JPH0640155A - Heat-sensitive recording material - Google Patents
Heat-sensitive recording materialInfo
- Publication number
- JPH0640155A JPH0640155A JP4217379A JP21737992A JPH0640155A JP H0640155 A JPH0640155 A JP H0640155A JP 4217379 A JP4217379 A JP 4217379A JP 21737992 A JP21737992 A JP 21737992A JP H0640155 A JPH0640155 A JP H0640155A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- liquid
- parts
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、感熱記録用材料に関
し、特にフルオレン化合物を用いた感熱記録用材料に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material using a fluorene compound.
【０００２】[0002]
【従来の技術】感熱記録用材料は、ファクシミリ、プリ
ンタ、医療用計測機、券売機等に広く利用されており、
電子供与性無色発色剤であるロイコ染料と電子受容性顕
色性物質である酸性顕色剤とを熱で溶融させ、両者を会
合させて発色させる原理を利用している。また、この際
の感度を向上させるため、材料中に増感剤を配合するこ
とが行われている。近年、家庭用ファクシミリが普及す
るに伴って、感熱記録用材料に対する高性能化が求めら
れている。従来より、ビスフェノ−ルＡ等のフェノ−ル
化合物の顕色剤、また、増感剤としてp-ベンジルビフェ
ニル等が知られているが、現在までに知られている顕色
剤、増感剤を用いた感熱記録用材料では、高白色度、耐
白化性及び耐可塑剤性のより一層の向上という要求を満
たすには不十分である。これらの性能を向上させるべ
く、特開平3-140289号公報ではフルオレン系化合物を添
加分散させる方法が提案されているが、フルオレン系化
合物の融点が高く、発色濃度が不充分であった。2. Description of the Related Art Thermal recording materials are widely used in facsimiles, printers, medical measuring instruments, ticket vending machines, etc.
The principle is utilized in which a leuco dye, which is an electron-donating colorless color former, and an acidic developer, which is an electron-accepting color-developing substance, are melted by heat and the two are associated to develop a color. Further, in order to improve the sensitivity at this time, a sensitizer is blended in the material. In recent years, with the spread of household facsimiles, there has been a demand for higher performance of thermosensitive recording materials. Conventionally, a developer for a phenol compound such as bisphenol A, and p-benzylbiphenyl as a sensitizer have been known, but the developer and sensitizer known to date. The heat-sensitive recording material using is not sufficient to satisfy the demands for further improvement in high whiteness, whitening resistance and plasticizer resistance. In order to improve these properties, JP-A-3-140289 proposes a method of adding and dispersing a fluorene compound, but the melting point of the fluorene compound was high and the color density was insufficient.
【０００３】[0003]
【発明が解決しようとする課題】本発明は上記の様な問
題点を解決することを目的とするものであり、高白色
度、耐白化性及び耐可塑剤性に優れ、且つ、高感度の感
熱記録用材料を提供することを目的とする。SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and is excellent in high whiteness, whitening resistance and plasticizer resistance, and high sensitivity. An object is to provide a thermosensitive recording material.
【０００４】[0004]
【課題を解決するための手段】本発明はロイコ染料、酸
性顕色剤及び増感剤を有する感熱記録用材料において、
一般式（１）で示される化合物を前記酸性顕色剤及び前
記増感剤のいずれか一方又は両者と溶融混合させて存在
させてなる感熱記録用材料である。The present invention provides a heat-sensitive recording material having a leuco dye, an acid developer and a sensitizer,
A heat-sensitive recording material comprising a compound represented by the general formula (1), which is melt-mixed with one or both of the acidic developer and the sensitizer and is allowed to exist.
【化２】 （式中、Ｒ1 は−Ｈ、−ＯＨ、−ＮＨ2 又は−ＯＣＨ2
ＣＨ2 ＯＨを示し、Ｒ2は−ＯＨ又は−Ｃn Ｈ2n+1（０
≦ｎ≦５）、Ｒ3 は−Ｈ又は−ＣＯＯＨを示し、これら
は同一であっても、異なってもよい)[Chemical 2] (In the formula, R 1 is —H, —OH, —NH 2 or —OCH 2
CH 2 OH, R 2 is —OH or —C n H 2n + 1 (0
≦ n ≦ 5), R 3 represents —H or —COOH, which may be the same or different.)
