JPH0323351B2 - - Google Patents
Info
- Publication number
- JPH0323351B2 JPH0323351B2 JP55129579A JP12957980A JPH0323351B2 JP H0323351 B2 JPH0323351 B2 JP H0323351B2 JP 55129579 A JP55129579 A JP 55129579A JP 12957980 A JP12957980 A JP 12957980A JP H0323351 B2 JPH0323351 B2 JP H0323351B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive
- sensitive recording
- color
- nitrate
- 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 - Lifetime
Links
- 239000000463 material Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- -1 acylated leucomethylene blue compound Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000001989 diazonium salts Chemical group 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229920005596 polymer binder Polymers 0.000 claims description 2
- 239000002491 polymer binding agent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000006103 coloring component Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 2
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical class C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GREMVPUSQUHWDU-UHFFFAOYSA-M 4-anilinobenzenediazonium;chloride Chemical compound [Cl-].C1=CC([N+]#N)=CC=C1NC1=CC=CC=C1 GREMVPUSQUHWDU-UHFFFAOYSA-M 0.000 description 1
- YZYFPMLAGIGAJJ-UHFFFAOYSA-N 4-diazo-n,n-diethylcyclohexa-1,5-dien-1-amine Chemical compound CCN(CC)C1=CCC(=[N+]=[N-])C=C1 YZYFPMLAGIGAJJ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- DSDKZZYDFANVIJ-UHFFFAOYSA-N N-(2-chloro-4-diazo-5-methoxycyclohexa-1,5-dien-1-yl)benzamide Chemical compound [N+](=[N-])=C1CC(=C(NC(C2=CC=CC=C2)=O)C=C1OC)Cl DSDKZZYDFANVIJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- SBXKRBZKPQBLOD-UHFFFAOYSA-N aminohydroquinone Chemical compound NC1=CC(O)=CC=C1O SBXKRBZKPQBLOD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical group [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
- 230000001546 nitrifying effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
【発明の詳細な説明】
本発明は、乾式で定着可能な感熱記録体に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-sensitive recording medium that can be fixed in a dry manner.
従来感熱記録方式には、大別して物理的による
ものと、化学的によるものとがある。 Conventional thermal recording methods can be roughly divided into physical and chemical methods.
化学的感熱記録には、原理的に２通りの方法が
あり、一方は、溶液状態で、直ちに反応するよう
な成分（発色剤と顕色剤）を微粒子としてバイン
ダー中に分散して感熱層をつくり、発色剤および
顕色剤、いずれか一方の融点を変換温度付近に選
ぶと、熱パターンにより融解し反応して着色画像
を形成する方法、もう一方は、熱分解反応を利用
して着色画像を形成する方法とがある。それらの
応用例として、前者は、クラトン型、ラクタム型
あるいは、フルオレン型などのロイコ染料を中心
とする発色剤と酸性物質／又は、フエノール性化
合物等の顕色剤からなる発色系の感熱記録材料、
後者としては、アシル化ロイコメチレンブルー化
合物／又はその酸付加塩の発色剤と熱時硝酸を遊
離する硝酸塩等の顕色剤から有る感熱記録材料等
がよく知られている。 In principle, there are two methods for chemical heat-sensitive recording. One is to form a heat-sensitive layer by dispersing immediately reactive components (color forming agent and color developer) in a binder as fine particles in a solution state. When the melting point of either the color forming agent or the color developer is selected near the conversion temperature, a thermal pattern causes the melting and reaction to form a colored image.The other method uses a thermal decomposition reaction to form a colored image. There is a method of forming the . As an example of their application, the former is a color-forming heat-sensitive recording material consisting of a color-forming agent, mainly a leuco dye such as a kraton type, a lactam type, or a fluorene type, and a color developer such as an acidic substance/or a phenolic compound. ,
As the latter, heat-sensitive recording materials are well known that are made of a color former of an acylated leucomethylene blue compound/or its acid addition salt and a color developer such as a nitrate that liberates nitric acid when heated.
しかし、かかる感熱記録体は、熱によつて記録
像を得る構成になつている為、末発色部分も熱時
発色する能力を有している。その為、誤つて熱源
に近づけると発色してしまい、記録媒体としての
能力を失うという欠陥を有している。 However, since such a heat-sensitive recording material is configured to obtain a recorded image using heat, the partially colored portion also has the ability to develop color when heated. Therefore, if it is mistakenly brought close to a heat source, it will develop color and lose its ability as a recording medium.
この為、保存を必要とするような証拠書類や、
偽造防止を必要とするカード類への適用が不可能
であつた。このような感熱記録体の構成に起因す
る欠陥を改良し、定着可能な永久画像を有する感
熱記録体が種々発明されている。具体例として、
特公昭54−1453号公報の、ベンゾイルロイコメチ
レンブルーと、硝酸尿素とから成る発色成分と、
該硝酸尿素を還元する光還元剤とを含む定着可能
な感光感熱組成物や、特開昭54−155060号公報
の、塩基性無色染料と、配性物質とから成る発色
成分と、水下溶性熱可塑性樹脂の微粒子を含む湿
式定着可能な感熱性組成物が知られている。前者
は乾式定着であるけれども、定着が不完全であ
り、後者は湿式定着であり、記録体としての簡易
性に欠け、一長一短がある。 For this reason, evidence documents that need to be preserved,
It was impossible to apply this method to cards that require counterfeit prevention. Various types of heat-sensitive recording bodies have been invented which improve the defects caused by the structure of such heat-sensitive recording bodies and have permanent images that can be fixed. As a specific example,
A coloring component consisting of benzoylleucomethylene blue and urea nitrate disclosed in Japanese Patent Publication No. 54-1453,
A fixable photo- and heat-sensitive composition containing a photoreducing agent that reduces the urea nitrate, a coloring component consisting of a basic colorless dye and a coordinating substance, and a water-soluble composition disclosed in JP-A No. 54-155060. Wet-fixable heat-sensitive compositions containing fine particles of thermoplastic resin are known. Although the former is a dry fixing method, the fixing is incomplete, and the latter is a wet fixing method, which lacks simplicity as a recording medium, and has both advantages and disadvantages.
そこで、本発明者等は、感熱記録体、その中で
アシル化ロイコメチレンブルー化合物系の乾式定
着方法について鋭意研究した結果、ジアゾニウム
化合物を感熱記録層に含有せしめることによつて
光により定着させることが出来ることを見出し、
本発明を完成するに至つた。すなわち本発明は、
アシル化ロイコメチレンブルー化合物質又は、そ
の酸付加塩と、硝酸塩等の酸性物質と、必要に応
じ還元剤とから成る感熱発色成分、ジアゾニウム
化合物である光定着剤及び高分子結着剤を含む感
熱記録層を支持体上に設けた事を特徴とする感熱
記録体である。具体的には、
ａ 潜在的顕色剤として加熱により、硝酸を遊離
する酸性物質
ｂ 発色剤として該硝酸との反応により発色する
アシル化ロイコメチレンブルー化合物又はその
酸付加塩
ｃ 光照射により前記酸性物質を不活性化する光
定着剤
これらａ）ｂ）ｃ）及び高分子結着剤を含む感
熱記録層を支持体上に設けた記録体で、記録後、
全面露光するか、又は像露光後全面加熱すること
により、永久像を形成するものである。 Therefore, the inventors of the present invention have conducted intensive research on heat-sensitive recording materials and dry fixing methods using acylated leucomethylene blue compounds therein. Find out what you can do,
The present invention has now been completed. That is, the present invention
A thermosensitive recording material containing a thermosensitive coloring component consisting of an acylated leucomethylene blue compound or its acid addition salt, an acidic substance such as a nitrate, and optionally a reducing agent, an optical fixing agent that is a diazonium compound, and a polymeric binder. This is a heat-sensitive recording material characterized by having a layer provided on a support. Specifically, a) an acidic substance that liberates nitric acid by heating as a latent color developer; b) an acylated leucomethylene blue compound or its acid addition salt that develops color upon reaction with the nitric acid as a color former; c) the acidic substance when irradiated with light. A recording medium in which a heat-sensitive recording layer containing a) b) c) and a polymeric binder is provided on a support, and after recording,
A permanent image is formed by exposing the entire surface to light or by heating the entire surface after image exposure.
本発明に使用される発色剤としては、各種公知
のアシル化ロイコメチレンブルー化合物／又はそ
の酸付加塩、であれば、いずれをも使用される。 As the coloring agent used in the present invention, any of various known acylated leucomethylene blue compounds/or acid addition salts thereof may be used.
本発明に使用される潜在的顕色剤としては、前
記した発色剤を加水分解、更に硝化反応を起す硝
酸基を含有する公知の化合物であればいずれをも
使用される。例えば、硝酸アンモン、硝酸ナトリ
ウム、硝酸亜鉛、硝酸尿素、硝酸グアニジン等で
ある。 As the latent color developer used in the present invention, any known compound containing a nitric acid group capable of hydrolyzing and further nitrifying the above-mentioned color former can be used. Examples include ammonium nitrate, sodium nitrate, zinc nitrate, urea nitrate, and guanidine nitrate.
また、本発明に使用される光定着剤としては、
各種公知のジアゾニウム化合物を使用することが
できる。例えば、下記が例示される。パラフエニ
レンジアミンＮ−Ｎ−置換化合物（４−ジアゾ−
Ｎ−Ｎ−ジエチルアニリンetc）、アミノハイドロ
キノンエーテル系（４−ジアゾ−２−５−ジブト
オキシ−Ｎ−Ｎ−ジエチルアニリン、４−ジアゾ
−２−クロロ−５メトキシ−Ｎ−ベンゾイルアニ
リンetc）、アミノジフエニル、アミノジフエニル
アミン及び類似化合物（４−ジアゾ−２−５−
4′−トリエトキシジフエニルアミン、etc）、ヘテ
ロサイクリツクアミンの誘導体（４−ジアゾ−２
−５−ジプトキシ−Ｎ−フエニルモルフオリン
etc）等である。以上述べたジアゾ化合物は、硫
酸塩または、塩酸塩として比較的安定なジアゾニ
ウム塩として用いるか更に塩化亜鉛等による複塩
として用いられる。 In addition, as the optical fixing agent used in the present invention,
Various known diazonium compounds can be used. For example, the following are exemplified. Paraphenylenediamine N-N-substituted compound (4-diazo-
N-N-diethylaniline etc), aminohydroquinone ether type (4-diazo-2-5-dibutoxy-N-N-diethylaniline, 4-diazo-2-chloro-5methoxy-N-benzoylaniline etc), aminodiphenyl , aminodiphenylamine and similar compounds (4-diazo-2-5-
4'-triethoxydiphenylamine, etc.), heterocyclic amine derivatives (4-diazo-2
-5-Dipoxy-N-phenylmorpholine
etc) etc. The diazo compounds described above are used as diazonium salts, which are relatively stable as sulfates or hydrochlorides, or as double salts with zinc chloride or the like.
さらに、本発明においては、発色成分の通常に
おいて安定性を増すために、チオ尿素、塩化第二
スズ、レゾルシン等の還元剤を発色成分中に含有
させることができる。 Furthermore, in the present invention, a reducing agent such as thiourea, stannic chloride, or resorcinol can be included in the coloring component in order to increase the stability of the coloring component.
本発明に使用される高分子結着剤としては、熱
可塑性樹脂であれば、水溶性、非水溶性樹脂をと
わず、市販のいずれをも使用することができる。
何等限定するものではない。 As the polymer binder used in the present invention, any commercially available thermoplastic resin can be used, including water-soluble and water-insoluble resins.
It is not limited in any way.
本発明において、定着可能な感熱記録体の感熱
記録層は、前記組成物が含有されている限り、公
知の方法に従つて行うことができる。 In the present invention, the heat-sensitive recording layer of the fixable heat-sensitive recording material can be formed according to a known method as long as the above-mentioned composition is contained.
例えば、水又は、有機溶媒に前記組成物を熱可
塑性樹脂とともに溶解乃至分散した組成物からな
る塗工液を紙又はフイルムのようなシート状物質
に塗布し発色温度以下で乾操することによつて定
着可能な感熱記録層が形成される。 For example, by applying a coating liquid consisting of the composition dissolved or dispersed together with a thermoplastic resin in water or an organic solvent to a sheet-like material such as paper or film, and drying at a temperature below the coloring temperature. A fixable heat-sensitive recording layer is then formed.
また、発色剤と潜在的顕色剤及び光定着剤とを
熱可塑性樹脂あるいは、直鎖脂肪酸等で二層に分
けて存在させることもできる。 Further, the color forming agent, latent color developer, and optical fixing agent can be separated into two layers using a thermoplastic resin, a straight chain fatty acid, or the like.
本発明における、発色剤と潜在的顕色剤の添加
割合は、モル比0.1〜10倍程度が好ましい。また、
定着剤の添加量は、少なくとも潜在的顕色剤の量
の等モル以上必要であり、好ましくは、２〜５倍
モル程度である。 In the present invention, the addition ratio of the color former and the latent color developer is preferably about 0.1 to 10 times the molar ratio. Also,
The amount of the fixing agent added must be at least the same molar amount as the amount of the latent color developer, and preferably about 2 to 5 times the molar amount.
かくして得られた感熱記録体の記録方法は、熱
源として、サーマルヘツド、熱ペン、熱ロール等
を用いることができる。また、ジアゾニウム化合
物を光分解する光源としてタングステンランプ、
水銀ランプ、及びキセノンフラツシユランプ等が
使用される。すなわち、これらのものを使用して
感熱記録後全面露光又は、像露光後全面加熱する
ことによつて熱的に安定な永久画像を形成するこ
とができる。 In the recording method of the heat-sensitive recording material thus obtained, a thermal head, a thermal pen, a thermal roll, etc. can be used as a heat source. In addition, tungsten lamps are used as light sources for photodecomposing diazonium compounds.
Mercury lamps, xenon flash lamps, etc. are used. That is, by using these materials, a thermally stable permanent image can be formed by exposing the entire surface after thermal recording or by heating the entire surface after image exposure.
本発明において、定着を可能に成し得たのは、
感熱記録機構が、酸化反応に起因する為であり、
該酸化反応を阻止することができれば定着がおこ
なわれるわけである。具体的には、加熱すること
に遊離する硝酸がアシル化ロイコメチレンブルー
化合物又はその酸付加塩と発色反応を引き起す前
に硝酸と反応するような塩基性物質を添加してや
れば良い。すなわち、光分解により塩基性物質を
示すジアゾニウム化合物を添加してやれば発色反
応を阻止することができる。 In the present invention, fixing can be achieved by:
This is because the heat-sensitive recording mechanism is caused by an oxidation reaction.
Fixing can be achieved if the oxidation reaction can be inhibited. Specifically, a basic substance that reacts with nitric acid may be added before the nitric acid liberated upon heating causes a coloring reaction with the acylated leucomethylene blue compound or its acid addition salt. That is, the coloring reaction can be inhibited by adding a diazonium compound that exhibits a basic substance upon photolysis.
本発明における定着可能な感熱記録体は次にあ
げるような利点を具備している。 The fixable heat-sensitive recording material according to the present invention has the following advantages.
熱と光を利用した非銀塩の画像形成方法であ
る。 This is a non-silver salt image forming method that uses heat and light.
定着ムラがなく、永久画像を形成する。 Forms permanent images without uneven fixing.
発色部分がメチレンブルー染料であるため、耐
光性にすぐれており、長期安定性を備えている。 Since the coloring part is methylene blue dye, it has excellent light resistance and long-term stability.
水溶性および非水溶性の高分子結着剤を使用す
ることができるのでベースの制限がない。 There are no base limitations as water-soluble and water-insoluble polymeric binders can be used.
発色機構が不可逆性であるため、耐溶剤性に優
れている。 Since the coloring mechanism is irreversible, it has excellent solvent resistance.
定着が可能な為に保存を必要とする記録への適
用ができる。 Since it can be fixed, it can be applied to records that require preservation.
このような利点を具備している為に種々の応用
が考えられる。例えば、保存を必要とする証拠書
類、及び偽造防止策の必要なチケツト、カード類
及び定期券等の印字記録媒体として使用すること
ができる。 Since it has such advantages, various applications can be considered. For example, it can be used as a print recording medium for documentary evidence that needs to be preserved, tickets, cards, commuter passes, etc. that need counterfeit prevention measures.
以下、本発明の実施例を示す。 Examples of the present invention will be shown below.
実施例 １
チオ尿素1.5ｇを添加した濃塩酸１mlを含む１
％PVA溶液（エタノール：水＝１：１）40ml中
に市販のベンゾイルロイコメチレンブルー0.6ｇ
を加えた。この溶液を白色上質紙にワイヤーバー
にて塗布し、乾燥した。その上に硝酸尿素0.8ｇ、
塩化Ｐ−ジアゾジエチルアニリン塩化亜鉛1.2ｇ
及び２，６−ジ−tert−ブチル−Ｐ−クレゾール
0.1ｇをエチルセルロースの１％アセトン溶液40
mlに溶解させた溶液をワイルヤーバーにて塗布
し、60℃の温度で乾燥し、感熱シートを作成し
た。この感熱シートに黒色画像を有する原稿を重
ね、市販ジアゾ複写機に通して露光後熱ロール機
にかけ、全面加熱すると鮮明なポジの青色画像を
有する複写物が得られた。Example 1 1 containing 1 ml of concentrated hydrochloric acid to which 1.5 g of thiourea was added
0.6 g of commercially available benzoylleucomethylene blue in 40 ml of % PVA solution (ethanol:water = 1:1)
added. This solution was applied to white high-quality paper using a wire bar and dried. On top of that, 0.8g of urea nitrate,
P-diazodiethylaniline chloride zinc chloride 1.2g
and 2,6-di-tert-butyl-P-cresol
0.1g of ethylcellulose in 1% acetone solution40
ml of the solution was applied using a Weyer bar and dried at a temperature of 60°C to prepare a heat-sensitive sheet. A document with a black image was placed on this heat-sensitive sheet, passed through a commercially available diazo copying machine, exposed, and then heated on a heat roll machine to obtain a copy with a clear positive blue image.
実施例 ２
常法により合成したパレロイルロイコメチレン
ブルー0.5ｇ、チオ尿素1.0ｇ、ハイドロキノン0.1
ｇ、硝酸グアニジン0.3ｇ及びＰ−フエニルアミ
ノベンゼンジアゾニウムクロライド塩化亜鉛塩
0.7ｇをポリエステル樹脂の２％アセトン溶液40
mlに溶解させた。この溶液をポリエステルフイル
ムにワイヤーバーにて塗布後60℃の温度で乾燥
し、感熱フイルムを作成した。この感熱フイルム
をサーマルプリンターにて印字後キヤノンフラツ
シユランプで露光すると鮮明な青色の永久画像が
得られた。かくして得られた熱的印字後全面露光
して光定着した感熱フイルムは、再度、未発色部
分を加熱しても発色しなかつた。Example 2 0.5 g of pareroyl leucomethylene blue, 1.0 g of thiourea, and 0.1 g of hydroquinone synthesized by a conventional method
g, 0.3 g of guanidine nitrate and P-phenylaminobenzenediazonium chloride zinc chloride salt
0.7 g of 2% acetone solution of polyester resin 40
ml. This solution was applied to a polyester film using a wire bar and then dried at a temperature of 60°C to prepare a heat-sensitive film. When this heat-sensitive film was printed with a thermal printer and exposed with a Canon flash lamp, a clear blue permanent image was obtained. The heat-sensitive film thus obtained, which was thermally printed and then completely exposed to light and photofixed, did not develop color even when the uncolored areas were heated again.
実施例 ３
塩化第二スズ２ｇを添加した濃塩酸５mlを含む
１％のカーボキシメチルセルロース水溶液50ml中
に、常法により合成した3.7−ビス（エチルアン）
−２，８−ビス（メチル）−プロプルエル10−フ
エノチアジン0.7ｇ及び硝酸ナトリウム３ｇを加
えた。この溶液を白色上質紙にワイヤーバーにて
塗布し乾燥した。乾燥後、中間層としてステアリ
ン酸５％エタノール溶液を同様な方法により塗布
し、乾燥した。Example 3 3.7-bis(ethylane) synthesized by a conventional method was placed in 50 ml of a 1% carboxymethyl cellulose aqueous solution containing 5 ml of concentrated hydrochloric acid to which 2 g of stannic chloride was added.
0.7 g of -2,8-bis(methyl)-propluel-10-phenothiazine and 3 g of sodium nitrate were added. This solution was applied to white high-quality paper using a wire bar and dried. After drying, a 5% ethanol solution of stearic acid was applied as an intermediate layer by the same method and dried.
その上に、硝酸ナトリウム３ｇ及び塩化４−ジ
アゾ−２，５−ジエトキシ−Ｎ−ベンゾイルアニ
リン塩化亜鉛塩５ｇをポリビニルアルコールの１
％溶液（エタノール：水＝１：１）40ml中に溶解
させた溶液をワイヤーバーにて塗布し、60℃の温
度で乾燥し感熱シートを作成した。この感熱シー
トを200℃の円形ハンダコテで加熱した後、全面
をキセノンフラツシユランプで露光すると円形の
青色画像が得られた、このものは、再度末発色部
分を加熱しても発色しなかつた。 On top of that, 3 g of sodium nitrate and 5 g of 4-diazo-2,5-diethoxy-N-benzoylaniline zinc chloride salt were added to 1 g of polyvinyl alcohol.
% solution (ethanol:water = 1:1) was applied using a wire bar and dried at a temperature of 60°C to prepare a heat-sensitive sheet. After heating this heat-sensitive sheet with a circular soldering iron at 200°C, the entire surface was exposed to light with a xenon flash lamp, and a circular blue image was obtained.This sheet did not develop color even when the partially colored portion was heated again.
参考例
比較の為、特公昭54−1453号公報の実施例１に
記載された方法に従つて感熱フイルムを作成し
た。Reference Example For comparison, a heat-sensitive film was prepared according to the method described in Example 1 of Japanese Patent Publication No. 1453/1983.
硝酸尿素0.25ｇ、ベンゾイルロイコメチレンブ
ルー0.78ｇ及び光還元剤であるα−ナフトキノン
0.63ｇをポリメタクリル酸メチルの２％アセトン
溶液40mlに溶解させた。この溶液をポリエステル
フイルムに、ワイヤーバーにて塗布し、50℃で乾
燥し、感熱フイルムを作成した。この感熱フイル
ムに黒色の画像を有する原稿を重ね、市販ジアゾ
機に通して露光後、熱ロール機にかけ、全面加熱
すると、露光部、未露光部との多少の濃度差はあ
るものの全面が濃い紫色に発色してしまい鮮明な
ポジの紫色画像を有する複写物が得られなかつ
た。 Urea nitrate 0.25g, benzoylleucomethylene blue 0.78g and photoreducing agent α-naphthoquinone
0.63 g was dissolved in 40 ml of a 2% acetone solution of polymethyl methacrylate. This solution was applied to a polyester film using a wire bar and dried at 50°C to produce a heat-sensitive film. When a document with a black image is placed on this thermosensitive film, exposed through a commercially available diazo machine, and then heated over the entire surface using a heat roll machine, the entire surface becomes a deep purple color, although there is a slight difference in density between the exposed and unexposed areas. As a result, a copy with a clear positive purple image could not be obtained.
Claims (1)
の酸付加塩と、硝酸塩等の酸性物質と、必要に応
じ還元剤とから成る感熱発色成分、ジアゾニウム
化合物である光定着剤及び高分子結着剤を含む感
熱記録層を支持体上に設けた事を特徴とする感熱
記録体。1. A heat-sensitive recording layer containing a heat-sensitive color forming component consisting of an acylated leucomethylene blue compound or its acid addition salt, an acidic substance such as a nitrate, and optionally a reducing agent, an optical fixing agent that is a diazonium compound, and a polymer binder. A heat-sensitive recording material, characterized in that it is provided on a support.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55129579A JPS5753390A (en) | 1980-09-18 | 1980-09-18 | Thermo-sensitive recording body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55129579A JPS5753390A (en) | 1980-09-18 | 1980-09-18 | Thermo-sensitive recording body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5753390A JPS5753390A (en) | 1982-03-30 |
| JPH0323351B2 true JPH0323351B2 (en) | 1991-03-28 |
Family
ID=15012944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55129579A Granted JPS5753390A (en) | 1980-09-18 | 1980-09-18 | Thermo-sensitive recording body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5753390A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005026454A1 (en) * | 2005-06-09 | 2006-12-14 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Mixtures of red vat dyes, process for their preparation and their use for dyeing hydroxyl-containing material |
-
1980
- 1980-09-18 JP JP55129579A patent/JPS5753390A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5753390A (en) | 1982-03-30 |
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