさないものが本発明における分散性
近赤外吸収剤である。The water-soluble near-infrared absorber in the present invention is one that can absorb near-infrared light and dissolve an amount of the near-infrared absorber that can release the amount of heat necessary to obtain the desired recording density. be. The amount cannot be determined unconditionally depending on the near-infrared absorption ability of the near-infrared absorber, the composition of the optical recording medium, or the relationship with the optical recording device such as the output of the laser beam, the degree of condensation, and the distance from the recording surface. According to experiments, if the solubility in water is 5% or more, it can often be used as a water-soluble near-infrared absorber. Preferably, the solubility in water is 10% or more. Therefore, the dispersible near-infrared absorber in the present invention does not satisfy the above conditions.
分散性近赤外吸収剤は、通常そのままでは粒径が大きい
ためか、近赤外光の吸収効率及び熱転換効率が悪（、所
望の記録濃度を得るのに十分な量を塗布すると、光記録
体の着色が強くなり、画像のコントラストを損なう傾向
がある。そこで、本発明においては、分散性近赤外吸収
剤は、微粒子化して使用する。微粒化の程度は、細かい
ほど好ましいが、実用上、平均粒径を３μ以下とすれば
よいことを本発明者らは見いだした。微粒化は、水溶性
バインダー中でアトライター サンドグラインダー等に
よって磨砕する。Dispersible near-infrared absorbers usually have poor absorption efficiency and heat conversion efficiency for near-infrared light, probably due to their large particle size (but when applied in sufficient amount to obtain the desired recording density, There is a tendency for the recording medium to be strongly colored and the contrast of the image to be impaired.Therefore, in the present invention, the dispersible near-infrared absorber is used in the form of fine particles.The finer the degree of atomization, the better. The present inventors have found that for practical purposes, the average particle size should be 3 μ or less.The particles are made fine by grinding with an attritor sand grinder or the like in a water-soluble binder.
基材上に感熱発色層を設け、該感熱発色層上に近赤外吸
収剤を含有した保護層を設けるのは、保護層によって感
熱発色層を保護することができることは勿論、支持体の
凹凸を感熱発色層によって均し、その上の光吸収性保護
層の厚みを均一にすることができるから、光吸収能及び
発熱能が均一になって均一な画像濃度が得られ易い。そ
の為には光吸収材料が水溶性か若しくは微粒子に分散さ
れていることによって均一な保護層を得ることができる
。特に、水溶性光吸収剤の使用は光吸収層の光透過性が
高（なり、光吸収層の全層にわたり光吸収が行なわれる
ので吸収効率が高くなる。The reason why a heat-sensitive coloring layer is provided on a base material and a protective layer containing a near-infrared absorber is provided on the heat-sensitive coloring layer is that the heat-sensitive coloring layer can be protected by the protective layer, and the unevenness of the support can be avoided. Since it is possible to equalize the thickness by the thermosensitive coloring layer and to make the thickness of the light-absorbing protective layer thereon uniform, the light-absorbing ability and heat-generating ability become uniform, and it is easy to obtain a uniform image density. For this purpose, a uniform protective layer can be obtained by making the light-absorbing material water-soluble or dispersed in fine particles. In particular, the use of a water-soluble light absorbing agent increases the light transmittance of the light absorbing layer, and the light absorption is performed throughout the entire layer of the light absorbing layer, resulting in high absorption efficiency.
光吸収層は、−船釣に近赤外吸収剤と、バインダー及び
必要に応じて白色顔料からなる塗料を親水性基材上に塗
布して得られる。The light absorption layer is obtained by coating a hydrophilic substrate with a paint consisting of a near-infrared absorber, a binder and, if necessary, a white pigment.
