JPH0694231B2 - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH0694231B2 JPH0694231B2 JP59112006A JP11200684A JPH0694231B2 JP H0694231 B2 JPH0694231 B2 JP H0694231B2 JP 59112006 A JP59112006 A JP 59112006A JP 11200684 A JP11200684 A JP 11200684A JP H0694231 B2 JPH0694231 B2 JP H0694231B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- liquid
- color
- heat
- recording material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は感熱記録材料に関し、特に画像の安定性にすぐ
れた感熱記録材料に関する。TECHNICAL FIELD The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material excellent in image stability.
近年、情報量の増大、省資源、省力化、無公害化等の社
会的要請に伴つて、情報記録分野においても種々の記録
方式の実用化や改良が進められているが、中でも感熱記
録材料を用いる感熱記録方式は、（１）１次発色で現像
工程が不要、（２）ハードが簡単で且つコンパクトにで
きる上、メンテナンスコストが安い、（３）普通紙に近
い感触でしかもシート自体も比較的安価等の特徴もあつ
て、コンピユーターのアウトプツト、医療計測用レコー
ダー分野、フアクシミリ分野、プリンター分野、POS用
ラベル、自動販売機用乗車券等への実用化がなされてい
る。このような方式に用いられる感熱記録材料として
は、支持体上にラクトン、ラクタム、又はスピロピラン
環を有する無色又は淡色のロイコ染料と酸性物質、例え
ば有機酸又はフエノール性化合物を含有する感熱発色層
を設けたもの（特公昭43−4160号、45−14039号等）が
公知である。しかしながら、前記のようなロイコ系の感
熱記録材料の場合、記録画像の安定性が悪く、消色しや
すいという欠点を有している。例えば、油やプラスチツ
クフイルム中の可塑剤（ジオクチルフタレート等）等と
接触すると、その記録画像が消色するという問題があ
り、この問題の解決がこの種の記録材料における大き技
術課題になつている。In recent years, along with social demands such as an increase in the amount of information, resource saving, labor saving, and pollution-free, various recording systems have been put to practical use and improved in the information recording field. The heat-sensitive recording method using (1) primary color development does not require a developing step, (2) hardware can be simple and compact, maintenance cost is low, (3) the feel is similar to plain paper, and the sheet itself Due to its relatively low cost, it has been put to practical use in computer output, medical measurement recorder fields, facsimile fields, printer fields, POS labels, vending machine tickets, etc. As the thermosensitive recording material used in such a system, a colorless or light-colored leuco dye having a lactone, lactam, or spiropyran ring on a support and an acidic substance, for example, a thermosensitive coloring layer containing an organic acid or a phenolic compound. Those provided (Japanese Patent Publication No. 43-4160, 45-14039, etc.) are known. However, the above-mentioned leuco-type heat-sensitive recording material has the drawback that the stability of the recorded image is poor and the color is easily erased. For example, there is a problem that when a contact is made with oil or a plasticizer (such as dioctyl phthalate) in plastic film, the recorded image is erased, and the solution of this problem has become a major technical problem for this type of recording material. .
従来も、この問題解決を目的としたものがいくつか提案
されており、例えば、感熱発色層中に、耐水及び耐薬品
性の良い樹脂を大量に含有させて感熱発色層の安定性を
高めたものや、感熱発色層中に熱又は光によつて硬化す
る樹脂を含有させて感熱発色層の安定性を高めたものが
ある他、感熱発色層の表面に樹脂保護層を形成して感熱
発色層を薬品や水の作用から保護したものなどがある。
一方、感圧紙の分野では、耐薬品の良い顕色剤を用いた
ものが提案されているが（特開昭48−５号716号、特公
昭51−25174号公報）、この場合、特定の顕色剤使用は
感圧紙に関しては有効であつても、感熱記録紙に関して
は有効でなく、可塑剤と接触した場合に発色部は安定で
あるが、地色部（非発色部）の発色が起るという問題が
ある。特開昭59−11286号公報にも特定の顕色剤が示さ
れているが、この顕色剤も感圧紙に適しているかも知れ
ないが、そのほとんどが感熱記録材料には不適当であ
る。すなわち、地色部の初期濃度が高く（地肌カブ
リ）、極めて低品位の感熱記録材料しか得ることができ
ない。さらに、その多くのものは前記感圧紙分野の顕色
剤と同様に、可塑剤との接触で地色部の発色が起つてし
まう。In the past, several proposals aimed at solving this problem have been proposed. For example, in the thermosensitive coloring layer, a large amount of a resin having good water resistance and chemical resistance was added to improve the stability of the thermosensitive coloring layer. In some cases, the thermosensitive coloring layer contains a resin that is cured by heat or light to improve the stability of the thermosensitive coloring layer.In addition, a resin protective layer is formed on the surface of the thermosensitive coloring layer to form a thermosensitive coloring. For example, the layer is protected from chemicals and water.
On the other hand, in the field of pressure-sensitive paper, a developer using a developer having good chemical resistance has been proposed (JP-A-48-5 / 716, JP-B-51-25174). Although the use of a color developer is effective for pressure-sensitive paper, it is not effective for heat-sensitive recording paper, and the color development part is stable when it comes into contact with a plasticizer, but the color development of the ground color part (non-color development part) There is a problem of happening. Japanese Patent Laid-Open No. 59-11286 also discloses a specific developer, which may be suitable for pressure-sensitive paper, but most of them are not suitable for heat-sensitive recording materials. . That is, the initial density of the background color portion is high (background fog), and only a very low-quality thermal recording material can be obtained. Further, most of them, like the color developing agent in the pressure sensitive paper field, cause the ground color portion to develop color upon contact with a plasticizer.
本発明の目的は、特定のフルオラン化合物とチオシアン
酸亜鉛のアンチピリン錯体との組み合せより、油や可塑
剤との接触において発色部の消色、地色部の発色がない
ばかりでなく、アルコールの付着によつても地色部の発
色が起らないという従来の感熱記録材料に見られない、
極めて画像安定性の高い感熱記録材料を提供することに
ある。The object of the present invention is that, in combination with a combination of a specific fluorane compound and an antipyrine complex of zinc thiocyanate, not only the decolorization of the color-developed part and the development of the ground-colored part do not occur upon contact with oil or a plasticizer, but also the adhesion of alcohol. This is not seen in the conventional heat-sensitive recording material in which the background color does not develop,
It is to provide a heat-sensitive recording material having extremely high image stability.
即ち、本発明の感熱記録材料は、一般式（Ｉ） （式中、R1,R2は炭素数１〜６のアルキル基、R3,R4は各
々炭素数１〜２のアルキル基又はハロゲン原子を示し、
k,lは各々独立に0,1,又は２の数を示し、ｍは０又は１
を示す） で表わされるフルオラン化合物及び、 一般式（II） （式中、R5,R6は各々独立に炭素数１〜６のアルキル
基、R7は炭素数１〜２のアルキル基又はハロゲン原子を
示し、ｎは0,1又は２の数を示す） で表わされるフルオラン化合物の中から選ばれる少なく
とも１種のフルオラン化合物と、下記構造式（III）で
表わされるチオシアン酸亜鉛のアンチピリン錯体との間
の発色反応を利用することを特徴とする。That is, the heat-sensitive recording material of the present invention has the general formula (I) (In the formula, R 1 and R 2 each represent an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 each represent an alkyl group having 1 to 2 carbon atoms or a halogen atom,
k and l each independently represent the number 0, 1, or 2, and m is 0 or 1.
And a general formula (II) (In the formula, R 5 and R 6 are each independently an alkyl group having 1 to 6 carbon atoms, R 7 is an alkyl group having 1 to 2 carbon atoms or a halogen atom, and n is a number of 0, 1 or 2 ) A color reaction between at least one fluorane compound selected from among the following fluorane compounds and an antipyrine complex of zinc thiocyanate represented by the following structural formula (III) is utilized.
前記一般式（Ｉ）で表わされるフルオラン化合物の具体
例としては、例えば、以下のものが挙げられる。 Specific examples of the fluoran compound represented by the general formula (I) include the followings.
３−（Ｎ−エチル−ｐ−トルイジノ）−６−メチル−７
−アニリノフルオラン、 ３−（Ｎ−メチル−Ｎ−フエチル）−６−エチル−７−
（ｐ−メチルアニリノ）フルオラン、 ３−（Ｎ−ノルマルヘキシル−ｐ−トルイジノ）−６−
クロロ−７−アニリノフルオラン、 ３−（Ｎ−エチル−Ｎ−フエチル）−６−メチル−７−
（ｐ−クロロアニリノ）フルオラン、 ３−（Ｎ−ノルマルブチル−o,p−ジメチルフエニル）
−６−メチル−７−アニリノフルオラン、 ３−（Ｎ−メチル−ｐ−トルイジノ）−７−（ｏ−クロ
ロアニリノ）フルオラン等。3- (N-ethyl-p-toluidino) -6-methyl-7
-Anilinofluorane, 3- (N-methyl-N-phenyl) -6-ethyl-7-
(P-methylanilino) fluorane, 3- (N-normalhexyl-p-toluidino) -6-
Chloro-7-anilinofluorane, 3- (N-ethyl-N-fuethyl) -6-methyl-7-
(P-chloroanilino) fluorane, 3- (N-normalbutyl-o, p-dimethylphenyl)
-6-methyl-7-anilinofluorane, 3- (N-methyl-p-toluidino) -7- (o-chloroanilino) fluorane and the like.
前記一般式（II）で表わされるフルオラン化合物の具体
例としては、例えば以下のものが挙げられる。Specific examples of the fluoran compound represented by the general formula (II) include the following.
３−ジエチルアミノ−７−（ｏ−クロロアニリノ）フル
オラン、 ３−ジノルマルブチルアミノ−７−（ｏ−クロロアニリ
ノ）フルオラン、 ３−（Ｎ−イソアミル−Ｎ−エチルアミノ）−７−（o,
p−ジクロロアニリノ）フルオラン、 ３−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−７−
（ｏ−クロロアニリノ）フルオラン、 ３−ジエチルアミノ−７−（ｏ−メチルアニリノ）フル
オラン等。3-diethylamino-7- (o-chloroanilino) fluorane, 3-dinormalbutylamino-7- (o-chloroanilino) fluorane, 3- (N-isoamyl-N-ethylamino) -7- (o,
p-dichloroanilino) fluorane, 3- (N-cyclohexyl-N-methylamino) -7-
(O-chloroanilino) fluorane, 3-diethylamino-7- (o-methylanilino) fluorane and the like.
前記したフルオラン化合物はいずれも単独又は２種以上
が混合又は積層されて使用される。ここで、ロイコ染料
とチオシアン酸亜鉛のアンチピリン錯体との重量比率は
1:1〜６程度が適当である。Each of the above-mentioned fluoran compounds is used alone, or two or more kinds thereof are mixed or laminated and used. Here, the weight ratio of the leuco dye and the antipyrine complex of zinc thiocyanate is
About 1: 1 to 6 is suitable.
なお、本発明の感熱発色層中には支持体上に結合支持さ
せるべく慣用の種々の結合剤を適宜用いることは差しつ
かえなく、例えば、ポリビニルアルコール、メトキシセ
ルロース、ヒドロキシエチルセルロース、カルボキシメ
チルセルロース、ポリビニルピロリドン、ポリアクリル
アミド、ポリアクリル酸、デンプン、ゼラチンなどのよ
うな水溶性のもの、あるいはポリスチレン、塩化ビニル
−酢酸ビニル共重合体、ポリブチルメタクリレートなど
のような水性エマルジヨンのものを結合剤として用いる
ことができる。In the thermosensitive color-developing layer of the present invention, various conventional binders may be appropriately used for binding and supporting on a support. A water-soluble substance such as polyacrylamide, polyacrylic acid, starch, gelatin, etc., or an aqueous emulsion such as polystyrene, vinyl chloride-vinyl acetate copolymer, polybutyl methacrylate, etc. may be used as the binder. it can.
また、本発明においては必要に応じ、更に、この種の感
熱記録材料に慣用される補助添加成分、例えば、填料、
界面活性剤、熱可融性物質、滑剤等を併用することがで
きる。この場合、填料としては、例えば、炭酸カルシウ
ム、シリカ、酸化亜鉛、酸化チタン、水酸化アルミニウ
ム、水酸化亜鉛、硫酸バリウム、クレー、タルク、表面
処理されたカルシウムやシリカ等の無機系微粉末の他、
尿素−ホルマリン樹脂、スチレン／メタクリル酸共重合
体、ポリスチレン樹脂等の有機系の微粉末を挙げること
ができ、熱可融性物質としては、例えば、高級脂肪酸又
はそのエステル、アミドもしくは金属塩の他、各種ワツ
クス類、芳香族カルボン酸とアミンとの縮合物、安息香
酸フエニルエステル、高級直鎖グリコール、3,4−エポ
キシ−ヘキサヒドロフタル酸ジアルキル、高級ケトン、
その他の熱可融性有機化合物等の50〜200℃程度の融点
を持つものが挙げられる。Further, in the present invention, if necessary, an auxiliary additive component such as a filler, which is commonly used in this type of heat-sensitive recording material, is further added.
A surfactant, a heat-fusible substance, a lubricant and the like can be used in combination. In this case, as the filler, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, inorganic fine powder such as surface-treated calcium or silica, etc. ,
Examples thereof include organic fine powders of urea-formalin resin, styrene / methacrylic acid copolymer, polystyrene resin and the like. Examples of the heat-fusible substance include higher fatty acids or their esters, amides or metal salts. , Various waxes, condensation products of aromatic carboxylic acid and amine, benzoic acid phenyl ester, higher linear glycol, 3,4-epoxy-dialkyl hexahydrophthalate, higher ketone,
Other examples include heat-fusible organic compounds having a melting point of about 50 to 200 ° C.
本発明の感熱記録材料は、例えば、前記した各成分を含
む感熱層形成用塗液を、紙、合成紙、プラスチツクフイ
ルムなどの適当な支持体上に塗布し、乾燥することによ
つて製造され、各種の記録分野に、殊に、油、可塑剤や
アルコールとの接触の機会が多いPOS用サーマルラベル
や、感熱乗車券、医療計測機用レコーダーに適用される
サーマルペーパー等に利用される。The heat-sensitive recording material of the present invention is produced, for example, by applying a heat-sensitive layer-forming coating liquid containing each of the above-mentioned components on a suitable support such as paper, synthetic paper, plastic film, and drying. It is used in various recording fields, in particular, for thermal labels for POS, which are often exposed to oil, plasticizer, and alcohol, thermal ticket, thermal paper applied to recorders for medical measuring instruments, and the like.
本発明の感熱記録材料は以下のような特長を持つてい
る。The heat-sensitive recording material of the present invention has the following features.
（１）前記構造式（III）で表わされるチオシアン酸亜
鉛のアンチピリン錯体は合成容易で、従つて入手上の問
題がなく、しかも高収率、高純度でかつ比較的安価に得
られる。(1) The antipyrine complex of zinc thiocyanate represented by the above structural formula (III) is easy to synthesize, and accordingly, there is no problem in availability, and it can be obtained in high yield, high purity and relatively inexpensively.
（２）前記一般式（Ｉ）及び（II）のフルオラン化合物
の中から選ばれる少なくとも１種と前記構造式（III）
で表わされるチオシアン酸亜鉛のアンチピリン錯体とを
組み合せることにより、地肌カブリがなく、油、可塑剤
との接触においても、発色部の消色や地色部の発色など
の現像がなく、更に、アルコールの付着によつても地色
部が発色しない極めて画像安定性の優れた感熱記録材料
が得られる。また、発色画像が経時的に消色したり、白
粉現象をおこしたりすることがなく、非常に安定してい
る。(2) At least one selected from the fluorane compounds represented by the general formulas (I) and (II) and the structural formula (III)
By combining with an antipyrine complex of zinc thiocyanate represented by, there is no background fog and no development such as decoloring of the color-developed part or development of the ground-colored part even in contact with oil or a plasticizer. It is possible to obtain a heat-sensitive recording material having extremely excellent image stability in which the ground color portion does not develop color even by the adhesion of alcohol. In addition, the color image does not fade over time or the white powder phenomenon does not occur, and is very stable.
次に本発明を実施例によりさらに詳細に説明する。なお
以下において示す部及び％はいずれも重量基準である。Next, the present invention will be described in more detail with reference to Examples. The parts and% shown below are based on weight.
参考例 硫酸亜鉛（ZnSO4・7H2O）14.4gとチオシアン酸カリウム
29.2gを水200mlに溶かす。アンチピリン18.8gを水200ml
に溶かした溶液を上記溶液に撹拌下に滴下すると直ちに
白色沈殿が生ずる。この沈殿を濾別し、水洗後、乾燥す
る。乾燥した白色粉末を水−エタノールの混合溶媒で再
結晶し、融点118〜120℃のチオシアン酸亜鉛のアンチピ
リン錯体の白色結晶24.2gを得た。Reference Example Zinc sulfate (ZnSO 4 · 7H 2 O) 14.4g of potassium thiocyanate
Dissolve 29.2 g in 200 ml of water. Antipyrine 18.8g water 200ml
When a solution dissolved in is dropped into the above solution with stirring, a white precipitate is immediately formed. The precipitate is filtered off, washed with water and dried. The dried white powder was recrystallized with a mixed solvent of water and ethanol to obtain 24.2 g of white crystals of an antipyrine complex of zinc thiocyanate having a melting point of 118 to 120 ° C.
実施例１ 下記組成よりなる混合物を各々別々に磁性ボールミルを
用いて２日間粉砕し、分散して〔Ａ〕液、〔Ｂ〕液、
〔Ｃ〕液を調製した。Example 1 A mixture having the following composition was separately pulverized for 2 days using a magnetic ball mill, and dispersed to obtain [A] liquid, [B] liquid,
A liquid [C] was prepared.
〔Ａ〕液 ３−（Ｎ−エチル−ｐ−トルイジノ）−６−メチル−７
−アニリノフルオラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 〔Ｂ〕液 チオシアン酸亜鉛のアンチピリン錯体 20部 ５％メチルセルロース水溶液 20部 水 60部 〔Ｃ〕液 尿素−ホルマリン縮合樹脂の微粉末 20部 ５％メチルセルロース水溶液 20部 水 60部 以上のようにして得られた〔Ａ〕液〜〔Ｃ〕液を用い、
下記組成の感熱発色層液を調製し、基準坪量50g/m2の市
販上質紙に乾燥塗布量４〜5g/m2となるようにワイヤー
バーを選んで塗布、乾燥し、次いで感熱発色層表面の平
滑度が、ベツク平滑度で500〜600秒になるよう、カレン
ダーがけし、本発明の感熱記録シート（ａ）を作つた。[A] Liquid 3- (N-ethyl-p-toluidino) -6-methyl-7
-Anilinofluoran 20 parts 10% hydroxyethylcellulose aqueous solution 20 parts water 60 parts [B] liquid zinc thiocyanate antipyrine complex 20 parts 5% methylcellulose aqueous solution 20 parts water 60 parts [C] liquid urea-formalin condensation resin fine powder 20 parts 5% aqueous methyl cellulose solution 20 parts water 60 parts Using the liquids [A] to [C] obtained as described above,
A thermosensitive coloring layer solution having the following composition was prepared, and a wire bar was selected and dried on a commercially available high-quality paper having a standard basis weight of 50 g / m 2 so that the dry coating amount was 4 to 5 g / m 2, and then the thermosensitive coloring layer. The heat-sensitive recording sheet (a) of the present invention was produced by calendering so that the surface smoothness was 500 to 600 seconds in terms of flat smoothness.
感熱発色層液 （１）〔Ａ〕液 10部 （２）〔Ｂ〕液 30部 （３）〔Ｃ〕液 30部 （４）イソブチレン−無水マレイン酸共重合体の20％ア
ルカリ水溶液 10部 実施例２ 実施例１の〔Ａ〕液のかわりに下記〔Ｄ〕液を使用する
以外はすべて実施例１と同様にして感熱記録シート
（ｂ）を作つた。Thermosensitive coloring layer liquid (1) [A] liquid 10 parts (2) [B] liquid 30 parts (3) [C] liquid 30 parts (4) Isobutylene-maleic anhydride copolymer 20% alkaline aqueous solution 10 parts Example 2 A thermosensitive recording sheet (b) was prepared in the same manner as in Example 1 except that the following liquid [D] was used instead of the liquid [A] of Example 1.
〔Ｄ〕液 ３−ジノルマルブチルアミノ−７−（ｏ−クロロアニリ
ノ）フルオラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 実施例３ 実施例１の〔Ａ〕液のかわりに下記〔Ｅ〕液を使用する
以外はすべて実施例１と同様にして感熱記録シート
（ｃ）を作つた。[D] Liquid 3-dinormal butylamino-7- (o-chloroanilino) fluorane 20 parts 10% hydroxyethyl cellulose aqueous solution 20 parts water 60 parts Example 3 The following [E] liquid was used instead of the [A] liquid of Example 1. A thermal recording sheet (c) was prepared in the same manner as in Example 1 except that the above was used.
〔Ｅ〕液 ３−ジエチルアミノ−７−（ｏ−クロロアニリノ）フル
オラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 比較例１ 実施例１の〔Ａ〕液のかわりに下記〔Ｆ〕液を使用する
以外はすべて実施例１と同様にして感熱記録シート
（ｄ）を作つた。[E] Liquid 3-diethylamino-7- (o-chloroanilino) fluorane 20 parts 10% aqueous solution of hydroxyethyl cellulose 20 parts water 60 parts Comparative Example 1 The following [F] liquid is used instead of the [A] liquid of Example 1. A thermal recording sheet (d) was prepared in the same manner as in Example 1 except for the above.
〔Ｆ〕液 ３−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−６−
メチル−７−アニリノフルオラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 比較例２ 実施例１の〔Ａ〕液のかわりに下記〔Ｇ〕液を使用する
以外はすべて実施例１と同様にして感熱記録シート
（ｅ）を作つた。[F] Liquid 3- (N-cyclohexyl-N-methylamino) -6-
Methyl-7-anilinofluorane 20 parts 10% Hydroxyethylcellulose aqueous solution 20 parts Water 60 parts Comparative Example 2 All the same as Example 1 except that the following [G] solution was used instead of the [A] solution of Example 1. Then, a thermal recording sheet (e) was prepared.
〔Ｇ〕液 ３−ジエチルアミノ−６−メチル−７−アニリノフルオ
ラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 比較例３ 実施例１の〔Ａ〕液のかわりに下記〔Ｈ〕液を使用する
以外はすべて実施例１と同様にして感熱記録シート
（ｆ）を作つた。[G] Liquid 3-diethylamino-6-methyl-7-anilinofluorane 20 parts 10% aqueous solution of hydroxyethyl cellulose 20 parts water 60 parts Comparative Example 3 The following [H] liquid was used instead of the [A] liquid of Example 1. A thermal recording sheet (f) was prepared in the same manner as in Example 1 except that it was used.
〔Ｈ〕液 ３−（Ｎ−イソアミル−Ｎ−エチルアミノ）−６−メチ
ル−７−アニリノフルオラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 比較例４ 実施例１の〔Ａ〕液のかわりに下記〔Ｉ〕液を使用する
以外はすべて実施例１と同様にして感熱記録シート
（ｇ）を作つた。[H] liquid 3- (N-isoamyl-N-ethylamino) -6-methyl-7-anilinofluorane 20 parts 10% hydroxyethylcellulose aqueous solution 20 parts water 60 parts Comparative Example 4 [A] liquid of Example 1 A thermosensitive recording sheet (g) was prepared in the same manner as in Example 1 except that the following liquid [I] was used instead of the above.
〔Ｉ〕液 ３−ジエチルアミノ−７−（ｍ−トリフルオロメチルア
ニリノ）−フルオラン 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 比較例５ 実施例２の〔Ｂ〕液のかわりに下記〔Ｊ〕液を使用する
以外はすべて実施例２と同様にして感熱記録シート
（ｈ）を作つた。[I] Solution 3-diethylamino-7- (m-trifluoromethylanilino) -fluorane 20 parts 10% aqueous solution of hydroxyethyl cellulose 20 parts water 60 parts Comparative Example 5 Instead of the solution [B] of Example 2, the following [J] was used. A thermal recording sheet (h) was prepared in the same manner as in Example 2 except that the liquid was used.
〔Ｊ〕液 チオシアン酸亜鉛のイミダゾール錯体 （融点143〜145℃） 20部 ５％メチルセルロース水溶液 20部 水 60部 比較例６ 実施例２の〔Ｂ〕液のかわりに下記〔Ｋ〕液を使用する
以外はすべて実施例２と同様にして感熱記録シート
（ｉ）を作つた。Liquid [J] Imidazole complex of zinc thiocyanate (melting point 143 to 145 ° C.) 20 parts 5% aqueous solution of methylcellulose 20 parts Water 60 parts Comparative Example 6 The following liquid [K] is used instead of the liquid [B] of Example 2. A thermal recording sheet (i) was prepared in the same manner as in Example 2 except for the above.
〔Ｋ〕液 ビスフエノールＡ 20部 10％ヒドロキシエチルセルロース水溶液 20部 水 60部 以上のようにして得られた感熱記録シート（ａ）〜
（ｉ）を熱傾斜試験機（東洋精機製）にて圧力2kg接触
時間１秒で150℃で印字した。（ａ）〜（ｉ）の感熱記
録シートの発色部と地色部に綿実油を薄く塗布し、室内
に24時間放置した後、変化の状態を調べたところ、実施
例のもの（ａ〜ｃ）及び比較例１〜４のもの（ｄ〜ｇ）
は発色部に消色、地色部の発色ともに見られなかつた
が、比較例５にもの（ｈ）は発色部の消色はなかつた
が、地色部の発色が見られた。また比較例６のもの
（ｉ）は、地色部の発色はなかつたが、発色部の消色が
見られた。[K] Liquid Bisphenol A 20 parts 10% Hydroxyethylcellulose aqueous solution 20 parts Water 60 parts Thermal recording sheet (a) obtained as above
(I) was printed at 150 ° C. with a thermal inclination tester (manufactured by Toyo Seiki) at a pressure of 2 kg and a contact time of 1 second. When cotton seed oil was thinly applied to the color-developed portion and the ground-colored portion of the heat-sensitive recording sheets (a) to (i) and left for 24 hours in the room, the state of change was examined. And those of Comparative Examples 1 to 4 (d to g)
Neither the color-developed portion nor the ground-colored portion was observed, but in Comparative Example 5 (h), the color-developed portion was not erased, but the ground-colored portion was observed. In Comparative Example 6 (i), the background color portion did not develop color, but the color development portion was decolored.
次に、感熱記録シート（ａ）〜（ｉ）を同様にして印字
し、印字部を中心に4cm四方を切り抜き、これにポリ塩
化ビニルフイルム（信越ポリマー（株）製、ポリラツプ
Ｖ−300）を１枚重ね、室温で荷重500g/cm2を24時間加
えた後、取り出して、地色部の濃度と発色部の濃度をマ
クベス濃度計（RD−514）で測定し、その発色部濃度
を、試験前の濃度と比較し、その結果を表−１に示す。Next, the thermosensitive recording sheets (a) to (i) were printed in the same manner, and a 4 cm square was cut out around the printed portion, and a polyvinyl chloride film (Polyrap V-300 manufactured by Shin-Etsu Polymer Co., Ltd.) was cut on this. After stacking one sheet and applying a load of 500 g / cm 2 at room temperature for 24 hours, take it out, measure the density of the background color part and the density of the color development part with a Macbeth densitometer (RD-514), and determine the density of the color development part, The results are shown in Table 1 in comparison with the concentration before the test.
次に、感熱記録シート（ａ）〜（ｉ）にエタノール（試
薬、特級）を薄く塗布し、エタノール蒸発後、塗布部の
濃度を測定した。その結果を表−２に示す。 Next, ethanol (reagent, special grade) was thinly applied to the thermal recording sheets (a) to (i), and after evaporation of ethanol, the concentration of the applied part was measured. The results are shown in Table-2.
以上より、本発明の感熱記録材料は地肌カブリもなく、
油、可塑剤との接触においても発色部の消色及び地色部
の発色がなく、更に、アルコールの付着によつても地色
部が発色しない極めて画像安定性の高い感熱記録材料で
あることがわかる。 From the above, the heat-sensitive recording material of the present invention has no background fog,
It is a heat-sensitive recording material with extremely high image stability, in which the color-developed part does not disappear even when contacted with oil or a plasticizer, and the ground-colored part does not develop due to the adhesion of alcohol. I understand.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−11286（ＪＰ，Ａ) 特開 昭58−89394（ＪＰ，Ａ) 特開 昭57−188393（ＪＰ，Ａ) 特開 昭57−167295（ＪＰ，Ａ) 特開 昭57−128593（ＪＰ，Ａ) 特開 昭57−120494（ＪＰ，Ａ) 特開 昭57−89994（ＪＰ，Ａ) 特開 昭57−29492（ＪＰ，Ａ) 特開 昭56−162690（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-59-11286 (JP, A) JP-A-58-89394 (JP, A) JP-A-57-188393 (JP, A) JP-A-57- 167295 (JP, A) JP 57-128593 (JP, A) JP 57-120494 (JP, A) JP 57-89994 (JP, A) JP 57-29492 (JP, A) JP-A-56-162690 (JP, A)
Claims (1)
各々炭素数１〜２のアルキル基又はハロゲン原子を示
し、ｋ、ｌは各々独立に０、１、又は２の数を示し、ｍ
は０又は１を示す） 一般式（II） （式中、R5、R6は各々独立に炭素数１〜６のアルキル
基、R7は炭素数１〜２のアルキル基又はハロゲン原子を
示し、ｎは０、１、又は２の数を示す） で表わされるフルオラン化合物の中から選ばれる少なく
とも１種のフルオラン化合物と、下記構造式（III） で表わされるチオシアン酸亜鉛のアンチピリン錯体との
間の発色反応を利用することを特徴とする感熱記録材
料。1. A general formula (I) (In the formula, R 1 and R 2 each represent an alkyl group having 1 to 6 carbon atoms, R 3 and R 4 each represent an alkyl group having 1 to 2 carbon atoms or a halogen atom, and k and l each independently represent 0 or 1 , Or the number of 2, m
Represents 0 or 1) General formula (II) (In the formula, R 5 and R 6 are each independently an alkyl group having 1 to 6 carbon atoms, R 7 is an alkyl group having 1 to 2 carbon atoms or a halogen atom, and n is 0, 1, or 2 And at least one fluorane compound selected from the fluorane compounds represented by the following structural formula (III) A heat-sensitive recording material characterized by utilizing a color-forming reaction with an antipyrine complex of zinc thiocyanate represented by:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59112006A JPH0694231B2 (en) | 1984-05-31 | 1984-05-31 | Thermal recording material |
| US06/736,848 US4608579A (en) | 1984-05-25 | 1985-05-22 | Thermosensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59112006A JPH0694231B2 (en) | 1984-05-31 | 1984-05-31 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60255484A JPS60255484A (en) | 1985-12-17 |
| JPH0694231B2 true JPH0694231B2 (en) | 1994-11-24 |
Family
ID=14575602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59112006A Expired - Fee Related JPH0694231B2 (en) | 1984-05-25 | 1984-05-31 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694231B2 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56162690A (en) * | 1980-05-21 | 1981-12-14 | Hodogaya Chem Co Ltd | Heat-sensitive recording paper |
| JPS5729492A (en) * | 1980-07-31 | 1982-02-17 | Oji Paper Co Ltd | Thermosensitive recording sheet |
| JPS5789994A (en) * | 1980-11-26 | 1982-06-04 | Honshu Paper Co Ltd | Heat-sensitive recording paper |
| JPS57120494A (en) * | 1981-01-19 | 1982-07-27 | Hodogaya Chem Co Ltd | Heat-sensitive recording paper |
| JPS57128593A (en) * | 1981-02-03 | 1982-08-10 | Ricoh Co Ltd | Thermosensitve recording material |
| JPS57167295A (en) * | 1981-04-09 | 1982-10-15 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS57188393A (en) * | 1981-05-15 | 1982-11-19 | Ricoh Co Ltd | Heat sensitive recording material |
| JPS5889394A (en) * | 1981-11-20 | 1983-05-27 | Ricoh Co Ltd | Heat-sensitive recording type magnetic ticket paper |
| ZA834588B (en) * | 1982-06-24 | 1984-03-28 | Ciba Geigy Ag | Pressure-sensitive or heat-sensitive recording material |
-
1984
- 1984-05-31 JP JP59112006A patent/JPH0694231B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60255484A (en) | 1985-12-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |