JPH0662006B2 - Thermal recording type card - Google Patents
Thermal recording type cardInfo
- Publication number
- JPH0662006B2 JPH0662006B2 JP61132695A JP13269586A JPH0662006B2 JP H0662006 B2 JPH0662006 B2 JP H0662006B2 JP 61132695 A JP61132695 A JP 61132695A JP 13269586 A JP13269586 A JP 13269586A JP H0662006 B2 JPH0662006 B2 JP H0662006B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- heat
- acid
- type card
- mol
- 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)
- Credit Cards Or The Like (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は身分証明書、免許証、名刺、定期券、会員カー
ドおよび旅券等のパーソナルカードとして使用する感熱
記録型カードであり、感熱プリンター等の熱印字手段に
より直接印字できるようにした感熱記録型カードに関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is a thermal recording type card used as a personal card such as an identification card, a license, a business card, a commuter pass, a membership card, and a passport, and a thermal printer. The present invention relates to a heat-sensitive recording type card capable of being directly printed by the thermal printing means.
＜従来の技術＞ 近年、省力化のための自動発券機の普及には目ざましい
ものがあり、これにともなって各種のカード類が使用さ
れるに至っているが、中でも自然紙性、低廉なこと、印
字機構が簡便であるとの理由で感熱記録型のカードが広
く知られている。<Prior Art> In recent years, there has been a remarkable spread of automatic ticket issuing machines for labor saving, and along with this, various types of cards have come to be used, but among them, natural paper, cheapness, A thermal recording type card is widely known because of its simple printing mechanism.
この場合の感熱記録型カードはラクトン化合物の如きロ
イコ染料とビスフェノールＡの如き有機酸又はフェノー
ル化合物を結合剤中に分散させてなる感熱発所層を支持
体上に塗布したものであり、画素状に加熱されることに
よりその加熱部分の発色性ラクトン化合物と、有機酸ま
たはフェノール化合物とが化学的に反応して発色する。
この場合加熱機録型カードに要求される基本的特性は、
その発色が良好であると同時に外観ができるだけ白くて
自然紙様であり、しかも長期保存性があり、特に重要不
可欠の特性として、(イ)感度の高いこと、(ロ)ステイッ
キング性がないこと、(ハ)サーマルヘッドに粕付着がな
くサーマルヘッドとの適合性のよいことなどが要請され
ている。The heat-sensitive recording type card in this case is one in which a leuco dye such as a lactone compound and an organic acid such as bisphenol A or a phenol compound are dispersed in a binder, and a heat-sensitive source layer is coated on a support. When heated, the color-forming lactone compound in the heated portion chemically reacts with the organic acid or the phenol compound to develop color.
In this case, the basic characteristics required for the heating memo type card are
Its color development is good and at the same time its appearance is as white and natural paper-like as it has long-term storage properties, and particularly important properties are (a) high sensitivity, (b) no stacking property, (C) It is demanded that the thermal head has no lees attached and has good compatibility with the thermal head.
このように感熱記録型カードは、その用途に応じて上記
特性を有することが望まれるが、この種のタイプの発色
染料は光、水、温度、可塑剤および油等に対して不安定
であるために、保存時の経時変化が常に問題となる。従
って、かかる感熱記録型カードに所望の印字を施す時
は、その記録発色は極めて鮮明に発現したとしても、本
発明のごときカード用に使用する場合、通常のファクシ
ミリ用と異なり、顧客の取扱い性、使用環境、使用頻度
等においてきわめて過酷な実用特性を要求される。例え
ば、この発色部に可塑剤を多く含んだプラスチックフィ
ルム（例えばポリ塩化ビニルの軟質フィルム）を密着さ
せたり、油や脂肪類を付着したまま保存したりすると、
その密着あるいは付着部分が退色してしまうとか、また
発色部が長時間水に接触した場合にも、著しい退色を生
ずることもしばしばみられる。As described above, the thermal recording type card is desired to have the above characteristics depending on its application, but this type of color-forming dye is unstable to light, water, temperature, plasticizer, oil and the like. Therefore, the change with time during storage is always a problem. Therefore, when the desired printing is performed on such a heat-sensitive recording type card, even if the recording color development appears extremely clearly, when it is used for a card such as the present invention, it is different from a usual facsimile type and is easy for the customer to handle. Extremely harsh practical characteristics are required in terms of usage environment, usage frequency, etc. For example, if a plastic film containing a large amount of plasticizer (for example, a soft film of polyvinyl chloride) is adhered to this colored portion, or if it is stored with oil or fat attached,
It is often observed that the adhered or adhered part is discolored or that the discolored part is significantly discolored even when the colored part is in contact with water for a long time.
従って、加熱記録型カードが、油や可塑剤と接触する場
合、上記の退色現象の防止方策の開発が強く要請されて
きた。Therefore, there has been a strong demand for the development of a measure for preventing the above-mentioned discoloration phenomenon when the heating recording type card comes into contact with oil or a plasticizer.
