JPH074968B2 - Thermal recording sheet - Google Patents
Thermal recording sheetInfo
- Publication number
- JPH074968B2 JPH074968B2 JP60238814A JP23881485A JPH074968B2 JP H074968 B2 JPH074968 B2 JP H074968B2 JP 60238814 A JP60238814 A JP 60238814A JP 23881485 A JP23881485 A JP 23881485A JP H074968 B2 JPH074968 B2 JP H074968B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- recording sheet
- heat
- cyclodextrin
- colorless dye
- 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
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
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)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、各種プリンタ、フアクシミリ等に使用され
る感熱記録シートに関するものである。The present invention relates to a heat-sensitive recording sheet used in various printers, facsimile machines and the like.
感熱記録シートは通常加熱によつて発色するいわゆる感
熱発色層を支持体、例えば紙の表面に形成した記録材料
であつても、加熱にはサーマルヘツドを内蔵したサーマ
ルプリンタなどが用いられる。上記のような記録材料を
用いる感熱記録方法は図書，文書などの複写に用いられ
るている他、電子計算機，フアクシミリ，計測機などの
出力記録にも用いられている。感熱記録シートとして従
来は例えば特開昭57−6793号公報にみられるように第２
図のようなものがあつた。図において、（２）は酸性物
質、（３）は無色染料、（４）は発色層、（５）は支持
体、（６）は感熱ヘツド、（７）は発色部分である。発
色層（４）は結着剤中に酸性物質（２）と無色染料
（３）を分散させたものである。Even if the heat-sensitive recording sheet is a recording material having a so-called heat-sensitive color-developing layer which is normally colored by heating on a support, for example, the surface of paper, a thermal printer having a built-in thermal head is used for heating. The heat-sensitive recording method using the recording material as described above is used not only for copying books and documents but also for output recording of electronic calculators, facsimiles, measuring machines and the like. Conventionally, as a heat-sensitive recording sheet, as described in, for example, JP-A-57-6793, the second recording sheet is used.
There was something like the figure. In the figure, (2) is an acidic substance, (3) is a colorless dye, (4) is a coloring layer, (5) is a support, (6) is a thermal head, and (7) is a coloring part. The coloring layer (4) is a binder in which the acidic substance (2) and the colorless dye (3) are dispersed.
次に動作について説明する。感熱ヘツド（６）によつて
加熱された酸性物質（２）は溶融し、無色染料（３）と
反応して無色染料が有色染料に変換され発色する。Next, the operation will be described. The acidic substance (2) heated by the heat-sensitive head (6) melts and reacts with the colorless dye (3) to convert the colorless dye into a colored dye and develop color.
従来の感熱記録シートは以上のように構成されている
が、無色染料が酸性物質により変換された有色染料は、
これは通常塩基性染料と言われているが、一般に耐光性
が悪いという問題点があつた。なお、これは恐らく一重
項酸素に対する感受性が強いためと思われる。The conventional thermal recording sheet is configured as described above, but the colored dye in which the colorless dye is converted by the acidic substance is
Although this is usually called a basic dye, there is a problem that the light resistance is generally poor. This is probably due to its high sensitivity to singlet oxygen.
この発明は上記のような問題点を解消するためになされ
たもので、無色染料から変換された有色染料の耐光性を
向上させると共に感度が従来のものと同程度の感熱記録
シートを得ることを目的としている。The present invention has been made to solve the above problems, and to improve the light resistance of a colored dye converted from a colorless dye and to obtain a heat-sensitive recording sheet having the same sensitivity as the conventional one. Has an aim.
この発明に係る感熱記録シートはシクロデキストリンに
包接された無色染料と、この無色染料を加熱により有色
染料に変換させる硝酸ニッケルを結着剤中に分散させた
ものである。The heat-sensitive recording sheet according to the present invention comprises a colorless dye encapsulated in cyclodextrin and nickel nitrate which converts the colorless dye into a colored dye by heating in a binder.