近赤外吸収剤としては、０．７〜３ｍμの近赤外領域に
吸収を持つものであればよ（、特開昭５４−４１４２号
、特開昭５８−２０９５９４号、特開昭５８−９４４９
４号公報に開示されている、シアニン色素、チオールニ
ッケル錯体、スクアリリウム色素を始め、「近赤外吸収
色素」 （化学工業４３．１９８６年５月号）にあるニ
トロン化合物およびその金属錯体、ポリメチン系色素（
シアニン系色素）、チオールとコバルトあるいはパラジ
ウムとの錯体、フタロシアニン系色素、 トリアリルメ
タン系色素、インモニウムあるいはジインモニウム系色
素、ナフトキノン系色素、あるいは本発明者らが見いだ
した１、３−ジフェニルチオウレアや１．３−ジベンジ
ルチオウレア等のチオ尿素誘導体と周期律表のＩＡ属及
びＩＡ属を除く原子ｆｆ１４０以上の金属の有機酸塩、
アルコラードあるいは水酸化物とを混合加熱処理して得
られる処理生成物、あるいは分散性近赤外吸収剤を使用
した光記録体に関する本発明者らの出願になる特願昭６
３−２７２７０２号に記載されている硫化銅や黒鉛など
の分散性近赤外吸収剤である。又、前記従来から知られ
ている、シアニン色素、チオールニッケル錯体、トリア
リルメタン系色素等は、水あるいは溶剤に溶解する近赤
外吸収剤であり、その具体例は、同じく特願昭６３−２
７２７０２号に記載されている。The near-infrared absorber may be one that has absorption in the near-infrared region of 0.7 to 3 mμ. 9449
In addition to cyanine dyes, thiol nickel complexes, and squarylium dyes disclosed in Publication No. 4, nitrone compounds and their metal complexes, and polymethine compounds in "Near-infrared absorption dyes" (Kagaku Kogyo 43, May 1986 issue). Pigment (
cyanine dyes), complexes of thiol and cobalt or palladium, phthalocyanine dyes, triallylmethane dyes, immonium or diimmonium dyes, naphthoquinone dyes, or 1,3-diphenylthiourea and the like discovered by the present inventors. 1. Thiourea derivatives such as 3-dibenzylthiourea and organic acid salts of metals with atoms ff 140 or more excluding Group IA and Group IA of the periodic table,
Patent application No. 6, filed by the present inventors, relating to an optical recording medium using a treatment product obtained by mixing and heat-treating Alcolade or hydroxide, or a dispersible near-infrared absorber.
It is a dispersible near-infrared absorber such as copper sulfide or graphite described in No. 3-272702. Further, the conventionally known cyanine dyes, thiol nickel complexes, triallylmethane dyes, etc. are near-infrared absorbers that dissolve in water or solvents, and specific examples thereof are also disclosed in Japanese Patent Application No. 1983- 2
No. 72702.
本発明の水溶性近赤外吸収剤の例として、ＩＣ１社製の
近赤外吸収剤である５１１６５１０，５１０９５６４、
及び下記に示す化合物を例示することができるが、これ
らに限定されるものでは無い。Examples of water-soluble near-infrared absorbers of the present invention include near-infrared absorbers 5116510, 5109564 manufactured by IC1,
Examples include, but are not limited to, the compounds shown below.
感熱発色層は、公知の電子供与性無色染料と電子受容性
有機顕色剤を発色成分とする感熱記録紙の発色層と全く
同一であり、感熱記録紙の発色層に対し知られている全
ての技術を適用することができる。塩基性無色染料は、
クリスタルバイオレットラクトン等のトリフェニルメタ
ン系、３−ジエチルアミノ−６−メチル−７−アニリノ
フルオラン等のフルオラン系、３−（４−ジエチルアミ
ノ−２−エトキシフェニル）−３−（１−エチル−２−
メチルインドール−３−イル）−４−アザフタリド等の
アザフタリド系、あるいは３，６゜６−トリス（ジメチ
ルアミノ）スピロ［フルオレイン−９，３−フタリド］
等のフルオレイン系染料などのロイコ染料である。The heat-sensitive coloring layer is exactly the same as the coloring layer of heat-sensitive recording paper, which contains a known electron-donating colorless dye and an electron-accepting organic color developer as color-forming components, and is completely different from all the known coloring layers of heat-sensitive recording paper. technology can be applied. Basic colorless dyes are
Triphenylmethane type such as crystal violet lactone, fluoran type such as 3-diethylamino-6-methyl-7-anilinofluorane, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2 −
azaphthalide series such as methylindol-3-yl)-4-azaphthalide, or 3,6゜6-tris(dimethylamino)spiro[fluorein-9,3-phthalide]
Leuco dyes such as fluorine dyes such as
有機顕色剤としては、ビスフェノールＡ類、４−ヒドロ
キシ安息香酸エステル、
４−ヒドロキシフタル酸ジエステル類、フタル酸モノエ
ステル類、ビス−（ヒドロキシフェニル）フェニルス、
４ルフィド類、４−ヒドロキシフェニルアリールスルホ
ン類、４−ヒドロキシフェニルアリールスルホナート類
、１．３−ジ［２−（ヒドロキシフェニル）−２−プロ
ピル］−ベンゼン類、４−ヒドロキシベンゾイルオキシ
安息香酸エステル、ビスフェノールスルホン類等がある
。Examples of organic color developers include bisphenol A, 4-hydroxybenzoic acid ester, 4-hydroxyphthalic acid diester, phthalic acid monoester, bis-(hydroxyphenyl)phenyls,
4-ruphides, 4-hydroxyphenylarylsulfones, 4-hydroxyphenylarylsulfonates, 1,3-di[2-(hydroxyphenyl)-2-propyl]-benzenes, 4-hydroxybenzoyloxybenzoic acid ester , bisphenol sulfones, etc.
バインダーとしては重合度が２００〜１９００の完全ケ
ン化ポリビニルアルコール、アミド変性ポリビニルアル
コール等の変性ポリビニルアルコール、ヒドロ牛ジエチ
ルセルロース、スチレンブタヂエン共重合体などである
。Examples of the binder include completely saponified polyvinyl alcohol having a degree of polymerization of 200 to 1900, modified polyvinyl alcohol such as amide-modified polyvinyl alcohol, hydrobovine diethylcellulose, styrene-butadiene copolymer, and the like.
又、脂肪酸アマイドやモンタンワックス等を増感剤ある
いは品質調整剤として使用し、クレー炭酸カルシウム、
あるいはプラスチックピグメント等、通常紙加工分野で
常用されている充填剤を加えることができる。特に、中
空プラスチックピグメントは近赤外光の反射がよく、又
、熱保持特性もよいので好ましいものである。これら感
熱発色層に用いられる諸材料は、本願発明者らの出願に
なる特願昭６３−２７２７０２号に記載されている塩基
性無色染料、有機顕色剤、バインダー増感剤、充填剤及
び品質調整剤を、本発明においても同等に使用すること
ができる。In addition, fatty acid amide, montan wax, etc. are used as sensitizers or quality control agents, and clay calcium carbonate,
Alternatively, fillers commonly used in the paper processing field, such as plastic pigments, can be added. In particular, hollow plastic pigments are preferred because they have good reflection of near-infrared light and good heat retention properties. The various materials used in these thermosensitive color forming layers include basic colorless dyes, organic color developers, binder sensitizers, fillers, and quality materials described in Japanese Patent Application No. 63-272702 filed by the present inventors. Modifiers can equally be used in the present invention.
本発明に使用する発色層中の有機顕色剤、塩基性無色染
料、バインダー 増感剤、充填剤及びその他の各種成分
の種類及び量は、要求される性能や記録適性にしたがっ
て決定され、特に限定されるものではないが、通常、塩
基性染料１部に対し、有機顕色剤３〜１２部、増感剤３
〜１２部、充填剤１〜２０部を使用し、バインダーは発
色層の全固形分中１０〜２５部が適当である。The types and amounts of the organic color developer, basic colorless dye, binder, sensitizer, filler, and other various components in the color forming layer used in the present invention are determined according to the required performance and recording suitability, and in particular, Although not limited, usually 3 to 12 parts of organic color developer and 3 parts of sensitizer to 1 part of basic dye.
-12 parts, 1-20 parts of filler are used, and the binder is suitably 10-25 parts based on the total solid content of the coloring layer.
有機顕色剤、塩基性無色染料、増感剤はそれぞれ別々に
、あるいは必要に応じて添加する材料とともに、ボール
ミル、アトライター サンドグラインダーなどの磨砕機
あるいは適当な乳化装置によって数μ以下の粒子径にな
るまで微粒化した後混合し、更にバインダー及び、必要
に応じて前記各種の品質調整剤を加えて感熱発色塗液と
する。The organic color developer, basic colorless dye, and sensitizer are each individually or together with other materials added as necessary, and are reduced to a particle size of several microns or less using a grinding machine such as a ball mill, attritor sand grinder, or an appropriate emulsifying device. The mixture is atomized until it becomes granulated, then mixed, and a binder and, if necessary, the various quality control agents mentioned above are added to form a heat-sensitive coloring coating liquid.
塗液は、基材上もしくは光吸収層上に塗布して感熱発色
層とする。光吸収層の上に感熱発色層を積層することに
より、光記録層の着色は一層隠蔽され好ましい外観の光
記録体となる。The coating liquid is applied onto a substrate or a light absorption layer to form a heat-sensitive coloring layer. By laminating the thermosensitive coloring layer on the light absorption layer, the coloring of the optical recording layer is further hidden, resulting in an optical recording medium with a desirable appearance.
感熱発色層の表面には、湿気、ガス、水、溶剤、油など
外部環境からの汚染を減少あるいは防止する保護層を設
けるのは好ましい方法である。It is a preferable method to provide a protective layer on the surface of the thermosensitive coloring layer to reduce or prevent contamination from the external environment such as moisture, gas, water, solvent, oil, etc.
保護層は、可視光に透明で感熱発色層に悪影響を及ぼさ
ないものであるものが好ましく、通常感熱発色層に使用
するバインダーの中から、一種以上選択して保護層とす
る。この保護層中あるいは保護層と感熱発色層の間に水
溶性近赤外吸収剤を含有させると、−届先記録体の感度
が増大する。The protective layer is preferably one that is transparent to visible light and does not have an adverse effect on the thermosensitive coloring layer, and one or more binders are selected from among the binders normally used for the thermosensitive coloring layer. When a water-soluble near-infrared absorber is contained in the protective layer or between the protective layer and the thermosensitive coloring layer, the sensitivity of the destination recording medium is increased.