＜発明が解決しようとする問題点＞ 本発明は上記の事情に鑑みてなされたものであり、加熱
により発色した画像の保存性、耐水性、耐油性および耐
可塑性を改良し、感熱記録型カードを提供するものであ
る。<Problems to be Solved by the Invention> The present invention has been made in view of the above circumstances, and has improved storability, water resistance, oil resistance and plasticity resistance of an image colored by heating, and a heat-sensitive recording card. Is provided.
＜問題点を解決するための手段＞ 本発明は (イ) 合成樹脂材料よりなる支持体層 (ロ) ロイコ染料系感熱発色層 (ハ) 必要によりバリヤー層 (ニ) 保護層 が上記順序に成層され、かつ該感熱発色層およびバリヤ
ー層のうちの少なくとも一層に、全ジカルボン酸中でス
ルホン酸塩基含有モノマーが６〜１５モル％、全グリコ
ール成分中でエチレングリコールが８５モル％以上で且
つエーテルグリコールが１５モル％以下であるスルホン
酸塩基含有ポリエステル樹脂を含有することを特徴とす
る感熱記録型カードに関するものである。<Means for Solving Problems> In the present invention, (a) a support layer made of a synthetic resin material (b) a leuco dye-based thermosensitive coloring layer (c) optionally a barrier layer (d) a protective layer formed in the above order And at least one of the thermosensitive coloring layer and the barrier layer contains 6 to 15 mol% of a sulfonate group-containing monomer in all dicarboxylic acids and 85 mol% or more of ethylene glycol in all glycol components and an ether glycol. The present invention relates to a heat-sensitive recording type card containing a sulfonate group-containing polyester resin whose content is 15 mol% or less.
本発明でいう合成樹脂材料よりなる支持体には塩化ビニ
ル樹脂、ポリエステル樹脂、ポリプロピレン樹脂等のシ
ート、合成紙、又はラミネート紙等の高度の耐水性、耐
薬品性、耐久性を有した合成樹脂シートが適用される。
特に本発明でいう特定の組成を有するスルホン酸塩基含
有ポリエステル樹脂と強い粘着力を示す塩化ビニル樹
脂、ポリエステル樹脂シートが好ましい。更にこれらの
樹脂シートからなる支持耐表面をマット化又はアンカー
コート層を設けて支持体と該感熱層間の結着力を高める
ことも可能である。The support made of the synthetic resin material in the present invention is a synthetic resin having a high degree of water resistance, chemical resistance, and durability such as vinyl chloride resin, polyester resin, polypropylene resin sheet, synthetic paper, or laminated paper. Sheets are applied.
In particular, a vinyl chloride resin and a polyester resin sheet showing a strong adhesive force with a sulfonate group-containing polyester resin having a specific composition as used in the present invention are preferable. Further, it is possible to increase the binding force between the support and the heat-sensitive layer by matting the support resistant surface made of these resin sheets or providing an anchor coat layer.
本発明のロイコ染料系感熱発色層および／またはバリヤ
ー層に使用する特定のスルホン酸塩基含有ポリエステル
樹脂は例えば次のようにして合成される。The specific sulfonate group-containing polyester resin used in the leuco dye-based thermosensitive coloring layer and / or barrier layer of the present invention is synthesized, for example, as follows.
すなわち、ジカルボン酸成分、エチレングリコール、エ
ーテルグリコール成分およびスルホン酸塩基含有ジカル
ボン酸をジブチルチンオキサイド、三酸化アンチモン等
のエステル化触媒の存在下に１７０〜２８０℃の温度で
エステル化反応したのち、重縮合触媒の存在下に０．５
〜１．０mmHgの真空下で２４０〜２８０℃で重縮合反応
させることにより得ることができる。下記(a)、(b)で規
定される各成分の含有量は各原料の仕込量にほぼ対応す
るので、目的とする(a)、(b)成分の含有量に応じて仕込
量を決定すれば良い。That is, a dicarboxylic acid component, an ethylene glycol, an ether glycol component, and a sulfonic acid group-containing dicarboxylic acid are subjected to an esterification reaction at a temperature of 170 to 280 ° C. in the presence of an esterification catalyst such as dibutyltin oxide, antimony trioxide and the like, 0.5 in the presence of condensation catalyst
It can be obtained by a polycondensation reaction at 240 to 280 ° C. under a vacuum of ˜1.0 mmHg. Since the content of each component specified in the following (a), (b) almost corresponds to the charged amount of each raw material, determine the charged amount according to the content of the target (a), (b) component Just do it.
(a)成分の含有量が６モル％以下では水溶性が低下して
塗工液の調製が困難となり、一方１５モル％以上の導入
は記録紙の耐水性を低下させる原因となって、実用性に
乏しい。When the content of the component (a) is 6 mol% or less, the water solubility is lowered and it becomes difficult to prepare a coating liquid. On the other hand, the incorporation of 15 mol% or more causes the water resistance of the recording paper to be lowered, Poor sex.
