JP2014136426A - Reversible thermosensitive recording material and reversible thermosensitive recording medium - Google Patents

Reversible thermosensitive recording material and reversible thermosensitive recording medium Download PDF

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JP2014136426A
JP2014136426A JP2013007933A JP2013007933A JP2014136426A JP 2014136426 A JP2014136426 A JP 2014136426A JP 2013007933 A JP2013007933 A JP 2013007933A JP 2013007933 A JP2013007933 A JP 2013007933A JP 2014136426 A JP2014136426 A JP 2014136426A
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reversible thermosensitive
thermosensitive recording
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protective layer
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JP6139142B2 (en
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Shintaro Inomata
慎太郎 猪股
Kaori Tsunoda
香織 角田
Masamitsu Nakanishi
真備 中西
Kiyoshi Hasegawa
潔 長谷川
Yoichiro Shinotani
洋一郎 篠谷
Yoshitaka Toda
嘉孝 戸田
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Kyodo Printing Co Ltd
JR East Mechatronics Co Ltd
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Kyodo Printing Co Ltd
JR East Mechatronics Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a reversible thermosensitive recording material which is improved in printing durability and a reversible thermosensitive recording medium which is improved in printing durability and flexural strength using the reversible thermosensitive recording material.SOLUTION: A reversible thermosensitive recording material 1 is a laminate which comprises: a reversible thermosensitive recording layer provided on a support; an anchor layer which is provided on the reversible thermosensitive recording layer and composed of a resin obtained by condensation of a compound having an isocyanate group and a compound having a hydroxyl group; and a protective layer composed of a resin provided on the anchor layer, wherein the compound having a hydroxyl group of the anchor layer has a glass transition temperature of exceeding 40°C and 90°C or less, a hydroxyl value of less than 150 mgKOH/g and a thickness of exceeding 0.2 μm and less than 2.5 μm, and the protective layer contains 3 to 11 pts.wt. of a tetrafluoroethylene resin and 12 to 17 pts.wt. of silica based on 100 pts.wt. of an ultraviolet curing resin containing an acrylate having a pentaerythritol group and a dipentaerythritol group and an urethane acrylate and has a layer thickness of 4 μm or more and less than 7 μm.

Description

本発明は、加熱温度及び加熱後の冷却速度の違いにより発色と消色とを発現し得る可逆性感熱記録材料に関し、さらにこの可逆性感熱記録材料をカード等の基材に積層した可逆性感熱記録媒体に関する。   The present invention relates to a reversible thermosensitive recording material capable of developing color and decoloring depending on the difference in heating temperature and cooling rate after heating, and further, reversible thermosensitive material in which the reversible thermosensitive recording material is laminated on a substrate such as a card. The present invention relates to a recording medium.

可逆性感熱記録材料は、ロイコ色素と顕減色剤とを含む可逆性感熱記録層を支持体上に備え、この可逆性感熱記録層が加熱されることにより可逆的に色素の発色と消色とが起こることを利用し、可逆性感熱記録層上で情報を書き換え可能としたものである。   The reversible thermosensitive recording material comprises a reversible thermosensitive recording layer containing a leuco dye and a developer / decolorizer on a support, and the reversible thermosensitive recording layer is heated to reversibly develop and decolorize the dye. This makes it possible to rewrite information on the reversible thermosensitive recording layer.

ロイコ色素及び顕減色剤を含む可逆性感熱記録材料は、様々な記録媒体に利用されており、可逆性感熱記録材料をPET−Gのような基材上に積層したプリペイドカード又はICカード等の記録媒体においては、書き換え可能な情報をカード上に表示するために用いられている。プリペイドカード及びICカードでは、カード支持体上に設けられた可逆性感熱記録層を保護するため、熱硬化性樹脂又は紫外線硬化性樹脂で形成された保護層が可逆性感熱記録層上に設けられている。   A reversible thermosensitive recording material containing a leuco dye and a developer color reducing agent is used in various recording media, such as a prepaid card or an IC card in which a reversible thermosensitive recording material is laminated on a substrate such as PET-G. In a recording medium, it is used for displaying rewritable information on a card. In prepaid cards and IC cards, a protective layer formed of a thermosetting resin or an ultraviolet curable resin is provided on the reversible thermosensitive recording layer in order to protect the reversible thermosensitive recording layer provided on the card support. ing.

可逆性感熱記録層を備える可逆性感熱材料又は可逆性感熱記録媒体は、印字機のサーマルヘッドにより保護層が加熱されることにより、可逆性感熱記録層に熱が伝わり、情報が書き換えられる。
ところが、繰り返し保護層が加熱されることにより、保護層と可逆性感熱記録層との剥離及び/又は保護層上に発生した傷による文字かすれ等の問題が発生していた。
また、印字機において、カードの書き換えが繰り返し行われることにより、サーマルヘッドに保護層の成分や傷に起因する汚れが発生し、保守点検を頻繁に行う必要があった。
In a reversible thermosensitive material or a reversible thermosensitive recording medium having a reversible thermosensitive recording layer, heat is transmitted to the reversible thermosensitive recording layer and information is rewritten when the protective layer is heated by a thermal head of a printing press.
However, when the protective layer is repeatedly heated, problems such as peeling of the protective layer and the reversible thermosensitive recording layer and / or blurring of characters due to scratches generated on the protective layer have occurred.
Further, in the printing machine, the rewriting of the card is repeatedly performed, so that the thermal head is contaminated due to the components of the protective layer and scratches, and it is necessary to frequently perform maintenance and inspection.

保護層の傷に関しては、保護層を形成する樹脂成分の耐熱性を向上すると共に、硬度を高めることにより、傷の防止が図られている。しかし、保護層の硬度を高めると、可逆性感熱記録媒体において、曲げ強度の低下が生じ、可逆性感熱記録媒体が破損しやすくなるという問題がある。
なお、保護層と可逆性感熱記録層との間にアンカー層を設けることにより、保護層と可逆性感熱記録層との接着性を改善できることが知られている(特許文献1参照)。
Regarding the scratches on the protective layer, the heat resistance of the resin component forming the protective layer is improved and the hardness is increased to prevent the scratches. However, when the hardness of the protective layer is increased, there is a problem in that the bending strength of the reversible thermosensitive recording medium is lowered and the reversible thermosensitive recording medium is easily damaged.
It is known that the adhesion between the protective layer and the reversible thermosensitive recording layer can be improved by providing an anchor layer between the protective layer and the reversible thermosensitive recording layer (see Patent Document 1).