このようにして得られた光記録体は、近赤外付近に主波
長を有するレーザー光を、焦点距離が０゜５〜５０ｍｍ
、開口数（ＮＡ）が０．１〜０．５の２枚以上の集光レ
ンズ群によって集光して記録することにより、低出力の
レーザー光で、コントラストのよい、鮮明な画像が得ら
れる。The optical recording medium obtained in this way emits a laser beam having a main wavelength near near infrared rays at a focal length of 0°5 to 50 mm.
By condensing and recording light using a group of two or more condensing lenses with a numerical aperture (NA) of 0.1 to 0.5, clear images with good contrast can be obtained using low-power laser light. .
光記録体への光記録に必要な光源としては、半導体レー
ザー、ダイオードボンピングＹＡＧレーザ−Ｈｅ−Ｎｅ
ガスレーザー 色素レーザー等であり、事務用記録装置
として使用し得るためには、装置の小型化、安全性、価
格などの点で、５ないし１００ ｍＷ程度の低出力のレ
ーザーが好ましい。Light sources necessary for optical recording on optical recording media include semiconductor lasers, diode bombing YAG lasers, He-Ne
These include gas lasers, dye lasers, etc., and in order to be used as an office recording device, a laser with a low output of about 5 to 100 mW is preferable from the viewpoint of device miniaturization, safety, cost, etc.
（作用）
上記の如く、塩基性染料と有機顕色剤とを含有する感熱
発色層と、近赤外吸収剤を含有する光吸収層を積層した
光記録体において、該記録体表面の記録レーザー光主波
長における反射率が１５〜８５％に調整された記録面に
、記録レーザー光照射により、肉眼で直接判読可能な画
像が得られる機構は明らかではないが、レーザー主波長
に対する光記録体表面の反射率が１５％未満の場合、そ
の波長において吸収はおおよそ８５％以上と十分になさ
れるから、画像濃度は十分高濃度であるが、地色との関
係で肉眼的コントラストが小さく肉眼での読取りが難し
く成る。また、レーザー主波長に対する光記録体表面の
反射率が８０％を超える場合は、低出力のレーザー光で
は光吸収が弱く発生する熱量が不十分で、画像が全く記
録できないか、記録できてもきわめて低濃度であって、
やはり地色との関係で肉眼的コントラストが小さく肉眼
での読み取りが難しいものと考えられる。(Function) As described above, in an optical recording medium in which a thermosensitive coloring layer containing a basic dye and an organic color developer and a light absorption layer containing a near-infrared absorber are laminated, a recording laser on the surface of the recording medium is used. The mechanism by which an image that can be directly read with the naked eye is obtained by irradiating a recording laser beam on a recording surface whose reflectance at the optical dominant wavelength is adjusted to 15% to 85% is not clear, but the optical recording surface at the optical dominant wavelength is When the reflectance is less than 15%, the absorption at that wavelength is approximately 85% or more, so the image density is sufficiently high, but the macroscopic contrast is small in relation to the background color, and it is It becomes difficult to read. In addition, if the reflectance of the surface of the optical recording medium with respect to the laser main wavelength exceeds 80%, low-output laser light will have weak light absorption and the amount of heat generated will be insufficient, resulting in an image not being able to be recorded at all, or even if it can be recorded. The concentration is extremely low,
It is thought that the contrast with the naked eye is small due to the background color, making it difficult to read with the naked eye.
（実施例）
次に本発明の実施例を記載する。実、施例中の部及び％
は重量部及び重量％である。(Example) Next, an example of the present invention will be described. Parts and percentages in examples
are parts by weight and % by weight.
夾息五−上
下記配合の染料分散液（Ａ液）と顕色剤分散液（Ｂ液）
を、それぞれ別々にサンドグラインダーで１時間湿式磨
砕し、次に、Ａ液６．３部、Ｂ液２５部にシリカの２５
％分散液２５部を混合して感熱発色塗液とし、この塗液
を、坪量６０ ｇ／ｒ＆の上質上に、メイヤバーを用い
て、５ｇ／ｍ塗布乾燥して感熱発色層とした。5 - Dye dispersion (Liquid A) and color developer dispersion (Liquid B) with the above and below compositions
were separately wet-ground for 1 hour using a sand grinder, and then 25 parts of silica was added to 6.3 parts of Part A and 25 parts of Part B.
% dispersion was mixed to obtain a heat-sensitive coloring coating liquid, and this coating liquid was coated and dried at 5 g/m using a Mayer bar on a high quality surface having a basis weight of 60 g/r to form a heat-sensitive coloring layer.
［感熱発色層］
（Ａ）液：染料分散液
黒色発色染料：ＯＤ８ ２．０部
１０％ＰＶＡ水溶液 ３．４部
水 １． ９部Ｏ
ＤＢ： ３−ジエチルアミノ−６−メチル−７−アニリ
ノフルオラン
（Ｂ）液：顕色剤分散液
顕色剤：ＢＰＡ ６．０部バラベンジルビ
フェニル ４．ｏ部
１０％ＰＶＡ水溶液 １２．５部
水 ２．５部ＢＰ
Ａ： ビスフェノールＡ
次に、下記配合の近赤外吸収剤水溶液（Ｃ液）６部と保
護層溶液（Ｄ液）１０５部を混合し、メイヤーバーを用
いて、近赤外吸収剤を含んだ保護層塗液を、上記感熱発
色層上に４ｇ／ｒｄ塗布して、光記録シートを得た。[Thermosensitive Coloring Layer] (A) Liquid: Dye dispersion Black coloring dye: OD8 2.0 parts 10% PVA aqueous solution 3.4 parts Water 1. 9th part O
DB: 3-diethylamino-6-methyl-7-anilinofluorane (B) solution: Color developer dispersion Color developer: BPA 6.0 parts Parabenzylbiphenyl 4. o part 10% PVA aqueous solution 12.5 parts water 2.5 parts BP
A: Bisphenol A Next, 6 parts of a near-infrared absorber aqueous solution (liquid C) and 105 parts of a protective layer solution (liquid D) of the following formulation were mixed, and using a Mayer bar, a solution containing a near-infrared absorber was mixed. A protective layer coating solution was applied onto the heat-sensitive coloring layer at a rate of 4 g/rd to obtain an optical recording sheet.
（Ｃ）液：近赤外吸収剤水溶液
近赤外吸収剤（ｒｃＩｓ１１６５１０） １０部
１０％ＰＶＡ水溶液 ５０部水
４０部これらをそれ
ぞれ加えて攪拌混合したところ、灰色に着色した水溶液
が得られた。(C) Liquid: Near-infrared absorber aqueous solution Near-infrared absorber (rcIs116510) 10 parts 10% PVA aqueous solution 50 parts water
When 40 parts of each of these were added and mixed by stirring, a gray colored aqueous solution was obtained.
（Ｄ）液：保護層
１０％ＰＶＡ水溶液 １００部グリオキザール
（４０％） ５部このようにして作成した光記録
紙に、半導体レーザーヘッド（レーザーダイオードコリ
メーターヘッドＬＤＣ−７８２０−Ｃ■Ｎｃ； アブラ
イドオブテック社製、中心波長７８０ｎｍ、 出力２
０ｍＷ）と、開口数０．２８の集光レンズを組み合わせ
た第１図に示す装置で、光記録紙にレーザー光を照射し
光印字した。照射時間は１１５００秒の条件で行った。(D) Solution: Protective layer 10% PVA aqueous solution 100 parts Glyoxal (40%) 5 parts The optical recording paper thus prepared was coated with a semiconductor laser head (laser diode collimator head LDC-7820-C■Nc; abraid). Manufactured by Obtec, center wavelength 780 nm, output 2
The optical recording paper was irradiated with a laser beam and optically printed using the apparatus shown in FIG. 1, which combined a condenser lens with a numerical aperture of 0.28 (0 mW) and a condensing lens with a numerical aperture of 0.28. The irradiation time was 11,500 seconds.
記録像及び地色の測定は次のように行ない、結果を表１
に示した。The recorded image and ground color were measured as follows, and the results are shown in Table 1.
It was shown to.
記録像（発色スポット）の濃度二マイクロデンシトメー
ター（小西六写真工業社製ＰＤＭ−５）を用いて測定し
、その測定値をマクベス濃度に変換した。 光記
録紙の地色：マクベス濃度計で測定した。The density of the recorded image (colored spot) was measured using a two-microdensitometer (PDM-5, manufactured by Konishiroku Photo Industry Co., Ltd.), and the measured value was converted into Macbeth density. Background color of optical recording paper: Measured with a Macbeth densitometer.
実１１件２３
７８０部ｍにおける表面反射率が３０％及び４０％とな
るように、実施例１の近赤外吸収剤溶液（Ｃ液）と保護
層溶液（Ｄ液）の混合比率を変えた外は、実施例１と同
様にして光記録紙を得、評価をした。結果は表１に示し
た。Actual 11 cases 23 The mixing ratio of the near-infrared absorber solution (liquid C) and the protective layer solution (liquid D) in Example 1 was changed so that the surface reflectance at 780 parts m was 30% and 40%. Optical recording paper was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.
支敷匠土−１
実施例１の水溶性近赤外吸収剤を、分散性近赤外吸収剤
であるＫａｙａｓｏｒｂ ＩＲ−７５０に替え、平均粒
径が２．５μ及び１．５μになるまでサンドグラインダ
ーで湿式分散し、７８０部ｍにおける表面反射率が７０
％及び８０％となるように保護層溶液と混合した外は、
実施例１と同様にして光記録紙を得、評価をした。結果
は表１に示した。Shishiki Takumi-1 The water-soluble near-infrared absorber of Example 1 was replaced with Kayasorb IR-750, which is a dispersible near-infrared absorber, and sanded until the average particle size became 2.5μ and 1.5μ. Wet-dispersed with a grinder, the surface reflectance at 780 parts m is 70
% and 80%, except for mixing with the protective layer solution.
Optical recording paper was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.
爽立勇１
感熱発色層に使用する、黒染料と顕色剤の組合せをＯＤ
Ｂ／ＰＯＢとした外は実施例１と同様に光記録紙を作成
評価し、結果を表１に示した。Souritsuyu 1 OD combination of black dye and color developer used in heat-sensitive coloring layer
Optical recording paper was prepared and evaluated in the same manner as in Example 1, except that B/POB was used, and the results are shown in Table 1.
黒色染料と顕色剤の構造を次ぎに示す。The structures of the black dye and developer are shown below.
顕色剤： ＰＯＢ： ｐ−ヒドロキシ安息香酸ベンジル
エステル
実」Ｌ憇１−
感熱発色層に使用する、黒染料と顕色剤の組合せを０Ｄ
Ｂ−２／ＢＰＡとした外は実施例１と同様に感熱発色層
とし、実施例１で用いた近赤外吸収剤をＩＣｌ５１０９
５６４に替えた溶液８部と保護層溶液１０５部を混合塗
布して感熱発色層上に光吸収層を作成し、８３０部ｍに
おける反射率が３０％の光記録体を得た。このようにし
て作成した光記録紙に、主波長８３０ｎｍの半導体レー
ザーヘッド（レーザーダイオードコリメーターヘッドＬ
ＤＣ−８３３０−ＣＩＮＣ；アプライドオブテック社製
、出力３０ｍＷ）を用いた外は実施例１の条件で記録評
価をした。結果を表１に示した。Color developer: POB: p-hydroxybenzoic acid benzyl ester 1- The combination of black dye and color developer used in the heat-sensitive coloring layer is 0D.
The heat-sensitive coloring layer was the same as in Example 1 except that B-2/BPA was used, and the near-infrared absorber used in Example 1 was ICl5109.
A light absorbing layer was prepared on the thermosensitive coloring layer by mixing and coating 8 parts of the solution replaced with 564 and 105 parts of the protective layer solution to obtain an optical recording medium with a reflectance of 30% at 830 parts m. A semiconductor laser head (laser diode collimator head L) with a dominant wavelength of 830 nm was attached to the optical recording paper thus prepared.
Recording evaluation was performed under the conditions of Example 1, except that DC-8330-CINC (manufactured by Applied Oftech, output 30 mW) was used. The results are shown in Table 1.
０ＤＢ−２： ジブチルアミノ−６−メチル−７−ア
ニリノフルオラン
実１０１炙
感熱発色層に使用する、黒染料と顕色剤の組合せをＳ−
２０５７ＢＰＡとした外は実施例１と同様に感熱発色層
とし、この上に、実施例１の水溶性近赤外吸収剤を、分
散性近赤外吸収剤であるＩＣｌ５１０９５６４／２に替
え、平均粒径が１．５μになるまでサンドグラインダー
で湿式分散し、８３０ｎｍにおける表面反射率が３０％
となるように保護層溶液と混合した外は、実施例１と同
様にして光記録紙を得、実施例７の条件で記録し評価を
した。0DB-2: Dibutylamino-6-methyl-7-anilinofluoran real 101 The combination of black dye and color developer used in the roasted heat-sensitive coloring layer is S-
2057BPA was used as in Example 1, and on top of this, the water-soluble near-infrared absorber in Example 1 was replaced with ICl5109564/2, which is a dispersible near-infrared absorber, and an average particle Wet dispersion with a sand grinder until the diameter is 1.5μ, and the surface reflectance at 830nm is 30%.
An optical recording paper was obtained in the same manner as in Example 1 except that it was mixed with the protective layer solution so that the following was obtained, and it was recorded and evaluated under the conditions of Example 7.
結果は表１に示した。The results are shown in Table 1.
黒染料二Ｓ−２０５： ａ−（Ｎ−エチル−Ｎ−イソア
ミル）−６−メチル−７−アニリツフルオラン
表１から明らかなように、記録レーザー光主波長におけ
る光記録体の表面反射が１５〜８０％の光記録体は、使
用する感熱発色材料や近赤外吸収剤の種類によらず発色
濃度と地色のバランスがよく肉眼で記録を読み取るのに
十分なコントラストを有していることが分かる。Black dye 2S-205: a-(N-ethyl-N-isoamyl)-6-methyl-7-anilite fluorane As is clear from Table 1, the surface reflection of the optical recording medium at the main wavelength of the recording laser beam is 15 ~80% of optical recording media must have a good balance between color density and background color and sufficient contrast to read the record with the naked eye, regardless of the type of thermosensitive coloring material or near-infrared absorber used. I understand.
ルｌ乳−」２
実施例１で使用した近赤外吸収剤溶液（Ｃ）液と保護層
溶液（Ｄ）液を、できあがった光記録体の７８０ｎｍに
おける反射率が９０％となるように混合した外は、実施
例１と同様にして光記録体を得、評価した。2. Mix the near-infrared absorber solution (C) and the protective layer solution (D) used in Example 1 so that the reflectance of the completed optical recording medium at 780 nm is 90%. An optical recording medium was obtained and evaluated in the same manner as in Example 1, except for the following.
塩１１−」一
実施例８で使用した近赤外吸収剤用液を、できあがった
光記録体の８３０ｎｍにおける反射率が９０％となるよ
うに保護層溶液に配合した外は実施例８と同様にして光
記録体を得、評価した。Salt 11-'' Same as Example 8 except that the near-infrared absorbent liquid used in Example 8 was blended into the protective layer solution so that the reflectance of the completed optical recording medium at 830 nm was 90%. An optical recording medium was obtained and evaluated.
匿蛛五−主
実施例１において、近赤外吸収剤溶液（Ｃ）液を使用し
なかった外は全〈実施例１と同様にして光記録体を得、
同様に記録評価した。5 - In Main Example 1, except that the near-infrared absorber solution (C) was not used, an optical recording medium was obtained in the same manner as in Example 1,
Records were evaluated in the same way.
比較例１，２及び３の評価を示した表１から、記録レー
ザー主波長における光記゛録体の表面反射が１５％未満
の光記録体は、濃度計でみた発色濃度は極めて濃いが、
地色も非常に濃いため肉眼でみたコントラストが乏しく
実用できるものではなく、又、記録レーザー主波長にお
ける光記録体の表面反射が８５％を超えるものは、地色
はよいが、感熱発色層を発色させる熱量を放出できるだ
け光を吸収しないので肉眼で判別し得る記録を生じさせ
ることはできないことが明かである。From Table 1 showing the evaluation of Comparative Examples 1, 2, and 3, optical recording materials whose surface reflection at the recording laser main wavelength is less than 15% have extremely high color density as seen with a densitometer, but
The background color is also very dark and the contrast seen with the naked eye is poor, making it unusable for practical use.Furthermore, if the surface reflection of the optical recording medium exceeds 85% at the main wavelength of the recording laser, the background color is good, but the thermosensitive coloring layer cannot be used. It is clear that since it absorbs as little light as possible to emit enough heat to produce color, it cannot produce a record that can be discerned with the naked eye.
−１１：二」− −ｊ」【圭− −−」Ｌ−」Ｌ−一 ＤＢ ＤＢ−２ ＤＢ ＤＢ ＰＡ ＯＢ ＰＡ ＰＡ ＰＡ ＰＡ ＰＡ ＩＣＩＳ１１６５１０ ＜溶解） Ｋａｙａｓｏｒｂ ＩＲ−７５０ １ｃＩｓＬ１６５１Ｑ （溶解） ＩＣＩＳ１０９５６４ （溶解） ｌｃＩｓ１０９５６４／２ ＩＣＩＳ１１６５１０ （溶解） ＩＣＩＳ１０９５６４／２ 使用せず ２．５μ ｍ、５μ ｍ。-11:2''- −j” [Kei− --"L-"L-1 DB DB-2 DB DB P.A. OB P.A. P.A. P.A. P.A. P.A. ICIS116510 <dissolution) Kayasorb IR-750 1cIsL1651Q (dissolved) ICIS109564 (dissolution) lcIs109564/2 ICIS116510 (melting) ICIS109564/2 Without using 2.5μ m, 5μ m.
１．５μ
３０％
（発明の効果）
以上説明したように、基材上に、塩基性染料と有機顕色
剤とを含有する感熱発色層と、近赤外吸収剤を含有する
光吸収層を積層した光記録体表面の記録レーザー光主波
長における反射率を１５〜８０％とすることにより、低
出力のレーザー光で肉眼で読み取るのに十分なコントラ
ストの記録を得ることができる。この反射率を得るため
に、水溶性近赤外吸収剤あるいは微粒化した分散性赤外
吸収剤を使用することによって、使用上の安全性と、製
造上の容易性が改善され実用的な光記録体とすることが
できるといった効果がある。1.5μ 30% (Effect of the invention) As explained above, a heat-sensitive coloring layer containing a basic dye and an organic color developer and a light absorption layer containing a near-infrared absorber are formed on a base material. By setting the reflectance of the surface of the laminated optical recording medium at the dominant wavelength of the recording laser beam to 15 to 80%, it is possible to obtain a record with sufficient contrast to be read with the naked eye using a low-power laser beam. In order to obtain this reflectance, by using a water-soluble near-infrared absorber or a finely divided dispersible infrared absorber, safety in use and ease of manufacture are improved, and practical light becomes possible. It has the effect of being able to be used as a recording medium.
第１図はレーザー光記録装置のブロック図１・・・・レ
ーザーダイオードコリメーターヘッド、２・・・・シャ
ッター ３・・・集光レンズ群、４・・・・光記録紙、
５・・・・電源
一−
第１図Figure 1 is a block diagram of a laser beam recording device. 1... Laser diode collimator head, 2... Shutter 3... Condensing lens group, 4... Optical recording paper,
5...Power source 1 - Figure 1
Claims (3)
記録する、基材上に、塩基性染料と有機顕色剤とを含有
する感熱発色層と、近赤外吸収剤を含有する光吸収層を
積層した光記録体において、該記録体表面のレーザー光
主波長における反射率が、１５〜８０％であることを特
徴とする光記録体。(1) A light absorption layer containing a heat-sensitive coloring layer containing a basic dye and an organic color developer and a near-infrared absorber on a base material, which is recorded using a laser beam having a main wavelength near the near-infrared. 1. An optical recording medium comprising laminated layers, characterized in that the surface of the recording medium has a reflectance of 15 to 80% at the dominant wavelength of laser light.
は微粒子化した有機近赤外吸収剤である請求項１記載の
光記録体。(2) The optical recording medium according to claim 1, wherein the near-infrared absorber is a water-soluble organic near-infrared absorber or a finely divided organic near-infrared absorber.
上である請求項２記載の光記録体。(3) The optical recording medium according to claim 2, wherein the water-soluble near-infrared absorber has a solubility in water of 5% or more.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1030677A JPH02209290A (en) | 1989-02-09 | 1989-02-09 | Optical recording material |
| EP90301047A EP0381492B1 (en) | 1989-02-03 | 1990-02-01 | Optical recording medium, optical recording method, and optical recording device used in method |
| DE69032232T DE69032232T2 (en) | 1989-02-03 | 1990-02-01 | Optical recording material, optical recording method and optical recording device for this method |
| CA002009088A CA2009088C (en) | 1989-02-03 | 1990-02-01 | Optical recording medium, optical recording method and optical recording device used in method |
| US07/474,932 US5100711A (en) | 1989-02-03 | 1990-02-05 | Optical recording medium optical recording method, and optical recording device used in method |
| US07/811,114 US5200947A (en) | 1989-02-03 | 1991-12-20 | Optical recording medium, optical recording method, and optical recording device used in method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1030677A JPH02209290A (en) | 1989-02-09 | 1989-02-09 | Optical recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02209290A true JPH02209290A (en) | 1990-08-20 |
Family
ID=12310340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1030677A Pending JPH02209290A (en) | 1989-02-03 | 1989-02-09 | Optical recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02209290A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5546117A (en) * | 1993-03-11 | 1996-08-13 | Kabushiki Kaisha Toshiba | Portable storage medium and apparatus for processing the same |
| JP2002170075A (en) * | 2000-11-30 | 2002-06-14 | Ricoh Co Ltd | Thermal recording medium, printing device, printing method, and printing system |
| JP2019104195A (en) * | 2017-12-14 | 2019-06-27 | トッパン・フォームズ株式会社 | Marking sheet, marked marking sheet, and method for manufacturing marking sheet |
| JP2020023138A (en) * | 2018-08-08 | 2020-02-13 | ローランドディー．ジー．株式会社 | Method of checking output of foil push apparatus, method of adjusting output of foil push apparatus, and foil push apparatus |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5714096A (en) * | 1980-06-30 | 1982-01-25 | Pentel Kk | Laser heatsensitive recording material |
-
1989
- 1989-02-09 JP JP1030677A patent/JPH02209290A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5714096A (en) * | 1980-06-30 | 1982-01-25 | Pentel Kk | Laser heatsensitive recording material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5546117A (en) * | 1993-03-11 | 1996-08-13 | Kabushiki Kaisha Toshiba | Portable storage medium and apparatus for processing the same |
| US5570124A (en) * | 1993-03-11 | 1996-10-29 | Kabushiki Kaisha Toshiba | Portable storage medium and apparatus for processing the same |
| JP2002170075A (en) * | 2000-11-30 | 2002-06-14 | Ricoh Co Ltd | Thermal recording medium, printing device, printing method, and printing system |
| JP2019104195A (en) * | 2017-12-14 | 2019-06-27 | トッパン・フォームズ株式会社 | Marking sheet, marked marking sheet, and method for manufacturing marking sheet |
| JP2020023138A (en) * | 2018-08-08 | 2020-02-13 | ローランドディー．ジー．株式会社 | Method of checking output of foil push apparatus, method of adjusting output of foil push apparatus, and foil push apparatus |
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