又、(b)成分中のエチレングリコールは８５モル％以上
が必要でこれ以下では耐溶剤性が低下する。更にエーテ
ルグリコールを１５モル％以上導入するとベトツキ、ブ
ロッキング等が発生したり、顕色剤の安定性を阻害する
欠点が生じる。Further, the ethylene glycol in the component (b) needs to be 85 mol% or more, and if it is less than this, the solvent resistance decreases. Furthermore, when ether glycol is introduced in an amount of 15 mol% or more, stickiness, blocking, etc. occur, and the stability of the color developer is impaired.
上記で使用されるジカルボン酸としては、テレフタル
酸、イソフタル酸、シュウ酸、マロン酸、こはく酸、ア
ジピン酸、セバシン酸等の酸あるいはこれらの無水物、
エステル、クロライド等であっても良い。Examples of the dicarboxylic acid used above include terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid and the like, or anhydrides thereof,
It may be ester, chloride or the like.
又、エーテルグリコール成分の導入には一般式 Ｈ−(ＯＣＨ2ＣＨ2)−ｎＯＨ〔n；２以上の整数〕 で示されるポリエチレングリコールが用いられ、具体的
にはジエチレングリコール、トリエチレングリコール、
テトラエチレングリコール等が挙げられる。Moreover, the general formula H- the introduction of ether glycol component (OCH 2 CH 2) - n OH [n; 2 integer greater than or equal with polyethylene glycol is used as shown, specifically diethylene glycol, triethylene glycol,
Examples thereof include tetraethylene glycol.
更にスルホン酸塩基含有ジカルボン酸としては５−ナト
リウスルホイソフタル酸、５−ナトリウムスルホフタル
酸、５−カリウムスルホイソフタル酸、５−カリウムス
ルホフタル酸あるいはこれらのアルキルエステル等が例
示される。勿論、本発明のポリエステル樹脂中には必要
に応じて前記以外の飽和又は不飽和のモノ又はポリカル
ボン酸や、1,3−ブチレングリコール、1,4−ブチレング
リコール、1,6−ヘキサンジオール、ネオベンチルグリ
コール等の多価アルコールの併用も可能である。Furthermore, examples of the dicarboxylic acid containing a sulfonate group include 5-naphthosulfoisophthalic acid, 5-sodium sulfophthalic acid, 5-potassium sulfoisophthalic acid, 5-potassium sulfophthalic acid, and alkyl esters thereof. Of course, in the polyester resin of the present invention, if necessary, a saturated or unsaturated mono- or polycarboxylic acid other than the above, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, It is also possible to use a polyhydric alcohol such as neobenthyl glycol together.
ロイコ染料系感熱発色層に上記スルホン酸塩基含有ポリ
エステル樹脂を使用する場合は、発色剤の結着剤として
使うのであるが、その場合下記に示すような水性樹脂と
併用することも可能であり、又、該ポリエステル樹脂を
使用しない場合は下記の水性樹脂単独でも本発明を実施
することができる。When using the sulfonate group-containing polyester resin in the leuco dye-based thermosensitive coloring layer, it is used as a binder of the coloring agent, in which case it is also possible to use in combination with an aqueous resin as shown below, Further, when the polyester resin is not used, the present invention can be carried out with the following aqueous resin alone.
例えばポリビニールアルコール、澱粉類、ヒドロキシエ
チルセルロース、アラビヤゴム、ポリビニルピロリド
ン、アクリル酸（またはメタアクリル酸）エステル共重
合体のアルカリ塩、スチレン／無水マレイン酸共重合体
のアルカリ塩、イソブチレン／無水マレイン酸共重合体
のアルカリ塩、アクリルアミド共重合体などの水溶性高
分子化合物およびスチレン／ブタジエン共重合体、ポリ
酢酸ビニル、アクリル酸エステル共重合体などの高分子
ラテックス、またはエマルジョンなどの水性樹脂が該当
する。For example, polyvinyl alcohol, starch, hydroxyethyl cellulose, arabic gum, polyvinylpyrrolidone, alkali salt of acrylic acid (or methacrylic acid) ester copolymer, alkali salt of styrene / maleic anhydride copolymer, isobutylene / maleic anhydride copolymer Water-soluble polymers such as alkali salts of polymers, acrylamide copolymers, and water-soluble polymers such as styrene / butadiene copolymers, polyvinyl acetate, acrylate copolymers, or emulsions .
このような結着剤に分散するロイコ染料としては、通常
無色又は淡色のトリフェニルメタン系、フルオラン系、
フェノチオジン系、オーラミン系、スピロピラン系等の
ロイコ体が適用され、又、前記ロイコ体と熱時発色反応
を起こし、該ロイコ体を発色せしめるαナフトール、β
ナフトール、ビスフェノールＡ、安息香酸、サリチル酸
等の酸性物質が本発明でいうロイコ染料系感熱発色層に
配合される。以上のごとき結着剤樹脂、ロイコ染料およ
び酸性物質からなる感熱発色塗液を支持体の表面に塗
布、乾燥してロイコ染料系感熱発色層を設ける。The leuco dye dispersed in such a binder is usually colorless or light-colored triphenylmethane type, fluorane type,
A leuco body such as a phenothiazine series, an auramine series, or a spiropyran series is applied, and α-naphthol and β which cause a color reaction with the leuco body under heat to cause the leuco body to develop color.
An acidic substance such as naphthol, bisphenol A, benzoic acid, and salicylic acid is mixed in the leuco dye-based thermosensitive coloring layer in the present invention. The heat-sensitive color forming coating liquid comprising the binder resin, leuco dye and acidic substance as described above is applied to the surface of the support and dried to form a leuco dye-based heat-sensitive color forming layer.
上記の如くして得られたロイコ染料系感熱発色層の上に
必要に応じてバリヤー層が設けられる。この場合におけ
るバリヤー層は溶剤系塗料からなる保護層と感熱発色層
とを隔離するためものでその材料としては一般に知られ
ている水溶性樹脂が使用されるが本発明においては、耐
水性、耐溶剤性およびロイコ染料系感熱発色層との親和
性からして前述のスルホン酸塩基含有ポリエステル樹脂
を主成分とすることが好ましい。なお本発明でいうバリ
ヤー層には、必要に応じて樹脂の硬化剤、塗工性調整剤
等の添加剤が配合されて使用される。A barrier layer is provided, if necessary, on the leuco dye-based thermosensitive coloring layer obtained as described above. In this case, the barrier layer is for separating the protective layer made of a solvent-based paint from the thermosensitive coloring layer, and a generally known water-soluble resin is used as the material thereof. From the viewpoint of solvent property and affinity with the leuco dye-based thermosensitive coloring layer, it is preferable to use the above-mentioned sulfonate group-containing polyester resin as a main component. Incidentally, the barrier layer in the present invention is used by adding additives such as a resin curing agent and a coatability adjusting agent, if necessary.
なお、バリヤーには、該バリヤー層の塗料性、塗工性お
よび塗膜を改質するために、例えばカゼイン、ゼラチ、
ポリビニルアルコール、変性ポリビニルアルコール、ポ
リビニルピロリドン、澱粉、変性澱粉、イソブチレン−
無水マレイン酸樹脂、ジイソブチレン−無水マレイン酸
樹脂、ポリアクリルアマイド、変性ポリアクリルアマイ
ド、メチルビニルエーテル、マレイン酸共重合体、カル
ボキシメチルセルロース、メチルセルロース、ヒドロキ
シエチルセルロース、ヒドロキシプロピレンセルロー
ス、さらに水溶性エマルジョンとして、酢酸ビニル、ポ
リスチレン、アクリル酸エステル、塩化ビニル−酢酸ビ
ニル共重合体等の樹脂を前述のスルホン酸塩基含有ポリ
エステル樹脂に混合することができる。又、バリヤー層
に該スルホン酸塩基含有ポリエステル樹脂を使用しない
場合は、上記各種の水溶性樹脂を単独で用いることがで
きる。又、バリヤー層には必要に応じて硬化剤、界面活
性剤あるいは感熱記録材料の耐光性向上のために酸化防
止剤、紫外線吸収剤等を含有させてもよい。The barrier may be, for example, casein, gelatin, or the like in order to modify the paintability, coatability and coating of the barrier layer.
Polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, starch, modified starch, isobutylene-
Maleic anhydride resin, diisobutylene-maleic anhydride resin, polyacrylic amide, modified polyacrylic amide, methyl vinyl ether, maleic acid copolymer, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropylene cellulose, and as a water-soluble emulsion, acetic acid. Resins such as vinyl, polystyrene, acrylic acid ester, vinyl chloride-vinyl acetate copolymer and the like can be mixed with the above-mentioned sulfonate group-containing polyester resin. Further, when the sulfonate group-containing polyester resin is not used for the barrier layer, the above various water-soluble resins can be used alone. Further, the barrier layer may contain a curing agent, a surfactant or an antioxidant, an ultraviolet absorber or the like for improving the light resistance of the heat-sensitive recording material, if necessary.
さらに本発明でいう保護層は感熱記録型カードに耐水
性、耐薬品性、耐擦損性等の向上、記録用サーマルヘッ
ドとのマッチングのために設けられ、例えばポリウレタ
ン樹脂、アクリル系樹脂、エポキシ樹脂、弗素系樹脂等
溶剤タイプの各種ポリマーが適用可能であるが、中でも
ポリウレタン樹脂が耐水性、耐擦損性の点でとくに本発
明に好適に使用される。Further, the protective layer referred to in the present invention is provided for the purpose of improving the water resistance, chemical resistance, scratch resistance and the like of the thermal recording type card and matching with the recording thermal head, and for example, polyurethane resin, acrylic resin, epoxy resin. Various types of solvent-type polymers such as resins and fluorine-based resins can be applied. Among them, polyurethane resin is particularly preferably used in the present invention in terms of water resistance and abrasion resistance.
又、本発明の感熱記録型カードには、ロイコ染料系感熱
発色層の反対側に位置する支持層上に表示事項を印刷し
てもよい。この場合の表示事項とは、会社名、注意書
き、コマーシャルおよび各種のマーク、模様印刷等をモ
ノ黒もしくはカラーで印刷するもので、よりファッショ
ナブルなカードとして用途が広がる。例えば遊園地等の
レジャー施設の記念カードとか、バレンタインディ、誕
生日等の贈物にメッセージをつけて送る場合の贈答品用
カード等一般消費者向けの各種のカードに適用可能であ
る。この場合の印刷は通常の印刷手段を用いて支持体の
面にダイレクトに印刷してもよいが支持体面上に一旦白
色もしくは有色の塗布層を設け、その上に所定の表示事
項を印刷してもよい。Further, in the heat-sensitive recording type card of the present invention, display items may be printed on the support layer located on the side opposite to the leuco dye-based heat-sensitive color developing layer. In this case, the display items are those for printing company names, notes, commercials and various marks, pattern printing, etc. in mono black or color, and the application spreads as a more fashionable card. For example, the present invention can be applied to various kinds of cards for general consumers, such as commemorative cards for leisure facilities such as amusement parks, gift cards when sending gifts such as Valentine's Day and birthday with a message. The printing in this case may be performed directly on the surface of the support using a usual printing means, but once a white or colored coating layer is provided on the surface of the support, and a predetermined display item is printed on it. Good.
以下本発明を実施例および比較例をもって詳細に述べ
る。なお配合表の中の部数は全て重量部を示すものとす
る。Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. It should be noted that all the parts in the formulation table indicate parts by weight.
＜実施例＞ 実施例１ 厚さ１８８μｍを有する酸化チタン練込み白色ポリエス
テルフィルムからなる支持体の上にロイコ染料系感熱発
色層、バリヤー層、保護層を下記の配合処方に従って順
次塗工積層して本発明の感熱記録型カードを作製した。<Example> Example 1 A leuco dye-based thermosensitive coloring layer, a barrier layer, and a protective layer were sequentially coated and laminated according to the following formulation on a support made of a titanium oxide-kneaded white polyester film having a thickness of 188 μm. A thermal recording type card of the present invention was produced.
まず結着剤とする特定組成のスルホン酸塩基含有ポリエ
ステル樹脂を以下のようにして合成した。First, a sulfonate group-containing polyester resin having a specific composition as a binder was synthesized as follows.
攪拌機、温度計、窒素吹込装置、充填塔付５００ccフラ
スコにテレフタル酸７６．４ｇ、イソフタル酸７６．４
ｇ、５−ナトリウムスルホイソフタル酸ジメチルエステ
ル２３．７ｇ、エチレングリコール９３．１ｇ、酢酸亜
鉛０．２ｇ、三酸化アンチモン０．４ｇを仕込み１９０
〜２２０℃、４時間エステル化反応をした後、２３０〜
２５０℃、１mmHg下で縮合反応を行い、全ジカルボン酸
中のスルホン酸塩基含有モノマーが８モル％、全グリコ
ール成分中でエチレングリコールが１００モル％、エー
テルグリコールが０モル％のスルホン酸塩基含有ポリエ
ステル樹脂を合成した。この樹脂を９０℃の熱水で２０
％スルホン酸塩基含有ポリエステル水溶液を調製した。Stirrer, thermometer, nitrogen blowing device, 76.4 g of terephthalic acid, 76.4 g of isophthalic acid in a 500 cc flask equipped with a packed tower
g, 5-sodium sulfoisophthalic acid dimethyl ester 23.7 g, ethylene glycol 93.1 g, zinc acetate 0.2 g, and antimony trioxide 0.4 g were charged 190
~ 220 ° C, after the esterification reaction for 4 hours, 230 ~
Condensation reaction is carried out at 250 ° C. under 1 mmHg, 8 mol% of sulfonic acid group-containing monomer in all dicarboxylic acids, 100 mol% of ethylene glycol in all glycol components, and 0 mol% of ether glycol in sulfonic acid group-containing polyester. A resin was synthesized. This resin is heated with hot water at 90 ° C for 20
An aqueous polyester solution containing a% sulfonate group was prepared.
次に感熱塗料を得るために下記の処方から成る混合を各
々ボールミルで１日粉砕・分散してＡ〜Ｃ液を調製し
た。Next, in order to obtain a heat-sensitive paint, a mixture consisting of the following formulations was ground and dispersed by a ball mill for 1 day to prepare liquids A to C.
Ａ液 Ｂ液 Ｃ液 上記のＡ液１０部、Ｂ液３３．３部、Ｃ液４９部、スル
ホン酸塩基含有ポリエステル水溶液１５部、水４６部を
混合して感熱記録用塗料を得た。該塗料を支持体の一方
の面に乾燥後の塗布量が６ｇ／m2になるように塗布、乾
燥してロイコ染料系感熱発色層を設けた。Liquid A B liquid C liquid A heat-sensitive recording coating material was obtained by mixing 10 parts of the above liquid A, 33.3 parts of liquid B, 49 parts of liquid C, 15 parts of a sulfonate group-containing polyester aqueous solution, and 46 parts of water. The coating material was applied on one surface of the support so that the coating amount after drying was 6 g / m 2 , and dried to form a leuco dye-based thermosensitive coloring layer.
上記ロイコ染料系感熱発色層に使用したポリエステル樹
脂を使用し下記配合のバリヤー層塗液を調製し、感熱発
色層の上に塗布、乾燥して塗布量３ｇ／m2のバリヤー層
を形成した。A barrier layer coating solution having the following composition was prepared by using the polyester resin used for the above-mentioned leuco dye-based thermosensitive coloring layer, coated on the thermosensitive coloring layer and dried to form a barrier layer having a coating amount of 3 g / m 2 .
〔保護層〕 下記配合からなる保護層塗液を調製し、バリヤー層上に
塗布、乾燥して保護層を形成し、感熱記録シートを作製
し、さらに所定の寸法、形状に打ち抜き加工して本発明
の感熱記録型カードを得た。 [Protective layer] A protective layer coating solution having the following composition is prepared, coated on the barrier layer and dried to form a protective layer, a thermal recording sheet is prepared, and punched into a predetermined size and shape to prepare a protective layer. A heat-sensitive recording type card of the invention was obtained.
本発明の感熱記録型カードの感熱記録層に対して、ライ
ンドット型薄膜熱ヘッドを用い、０．４５Ｗ（１mJ／do
t）のエネルギーで画像記録を行い、その黒ベタ部分を
マクベス濃度系で測定したところ、１．１８の鮮明な発
色画像が得られた。次に耐水性試験として上記発色直後
のサンプルを２０℃の水に３日間浸漬後の濃度低下をマ
クベス濃度計でみたところ１．１４を示し十分な耐水性
が確認された。又、温湿度保存安定性をみるため、温度
４０℃、相対湿度９０％の恒温槽中に１週間放置後の発
色特性をみたところ、マクベス濃度計で１．１６が得ら
れすぐれた保存安定性が確認された。さらに又、発色記
録面を可塑剤含有プラスチック消ゴムと重ね合わせて２
kg／cm2の圧力で圧着し２４時間放置後、消ゴムをはが
して記録面を調べたところ全く変化が認められずすぐれ
た耐可塑剤性が確認された。 For the heat-sensitive recording layer of the heat-sensitive recording type card of the present invention, a line dot type thin film thermal head was used, and 0.45 W (1 mJ / do
Image recording was performed with the energy of t), and the black solid portion was measured with a Macbeth density system, and a clear color image of 1.18 was obtained. Next, as a water resistance test, when the sample immediately after color development was immersed in water at 20 ° C. for 3 days and the decrease in density was observed by a Macbeth densitometer, it was 1.14, and sufficient water resistance was confirmed. In addition, in order to check the storage stability of temperature and humidity, when the color development characteristics were observed after leaving it in a thermostatic chamber at a temperature of 40 ° C and a relative humidity of 90% for 1 week, 1.16 was obtained with a Macbeth densitometer and excellent storage stability. Was confirmed. Furthermore, the color recording surface is overlaid with a plasticizer-containing plastic eraser, and 2
After pressure bonding at a pressure of kg / cm 2 and leaving for 24 hours, the eraser was peeled off and the recording surface was examined. No change was observed and excellent plasticizer resistance was confirmed.
実施例２ 厚さ１８８μｍを有するポリエステルフィルムの片面に
マット加工を施し、もう一方の面にカラー印刷を施すた
めの酸化チタンとアクリル系接着剤からなる白色層を設
けた支持体の該マット加工面に実施例１で使用した感熱
記録用塗料を乾燥後の塗布量が６０／m2になるように塗
布・乾燥した後、下記Ｄ液で示す組成の紫外線硬化性イ
ンキを２μｍ膜厚になるように塗布後、紫外線照射装置
（１．２Kw水銀ランプ１灯）を用いランプからの距離１
０cm、搬送スピード１５ｍ／分で紫外線を照射、紫外線
硬化保護層を有する感熱記録シートを作製し、さらに所
定の寸法、形状のカードに打ち抜き加工し裏面の白色層
にファッショナブルなカラー印刷を施して本発明の感熱
記録型カードを得た。Example 2 A matte surface of a support provided with a polyester film having a thickness of 188 μm on one surface of which matte processing is performed, and on the other surface of which a white layer made of titanium oxide and an acrylic adhesive for color printing is provided. Then, the heat-sensitive recording coating composition used in Example 1 was applied and dried so that the coating amount after drying was 60 / m 2, and then an ultraviolet curable ink having the composition shown by the following liquid D was formed to a film thickness of 2 μm. After applying to the, using an ultraviolet irradiation device (1.2Kw mercury lamp 1 lamp) distance from the lamp 1
Ultraviolet rays are irradiated at 0 cm and a conveying speed of 15 m / min to prepare a heat-sensitive recording sheet having a UV-curing protective layer, which is then punched into a card having a predetermined size and shape, and a fashionable color print is applied to the white layer on the back side. A thermal recording type card of the present invention was obtained.