この発明における無色染料は、熱により硝酸ニッケルか
ら生成した酸性物質（硝酸）によりシクロデキストリン
に包接されたままの状態で、有色染料に変換されるので
ケイ光収率増大に伴ない励起一重項から励起三重項への
遷移の確率が小さくなり耐光性が向上する。即ち、シク
ロデキストリンは疎水孔で包接するが、硝酸ニッケル、
熱により硝酸ニッケルから生成した硝酸およびニッケル
イオンには疎水部が存在しないので、シクロデキストリ
ンによる包接が起こらないため、染料とシクロデキスト
リンの包接が外れることなしに有色染料に変換されるの
である。The colorless dye in the present invention is converted to a colored dye while being included in cyclodextrin by an acidic substance (nitric acid) generated from nickel nitrate by heat, and thus is excited singlet with an increase in fluorescent yield. To the excited triplet, the probability of transition is reduced, and the light resistance is improved. That is, cyclodextrin is clathrated by hydrophobic pores, but nickel nitrate,
Since nitric acid and nickel ions generated from nickel nitrate by heat do not have a hydrophobic part, inclusion by cyclodextrin does not occur, so it is converted to a colored dye without the inclusion of the dye and cyclodextrin coming off. .
以下、この発明の一実施例を図について説明する。第１
図において、（１）はシクロデキストリンに包接された
無色染料、発色層（４）は結着剤中に無色染料（１）と
熱により酸性物質を放出する物質である硝酸ニッケル
（21）を分散させたものである。An embodiment of the present invention will be described below with reference to the drawings. First
In the figure, (1) is a colorless dye encapsulated in cyclodextrin, and coloring layer (4) is a colorless dye (1) in a binder and nickel nitrate (21) which is a substance that releases an acidic substance by heat. It is dispersed.
次に動作について説明する。感熱ヘツド（６）によつて
加熱されると熱により硝酸ニッケル（21）が硝酸を放出
し、シクロデキストリンに包接された無色染料は包接さ
れたままで有色染料に変換される。この時シクロデキス
トリンの存在により有色染料への変換速度は影響を受け
ない。形成された有色染料はシクロデキストリンに包接
されたままの状態で染料のケイ光収率が増大することに
より、染料の励起一重項から三重項状態への遷移の確率
が小さくなり、結果として励起三重項の量が少なくな
る。染料の退色は励起三重項を経由して行なわれてお
り、この三重項の量が減れば染料の光退色速度は小さく
なる。このため感熱記録シートの発色部分（７）の耐光
性が向上すると思われる。Next, the operation will be described. When heated by the heat-sensitive head (6), the nickel nitrate (21) releases nitric acid by the heat, and the colorless dye clathrated by the cyclodextrin is converted to the colored dye while being clathrated. At this time, the presence of cyclodextrin does not affect the conversion rate to the colored dye. The formed colored dye increases the fluorescent yield of the dye while being encapsulated in cyclodextrin, which reduces the probability of transition from the excited singlet to the triplet state of the dye, resulting in excitation. The amount of triplets is reduced. The fading of the dye is carried out via the excited triplet, and the photobleaching speed of the dye becomes smaller if the amount of the triplet is reduced. Therefore, it is considered that the light resistance of the colored portion (7) of the thermosensitive recording sheet is improved.
この発明に用いられる無色染料としては、ロイコメチレ
ンブルー，ロイコマラカイレグリーン，クリスタルバイ
オレツトラクトン，ローダミンＢラクタム等が挙げられ
る。Examples of the colorless dye used in the present invention include leuco methylene blue, leucomara kaile green, crystal violet lettactone, rhodamine B lactam and the like.
またシクロデキストリンとしては、α−，β−，γ−，
シクロデキストリン,2,3,5−ｏ−トリメトキシ−β−シ
クロデキストリンなどが挙げられる。As cyclodextrin, α-, β-, γ-,
Examples thereof include cyclodextrin and 2,3,5-o-trimethoxy-β-cyclodextrin.
また、結着剤としては、ポリビニルアルコール，ポリビ
ニルピロリドン，でんぷん，ポリメタクリル酸メチル，
ポリスチレン，メチルセルロース等が挙げられる。As the binder, polyvinyl alcohol, polyvinylpyrrolidone, starch, polymethylmethacrylate,
Examples include polystyrene and methyl cellulose.
さらに、硝酸ニッケルは熱により酸性物質（硝酸）とニ
ッケルイオンに分解され、この硝酸により無色染料を有
色染料に変換するものである。Further, nickel nitrate is decomposed into an acidic substance (nitric acid) and nickel ions by heat, and this nitric acid converts a colorless dye into a colored dye.
実施例１ ベンゾイルロイコメチレンブルー0.5重量部，β−シク
ロデキストリン２重量部をジメチルスルホキシド100重
量部に溶解して後、ロータリーエバポレーターで溶媒を
除去する。このもの2.5重量部と100重量部の10％ポリビ
ニルアルコール水溶液をボールミルで一昼夜混練する。
このものに１重量部の硝酸ニツケルを加え、最終厚さ10
μｍになるように上質紙へワイヤバーで塗布し、室温で
乾燥する。できた感熱記録紙へ150℃に暖めた分銅を５
秒間おくと、0D（吸光度）1.1の青い印字が得られた。
この印字の半分をアルミホイルで覆い、150mW/cm2の光
強度の超高圧水銀灯光を30分間照射しても、照射部と非
照射部の区別がつかなかつた。Example 1 0.5 parts by weight of benzoyl leuco methylene blue and 2 parts by weight of β-cyclodextrin were dissolved in 100 parts by weight of dimethyl sulfoxide, and then the solvent was removed by a rotary evaporator. 2.5 parts by weight of this product and 100 parts by weight of 10% aqueous polyvinyl alcohol solution are kneaded in a ball mill for 24 hours.
To this, add 1 part by weight of nickel nitrate to a final thickness of 10
Apply to a fine paper with a wire bar to a thickness of μm, and dry at room temperature. Add 5 weights to the thermosensitive recording paper
After standing for 2 seconds, a blue print of 0D (absorbance) 1.1 was obtained.
Even if half of this print was covered with aluminum foil and irradiated with ultra-high pressure mercury lamp light with a light intensity of 150 mW / cm 2 for 30 minutes, it was not possible to distinguish between the irradiated part and the non-irradiated part.
比較例 ベンゾイルロイコメチレンブルー0.5重量部と100重量部
の10％ポリビニルアルコール水溶液をボールミルで一昼
夜混練する。このものに１重量部の硝酸ニツケルを加
え、最終厚さ10μｍになるように上質紙へワイヤバーで
塗布し、室温で乾燥する。できた感熱記録紙へ150℃に
暖めた分銅を５秒間おくと0D1.2の青い印字が得られ、
実施例１とほとんど同じ感度であることが判つた。この
印字の半分をアルミホイルで覆い、150mW/cm2の光強度
の超高圧水銀灯光を10分間照射すると、照射部の退色が
認められた。Comparative Example 0.5 parts by weight of benzoyl leuco methylene blue and 100 parts by weight of a 10% aqueous solution of polyvinyl alcohol are kneaded with a ball mill overnight. To this, 1 part by weight of nickel nitrate is added, coated on a fine paper with a wire bar to a final thickness of 10 μm, and dried at room temperature. Put a weight warmed to 150 ℃ on the resulting thermal recording paper for 5 seconds, and a blue print of 0D1.2 is obtained.
It was found that the sensitivity was almost the same as in Example 1. When half of this print was covered with aluminum foil and irradiated with ultrahigh pressure mercury lamp light with a light intensity of 150 mW / cm 2 for 10 minutes, discoloration of the irradiated part was observed.
以上実施例と比較例との比較から、実施例において従来
と感度はほとんど変わらず、印字後の耐光性は優れてい
るということが明らかである。From the above comparison between the example and the comparative example, it is apparent that the sensitivity of the example is almost the same as that of the conventional example and the light resistance after printing is excellent.
以上のように、この発明によればシクロデキストリンに
包接された無色染料と、この無色染料を加熱により有色
染料に変換させる硝酸ニッケルを結着剤中に分散させた
ので、印字後の耐光性に優れ、かつ感度も従来のものと
同程度の感熱記録シートが得られるという効果がある。As described above, according to the present invention, since the colorless dye clathrated in cyclodextrin and nickel nitrate that converts the colorless dye into the colored dye by heating are dispersed in the binder, the light resistance after printing is improved. There is an effect that a heat-sensitive recording sheet which is excellent in sensitivity and has the same sensitivity as the conventional one can be obtained.
第１図はこの発明の一実施例による感熱記録シートを示
す断面図、第２図は従来の感熱記録シートを示す断面図
である。 図において、（１）はシクロデキストリンに包接された
無色染料、（21）は熱により酸性物質を放出する物質で
ある硝酸ニッケル、（４）は発色層、（５）は支持体、
（６）は感熱ヘツド、（７）は発色部分である。 なお、図中、同一符号は同一又は相当部分を示す。FIG. 1 is a sectional view showing a thermosensitive recording sheet according to an embodiment of the present invention, and FIG. 2 is a sectional view showing a conventional thermosensitive recording sheet. In the figure, (1) is a colorless dye included in cyclodextrin, (21) is nickel nitrate which is a substance that releases an acidic substance by heat, (4) is a coloring layer, (5) is a support,
(6) is a heat-sensitive head, and (7) is a colored portion. In the drawings, the same reference numerals indicate the same or corresponding parts.
Claims (4)
と、この無色染料を加熱により有色染料に変換させる硝
酸ニッケルを結着剤中に分散させた感熱記録シート。1. A heat-sensitive recording sheet in which a colorless dye clathrated in cyclodextrin and nickel nitrate for converting the colorless dye into a colored dye by heating are dispersed in a binder.
囲第１項記載の感熱記録シート。2. The heat-sensitive recording sheet according to claim 1, wherein the colorless dye is a leuco dye.
ーである特許請求の範囲第１項または第２項記載の感熱
記録シート。3. The heat-sensitive recording sheet according to claim 1 or 2, wherein the colorless dye is benzoyl leuco methylene blue.
リンである特許請求の範囲第１項ないし第３項の何れか
に記載の感熱記録シート。4. The thermosensitive recording sheet according to claim 1, wherein the cyclodextrin is β-cyclodextrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60238814A JPH074968B2 (en) | 1985-10-23 | 1985-10-23 | Thermal recording sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60238814A JPH074968B2 (en) | 1985-10-23 | 1985-10-23 | Thermal recording sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6297881A JPS6297881A (en) | 1987-05-07 |
| JPH074968B2 true JPH074968B2 (en) | 1995-01-25 |
Family
ID=17035681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60238814A Expired - Lifetime JPH074968B2 (en) | 1985-10-23 | 1985-10-23 | Thermal recording sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH074968B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63190815A (en) * | 1987-02-04 | 1988-08-08 | Hoou Kk | Powdery hair dye composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231736A (en) * | 1975-09-05 | 1977-03-10 | Nippon Kogaku Kk <Nikon> | Ttl light measure device for single lens reflex camera |
| JPS55113036A (en) * | 1979-02-24 | 1980-09-01 | Ricoh Co Ltd | Photosensitive and thermosensitive copying material |
| JPS55113034A (en) * | 1979-02-24 | 1980-09-01 | Ricoh Co Ltd | Photosensitive and thermosensitive copying material |
| JPS58124692A (en) * | 1982-01-21 | 1983-07-25 | Ricoh Co Ltd | heat sensitive recording material |
-
1985
- 1985-10-23 JP JP60238814A patent/JPH074968B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6297881A (en) | 1987-05-07 |
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