JPS61249789A - Thermal recording sheet - Google Patents

Thermal recording sheet

Info

Publication number
JPS61249789A
JPS61249789A JP60093262A JP9326285A JPS61249789A JP S61249789 A JPS61249789 A JP S61249789A JP 60093262 A JP60093262 A JP 60093262A JP 9326285 A JP9326285 A JP 9326285A JP S61249789 A JPS61249789 A JP S61249789A
Authority
JP
Japan
Prior art keywords
color
acylamino acid
recording sheet
dye precursor
overcoat layer
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.)
Granted
Application number
JP60093262A
Other languages
Japanese (ja)
Other versions
JPH0534148B2 (en
Inventor
Masahiro Miyauchi
雅浩 宮内
Haruhiko Ikeda
晴彦 池田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Priority to JP60093262A priority Critical patent/JPS61249789A/en
Publication of JPS61249789A publication Critical patent/JPS61249789A/en
Publication of JPH0534148B2 publication Critical patent/JPH0534148B2/ja
Granted legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/423Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers
    • B41M5/44Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

PURPOSE:To prevent the deterioration of a white paper part and a developed color part due to chemicals and to enhance ink receptivity, in a thermal recording sheet based on a dye precursor and a coupler for allowing said dye precursor to develop a color at the time of heating, by providing an overcoat layer excellent in film characteristics. CONSTITUTION:In a thermal recording sheet having such a system that a dye precursor such as Crystal Violet lactone and an acidic coupler such as a phenol compound are discontinuously dispersed and applied and one of them or both of them is melted under heating to form a color, N-acylamino acid ester, N- acylamino acid amide or N-acylamino acid amine is contained in the overcoat layer based on a water-soluble high-molecular compound provided on the thermal color forming layer. The addition amount of said additive to the overcoat layer is 0.5wt% or more, desirably, 1-60wt% from the aspect of ink receptivity enhancing effect, color forming sensitivity and printability.

Description

【発明の詳細な説明】 (A)産業上の利用分桁 本発明は、染料前、躯体と該染料前駆体を加熱時に発色
させる顕色剤を主たる構成要素とする感熱記録シートに
関し、皮膜特性の秀jたオーバーコート層を設けること
により、白紙部および発色部の薬品による劣化を防上し
、かつインク受理性を向上した感熱記録シートに関する
DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application The present invention relates to a heat-sensitive recording sheet whose main components include a dye precursor, a framework, and a color developer that develops color when the dye precursor is heated. The present invention relates to a heat-sensitive recording sheet that prevents deterioration caused by chemicals in the white paper area and the colored area and improves ink receptivity by providing an excellent overcoat layer.

(R)従来技術およびその間噸点 感熱記録紙には、(1)基質上にカーボンや着色染顔料
を塗工し、その上に不透明熱可融性物質を塗工したもの
で、加熱により不透明層が透明化し下層の着色層による
画像が形成される方式。(2)熱により電子供与体と電
子受容体の錯化合物形成による方式。(3)クリスタル
バイオレットラクトンのごとき染料前1枢体とフェノー
ル化合物の様な酸性顕色剤を不連続に分散、塗工し加熱
により一方又は両者が溶解して発色する方式などがある
。これ等のうち画像の鮮明さ、解像力、画像の色調、カ
スの問題等々総合的に見てすぐjているため(3)の方
式が、一般のファクシミリ、プリンターなどに使用さ力
ている。
(R) Conventional technology and its drawbacks Heat-sensitive recording paper consists of (1) a substrate coated with carbon or colored dyes and pigments, and coated with an opaque thermofusible substance, which becomes opaque when heated; A method in which the layer becomes transparent and an image is formed by the colored layer underneath. (2) A method that uses heat to form a complex between an electron donor and an electron acceptor. (3) There is a method in which a central dye such as crystal violet lactone and an acidic color developer such as a phenol compound are dispersed and applied discontinuously, and one or both are dissolved by heating to develop color. Among these methods, method (3) is most commonly used in general facsimile machines, printers, etc. because it is the best overall in terms of image clarity, resolution, image color tone, and problems with dust.

この種の感熱記録紙に要求される特性として、各種用途
に応じた感度を備えていることはもちろんのことであり
、地肌が白いこと、発色画像が長期間安定で消えないこ
と、記録時にカスが生じないこと、記録時熱ヘッドに付
着(スティッキング)しないこと等々がある。こねらの
要求の多くを備えた優ねたものが製作さj得るが、記録
した後の実用的々取扱い上、可塑剤を多量に含有した消
しゴムや塩化ビニール製の袋に接触した場合、ノパンド
クリームや整髪用オイルの付着した手で触jた場合、現
像処理直後のジアゾ感光紙と重ね合わせた場合、螢光ペ
ンでアンダーライン等の書き込みをした場合等で、画像
が消えたり、地肌が発色カブリを生じ、記録画像の判読
が困難になるという欠点が有る。この消色現゛象は、酸
性顕色剤で開環さねた発色性ラクトン化合物のラクトン
環が、ジブチルフタレート、ジオクチルフタレート、ジ
オクチルアジペートの様な可塑剤やエチレングリコール
の様な螢光ペンの保湿剤の存在下で閉環されてしまうた
めと考えらねている。壕だ、カプリ現象はジアゾ感光紙
の現像液や螢光ペンに含まれる溶剤が顕色剤を溶解し、
染料前駆体と接触させ発色反応をしてしまうためと考え
らjている。
The characteristics required for this type of thermal recording paper include, of course, sensitivity suitable for various uses, as well as a white background, long-term stable colored images that do not fade, and the ability to avoid any noise during recording. There are some problems, such as the fact that there is no sticking to the thermal head during recording, and so on. Although excellent products have been manufactured that meet many of the requirements of the manufacturer, in practical handling after recording, if they come into contact with an eraser containing a large amount of plasticizer or a bag made of vinyl chloride, the If you touch it with hands that have pando cream or hair styling oil on it, if you overlap it with diazo photosensitive paper that has just been developed, or if you write underlines etc. with a fluorescent pen, the image may disappear or the background may appear. However, this method has the disadvantage that it causes color fog, making it difficult to read the recorded image. This decoloring phenomenon is caused by the lactone ring of the color-forming lactone compound that has been ring-opened by an acidic color developer, and the lactone ring of the color-forming lactone compound that has been ring-opened by an acidic color developer. It is thought that this is because the ring is closed in the presence of a humectant. The Capri phenomenon is caused by the solvent contained in the developer of diazo photosensitive paper and the fluorescent pen dissolving the color developer.
It is thought that this is because a coloring reaction occurs when it comes into contact with a dye precursor.

そこで、感熱記録紙上に可塑剤等の浸透を妨げるための
皮膜を形成すわば、この様な現象の起こらないことも提
案さ力ている。(特開昭54−128347号、特開昭
54−3549号)また、本発明者らも、耐薬品性を有
するオーバーコート剤を開発して特願昭55−1825
57号、特願昭56−981号に出願をしている。
Therefore, it has been proposed that this phenomenon can be prevented by forming a film on the heat-sensitive recording paper to prevent the penetration of plasticizers and the like. (Japanese Patent Application Laid-open Nos. 54-128347 and 1982-3549) The present inventors also developed an overcoat agent with chemical resistance and filed a patent application in 1982-1825.
No. 57 and Japanese Patent Application No. 56-981.

しかしながら、オーバーコート層の表面特性に関して、
水溶性高分子化合物を主体としているだめ、感熱記録紙
の表面と裏面が、部分的に接着してしまう、いわゆるブ
ロッキングを生じ易い0この現象は、加工段階で、オー
バーコート層の破壊や紙切1等を引き起こしてしまうの
で、防止対策として、種々の耐水化剤の添加や、離型剤
の添加等が試みらjている。
However, regarding the surface properties of the overcoat layer,
Since the thermosensitive recording paper is mainly composed of water-soluble polymer compounds, it tends to cause so-called blocking, where the front and back sides of the thermal recording paper partially adhere to each other. As preventive measures, attempts have been made to add various waterproofing agents and release agents.

さらに、水や油に対する保護効率の増加を目的として、
オーバーコート層中にフッ素樹脂等の撥水・撥油剤を添
加し、耐水性・耐油性の向上も図られている。
Furthermore, with the aim of increasing the protection efficiency against water and oil,
Water and oil repellents such as fluororesin are added to the overcoat layer to improve water and oil resistance.

しかるに、これらの添加剤は、印刷・スタンプ・サイン
ペンによる筆記等を実施する際、インクの一3= 乾燥が悪かったり、にじみが極めて大きく、即ちインク
受理性が悪く、場合によっては判読不能となってしまう
不都合を生じる。この欠点を改良するだめに吸油量の大
きな白色顔料を添加することにより、ある程度効果を上
げら力るが、フィルム状皮膜の形成阻害、発色感度の低
下、ファクシミリ熱ヘッドの摩耗を生ずるので量的に限
界があり、現状では満足のいくものは得られていない。
However, when printing, stamping, writing with a felt-tip pen, etc., these additives can cause the ink to dry poorly or bleed extremely large, which means poor ink receptivity and, in some cases, to be unreadable. This may cause inconvenience. In order to improve this drawback, adding a white pigment with a large oil absorption amount can be effective to some extent, but the amount is limited because it inhibits the formation of a film-like film, reduces coloring sensitivity, and wears out the facsimile heat head. There are limits to this, and as of now, nothing satisfactory has been achieved.

(・発明の目的 本発明者等は、発色阻害や感度低下、ファクシミリ熱ヘ
ッドの摩耗を生じない、インク受理性の良好なるオーバ
ーコート層を設けた感熱記録シートに関して鋭意検討し
た結果、本発明に到達した。
(・Purpose of the Invention The present inventors have conducted extensive studies on a thermal recording sheet provided with an overcoat layer that has good ink receptivity and does not inhibit color development, decrease sensitivity, or wear out facsimile thermal heads, and as a result, the present inventors have developed the present invention. Reached.

(D)発明の構成 即ち、本発明は、前記(3)の方式の感熱記録シートに
おいて、感熱発色層上に設けた水溶性高分子化合物を主
体としたオーバーコート層中に、N−アシルアミノ酸エ
ステル、N−アシルアミノ酸アミドまたはN−アシルア
ミノ酸アミン塩を含有せしめることを特徴とする特許請
求の範囲と同じ」感熱記録シートを提供することにある
(D) Structure of the Invention That is, the present invention provides that in the heat-sensitive recording sheet of the method (3) above, N-acylamino acid The object of the present invention is to provide a heat-sensitive recording sheet according to the claims, characterized in that it contains an ester, an N-acylamino acid amide, or an N-acylamino acid amine salt.

本発明に用いる主な成分を以下に詳細に説明するが、本
発明の要旨を越えない限り、本発明を限定するものでは
ない。
The main components used in the present invention will be explained in detail below, but the present invention is not limited thereto unless it exceeds the gist of the present invention.

フェノール性物質または有機酸により発色する染料前駆
体の代表例を表−1に示す0 表−1 (1)  クリスタルバイオレットラクトン(2)3−
インドリノ−3−P−ジメチルアミノフェニル−6−シ
メチルアミノフタリ′ド (3)3−ジエチルアミノ−7−クロロフルオラン(4
)3−ジエチルアミノ−7−シクロヘキシルアミノフル
オラン (5)3−ジエチルアミノ−5−メチル−7−t−ブチ
ルフルオラン (6)3−ジエチルアミノ−6−メチル−7−アニリノ
フルオラン (7)3−ジエチルア之ノー6−メチル−′7−p−プ
チルアニリノフルオラン (8)2−(N−フェニル−N−エチル)アミノフルオ
ラン(9)  3−ジエチルアミノ−7−ジベンジルア
ミノフルオラン(In)  3−シクロヘキシルアミノ
−6−クロロフルオラン2(11) 3−ジエチルアミ
ノ−6−メチル−7−キシリジノフルオラン (12) 2−アニリノ−3−メチル−6−(N−エチ
ル−p−トルイジノ)フルオラン (13) 3−ピロリジノ−6−メチル−7−アニリノ
フルオラン(14) 3−ピロリジノ−7−シクロヘキ
シルアミノフルオラン(15) 3−ピペリジノ−6−
メチル−7−トルイジノフルオラン (16) 3−ピペリジノ−6−メチル−7−アニリノ
フルオラン(17) 3− (N−メチルシクロヘキシ
ルアミノ)−6−メチル−7−アニリノフルオラン (18) 3−ジエチルアミノ−7−、(m−)リフル
オロメチルアニリノ)フルオラン (19) 3−ジエチルアミノ−6−メチル−7−クロ
ロフルオラン 次に、本発明に用いられるフェノール性物質または、有
機酸(顕色剤)の代表例を表−2に示す。
Typical examples of dye precursors that develop color with phenolic substances or organic acids are shown in Table 10 Table 1 (1) Crystal violet lactone (2) 3-
Indolino-3-P-dimethylaminophenyl-6-dimethylaminophthalide (3) 3-diethylamino-7-chlorofluorane (4
) 3-diethylamino-7-cyclohexylaminofluorane (5) 3-diethylamino-5-methyl-7-t-butylfluorane (6) 3-diethylamino-6-methyl-7-anilinofluorane (7) 3 -diethylamino-6-methyl-'7-p-butylanilinofluorane (8) 2-(N-phenyl-N-ethyl)aminofluorane (9) 3-diethylamino-7-dibenzylaminofluorane ( In) 3-cyclohexylamino-6-chlorofluorane 2 (11) 3-diethylamino-6-methyl-7-xylidinofluorane (12) 2-anilino-3-methyl-6-(N-ethyl-p- Toluidino) fluorane (13) 3-pyrrolidino-6-methyl-7-anilinofluorane (14) 3-pyrrolidino-7-cyclohexylaminofluorane (15) 3-piperidino-6-
Methyl-7-toluidinofluorane (16) 3-piperidino-6-methyl-7-anilinofluorane (17) 3-(N-methylcyclohexylamino)-6-methyl-7-anilinofluorane ( 18) 3-diethylamino-7-,(m-)lifluoromethylanilino)fluorane (19) 3-diethylamino-6-methyl-7-chlorofluorane Next, the phenolic substance or organic Typical examples of acids (color developers) are shown in Table 2.

表−2 (1) 4.4’−イソプロピリデンジフェノール(2
) 4.4’−イソプロピリデンビス(2−クロルフェ
ノール) (3)4.4’−イソプロピリデンビス(2−ターシャ
リ−ブチルフェノール) (4) 4.4’→カンダリープチリデンジフエノール
(5) 4 、4’7(1−メチル−ノルマル−ヘキシ
リデン)ジフェノール (6)4−フェニルフェノール (7) 4−ヒドロキシジフェノキシド(8)メチル−
4−ヒドロキシベンゾエート(9)フェニル−4−ヒド
ロキシベンゾエート(10)  4−ヒドロキシアセト
フェノン(11)サリチル酸アニリド (12)  4.4’−シクロヘキシリデンジフェノー
ル(13)  4.4’→クロヘキシリゾ/ビス(2−
メチルフェノール) (14)  4.4’−ベンジリデンジフェノール(1
5)  4.4’−チオビス(6−ターシャリ−ブチル
−3メチルフェノール) (16)  4.、4’τイソプ、ロピリデンビス(2
−メチルフェノール) (17)  4.4’−エチレンビス(2−メチルフェ
ノール)(18) 、4 、4’−シクロヘキシリデン
ビス(2−イソプロピルフェノール) (19)  2.2’−ジヒドロキシジフェニル(20
)  2.2’−メチレンビス(4−クロロフェノール
)(21)  2.2’−メチレンビス(4−メチル−
6−t−ブチルフェノール) (22)  1. 1’−ビス(4−ヒドロキシフェノ
ール)−シクロヘキサン (23)  2.2−ヒス(4′−ヒドロキシフェニル
)フロパン(24)ノボラック型フェノール樹脂 (25)ハロゲン化ノボラック型フェノール樹脂(26
)α−ナフトール 、、(27)  β−ナフトール (28)  3.5−ジ−t−ブチルサリチル酸(29
)3.5〜ジーα−メチルベンジルサリチル酸(31)
)  3−メチル−5−重−ブチルサリチル酸(31)
フタル酸モノアニリドバラエトキシ安息香酸(32)バ
ラベンジルオキシ安息香酸 (33)バラヒドロキシ安息香酸ベンジルエステル本発
明の感熱記録紙は、次の方法によって得ることが、でき
る。即ち、フェノール物質または有機酸、該フェノール
物質または有機酸で発色する染料前駆体を別々にあるい
は同時に粉砕機で微細粒子状に粉砕分散し、結合剤、顔
料等と混合、し、必要に応じて各種添加剤を加えること
により塗液を調製する。
Table-2 (1) 4.4'-isopropylidenediphenol (2
) 4.4'-Isopropylidene bis(2-chlorophenol) (3) 4.4'-isopropylidene bis(2-tert-butylphenol) (4) 4.4'→Candalybutylidene diphenol (5) 4 , 4'7(1-methyl-n-hexylidene)diphenol (6) 4-phenylphenol (7) 4-hydroxydiphenoxide (8) Methyl-
4-Hydroxybenzoate (9) Phenyl-4-hydroxybenzoate (10) 4-Hydroxyacetophenone (11) Salicylic acid anilide (12) 4.4'-Cyclohexylidene diphenol (13) 4.4'→Chlohexylizo/bis(2) −
Methylphenol) (14) 4.4'-benzylidenediphenol (1
5) 4.4'-thiobis(6-tert-butyl-3methylphenol) (16) 4. , 4'τ isop, ropylidene bis(2
-methylphenol) (17) 4,4'-ethylenebis(2-methylphenol) (18) ,4,4'-cyclohexylidenebis(2-isopropylphenol) (19) 2,2'-dihydroxydiphenyl( 20
) 2.2'-methylenebis(4-chlorophenol) (21) 2.2'-methylenebis(4-methyl-
6-t-butylphenol) (22) 1. 1'-bis(4-hydroxyphenol)-cyclohexane (23) 2.2-his(4'-hydroxyphenyl)furopane (24) Novolac type phenolic resin (25) Halogenated novolac type phenolic resin (26)
) α-naphthol, (27) β-naphthol (28) 3.5-di-t-butylsalicylic acid (29
) 3.5-di-α-methylbenzyl salicylic acid (31)
) 3-Methyl-5-heavy-butylsalicylic acid (31)
Phthalic acid monoanilide Barra ethoxybenzoic acid (32) Barra benzyloxybenzoic acid (33) Barra hydroxybenzoic acid benzyl ester The thermal recording paper of the present invention can be obtained by the following method. That is, a phenolic substance or an organic acid, and a dye precursor that develops color with the phenolic substance or organic acid are ground and dispersed separately or simultaneously in a grinder into fine particles, mixed with a binder, a pigment, etc., and as necessary. A coating liquid is prepared by adding various additives.

結合剤としては、例えば、澱粉類、ヒドロキシエチルセ
ルロース、メチルセルロース、ポリビニルアルコール、
スチレン−無水マレイン酸共重合体、スチレン−ブタジ
ェン共重合体、ポリアクリルアミド、カルボキシメチル
セルロース、アラビアゴム、カゼイン等の水溶性結合剤
スチレン−ブタジェンラテックス等のラテックス類を用
いることができる。
Examples of binders include starches, hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol,
Water-soluble binders such as styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyacrylamide, carboxymethyl cellulose, gum arabic, casein, etc. Latexes such as styrene-butadiene latex can be used.

顔料としては、ケイソウ土、メルク、カオリン、焼成カ
オリン、炭酸カルシウム、炭酸マグネシウム、酸化チタ
ン、酸化亜鉛、酸化ケイ素、水酸化アルミニウム、尿素
−ホルマリン樹脂などが挙げられる。
Examples of the pigment include diatomaceous earth, Merck, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and the like.

その他に、ステアリン酸亜鉛、ステアリン酸カルシウム
等の高級脂肪酸金属塩、パラフィン、酸化ハラフィン、
ポリエチレン、酸化ポリエチレン、ステアリン酸アミド
、カスターワックス等のワックス類を、また、ジオクチ
ルスルホコハク酸ナトリウム等の湿潤剤、ベンゾフェノ
ン系、ベンゾトリアゾール系などの紫外線吸収剤、さら
に界面活性剤、螢光染料などが用いらj得る。
In addition, higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin, halafine oxide,
Waxes such as polyethylene, polyethylene oxide, stearamide, castor wax, wetting agents such as sodium dioctyl sulfosuccinate, ultraviolet absorbers such as benzophenone and benzotriazole, surfactants, fluorescent dyes, etc. get used.

本発明による感熱記録材に用いらねる支持体としては紙
が主として用いらjるが、各種不織布、プラスチックフ
ィルム、合成紙、金属箔等あるいはこれらを組み合わせ
た複合シートを任意に用いることができる。
Although paper is mainly used as the support for the heat-sensitive recording material according to the present invention, various nonwoven fabrics, plastic films, synthetic papers, metal foils, etc., or composite sheets made of a combination of these can also be used as desired.

次に、本発明に於けるオーバーコート層を形成する素材
について述べると、一般に、水溶性高分子化合物が良く
、アルギン酸塩、ヒドロキシエチルセルロース、メチル
セルロース、カルボキシメチルセルロース、ポリビニル
アルコール、ポリビニルアルコールとアクリルアミド等
のアクリル系単骨体とのグラフト共重合体の曝用または
2種以上の併用したものが良い。
Next, regarding the material forming the overcoat layer in the present invention, water-soluble polymer compounds are generally preferred, and acrylic materials such as alginate, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, and polyvinyl alcohol and acrylamide are preferred. It is preferable to use a graft copolymer with a single skeleton or to use two or more types in combination.

また、例えば、アクリル系ラテックス、ビニル系アクリ
ル樹脂、酢酸ビニル・エチレン共重合物、シリコン・ア
クリレ−1脂、スチレン・ブタジェン系ラテックス等の
皮膜形成高分子エマルジαンの導入も図らねており、効
果を挙げているが、水溶性高分子化合物が主体である事
が必要である。
We are also planning to introduce film-forming polymer emulsions such as acrylic latex, vinyl acrylic resin, vinyl acetate/ethylene copolymer, silicone/acrylate-1 resin, and styrene/butadiene latex. Although it has been effective, it is necessary that the main ingredient is a water-soluble polymer compound.

さらには、耐水化剤、紫外線吸収剤、離型剤の1種また
は2種以上を併用して、耐水性・耐光性を賦与し、粘着
による皮膜剥離(ブロッキング)を防止したものが好ま
しい。
Furthermore, it is preferable to use one or more of a water resistant agent, an ultraviolet absorber, and a mold release agent in combination to impart water resistance and light resistance and prevent film peeling (blocking) due to adhesion.

本発明の特徴であるN−アシルアミノ酸エステル、N−
アシルアミノ酸アミドまだはN−アシルアミノ酸アミン
塩は、例えば特公昭53−13434号に公示さねてい
るいわゆるアミノ酸系ゲル化剤が使用可能である。更に
詳細には、(1)N−カプロイル−グリシンステアリル
アミド(2) N”・N6−ジカプロイルリジンラウリ
ルアミド(3)N−ラウロイルグルタミン酸ジ−ラウリ
ルエステル(4) N”* N”−シカブロイルリジン
ステアリルアミン塩(5)N−ラウロイルグルタミン酸
ジラウリルアミド(6)N−ラウロイルグルタミン酸ジ
ブチルアミド(7)N−カプロイルグルタミン酸ジラウ
リルアミド(8)N−ラウロイルグルタミン酸ステアリ
ルアミド(9) Na・No−シカブロイルリジンラウ
リルエステル(10)  N”・No−ジステアロイル
リジンオクチルエステル(11)  N−ステアロイル
グリシンラウリルアミド(12) pJ−バルミトイル
−i−アミノカプロン酸ラウリルエステル (13)  Na・No−シカプリロイルリジンステア
リルアミン塩(14)  N“・Na1−ジラウロイル
リジンステアリルアミン塩(15) N−ラウロイルバ
リンラウリルアミン塩(16) N−ラウロイルグルタ
ミン酸ジオクチルアミド(17) N−ラウロイルフェ
ニルアラニンラウリルアミド等が挙げられるが、原料と
なるN−アシルアミノ酸とアルコールまたはアミンの種
々の組み合わせが可能である。また、単用添加ばかりで
なく併用添加も有効である。
N-acyl amino acid ester, N-
As the acylamino acid amide or N-acylamino acid amine salt, for example, a so-called amino acid-based gelling agent disclosed in Japanese Patent Publication No. 13434/1988 can be used. More specifically, (1) N-caproyl-glycine stearylamide (2) N''.N6-dicaproylridine laurylamide (3) N-lauroylglutamic acid di-lauryl ester (4) N''*N''-ca Broyl lysine stearylamine salt (5) N-lauroylglutamic acid dilaurylamide (6) N-lauroylglutamic acid dibutylamide (7) N-caproylglutamic acid dilaurylamide (8) N-lauroylglutamic acid stearylamide (9) Na/No -Cicabroylridine lauryl ester (10) N''.No-distearoylridine octyl ester (11) N-stearoylglycine laurylamide (12) pJ-valmitoyl-i-aminocaproic acid lauryl ester (13) Na.No-Cicapri Leuroylridine stearylamine salt (14) N"・Na1-dilauroylridine stearylamine salt (15) N-lauroylvaline laurylamine salt (16) N-lauroylglutamic acid dioctylamide (17) N-lauroylphenylalanine laurylamide, etc. However, various combinations of the raw material N-acyl amino acid and alcohol or amine are possible.Additionally, not only single addition but also combined addition is effective.

−IQ−−+ なお、本発明でのN−アシルアミノ酸エステル、N−ア
シルアミノ酸アミドまたはN−アシルアミノ酸アミン塩
のオーバーコート層中への添加量は一〇、5重量%以上
、望ましくは、1〜60重量%がインク受理性向上効果
、発色感度、印字性の面から良好である。なぜなら、添
加量が0.5重量%より少ないと、インク受理性向上効
果が十分に得られない傾向にある。まだ、60重量%を
越えると、インク受理性向上効果は十分であるが、発色
層への熱伝導を明害するため、発色感度や印字性に悪影
響を及ぼす傾向にある。
-IQ--+ In the present invention, the amount of N-acylamino acid ester, N-acylamino acid amide, or N-acylamino acid amine salt added to the overcoat layer is 10.5% by weight or more, preferably, A content of 1 to 60% by weight is good in terms of ink receptivity improvement effect, color development sensitivity, and printability. This is because if the amount added is less than 0.5% by weight, the effect of improving ink receptivity tends to be insufficient. If the amount exceeds 60% by weight, the effect of improving ink receptivity is sufficient, but the heat conduction to the coloring layer is obstructed, which tends to have an adverse effect on coloring sensitivity and printability.

(匂 実施例 実施例によって本発明をさらに詳しく説明する。(Odor Example The present invention will be explained in more detail by way of examples.

A液 B液 〔p−ヒドロキシ安息香酸ベンジル     ・曲・4
0IA液とD液を別々のボールミルで48時間粉砕、分
散し、次の配合で塗液を調製した。
A liquid B liquid [benzyl p-hydroxybenzoate・Song・4
Solution 0IA and Solution D were ground and dispersed in separate ball mills for 48 hours, and a coating solution was prepared using the following formulation.

調製した塗液を坪量491 / m”の原紙に乾燥後の
塗布量が5117m”になるように塗工し、60℃で1
分間乾燥した後、スーパー・カレンダーでベック平滑度
が100秒以上となるようにして、感熱記録紙を作製し
た。
The prepared coating solution was applied to base paper with a basis weight of 491/m" so that the coated amount after drying was 5117 m", and the coating was heated at 60°C for 1
After drying for a minute, a heat-sensitive recording paper was prepared by using a super calendar to obtain Bekk smoothness of 100 seconds or more.

C液 り液 り液をボールミルにて48時間粉砕分散した。C liquid liquid The liquid was pulverized and dispersed in a ball mill for 48 hours.

0液に対してD液を3g添加することにより調製したオ
ーバーコート塗液を乾燥膜厚が約6μmになるように上
記感熱記録紙に塗布し、スーパー・カレンダーにて、ベ
ック平滑度が約800秒となるようにし、オーバーコー
ト感熱配録紙を作製した。
An overcoat coating liquid prepared by adding 3 g of liquid D to liquid 0 was applied to the above heat-sensitive recording paper so that the dry film thickness was approximately 6 μm, and the Bekk smoothness was approximately 800 using a super calender. An overcoated heat-sensitive recording paper was prepared.

比較例 実施例の0液のみを用いる以外は同様にして、オーバー
コート感熱記録紙を作製した。
Comparative Example An overcoated thermal recording paper was produced in the same manner as in Example except that only the 0 liquid was used.

試験例 耐ジアゾ現像液試験: 実施例および比較例で得たオーバーコート感熱記録紙を
、松下電送■製パナファックスUP−920にて光学濃
度1.20に発色させた後、オーバーコート処理面に、
現像処理後のジアゾ感光紙(現像液アクチベータPD)
面と重ね合わせた後、室温にて3分間放置して地肌部の
カプリ、発色部の劣化の有無を観察しだ。上記試験によ
り、オーバーコート層の耐薬品性の有無、即ち皮膜完成
度を把握することができる。
Test Example Diazo developer resistance test: The overcoated thermal recording paper obtained in the Examples and Comparative Examples was developed to an optical density of 1.20 using Panafax UP-920 manufactured by Matsushita Densen, and then the overcoated surface was ,
Diazo photosensitive paper after development (developer activator PD)
After overlapping the surface, it was left at room temperature for 3 minutes and observed for deterioration of the capri in the background area and the colored area. Through the above test, it is possible to determine whether or not the overcoat layer has chemical resistance, that is, the degree of film completion.

特に白紙部を観察すると、皮膜で保護さねていない箇所
がジアゾ現像液で黒発色することから、ハジキ・ピンホ
ール・ムラの存在が識別できる。
In particular, when observing blank areas, the presence of repellents, pinholes, and unevenness can be identified because the areas that are not protected by the film turn black with the diazo developer.

インクにじみ性試験: 実施例および比較例のオーバーコート感熱記録紙の白紙
部に、シャチハタ工業■製、商品名:シャチハタXスタ
ンバ−(染料系インキ)およびパイロット萬年筆■製、
パイロットスタンプパッドによりスタンプをし、室温に
て24時間放置した後、インクのにじみを観測した。
Ink bleed test: On the blank part of the overcoated thermal recording paper of Examples and Comparative Examples, Shachihata Co., Ltd., product name: Shachihata
A stamp was applied using a pilot stamp pad, and after being left at room temperature for 24 hours, ink bleeding was observed.

結果として、比較例のものは、ジアゾ感光紙用現像液に
よる地肌のカプリ現象による発色部の判読劣化は生じな
かったが、スタンプのインクにじみが激しく、判読がほ
とんど不可能になってしまった。
As a result, in the comparative example, although there was no deterioration in legibility of the colored part due to the capri phenomenon of the background caused by the developer for diazo photosensitive paper, the ink bleeding of the stamp was so severe that legibility became almost impossible.

一方、本発明品は、ジアゾ感光紙用現像液による判読劣
化現象のないことはもちろんのこと、スタンプ等のイン
クにじみが全くなく、細かい部分の文字のつぶjさえも
見られず、極めて満足のいくインク受理性を得ることが
できた。
On the other hand, the product of the present invention not only has no deterioration in legibility caused by the developer for diazo photosensitive paper, but also has no ink bleeding from stamps, etc., and no visible blemishes of letters in small areas, which is extremely satisfactory. I was able to obtain good ink receptivity.

(F)発明の効果 染料前駆体を用いた感熱記録シートにおいて画像劣化や
インクにじみのない高信頼性のものが得られた。ファク
シミリ用紙、POi9ラベル、切符、計測記録チャート
等で、極めて高い利用価値が認めらjるものであり、今
後、更に多くの分野で使用される可能性がある。
(F) Effects of the Invention A highly reliable thermosensitive recording sheet without image deterioration or ink bleeding was obtained using the dye precursor. It has been found to have extremely high utility value in facsimile paper, POi9 labels, tickets, measurement record charts, etc., and there is a possibility that it will be used in even more fields in the future.

Claims (1)

【特許請求の範囲】[Claims] (1)無色ないし淡色の染料前駆体と、加熱時反応して
該染料前駆体を発色せしめる顕色剤を主たる構成要素と
する感熱発色層を設け、更に、この感熱発色層の上に水
溶性高分子化合物を主体とするオーバーコート層を設け
た感熱記録シートにおいて、該オーバーコート層中に、
N−アシルアミノ酸エステル、N−アシルアミノ酸アミ
ドまたはN−アシルアミノ酸アミン塩を含有することを
特徴とする感熱記録シート。
(1) A thermosensitive coloring layer is provided whose main components are a colorless or light-colored dye precursor and a color developer that reacts with the dye precursor when heated, and furthermore, a water-soluble coloring layer is provided on this thermosensitive coloring layer. In a heat-sensitive recording sheet provided with an overcoat layer mainly composed of a polymer compound, in the overcoat layer,
A heat-sensitive recording sheet characterized by containing an N-acylamino acid ester, an N-acylamino acid amide, or an N-acylamino acid amine salt.
JP60093262A 1985-04-30 1985-04-30 Thermal recording sheet Granted JPS61249789A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60093262A JPS61249789A (en) 1985-04-30 1985-04-30 Thermal recording sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60093262A JPS61249789A (en) 1985-04-30 1985-04-30 Thermal recording sheet

Publications (2)

Publication Number Publication Date
JPS61249789A true JPS61249789A (en) 1986-11-06
JPH0534148B2 JPH0534148B2 (en) 1993-05-21

Family

ID=14077569

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60093262A Granted JPS61249789A (en) 1985-04-30 1985-04-30 Thermal recording sheet

Country Status (1)

Country Link
JP (1) JPS61249789A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01264890A (en) * 1988-04-15 1989-10-23 Kanzaki Paper Mfg Co Ltd Heat sensitive recording material
JPH02112983A (en) * 1988-10-21 1990-04-25 Mitsubishi Paper Mills Ltd Heat sensitive recording material
US7071144B2 (en) 2000-08-09 2006-07-04 Mitsubishi Paper Mills, Ltd. Thermal recording material
DE10197272B4 (en) * 2001-09-28 2015-10-29 Mitsubishi Paper Mills Ltd. Thermal recording material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01264890A (en) * 1988-04-15 1989-10-23 Kanzaki Paper Mfg Co Ltd Heat sensitive recording material
JPH02112983A (en) * 1988-10-21 1990-04-25 Mitsubishi Paper Mills Ltd Heat sensitive recording material
US7071144B2 (en) 2000-08-09 2006-07-04 Mitsubishi Paper Mills, Ltd. Thermal recording material
DE10197272B4 (en) * 2001-09-28 2015-10-29 Mitsubishi Paper Mills Ltd. Thermal recording material

Also Published As

Publication number Publication date
JPH0534148B2 (en) 1993-05-21

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