特許文献1:特開平1−133781号公報     Patent Document 1: Japanese Patent Laid-Open No. 1-133781

本発明は、印字耐久性を向上させた可逆性感熱記録材料及び印字耐性と曲げ強度の向上した可逆性感熱記録媒体を提供することを目的とする。   An object of the present invention is to provide a reversible thermosensitive recording material with improved printing durability and a reversible thermosensitive recording medium with improved printing durability and bending strength.

本発明者らは、可逆性感熱記録層と保護層との接着性を良くするために設けられているアンカー層に注目し、鋭意研究をすすめたところ、アンカー層を形成する樹脂の種類とアンカー層の膜厚が、可逆性感熱記録材料の保護層の印字耐久性、そして、曲げ強度に影響を与えていることを見出した。
なお、前述したように、特許文献1は、可逆性感熱記録層と保護層との接着性を良くするために、アンカー層を設けることを開示するものであるが、アンカー層が可逆性記録媒体の曲げ強度及び保護層の耐久性に関与することを示唆する記載はない。
The present inventors paid attention to an anchor layer provided to improve the adhesion between the reversible thermosensitive recording layer and the protective layer, and conducted extensive research. As a result, the types of resins forming the anchor layer and the anchors were investigated. It has been found that the film thickness of the layer affects the printing durability and the bending strength of the protective layer of the reversible thermosensitive recording material.
As described above, Patent Document 1 discloses providing an anchor layer in order to improve the adhesion between the reversible thermosensitive recording layer and the protective layer. The anchor layer is a reversible recording medium. There is no description suggesting that it is involved in the bending strength and the durability of the protective layer.

さらに、本発明者らは、保護層に滑剤として含まれるシリコーンオイルがサーマルヘッドの汚れの一因であることを見出し、シリコーンオイルを含まない保護層について検討してきた。しかし、保護層にシリコーンオイルを含ませないと、サーマルヘッドの滑りが悪くなるため、保護層が傷つきやすく印字耐久性が低下するという問題に直面した。
また、保護層としてウレタンアクリレートを使用すると、300回もの書き換えに耐え切れないという問題にも直面した。
しかし、さらに検討を進めた結果、(1)アンカー層の樹脂成分を、イソシアネート基を有する化合物と、ガラス転移温度が40℃を超え、90℃以下であり、水酸基価が150mgKOH/g未満である水酸基を有する化合物とが縮合した樹脂とし、膜厚を調整すること、及び、(2)保護層の樹脂にペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとウレタンアクリレートとを含み、四フッ化エチレン樹脂とシリカとを含有すること、および保護層の膜厚を調整することで、保護層の印字耐久性が改善されることを見出し、本発明を完成するに至った。
Furthermore, the present inventors have found that silicone oil contained as a lubricant in the protective layer contributes to the contamination of the thermal head, and have studied a protective layer that does not contain silicone oil. However, if silicone oil is not included in the protective layer, the thermal head slips, resulting in a problem that the protective layer is easily damaged and the printing durability is lowered.
In addition, when urethane acrylate was used as the protective layer, we faced the problem that it could not withstand 300 times of rewriting.
However, as a result of further investigation, (1) the resin component of the anchor layer is a compound having an isocyanate group, a glass transition temperature of more than 40 ° C. and 90 ° C. or less, and a hydroxyl value of less than 150 mgKOH / g. A resin condensed with a compound having a hydroxyl group, adjusting the film thickness, and (2) a resin for the protective layer containing an acrylate having a pentaerythritol group or a dipentaerythritol group and a urethane acrylate, and containing tetrafluoroethylene It has been found that the printing durability of the protective layer is improved by containing the resin and silica and adjusting the film thickness of the protective layer, and the present invention has been completed.

本発明の可逆性感熱記録材料は、支持体上に設けられた可逆性感熱組成物を含有する可逆性感熱記録層と、可逆性感熱記録層上に設けられたイソシアネート基を有する化合物と水酸基を有する化合物とが縮合した樹脂からなるアンカー層と、アンカー層上に設けられた保護層とを有する積層体であって、水酸基を有する化合物は、ガラス転移温度が40℃を超え90℃以下であり、水酸基価が150mgKOH/g未満であり、アンカー層の厚みは、0.2μmを超え2.5μm未満であり、保護層は、ウレタンアクリレートとペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとを含む紫外線硬化樹脂100重量部に対し四フッ化エチレン樹脂を3〜11重量部及びシリカを12〜17重量部含有しており、かつ層厚が4μm以上7μm未満であることを特徴とする。
また、本発明の可逆性感熱記録媒体は、上記可逆性感熱記録材料の支持体に基材を積層させたことを特徴とする。
The reversible thermosensitive recording material of the present invention comprises a reversible thermosensitive recording layer containing a reversible thermosensitive composition provided on a support, a compound having an isocyanate group and a hydroxyl group provided on the reversible thermosensitive recording layer. A compound having an anchor layer made of a resin condensed with a compound having a protective layer provided on the anchor layer, and the compound having a hydroxyl group has a glass transition temperature of more than 40 ° C. and 90 ° C. or less. The hydroxyl value is less than 150 mgKOH / g, the thickness of the anchor layer is more than 0.2 μm and less than 2.5 μm, and the protective layer contains urethane acrylate and an acrylate having a pentaerythritol group or a dipentaerythritol group. Layer containing 3 to 11 parts by weight of tetrafluoroethylene resin and 12 to 17 parts by weight of silica with respect to 100 parts by weight of the ultraviolet curable resin, and a layer The thickness is 4 μm or more and less than 7 μm.
The reversible thermosensitive recording medium of the present invention is characterized in that a substrate is laminated on the support of the reversible thermosensitive recording material.

本発明の可逆性感熱記録材料は、サーマルヘッドによる加熱を繰り返しても保護層の表面に傷が発生しにくく、印字が濃いという効果を有する。
本発明の可逆性感熱記録媒体は、保護層の表面に傷が発生しにくく、印字が濃いという効果に加え、曲げ強度があるため、破損し難い。
The reversible thermosensitive recording material of the present invention has an effect that the surface of the protective layer is hardly scratched even when heating by a thermal head is repeated, and printing is dark.
The reversible thermosensitive recording medium of the present invention is less likely to be damaged because it has a bending strength in addition to the effect that the surface of the protective layer is hardly scratched and the printing is dark.

本発明の可逆性感熱記録媒体の一例を示す模式図である。It is a schematic diagram which shows an example of the reversible thermosensitive recording medium of this invention.

以下、本発明を実施形態に基づいて詳細に説明する。
本実施形態の可逆性感熱記録材料は、支持体上に設けられた可逆性感熱組成物を含有する可逆性感熱記録層と、可逆性感熱記録層上に設けられたイソシアネート基を有する化合物と水酸基を有する化合物とが縮合した樹脂からなるアンカー層と、アンカー層上に設けられた保護層とを有する積層体であって、上記水酸基を有する化合物は、ガラス転移温度が40℃を超え、90℃以下であり、水酸基価が150mgKOH/g未満であり、上記アンカー層の厚みは、0.2μmを超え、2.5μm未満である。さらに、上記保護層は、ウレタンアクリレートとペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとを含む紫外線硬化樹脂100重量部に対し四フッ化エチレン樹脂が3〜11重量部、シリカが12〜17重量部が含有されており、かつ層厚が4μm以上、7μ未満μmである。
Hereinafter, the present invention will be described in detail based on embodiments.
The reversible thermosensitive recording material of the present embodiment comprises a reversible thermosensitive recording layer containing a reversible thermosensitive composition provided on a support, a compound having an isocyanate group and a hydroxyl group provided on the reversible thermosensitive recording layer. And a protective layer provided on the anchor layer, wherein the compound having a hydroxyl group has a glass transition temperature of more than 40 ° C., 90 ° C. The hydroxyl value is less than 150 mgKOH / g, and the thickness of the anchor layer is more than 0.2 μm and less than 2.5 μm. Further, the protective layer is composed of 3 to 11 parts by weight of a tetrafluoroethylene resin and 12 to 17 parts by weight of silica with respect to 100 parts by weight of an ultraviolet curable resin containing urethane acrylate and an acrylate having a pentaerythritol group or a dipentaerythritol group. Part is contained, and the layer thickness is 4 μm or more and less than 7 μm.

支持体は、ポリエチレンテレフタレート(PET)、ポリアセテート、ポリスチレン(PS)、エボキシ樹脂、ポリ塩化ビニル(PVC)及びポリカーボネート(PC)等の合成樹脂シート又は合成紙等を用いることができる。支持体の厚さは通常、20〜300μm程度である。   As the support, a synthetic resin sheet or synthetic paper such as polyethylene terephthalate (PET), polyacetate, polystyrene (PS), epoxy resin, polyvinyl chloride (PVC), and polycarbonate (PC) can be used. The thickness of the support is usually about 20 to 300 μm.

可逆性感熱記録層は、加熱温度及び加熱後の冷却速度の違いにより相対的に発色した状況を形成し得る可逆性感熱組成物を含有する樹脂層であり、熱によって可逆的に発色/消色を繰り返す層である。可逆性感熱組成物は、ロイコ染料及び顕減色剤により構成される。ロイコ染料および顕減色剤としては、可逆性感熱組成物に用いられている従来公知の材料を使うことができる。   A reversible thermosensitive recording layer is a resin layer containing a reversible thermosensitive composition that can form a relatively colored state due to the difference in heating temperature and cooling rate after heating. It is a layer that repeats. The reversible thermosensitive composition is composed of a leuco dye and a developer / color reducing agent. As the leuco dye and the developing / subtracting color reducing agent, conventionally known materials used in the reversible thermosensitive composition can be used.

ロイコ染料としては、クリスタルバイオレットラクトン、3−インドリノ−3−p−ジメチルアミノフェニル−6−ジメチルアミノフタリド、3−ジエチルアミノ−7−クロロフルオラン、2−(2−クロルフェニルアミン)−ジエチルアミノフルオラン、2−(2−フルオロフェニルアミノ)−6−ジエチルアミノフルオ)ラン、2−(2−フルオロフェニルアミノ)−6−ジ−n−ブチルアミノフルオラン、3−ジエチルアミノ−7−シクロヘキシルアミノフルオラン、3−ジエチルアミノ−5−メチル−7−t−ブチルフルオラン、3−ジエチルアミノ−6−メチル−7−アニリノフルオラン、3−ジエチルアミノ−6−メチル−7−p−ブチルアニリノフルオラン、3−シクロヘキシルアミノ−6−クロロフルオラン、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、3−ピロリジノ−6−メチル−7−アニリノフルオラン、3−ピロリジノ−7−シクロヘキシルアミノフルオラン、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、3−N−エチルペンチルアミノ−6−メチル−7−アニリノフルオラン等を挙げることができる。   Examples of leuco dyes include crystal violet lactone, 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 2- (2-chlorophenylamine) -diethylaminofluoride. Oran, 2- (2-fluorophenylamino) -6-diethylaminofluor) lane, 2- (2-fluorophenylamino) -6-di-n-butylaminofluorane, 3-diethylamino-7-cyclohexylaminofluorane 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-p-butylanilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 2-anilino 3-methyl-6- (N-ethyl-p-toluidino) -fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-7-cyclohexylaminofluorane, 3-N-methylcyclohexyl Examples include amino-6-methyl-7-anilinofluorane and 3-N-ethylpentylamino-6-methyl-7-anilinofluorane.

顕減色剤としては、(N−(p−ヒドロキシフェニル)−N’−n−オクタデシルチオ尿素、N−(p−ヒドロキシフェニル)−N’−n−オクタデシル尿素、N−(p−ヒドロキシフェニル)−N’−n−オクタデシルチオアミド、4’−オクタデカンアニリド、2−オクタデシルテレフタル酸、N−オクタデシル(p−ヒドロキシフェニル)アミド、N−(p−ヒドロキシベンゾイル)−N−オクタデカノイルアミン、N−[3−(p−ヒドロキシフェニル)プロピオノ]−N’−オクタデカノヒドテジド、N−[(p−ヒドロキシフェニル)メチル]−n−オクタデシルアミド、N−[(p−ヒドロキシフェニル)メチル]−n−オクタデシル尿素、N−[(p−ヒドロキシフェニル)メチル]−N’−n−オクタデシルオキサミド等を挙げることができる。   As the color reducing agent, (N- (p-hydroxyphenyl) -N′-n-octadecylthiourea, N- (p-hydroxyphenyl) -N′-n-octadecylurea, N- (p-hydroxyphenyl) -N'-n-octadecylthioamide, 4'-octadecananilide, 2-octadecylterephthalic acid, N-octadecyl (p-hydroxyphenyl) amide, N- (p-hydroxybenzoyl) -N-octadecanoylamine, N- [3- (p-Hydroxyphenyl) propiono] -N′-octadecanohydrate, N-[(p-hydroxyphenyl) methyl] -n-octadecylamide, N-[(p-hydroxyphenyl) methyl]- n-octadecylurea, N-[(p-hydroxyphenyl) methyl] -N′-n-octadecyloxamide, etc. Can be mentioned.

可逆性感熱記録層に使用される樹脂は、透明性が良く、製膜性の良い熱硬化性樹脂が好ましく、ポリ塩化ビニル、塩化ビニル系共重合体、塩化ビニリデン系共重合体、ポリエステル、ポリアミド又はポリアクリレート等の樹脂を挙げることができる。   The resin used for the reversible thermosensitive recording layer is preferably a thermosetting resin with good transparency and good film forming properties, such as polyvinyl chloride, vinyl chloride copolymer, vinylidene chloride copolymer, polyester, polyamide. Or resin, such as polyacrylate, can be mentioned.

本発明において、アンカー層を形成する樹脂は、イソシアネート基を有する化合物と水酸基を有する化合物とがウレタン結合を介して縮合したポリマーである。イソシアネート基を有する化合物としては、ヘキサメチレンジイソシアネート(HDI)、トリレンジイソシアネート(TDI)、キシリレンジイソシアネート(XDI)、イソフォロンジイソシアネート(IPDI)等を挙げることができる。   In the present invention, the resin forming the anchor layer is a polymer in which a compound having an isocyanate group and a compound having a hydroxyl group are condensed via a urethane bond. Examples of the compound having an isocyanate group include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and isophorone diisocyanate (IPDI).

水酸基を有する化合物とは、分子内に水酸基を2個以上有する樹脂であって、イソシアネート基と反応してウレタン結合を形成可能な化合物である。例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリカプロンラクトンポリオール等がある。
この水酸基を有する化合物は、ガラス転移温度が40℃を超え、90℃以下のものが好ましい。さらに好ましくは、60℃以上、90℃以下である。ガラス転移温度が40℃以下だと、アンカー層が柔らかくなりすぎ、印字により保護層に傷が付きやすくなる。また、ガラス転移温度が90℃を超えるとアンカー層が硬くなりすぎ、可逆性感熱記録材料の曲げ強度がなくなるため好ましくない。
The compound having a hydroxyl group is a resin having two or more hydroxyl groups in the molecule and capable of reacting with an isocyanate group to form a urethane bond. For example, there are polyether polyol, polyester polyol, polycarbonate polyol, polycapron lactone polyol and the like.
The compound having a hydroxyl group preferably has a glass transition temperature of more than 40 ° C. and 90 ° C. or less. More preferably, it is 60 degreeC or more and 90 degrees C or less. When the glass transition temperature is 40 ° C. or lower, the anchor layer becomes too soft, and the protective layer is easily damaged by printing. On the other hand, if the glass transition temperature exceeds 90 ° C., the anchor layer becomes too hard and the bending strength of the reversible thermosensitive recording material is lost, such being undesirable.

また、水酸基を有する化合物は、水酸基価が150mgKOH/g未満の条件を満たすことが望ましい。好ましくは、3mgKOH/g以上、100mgKOH/g以下の範囲である。水酸基価が150mgKOH/g以上になると、印字濃度が薄くなる傾向がある。   The compound having a hydroxyl group preferably satisfies the condition that the hydroxyl value is less than 150 mgKOH / g. Preferably, it is the range of 3 mgKOH / g or more and 100 mgKOH / g or less. When the hydroxyl value is 150 mgKOH / g or more, the print density tends to decrease.

アンカー層の厚みは、可逆性感熱記録材料の印字耐久性及び可逆性感熱記録媒体の曲げ強度に影響を及ぼす。アンカー層の厚みは、0.2μmを超え、2.5μm未満の範囲であることが好ましい。
アンカー層の厚みを増すと、印字耐久性が向上するが、印字濃度が薄くなり、また、可逆性感熱記録媒体の曲げ強度が悪くなる。すなわち、厚みが0.2μm以下になると印字耐久性が低下し、2.5μm以上になると印字濃度が薄くなるとともに、可逆性感熱記録媒体の曲げ強度が悪くなる。さらに好ましくは、0.3μm以上、2.0μm以下の範囲である。
The thickness of the anchor layer affects the printing durability of the reversible thermosensitive recording material and the bending strength of the reversible thermosensitive recording medium. The thickness of the anchor layer is preferably more than 0.2 μm and less than 2.5 μm.
When the thickness of the anchor layer is increased, the printing durability is improved, but the printing density is reduced, and the bending strength of the reversible thermosensitive recording medium is deteriorated. That is, when the thickness is 0.2 μm or less, the printing durability is lowered, and when it is 2.5 μm or more, the printing density is decreased and the bending strength of the reversible thermosensitive recording medium is deteriorated. More preferably, it is the range of 0.3 micrometer or more and 2.0 micrometers or less.

保護層は、ウレタンアクリレートとペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとを含む紫外線硬化樹脂を主成分とする樹脂層であり、さらに、この樹脂層は、紫外線硬化樹脂100重量部に対し四フッ化エチレン樹脂を3〜11重量部、シリカ12〜17重量を含有している。
ペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとしては、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレートなどが挙げることができる。
また、保護層の厚みは、層厚が4μm以上、7μm未満の範囲が好ましい。厚みが4μm以下になると、印字耐久性が低下し、サーマルヘッドの汚れが生じやすい。厚みが7μm以上になると、可逆性感熱記録層に記録された情報の消去性が悪くなるので好ましくない。なお、保護層の厚みは、より好ましくは、4μm以上、6μm以下である。
The protective layer is a resin layer mainly composed of an ultraviolet curable resin containing urethane acrylate and an acrylate having a pentaerythritol group or a dipentaerythritol group. Further, the resin layer is formed in four parts per 100 parts by weight of the ultraviolet curable resin. It contains 3 to 11 parts by weight of a fluoroethylene resin and 12 to 17 parts by weight of silica.
Examples of the acrylate having a pentaerythritol group or a dipentaerythritol group include pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.
The thickness of the protective layer is preferably in the range of 4 μm or more and less than 7 μm. When the thickness is 4 μm or less, the printing durability is lowered and the thermal head is likely to be stained. When the thickness is 7 μm or more, the erasability of information recorded on the reversible thermosensitive recording layer is deteriorated, which is not preferable. The thickness of the protective layer is more preferably 4 μm or more and 6 μm or less.

可逆性感熱記録材料は、それぞれの層を形成する樹脂を順に支持体上にワイヤーバーで塗工し乾燥することで製造することができる。   The reversible thermosensitive recording material can be produced by sequentially coating the resin forming each layer on a support with a wire bar and drying.

可逆性感熱記録材料は、可逆性感熱記録材料の支持体の下層にさらに、PET−G、PET、PVC、紙等を単独又は組み合わせた基材を積層して可逆性感熱記録媒体としてもよい。支持体と基材の積層は、熱プレス、ラミネート等によって行えばよい。
また、図1に示すように、可逆性感熱記録材料1の下層の基材2には、ICチップ3及びアンテナ4を搭載してもよい。
なお、可逆性感熱記録媒体の厚みは、JIS X6301に定められた範囲に設定すればよい。
The reversible thermosensitive recording material may be used as a reversible thermosensitive recording medium by further laminating a base material of PET-G, PET, PVC, paper or the like alone or in combination on the lower layer of the support of the reversible thermosensitive recording material. Lamination of the support and the substrate may be performed by hot pressing, lamination, or the like.
Further, as shown in FIG. 1, an IC chip 3 and an antenna 4 may be mounted on the base material 2 under the reversible thermosensitive recording material 1.
Note that the thickness of the reversible thermosensitive recording medium may be set within a range defined in JIS X6301.

以上説明したように、アンカー層を形成する化合物が上述のガラス転移温度条件及び水酸基価の条件を満たし、かつアンカー層の厚みが上述した条件を満たす可逆性感熱記録材料は、印字が濃く、サーマルヘッドによる加熱を繰り返しても保護層の表面に傷が発生しにくい。   As described above, the reversible thermosensitive recording material in which the compound forming the anchor layer satisfies the glass transition temperature condition and the hydroxyl value condition described above, and the thickness of the anchor layer satisfies the above-described condition is high in printing, Even if the heating by the head is repeated, the surface of the protective layer is hardly damaged.

以下、実施例及び比較例により本発明をさらに詳しく説明する。
[アンカー層を形成する樹脂成分及び層厚が保護層に及ぼす影響についての試験]
以下に示す(1)〜(4)の材料をペイントシェーカーで18時間混合して塗料とし、支持体(三菱樹脂製W−400J)上にワイヤーバーで塗工し、100℃で2分間乾燥して、乾燥膜厚11μmの可逆性感熱記録層を形成した。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[Test on the effect of resin component and layer thickness forming the anchor layer on the protective layer]
The following materials (1) to (4) are mixed with a paint shaker for 18 hours to form a paint, coated on a support (Mitsubishi Resin W-400J) with a wire bar, and dried at 100 ° C. for 2 minutes. Thus, a reversible thermosensitive recording layer having a dry film thickness of 11 μm was formed.

(1)熱硬化性ポリアクリル樹脂(DIC製 WBU−1218):25重量部
(2)ロイコ染料(山本化成製 Blue63):10重量部
(3)顕減色剤(N−[3−(p−ヒドロキシフェニル)プロピオノ]−N′−n−ドコサノヒドラジド):40重量部
(4)XDI系硬化剤(三井化学製 タケネート500):25重量部
(1) Thermosetting polyacrylic resin (DIC-made WBU-1218): 25 parts by weight (2) Leuco dye (Yamamoto Kasei Blue63): 10 parts by weight (3) Reducing colorant (N- [3- (p- Hydroxyphenyl) propiono] -N′-n-docosanohydrazide): 40 parts by weight (4) XDI curing agent (Mitsui Chemicals Takenate 500): 25 parts by weight

表1に示す水酸基を有する化合物80重量部とXDI系硬化剤(三井化学製 D−110):20重量部とを混合し、可逆性感熱記録層上にワイヤーバーで塗工し、100℃で1分間乾燥して、乾燥膜厚0.2〜2.5μmのアンカー層を形成した。   80 parts by weight of the compound having a hydroxyl group shown in Table 1 and 20 parts by weight of an XDI curing agent (D-110 manufactured by Mitsui Chemicals) are mixed, and coated on the reversible thermosensitive recording layer with a wire bar at 100 ° C. An anchor layer having a dry film thickness of 0.2 to 2.5 μm was formed by drying for 1 minute.

Figure 2014136426
Figure 2014136426

以下に示す(5)〜(8)の材料を混合してアンカー層上にワイヤーバーで塗工し、100℃で1分間乾燥し、乾燥膜厚5μmの保護層を形成して、可逆性感熱記録材料を作製した。   The following materials (5) to (8) are mixed and coated on the anchor layer with a wire bar, dried at 100 ° C. for 1 minute to form a protective layer with a dry film thickness of 5 μm, and reversible thermosensitive A recording material was prepared.

(5)紫外線硬化性ウレタンアクリレート樹脂(DIC製 ユニディックC7−164):88重量部
(6)シリカ(富士シリシア製 サイシリア436):6重量部
(7)ポリ四フッ化エチレン(喜多村製 KTL−4N):5重量部
(8)シリコーンオイル(藤倉化成製 AD−8719D):1重量部
(5) UV curable urethane acrylate resin (Unidic C7-164 manufactured by DIC): 88 parts by weight (6) Silica (Cycilia 436 manufactured by Fuji Silysia): 6 parts by weight (7) Polytetrafluoroethylene (manufactured by Kitamura KTL- 4N): 5 parts by weight (8) Silicone oil (AD-8719D manufactured by Fujikura Kasei): 1 part by weight

作製した可逆性感熱記録材料を最上層となるように、PET−Gシート(500μm)及びPET(100μm)を積層し、熱プレスで貼合し、型抜きして得られたカードを使用して、印字機による保護層の傷つき具合の評価、鉛筆硬度試験、印字濃度評価及び可逆性感熱記録媒体の曲げ強度の評価を実施した。結果を表2に示す。   Using the card obtained by laminating a PET-G sheet (500 μm) and PET (100 μm) so that the produced reversible thermosensitive recording material is the uppermost layer, bonding them with a hot press, and die-cutting. The evaluation of the degree of damage to the protective layer by the printing machine, the pencil hardness test, the evaluation of the printing density, and the bending strength of the reversible thermosensitive recording medium were carried out. The results are shown in Table 2.

印字機による傷付き具合の評価は、印字機TH−TCP(オオクラエンジニアリング製)にて消去・印字を60回繰り返し、表面の傷の深さを測定した。
鉛筆硬度は、JIS K 5600 5.4に規定する鉛筆引っかき値試験法に基づき、表面の硬さを測定した。
印字濃度は、印字機TH−TCP(オオクラエンジニアリング製)にて印字し、マクベス濃度計にて印字濃度を測定した。印字濃度は、0.9以上を○印、0.9未満を×印で示した。なお、目視による判断において、印字濃度が0.9未満になると視認性が悪くなるという知見に基づき、0.9を境として基準としたものである。
可逆性感熱記録媒体の曲げ強度は、「JIS6305−1 5.8動的曲げ強さ」に基づき、評価した。保護層に異常の見つからなかった場合を○印、ひびが入った場合を×印で示した。
Evaluation of the degree of damage by the printing machine was performed by repeating erasing and printing 60 times with a printing machine TH-TCP (manufactured by Okura Engineering Co., Ltd.), and measuring the depth of the scratch on the surface.
The pencil hardness was determined by measuring the surface hardness based on the pencil scratch value test method specified in JIS K 5600 5.4.
The printing density was printed by a printing machine TH-TCP (manufactured by Okura Engineering), and the printing density was measured by a Macbeth densitometer. The printing density is indicated by a circle mark of 0.9 or more and a cross mark of less than 0.9. In the visual judgment, 0.9 is used as a reference based on the knowledge that the visibility deteriorates when the print density is less than 0.9.
The bending strength of the reversible thermosensitive recording medium was evaluated based on “JIS6305-15.8 Dynamic bending strength”. A case where no abnormality was found in the protective layer was indicated by a circle, and a case where a crack was found was indicated by a cross.

Figure 2014136426
Figure 2014136426

実験例1〜6及び比較例1〜7は、保護層を形成する樹脂と厚みを同じ条件(乾燥膜厚5μm)とし、アンカー層を形成する樹脂成分と層厚を変えることにより、保護層の印字耐久性(傷つき具合の評価)、鉛筆硬度試験、印字濃度評価及び可逆性感熱記録媒体の曲げ強度を調べたものである。   In Experimental Examples 1 to 6 and Comparative Examples 1 to 7, the thickness of the protective layer is the same as that of the resin forming the protective layer (dry film thickness 5 μm), and the protective layer is changed by changing the resin component and the layer thickness forming the anchor layer. Printing durability (evaluation of scratch condition), pencil hardness test, printing density evaluation, and bending strength of a reversible thermosensitive recording medium were examined.

表2から、水酸基を有する化合物のガラス転移温度が40℃を超えると、保護層の印字耐久性、鉛筆硬度が向上することがわかる。しかし、90℃を超えると可逆性感熱記録媒体にひびが発生している(実験例1〜4と比較例7とを参照)。
また、ガラス転移温度が40℃を超え、90℃の以下の範囲であっても、アンカー層の厚みが増すと、印字濃度が薄くなることがわかる(実験例6及び比較例6を参照)。さらに、アンカー層の厚みが2.5μmになると、可逆性感熱記録媒体にひびが発生していることがわかる(比較例6)。
From Table 2, it can be seen that when the glass transition temperature of the compound having a hydroxyl group exceeds 40 ° C., the printing durability and the pencil hardness of the protective layer are improved. However, when the temperature exceeds 90 ° C., cracks occur in the reversible thermosensitive recording medium (see Experimental Examples 1 to 4 and Comparative Example 7).
Further, it can be seen that even when the glass transition temperature exceeds 40 ° C. and is in the following range of 90 ° C., the printing density decreases as the thickness of the anchor layer increases (see Experimental Example 6 and Comparative Example 6). Further, it can be seen that when the thickness of the anchor layer is 2.5 μm, the reversible thermosensitive recording medium is cracked (Comparative Example 6).

水酸基価は、150mgKOH/g未満、好ましくは、3mgKOH/g以上、100mgKOH/g以下の範囲である。水酸基価が150mgKOH/g未満である場合には、アンカー層が保護層と可逆性感熱記録層との間でクッションの役割を持つと考えられる。   The hydroxyl value is less than 150 mgKOH / g, preferably in the range of 3 mgKOH / g or more and 100 mgKOH / g or less. When the hydroxyl value is less than 150 mgKOH / g, the anchor layer is considered to have a cushioning role between the protective layer and the reversible thermosensitive recording layer.

以上のことから、水酸基を有する化合物のガラス転移温度が60℃以上、90℃以下、かつ水酸基価が150mgKOH/g未満であり、アンカー層の厚みが、0.2μmを超え、2.5μm未満の条件を満たす場合に、印字を繰り返しても保護層に傷が付き難く、印字かすれのない状態で印字ができることがわかる。   From the above, the glass transition temperature of the compound having a hydroxyl group is 60 ° C. or more and 90 ° C. or less, the hydroxyl value is less than 150 mgKOH / g, and the thickness of the anchor layer is more than 0.2 μm and less than 2.5 μm. When the conditions are satisfied, it can be seen that even if printing is repeated, the protective layer is hardly damaged and printing can be performed without fading.

[保護層を形成する樹脂成分と印字耐久性、ヘッド汚れ、可逆性感熱記録媒体の曲げ強度についての試験]
以下に示す(a)〜(d)の材料をペイントシェーカーで18時間混合して塗料とし、支持体(三菱樹脂製W−400J)上にワイヤーバーで塗工し、100℃で2分間乾燥して、乾燥膜厚11μmの可逆性感熱記録層を形成した。
[Test of resin component forming protective layer and printing durability, head dirt, bending strength of reversible thermosensitive recording medium]
The following materials (a) to (d) are mixed with a paint shaker for 18 hours to form a paint, coated on a support (Mitsubishi Resin W-400J) with a wire bar, and dried at 100 ° C. for 2 minutes. Thus, a reversible thermosensitive recording layer having a dry film thickness of 11 μm was formed.

(a)熱硬化性ポリアクリル樹脂(DIC製 WBU−1218):25重量部
(b)ロイコ染料(山本化成製 Blue63):10重量部
(c)顕減色剤(N−[3−(p−ヒドロキシフェニル)プロピオノ]−N′−n−ドコサノヒドラジド):40重量部
(d)XDI系硬化剤(三井化学製 タケネート500):25重量部
(A) Thermosetting polyacrylic resin (WBU-1218 manufactured by DIC): 25 parts by weight (b) Leuco dye (Blue 63 manufactured by Yamamoto Kasei): 10 parts by weight (c) Reducing colorant (N- [3- (p- Hydroxyphenyl) propiono] -N′-n-docosanohydrazide): 40 parts by weight (d) XDI curing agent (Takenate 500 manufactured by Mitsui Chemicals): 25 parts by weight

表3に示す水酸基を有する化合物80重量部とXDI系硬化剤(三井化学製 D−110N):20重量部とを混合し、可逆性感熱記録層上にワイヤーバーで塗工し、100℃で1分間乾燥して、乾燥膜厚0.5μmのアンカー層を形成した。   80 parts by weight of the compound having a hydroxyl group shown in Table 3 and XDI curing agent (D-110N, manufactured by Mitsui Chemicals): 20 parts by weight are mixed and coated on the reversible thermosensitive recording layer with a wire bar at 100 ° C. An anchor layer having a dry film thickness of 0.5 μm was formed by drying for 1 minute.

Figure 2014136426
Figure 2014136426

以下に示す(e)〜(j)の材料を表4に示す割合で配合し、トルエンで希釈して(固形分濃度を20%に調整)、アンカー層上にワイヤーバーで塗工し、100℃で1分間乾燥後、紫外線照射(160W/cm、30m/分、1パス)を行って硬化させ、表乾燥膜厚5μmの保護層を形成し、可逆性感熱記録材料を作製した。
なお、比較例18の保護層のみ、DIC製ユニディックC7−164を100重量部使用した。
また、(g)〜(j)の配合割合は、(e)及び(f)の合計である100重量部に対する割合である。
The following materials (e) to (j) are mixed in the proportions shown in Table 4, diluted with toluene (the solid content concentration is adjusted to 20%), coated on the anchor layer with a wire bar, and 100 After drying at a temperature of 1 ° C. for 1 minute, ultraviolet ray irradiation (160 W / cm, 30 m / min, 1 pass) was performed to cure, and a protective layer having a surface dry film thickness of 5 μm was formed to prepare a reversible thermosensitive recording material.
In addition, 100 parts by weight of DIC Unidic C7-164 was used only for the protective layer of Comparative Example 18.
Moreover, the blending ratio of (g) to (j) is a ratio with respect to 100 parts by weight which is the sum of (e) and (f).

(e)紫外線硬化性ウレタン−アクリレート樹脂:DIC製 V−4018
(f)紫外線硬化性ペンタエリスリトールテトラアクリレート樹脂:共栄社化学製 PE−4A
(g)シリカ:富士シリシア製 サイシリア436
(h)ポリ四フッ化エチレン(表3中、PTFEと表記):喜多村製 KTL−4N
(i)シリコーンオイル:藤倉化成製AD8719D
(j)光重合開始剤(BASF製 イルガキュア184)
(E) UV curable urethane-acrylate resin: V-4018 made by DIC
(F) UV curable pentaerythritol tetraacrylate resin: PE-4A manufactured by Kyoeisha Chemical Co., Ltd.
(G) Silica: Cicilia 436 manufactured by Fuji Silysia
(H) Polytetrafluoroethylene (indicated as PTFE in Table 3): Kitamura KTL-4N
(I) Silicone oil: AD8719D manufactured by Fujikura Kasei
(J) Photopolymerization initiator (Irgacure 184 manufactured by BASF)

作製した可逆性感熱記録材料を最上層となるように、PET−Gシート(500μm)及びPET(125μm)を積層し、熱プレスで貼合し、型抜きして得られた可逆性感熱記録媒体(以下、カードという。)を用い、保護層について、印字耐久性、ヘッド汚れ、消去性、及びカードの曲げによるひび割れの4つの項目で評価を実施した。結果を表4に示す。   A reversible thermosensitive recording medium obtained by laminating a PET-G sheet (500 μm) and PET (125 μm) so that the produced reversible thermosensitive recording material is the uppermost layer, bonding them with a hot press, and die cutting. (Hereinafter, referred to as a card), the protective layer was evaluated in four items: printing durability, head contamination, erasability, and cracking due to bending of the card. The results are shown in Table 4.

Figure 2014136426
Figure 2014136426

なお、印字耐久性、ヘッド汚れ、消去性、カード曲げによるひび割れは以下のように評価した。
印字耐久性は、印字機TH−TCP(オオクラエンジニアリング製)を使用して、印字と消去を300回繰り返し、可逆性感熱記録層が露出している場合を×、露出していない場合を○として評価した。
In addition, printing durability, head stains, erasability, and cracks due to card bending were evaluated as follows.
For printing durability, using a printing machine TH-TCP (manufactured by Okura Engineering Co., Ltd.), printing and erasing were repeated 300 times. When the reversible thermosensitive recording layer was exposed, x, and when it was not exposed, ○ evaluated.

ヘッド汚れは、印字耐久性の300回目の印字に文字かすれがあった場合を×、正常に印字されていた場合を○と評価した。   The head stain was evaluated as x when the characters were faint in the 300th printing for printing durability, and evaluated as o when the characters were printed normally.

消去性は、印字機TH−TCP(オオクラエンジニアリング製)を使用して、印字と消去を1回行ったのち、保護層上で、印字が消去された場所の表面粗さと印字が無かった場所の表面粗さの差を指標とした。印字部分の表面粗さRa値と未印字部分との表面粗さRa値との差が0.03以下の場合を○印、0.03を超えた場合を×印で示した。表面粗さRa値が0.03を超えると、カードに光を反射させて斜めに傾けて表面を観察すると、サーマルヘッドの打痕跡が見え、見栄えが悪くなってしまう。表面粗さRa値は、JIS X6305.2「5.3磁気ストライプの表面粗さ」に基づいて測定した。   The erasability of the place where there was no surface roughness and no printing on the protective layer after printing and erasing once using a printing machine TH-TCP (manufactured by Okura Engineering). The difference in surface roughness was used as an index. The case where the difference between the surface roughness Ra value of the printed part and the surface roughness Ra value of the unprinted part is 0.03 or less is indicated by ◯, and the case where it exceeds 0.03 is indicated by ×. When the surface roughness Ra value exceeds 0.03, if the light is reflected on the card and tilted obliquely and the surface is observed, the trace of the thermal head will be seen and the appearance will deteriorate. The surface roughness Ra value was measured based on JIS X6305.2 “5.3 Surface roughness of magnetic stripe”.

カード曲げによるひび割れは、JIS X6305−1「5.8動的曲げ力(曲げ特性)」に従って試験を行い、異常が無い場合を○印、ひびが入った場合を×印で示した。   Cracks due to card bending were tested in accordance with JIS X6305-1 “5.8 Dynamic Bending Force (Bending Characteristics)”, and a case where there was no abnormality was indicated by a circle, and a case where a crack was present was indicated by a cross.

表4から、以下の(1)〜(7)の条件全てを満たさない場合、印字耐久性、ヘッド汚れ、消去性、カード曲げによるひび割れのいずれかの評価値が劣ることがわかる。
(1)アンカー層の水酸基を有する化合物のガラス転移温度が、40℃を超え、90℃以下であること、
(2)アンカー層の水酸基を有する化合物の水酸基価が、150mgKOH/g未満であること、
(3)保護層の樹脂が、ペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとウレタンアクリレートとを含むこと、
(4)保護層の樹脂中に、紫外線硬化樹脂100重量部に対し四フッ化エチレン樹脂が3〜11重量部含まれていること、
(5)保護層の樹脂中に、シリカが12〜17重量部で含有されていること、
(6)保護層の厚みが4μm以上、7μm未満であること、及び
(7)保護層中にシリコーンオイルが含まれていないこと。
From Table 4, it can be seen that when all of the following conditions (1) to (7) are not satisfied, the evaluation value of any of printing durability, head contamination, erasability, and cracking due to card bending is inferior.
(1) The glass transition temperature of the compound having a hydroxyl group of the anchor layer is more than 40 ° C. and 90 ° C. or less,
(2) The hydroxyl value of the compound having a hydroxyl group of the anchor layer is less than 150 mgKOH / g,
(3) The resin of the protective layer contains an acrylate having a pentaerythritol group or a dipentaerythritol group and a urethane acrylate,
(4) The resin of the protective layer contains 3 to 11 parts by weight of a tetrafluoroethylene resin with respect to 100 parts by weight of the ultraviolet curable resin,
(5) 12 to 17 parts by weight of silica is contained in the protective layer resin;
(6) The thickness of the protective layer is 4 μm or more and less than 7 μm, and (7) The protective layer does not contain silicone oil.

Claims (3)

支持体上に設けられた可逆性感熱組成物を含有する可逆性感熱記録層と、該可逆性感熱記録層上に設けられたイソシアネート基を有する化合物と水酸基を有する化合物とが縮合した樹脂からなるアンカー層と、該アンカー層上に設けられた保護層とを有する積層体であって、
上記水酸基を有する化合物は、ガラス転移温度が40℃を超え、90℃以下であり、水酸基価が150mgKOH/g未満であり、
上記アンカー層の厚みは、0.2μmを超え、2.5μm未満であり、
上記保護層は、ウレタンアクリレートとペンタエリスリトール基又はジペンタエリスリトール基を有するアクリレートとを含む紫外線硬化樹脂100重量部に対し四フッ化エチレン樹脂を3〜11重量部及びシリカを12〜17重量部含有しており、かつ層厚が4μm以上、7μm未満である、可逆性感熱記録材料。
A reversible thermosensitive recording layer containing a reversible thermosensitive composition provided on a support, and a resin obtained by condensing a compound having an isocyanate group and a compound having a hydroxyl group provided on the reversible thermosensitive recording layer. A laminate having an anchor layer and a protective layer provided on the anchor layer,
The compound having a hydroxyl group has a glass transition temperature of more than 40 ° C. and 90 ° C. or less, and a hydroxyl value of less than 150 mgKOH / g,
The anchor layer has a thickness of more than 0.2 μm and less than 2.5 μm,
The protective layer contains 3 to 11 parts by weight of a tetrafluoroethylene resin and 12 to 17 parts by weight of silica with respect to 100 parts by weight of an ultraviolet curable resin containing urethane acrylate and an acrylate having a pentaerythritol group or a dipentaerythritol group. A reversible thermosensitive recording material having a layer thickness of 4 μm or more and less than 7 μm.
前記保護層は、シリコーンオイルを含有しない、請求項1記載の可逆性感熱記録材料。   The reversible thermosensitive recording material according to claim 1, wherein the protective layer does not contain silicone oil. 請求項1又は請求項2の可逆性感熱記録材料の支持体に基材を積層させた、可逆性感熱記録媒体。

A reversible thermosensitive recording medium comprising a substrate laminated on the support of the reversible thermosensitive recording material according to claim 1 or 2.

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