【０００５】前記一般式（１）で示される化合物として
は、9,9-ビス(4- ヒドロキシフェニル) フルオレンが好
ましいものとして挙げられる。一般に５０〜２００℃の
範囲に融点を有するものが好ましい。この化合物は、酸
性顕色剤又は増感剤又はこの両者と溶融混合した状態で
感熱記録材料中に存在させる。溶融混合させて存在させ
ることにより、高白色度、耐白化性、耐可塑剤性や感度
がより向上する。As the compound represented by the general formula (1), 9,9-bis (4-hydroxyphenyl) fluorene is preferred. Generally, those having a melting point in the range of 50 to 200 ° C. are preferable. This compound is present in the heat-sensitive recording material in a state of being melt-mixed with the acidic developer or the sensitizer or both of them. By being melt-mixed and present, high whiteness, whitening resistance, plasticizer resistance and sensitivity are further improved.
【０００６】本発明の感熱記録材料は、ロイコ染料、酸
性顕色剤及び増感剤を含むものであるが、ロイコ染料と
しては、電子供与性の無色染料であればよく、トリアリ
ルメタン系、キサンテン系、チアジン系、オキサジン
系、スピロピラン系、フルオレン系等各種のロイコ染料
を使用することができる。酸性顕色剤としては、電子受
容性化合物、例えばフェノ−ル系、有機酸系、ヒドロキ
シ安息香酸系等各種の顕色剤を使用することができる。
増感剤としては、５０〜１５０℃程度の範囲に融点を有
する化合物、例えばｐ−ベンジルビフェニル、ｍ−タ−
フェニル等の芳香族炭化水素系、エステル系、アミド
系、アミン系等各種の増感剤を使用することができる。The heat-sensitive recording material of the present invention contains a leuco dye, an acidic developer and a sensitizer. The leuco dye may be any electron-donating colorless dye, such as triallylmethane type and xanthene type. Various leuco dyes such as thiazine-based, oxazine-based, spiropyran-based and fluorene-based can be used. As the acidic developer, various developers such as electron-accepting compounds such as phenol type, organic acid type and hydroxybenzoic acid type can be used.
As the sensitizer, a compound having a melting point in the range of about 50 to 150 ° C., such as p-benzylbiphenyl, m-tertiary
Various sensitizers such as aromatic hydrocarbons such as phenyl, ester, amide, amine and the like can be used.
【０００７】ロイコ染料、酸性顕色剤及び増感剤の配合
割合は、公知の範囲で差し支えなく、また一般式（１）
で示される化合物はロイコ染料に対して０．２〜１０重
量倍、好ましくは０．５〜３重量倍である。一般式
（１）で示される化合物は、酸性顕色剤又は増感剤又は
両者と溶融混合されたのち、１〜１０重量％の水溶性高
分子溶液中でボ−ルミル等で分散され、これにタルク等
の無機顔料を加えて塗液を作成し、この塗液を紙等に塗
布するというような方法で使用される。The leuco dye, the acid developer and the sensitizer may be mixed in the known proportions, and the formula (1) may be used.
The compound represented by is 0.2 to 10 times by weight, preferably 0.5 to 3 times by weight that of the leuco dye. The compound represented by the general formula (1) is melt-mixed with an acidic developer or a sensitizer or both, and then dispersed in a water-soluble polymer solution of 1 to 10% by weight with a ball mill or the like. It is used in such a method that an inorganic pigment such as talc is added to prepare a coating liquid, and the coating liquid is applied to paper or the like.
【０００８】[0008]
【実施例】以下、本発明を実施例により具体的に説明す
る。部は重量部を表す。 分散液の作成 (1) 液（染料分散液） 3-ジエチルアミノ-6- メチル-7- アニリノフルオラン 2 部 ポリビニルアルコ−ル（PVA ） 2 部 水 6 部 (2) 液（顕色剤分散液） 9,9-ビス(4- ヒドロキシフェニル) フルオレンとビスフェノ−ルＡを、2 ：8 の 比で溶融混合した物 1 部 PVA 4 部 水 9 部 (3) 液（顕色剤分散液） 9,9-ビス(4- ヒドロキシフェニル) フルオレン 1 部 PVA 4 部 水 9 部 (4) 液（顕色剤分散液） ビスフェノ−ルＡ 1 部 PVA 4 部 水 9 部 (5) 液（増感剤分散液） 9,9-ビス(4- ヒドロキシフェニル) フルオレンとp-ベン
ジルビフェニルを、2 ：8 の比で溶融混合した物 1 部 PVA 4 部 水 9 部 (6) 液（増感剤分散液） p-ベンジルビフェニル 1 部 PVA 4 部 水 9 部 (7) 液（顕色増感剤分散液） 9,9-ビス(4- ヒドロキシフェニル) フルオレンとビスフ
ェノ−ルＡとp-ベンジルビフェニルを、2 ：4 ：4 の比
で溶融混合した物 1 部 PVA 4 部 水 9 部 (1) 〜(7) 液には、各々に添加剤として、炭酸カルシウ
ム、ステアリン酸亜鉛、酸化防止剤、紫外線吸収剤を適
量加え、各々の液を数μまで粉砕した。EXAMPLES The present invention will be specifically described below with reference to examples. Parts represent parts by weight. Preparation of dispersion (1) Liquid (dye dispersion) 3-diethylamino-6-methyl-7-anilinofluorane 2 parts Polyvinyl alcohol (PVA) 2 parts Water 6 parts (2) liquid (developer dispersion) Liquid) 9,9-bis (4-hydroxyphenyl) fluorene and bisphenol A melt-mixed in a ratio of 2: 8 1 part PVA 4 parts water 9 parts (3) liquid (developer dispersion) 9,9-Bis (4-hydroxyphenyl) fluorene 1 part PVA 4 parts Water 9 parts (4) solution (Developer dispersion) Bisphenol A 1 part PVA 4 parts Water 9 parts (5) solution (sensitized Agent dispersion liquid) 9,9-bis (4-hydroxyphenyl) fluorene and p-benzylbiphenyl melt-mixed in a ratio of 2: 8 1 part PVA 4 parts water 9 parts (6) liquid (sensitizer dispersion Liquid) p-benzylbiphenyl 1 part PVA 4 parts Water 9 parts (7) Liquid (developer sensitizer dispersion) 9,9-bis (4-hydroxyphenyl) fluorene, bisphenol A and p-benzylbiphenyl 1 part PVA 4 parts water 9 parts (1) to (7) liquids mixed in a ratio of 2: 4: 4 with calcium carbonate, zinc stearate, an antioxidant, and An appropriate amount of ultraviolet absorber was added, and each liquid was pulverized to several μ.
【０００９】実施例１ 上記分散液を、下記の割合で混合して感熱記録用塗液と
した。 (1) 液 5 部 (2) 液 14部 (5) 液 14部 この塗液をワイヤ−バ−コ−ティングにより、上質紙の
片面に6 ｇ／ｍ2 塗布し、乾燥させ感熱記録紙を作製し
た。Example 1 The above dispersions were mixed in the following proportions to prepare a thermal recording coating liquid. (1) Liquid 5 parts (2) Liquid 14 parts (5) Liquid 14 parts Apply 6 g / m 2 of this coating liquid to one side of wood free paper by wire bar coating, and dry to make a thermosensitive recording paper. It was made.
【００１０】実施例２ 下記の割合で各液を混合して感熱記録用塗液とした。 (1) 液 5 部 (2) 液 14部 (6) 液 14部 上記塗液を用い、実施例１と同様にして感熱記録紙を作
製した。Example 2 The respective liquids were mixed in the following proportions to prepare a heat-sensitive recording coating liquid. (1) Liquid 5 parts (2) Liquid 14 parts (6) Liquid 14 parts Using the above coating liquid, a thermal recording paper was prepared in the same manner as in Example 1.
【００１１】実施例３ 下記の割合で各液を混合して感熱記録用塗液とした。 (1) 液 5 部 (4) 液 14部 (5) 液 14部 上記塗液を用い、実施例１と同様にして感熱記録紙を作
製した。Example 3 The respective liquids were mixed in the following proportions to prepare a thermal recording coating liquid. (1) Liquid 5 parts (4) Liquid 14 parts (5) Liquid 14 parts Using the above coating liquid, a thermal recording paper was prepared in the same manner as in Example 1.
【００１２】実施例４ 下記の割合で各液を混合して感熱記録用塗液とした。 (1) 液 5 部 (7) 液 28部 上記塗液を用い、実施例１と同様にして感熱記録紙を作
製した。Example 4 The respective liquids were mixed in the following proportions to prepare a heat-sensitive recording coating liquid. (1) Liquid 5 parts (7) Liquid 28 parts Using the above coating liquid, a thermal recording paper was prepared in the same manner as in Example 1.
【００１３】比較例１ 9,9-ビス(4- ヒドロキシフェニル) フルオレンとビスフ
ェノ−ルＡを添加分散で2 ：8 の比で混合すべく、下記
の割合で各液を混合して感熱記録用塗液とした。 (1) 液 5 部 (3) 液 2.8 部 (4) 液 11.2部 (6) 液 14部 上記混合感熱記録用塗液を用い、実施例１と同様にして
感熱記録紙を作製した。Comparative Example 1 9,9-Bis (4-hydroxyphenyl) fluorene and bisphenol A were added and dispersed at a ratio of 2: 8 so that the respective liquids were mixed at the following ratios for heat-sensitive recording. It was used as a coating liquid. (1) Liquid 5 parts (3) Liquid 2.8 parts (4) Liquid 11.2 parts (6) Liquid 14 parts A thermosensitive recording paper was prepared in the same manner as in Example 1 using the above mixed thermosensitive recording liquid.
【００１４】比較例２ 一般式（１）で示される化合物を含まない感熱記録用塗
液とすべく、下記の割合で各液を混合して感熱記録用塗
液とした。 (1) 液 5 部 (4) 液 14部 (6) 液 14部 上記混合感熱記録用塗液を用い、実施例１同様にして感
熱記録紙を作製した。Comparative Example 2 In order to obtain a thermosensitive recording liquid containing no compound represented by the general formula (1), the respective liquids were mixed in the following proportions to prepare a thermosensitive recording liquid. (1) Liquid 5 parts (4) Liquid 14 parts (6) Liquid 14 parts A thermosensitive recording paper was prepared in the same manner as in Example 1 using the above mixed thermosensitive recording liquid.
【００１５】実施例１〜実施例４、比較例１〜比較例２
で得られた感熱記録紙について行った試験方法を次に示
す。 白色度( 地肌カブリ) ： 70℃で発色させた後の画像部
の濃度を測定し、値が0.2 以上のものを×とした。 白化( 粉ふき) ： 発色後、画像部に白い粉が浮いて出
る現象の有無。 発色濃度： 得られた感熱記録紙を各温度で発色させ
て、反射濃度計により発色濃度を測定した。 耐可塑剤性： プラスチック消しゴムを発色濃度試験
で発色させた画像部の上に乗せ24時間放置後、画像部の
濃度を測定した。 結果を次表に示す。Examples 1 to 4, Comparative Examples 1 to 2
The test method carried out on the thermosensitive recording paper obtained in 1. is shown below. Whiteness (background fog): The density of the image area after color development at 70 ° C was measured, and the value of 0.2 or more was evaluated as x. Whitening (powder wiping): Presence or absence of the phenomenon that white powder appears in the image area after coloring. Color density: The obtained thermosensitive recording paper was colored at each temperature, and the color density was measured by a reflection densitometer. Plasticizer resistance: A plastic eraser was placed on the image portion developed in the color density test and allowed to stand for 24 hours, after which the density of the image area was measured. The results are shown in the table below.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明の感熱記録材料は、従来公知の顕
色剤、増感剤を用いた材料と比べて、白色度、白化、耐
可塑剤性が良好で、しかも、発色濃度が著しく改善され
る。The heat-sensitive recording material of the present invention has better whiteness, whitening and plasticizer resistance than the materials using conventionally known color developers and sensitizers, and has a remarkable color density. Be improved.
Claims (1)
する感熱記録用材料において、下記一般式（１）で示さ
れる化合物を前記顕色剤及び／又は前記増感剤と溶融混
合させて存在させたことを特徴とする感熱記録用材料。 【化１】 （式中、Ｒ1 は−Ｈ、−ＯＨ、−ＮＨ2 又は−ＯＣＨ2
ＣＨ2 ＯＨを示し、Ｒ2は−ＯＨ又は−Ｃn Ｈ2n+1（０
≦ｎ≦５）、Ｒ3 は−Ｈ又は−ＣＯＯＨを示し、これら
は同一であっても、異なってもよい)1. A heat-sensitive recording material having a leuco dye, an acidic developer and a sensitizer, wherein a compound represented by the following general formula (1) is melt-mixed with the developer and / or the sensitizer. A heat-sensitive recording material characterized in that it is present. [Chemical 1] (In the formula, R 1 is —H, —OH, —NH 2 or —OCH 2
CH 2 OH, R 2 is —OH or —C n H 2n + 1 (0
≦ n ≦ 5), R 3 represents —H or —COOH, which may be the same or different.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4217379A JPH0640155A (en) | 1992-07-24 | 1992-07-24 | Heat-sensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4217379A JPH0640155A (en) | 1992-07-24 | 1992-07-24 | Heat-sensitive recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0640155A true JPH0640155A (en) | 1994-02-15 |
Family
ID=16703256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4217379A Withdrawn JPH0640155A (en) | 1992-07-24 | 1992-07-24 | Heat-sensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004083855A (en) * | 2002-06-28 | 2004-03-18 | Osaka Gas Co Ltd | Fluorene-containing resin |
-
1992
- 1992-07-24 JP JP4217379A patent/JPH0640155A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004083855A (en) * | 2002-06-28 | 2004-03-18 | Osaka Gas Co Ltd | Fluorene-containing resin |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19991005 |