Ｄ液 得られた感熱記録型カードいについて実施例１と同じ要
領で特性を評価したところ、ロイコ染料系感熱発色層に
関してすぐれた発色特性、耐水性、保存安定性および耐
可塑剤性が確認された。Liquid D When the characteristics of the obtained thermosensitive recording type card were evaluated in the same manner as in Example 1, excellent color forming characteristics, water resistance, storage stability and plasticizer resistance were confirmed for the leuco dye-based thermosensitive coloring layer.
実施例３ 実施例１におけるバリヤー層を下記配合に代えた以外
は、実施例１と全く同様にして本発明の感熱記録型カー
ドを得た。Example 3 A thermosensitive recording card of the present invention was obtained in exactly the same manner as in Example 1 except that the barrier layer in Example 1 was changed to the following composition.
得られた感熱記録型カードについては実施例１と同じ要
領で特性を評価したところ、ロイコ染料系感熱発色層に
関してすぐれた発色特性、耐水性、保存安定性および耐
可塑剤性が確認され、さらに市販の感熱プノンターに適
用し所定の情報記録を感熱記録面に施したところ、実用
上全く支障のないことが確認された。 The obtained thermosensitive recording type card was evaluated for characteristics in the same manner as in Example 1. As a result, excellent color forming characteristics, water resistance, storage stability and plasticizer resistance were confirmed for the leuco dye-based thermosensitive coloring layer. When it was applied to a commercially available heat sensitive printer and predetermined information was recorded on the heat sensitive recording surface, it was confirmed that there was no problem in practical use.
比較例 実施例１で使用したスルホン酸塩基含有ポリエステル樹
脂に代えて以下に示す合成手段によるスルホン酸塩基含
有ポリエステル樹脂を使用したほかは、全て実施例１と
同様にして比較用の感熱記録型カードを得た。Comparative Example A heat-sensitive recording type card for comparison in the same manner as in Example 1 except that the sulfonate group-containing polyester resin used in Example 1 was replaced by the sulfonate group-containing polyester resin obtained by the following synthesis means. Got
すなわち、撹攪機、温度計、窒素吹込装置、充填塔付５
００ccフラスコにテレフタル酸１１６．３ｇ、アジピン
酸２１．９ｇ、５−ナトリウムスルホイソフタル酸ジメ
チルエステル４４．４ｇ、エチレングリコール６２．１
ｇ、ジエチレングリコール５３．１ｇ、酢酸亜鉛０．２
ｇ、三酸化アンチモン０．４ｇを仕込み１９０〜２２０
℃で４時間エステル化反応をした後、２３０〜２５０
℃、１mmHg下で縮合反応を行い、全カルボン酸中のスル
ホン酸塩基モノマーが８モル％、全グリコール成分中で
エチレングリコールが６７モル％、エーテルグリコール
が３３モル％のスルホン酸塩基含有ポリエステル樹脂を
合成した。That is, with a stirrer, thermometer, nitrogen blowing device, and packed tower 5
Terephthalic acid 116.3 g, adipic acid 21.9 g, 5-sodium sulfoisophthalic acid dimethyl ester 44.4 g, ethylene glycol 62.1 in a 00 cc flask.
g, diethylene glycol 53.1 g, zinc acetate 0.2
g, antimony trioxide 0.4g charged 190-220
After the esterification reaction at 4 ° C. for 4 hours, 230-250
The condensation reaction is performed at 1 ° C and 1 mmHg to obtain a sulfonate group-containing polyester resin containing 8 mol% of sulfonate group monomers in all carboxylic acids, 67 mol% of ethylene glycol and 33 mol% of ether glycol in all glycol components. Synthesized.
得られた比較用の感熱記録型カードに対して、実施例１
と同要領にてラインドット型薄膜熱ヘッドを用い、０．
４５Ｗ（1mJ/dot）のエネルギーで画像記録を行い、そ
の黒ベタ部分をマクベス濃度計で測定したところ、１．
１８の鮮明な発色画像が得られた。次に耐水性試験とし
て上記発色直後のサンプルを２０℃の水に３日間浸漬後
の濃度低下をマクベス濃度計でみたところ０．４１を示
し耐水性の不足が確認された。又、温湿度保存安定性を
みるため、温度４０℃、相対湿度９０％の恒温槽中に１
週間放置後の発色特性をみたところ、マクベス濃度計で
０．３７が得られ保存安定性においても著しく実用特性
上問題を有するものであった。Example 1 was applied to the obtained thermal recording card for comparison.
In the same manner as above, a line dot type thin film thermal head was used.
Image recording was performed with an energy of 45 W (1 mJ / dot), and the black solid portion was measured with a Macbeth densitometer.
18 clear color images were obtained. Next, as a water resistance test, when the sample immediately after color development was immersed in water at 20 ° C. for 3 days and the decrease in density was observed by a Macbeth densitometer, it was 0.41 and it was confirmed that the water resistance was insufficient. In addition, in order to check the storage stability of temperature and humidity, 1 in a constant temperature bath at a temperature of 40 ° C and relative humidity of 90%.
When the color development characteristics after standing for a week were examined, it was 0.37 with a Macbeth densitometer, and the storage stability was remarkably problematic in practical characteristics.
＜発明の効果＞ 本発明の感熱記録型カードは、その積層構成中のロイコ
染料系感熱発色層およびバリヤー層のうちの少なくとも
一層に特定の組成を有するスルホン酸塩基含有ポリエス
テル樹脂を配合してあるので、該感熱発色層は顧客の過
酷な使用条件下において使用されても、耐水性、温湿度
依存性、耐可塑剤性等においてきわめてすぐれた耐用性
が確認された。<Effects of the Invention> The heat-sensitive recording type card of the present invention comprises a sulfonate group-containing polyester resin having a specific composition in at least one of the leuco dye-based heat-sensitive coloring layer and the barrier layer in the laminated structure. Therefore, it was confirmed that the thermosensitive color developing layer has extremely excellent durability in terms of water resistance, temperature / humidity dependency, plasticizer resistance and the like even when used under the severe usage conditions of the customer.
又、本発明でいう特定の組成を有するスルホン酸塩基含
有ポリエステル樹脂は各種合成樹脂製支持体との接着性
がよいので感熱発色層の結着剤として配合した場合、折
り曲げ等によっても塗布層が剥離することなくすぐれた
実用特性を得ることができる。In addition, since the sulfonate group-containing polyester resin having a specific composition referred to in the present invention has good adhesiveness with various synthetic resin supports, when blended as a binder for the thermosensitive coloring layer, the coating layer may be bent or the like. Excellent practical properties can be obtained without peeling.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 武 静岡県静岡市用宗巴町３番１号 株式会社 巴川製紙所技術研究所内 (72)発明者 重松 貞夫 兵庫県尼崎市塚口本町６−３−58 (72)発明者 楠田 俊之 大阪府茨木市平田台13−３ (56)参考文献 特開 昭61−116587（ＪＰ，Ａ) 実開 昭61−40262（ＪＰ，Ｕ) ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Takeshi Suzuki 3-1, Somune-cho, Shizuoka-shi, Shizuoka Pref., Technical Research Institute, Tomagawa Paper Mill Co., Ltd. (72) Sadao Shigematsu, 6-3 Tsukaguchimoto-cho, Amagasaki-shi, Hyogo -58 (72) Inventor Toshiyuki Kusunita 13-3 Hiratadai, Ibaraki City, Osaka Prefecture (56) References JP-A-61-116587 (JP, A) Actually developed Shou 61-40262 (JP, U)
Claims (2)
ー層のうちの少なくとも一層に、全ジカルボン酸中でス
ルホン酸塩基含有モノマーが６〜１５モル％、全グリコ
ール成分中でエチレングリコールが８５モル％以上で且
つエーテルグリコールが１５モル％以下であるスルホン
酸塩基含有ポリエステル樹脂を含有することを特徴とす
る感熱記録型カード。1. A support layer composed of (a) a synthetic resin material, (b) a leuco dye-based thermosensitive coloring layer, (c) a barrier layer (d) a protective layer if necessary, and the thermosensitive coloring layer and the protective layer. At least one of the barrier layers contains 6 to 15 mol% of a sulfonate group-containing monomer in all dicarboxylic acids, 85 mol% or more of ethylene glycol and 15 mol% or less of ether glycol in all glycol components. A heat-sensitive recording type card containing an acid-base containing polyester resin.
る支持体層上に所定の表示事項が印刷されていることを
特徴とする特許請求の範囲第１項に記載の感熱記録型カ
ード。2. A heat-sensitive recording type card according to claim 1, wherein a predetermined display item is printed on a support layer located on the opposite side of the leuco dye-based heat-sensitive color developing layer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61132695A JPH0662006B2 (en) | 1986-06-10 | 1986-06-10 | Thermal recording type card |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61132695A JPH0662006B2 (en) | 1986-06-10 | 1986-06-10 | Thermal recording type card |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62290578A JPS62290578A (en) | 1987-12-17 |
| JPH0662006B2 true JPH0662006B2 (en) | 1994-08-17 |
Family
ID=15087381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61132695A Expired - Lifetime JPH0662006B2 (en) | 1986-06-10 | 1986-06-10 | Thermal recording type card |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662006B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0630462Y2 (en) * | 1988-05-02 | 1994-08-17 | 株式会社小林 | Card management sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6140262U (en) * | 1984-08-20 | 1986-03-14 | 株式会社リコー | Thermal recording release paper |
| JPS61116587A (en) * | 1984-11-12 | 1986-06-04 | Ricoh Co Ltd | Transparent thermal recording material suitable for intermediate print |
-
1986
- 1986-06-10 JP JP61132695A patent/JPH0662006B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62290578A (en) | 1987-12-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |