JPH0441075B2 - - Google Patents
Info
- Publication number
- JPH0441075B2 JPH0441075B2 JP57217063A JP21706382A JPH0441075B2 JP H0441075 B2 JPH0441075 B2 JP H0441075B2 JP 57217063 A JP57217063 A JP 57217063A JP 21706382 A JP21706382 A JP 21706382A JP H0441075 B2 JPH0441075 B2 JP H0441075B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- dye
- sublimable
- layer
- thermal
- 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
- 238000000034 method Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000859 sublimation Methods 0.000 claims description 10
- 230000008022 sublimation Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 239000000975 dye Substances 0.000 description 44
- 239000000123 paper Substances 0.000 description 25
- 238000002844 melting Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004203 carnauba wax Substances 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
Description
〔産業上の利用分野等〕
本発明は昇華性色素を熱転写させて色素画像を
形成できる感熱転写記録媒体及び感熱転写記録方
法に関する。更に詳しくは、熱、光等に対して安
定な高鮮鋭性かつ多階調性を有する色素画像を昇
華性色素を用いる熱転写工程により普通紙等の記
録シート上に得ることができる感熱転写記録媒体
及び感熱転写記録方法に関する。
〔従来技術〕
従来より厚膜抵抗、薄膜抵抗、半導体抵抗等で
構成されたサーマルヘツド若しくはレーザー、キ
セノンランプ等の熱源により、感熱紙を発色させ
画像等を記録する方法が知られているが、これら
の方法では感熱紙を用いるため画像の熱、光に対
する安定性に問題があり、また製造コストが高い
という欠点があり、さらにカラー化については発
色層を多層にする必要があり、２色程度が限度で
あるという欠点があつた。
上記の欠点を解決する熱記録方式としては、例
えば特開昭51−15446号公報に記載されているよ
うな、常温では固体又は半固体状の色材を紙、樹
脂フイルム等の支持体上に塗布しておき、該支持
体上の色材と記録シートとを接触せしめ、画像情
報に応じて制御された熱源により、前記支持体上
の色材を加熱して、選択的に記録シートにさせて
記録を行なう感熱転写方式が知られている。該方
式における熱転写工程には、融点が低く熱容量の
小さい溶剤中に色素を混合させた色材を用い、溶
剤と共に色素を熱転写させる溶融転写型と、色材
として昇華性色素を用い、色素単独で昇華転写さ
せる昇華転写型が知られている。このうち溶融転
写型ではある一定の量以上の熱エネルギーを与え
ると色材が全て転写するため画像の階調性を得る
ことが難かしいという欠点があつた。これに対し
て昇華転写型では与えられる熱エネルギーの量に
応じて色素が転写されるため階調性を得るために
は望ましい方式である。しかしながら昇華転写型
では、画像形成に昇華性色素が用いられているた
め、色素の再昇華により画像の定着性や保存性に
問題があり、特に普通紙に転写させる場合には、
色濃度が低く、又経時に色素が再昇華することに
より色濃度の減少が著しいという欠点があつた。
そこで多階調な画像記録を得るためには有利な
昇華性色素を用い、しかも普通紙等に安定な画像
を形成できる感熱転写記録媒体及び感熱転写記録
方法の開発が切望されている。
〔発明の目的〕
本発明は上記要請を満足するためになされたも
ので、その目的は普通紙等に転写濃度の高い高鮮
鋭性かつ多階調性を有する色素画像を得ることが
できる感熱転写記録媒体及び感熱転写記録方法を
提供することにある。
〔発明の構成〕
本発明において昇華性層は常温では固体であり
加熱により昇華転写可能な色素（以下、昇華性色
素という。）を含有し、該昇華性層上に設けられ
た熱溶融性層は熱溶融性化合物を含有する。
前記昇華性色素としては、60℃〜300℃で昇華
する色素、例えばアゾ色素、アントラキノン系色
素、キサンテン系色素、アゾメチ系色素、トリフ
エニルメタン系色素、ニトロ系色素及びキノリン
系色素等が挙げられる。
前記熱溶融性化合物としては、低融点の化合物
即ち65℃〜130℃の融点を有する無色又は白色の
化合物が好ましく、例えばカルナバロウ、密ロウ
及びカンテリワツクス等のワツクス、ステアリン
酸及びベヘン酸等の高級脂肪酸、キシリトール等
のアルコール類、アセトアミド及びベンゾアミド
等のアミド類、フエニルウレア及びジエチルウレ
ア等の尿素類等が挙げられる。
なお、前記熱溶融性化合物を含有する熱溶融性
層中には、ポリビニルピロリドン、ポリビニルブ
チラール、飽和ポリエステル等の色素の保持性に
優れたポリマーを加えてもよい。
本発明の感熱転写記録媒体の作製方法として
は、支持体上に昇華性層、熱溶融性層の順に塗布
されることによつて作製されることが望ましい。
具体的には、昇華転写可能な色素を適当なバイン
ダーにより支持体上に塗布するか、又は該色素だ
けを支持体上に塗布して昇華性層を形成し、その
上に熱溶融性化合物を適当なバインダーにより、
又は熱溶融性化合物自体がバインダーを兼ねるこ
とにより、塗布して熱溶融性層を形成すればよ
い。なお昇華性層と熱溶融性層の間に適当な中間
層を設けてもよい。なおまた、オーバーコート層
や下引層等を設けることも任意である。
前記塗布方法としては、前記本発明の化合物を
加熱し、ホツトメルトコーテイングして、塗布す
ることができる。塗布手段はワイヤバー塗布、ロ
ール塗布、グラビアロール塗布等が用いられる。
またトルエン、キシレン等の溶剤に溶解し、同様
の塗布手段で塗布することもできる。
前記バインダーとしては、ポリビニルブチラー
ル、ポリ酢酸ビニル、ポリビニルアルコール、ポ
リスチレン、スチレン−ブタジエン共重合体及び
エチルセルロース等のセルロースエステル類、メ
タアクリル酸メチル等のアクリル樹脂、ゼラチン
等を用いることができる。
前記支持体としては、耐熱強度を有し、平滑性
の高い支持体が望ましい。耐熱強度としては、サ
ーマルヘツドの加熱温度により軟質化、可塑化し
ない支持体としての強靭さを保持する強度を必要
とし、平滑性としては、支持体上の各層が良好な
転写率を示すに充分な平滑度が望まれる。平滑度
は、ベツク試験器による平滑度試験（JIS
P8119）で200sec以上あればよく、300sec以上で
あると良好な転写率で再現性のある画像が得られ
る。材質としては、例えば、普通紙、合成紙、ラ
ミネート紙などの紙類、あるいはポリエチレン、
ポリスチレン、ポリプロピレン、ポリイミドなど
の樹脂フイルム類及び紙−樹脂フイルム複合体な
どがいずれも好適に使用される。支持体の厚さは
良好な熱伝導性を得るうえで通常約60μm以下で
あるのが好ましい。
上記のように作製された感熱転写記録媒体の
各々の層は、厚さ１〜20μm程度とすることが良
好な画像を得る条件である。好ましくは１層が
15μm以下、より好ましくは2μm〜8μm程度が好
適である。
以下のような構成を有する本発明の感熱転写記
録媒体を用いて感熱転写記録する方法について以
下に述べる。
即ち、感熱転写記録媒体に画像の情報に応じて
支持体側からエネルギーを与えると、熱溶融性層
は一定値以上のエネルギーを与えられることによ
つて、記録紙に転写される。昇華性層からはエネ
ルギー量に応じて色素が昇華転写され、記録紙
（普通紙等）上には昇華性色素による画像が熱溶
融性層に溶け込んだ形で得られる。
本発明において上記のように支持体上に塗布さ
れた色素が記録紙へ転移し、記録シート上で定着
されるのは、熱によつて熱溶融性化合物を含有す
る熱溶融性層が記録紙上に熱溶融転写され、それ
と同時或いは後から昇華性色素が熱溶融性化合物
が転写された記録紙上に転写されるか、又は昇華
性色素が熱溶融性層に転写された後、昇華性色素
を含む熱溶融性色素が転写されることにより、記
録紙上で昇華性色素が熱溶融性層に溶け込んだ状
態で保持されるためである。従つて前述のよう
に、昇華転写可能な色素を含有する昇華性層と前
記熱溶融性層とは、支持体上に昇華性層、熱溶融
性層の順に塗布されるのが好ましいのである。
上述の如くして得られた画像は転写濃度も高
く、高鮮鋭性且つ多階調性を有しており、定着性
においても優れている。従つて記録紙としては普
通紙で良く、さらに紙だけでなく各種のプラスチ
ツクフイルムや布等にも色素画像を与えることが
できる。
〔実施例〕
以下に本発明の好ましい実施例を示すが本発明
はこの実施例に限定されるものではない。
先ず感熱転写記録媒体の作製手段について第１
図基づき説明する。
最初に厚さ6μのポリエチレンテレフタレート
フイルムベース１に下記組成物をウエツト膜厚
59.4μとなるようにワイヤーバーを用いて塗布、
乾燥し、昇華性層２を形成した。
二酢酸セルロース
下記昇華性色素Dye(1)
アセトン 0.6ｇ
0.3ｇ
20ml
続いて上記昇華性層の上に下記組成物をウエツ
ト膜厚27.4μとなるよう塗布、乾燥し溶融性層３
を形成し、感熱転写記録媒体Ａを作製した。
パーマリンPN（三洋化成製）
H2O
２％アニオン系活性剤 10ml
10ml
0.3ml
次に前記感熱転写記録媒体Ａを用いた感熱転写
記録試験について記述する。
感熱転写記録試験(1)
前記感熱転写記録媒体Ａの塗布面と白色の普通
紙４とを向い合わせにして重ね、感熱転写記録媒
体Ａの支持体１側からサーマルヘツド５により発
熱体６を介して加熱して色素７を転写させて転写
記録試験を行なつた。
本試験において、サーマルヘツド５の温度及び
電圧印加の時間を変化させた。その変化の状況を
第２図及び第３図に示す。第２図は温度と転写濃
度の関係を示し（このとき電圧印加時間を
0.8msecとした。）、第３図は印加時間と転写濃度
の関係を示す（このときサーマルヘツドの温度を
150℃とした。）。
同図に示すように本発明によればサーマルヘツ
ド５の温度又は印加時間の変化という簡単な操作
で、各々の変化に対応して画像の多階調性が得ら
れることが判つた。
感熱転写記録試験(2)
前記感熱転写記録媒体Ａと昇華性色素を下記
Dye(2)に変えた以外は同様の組成及び手段により
感熱転写記録媒体Ｂを、昇華性色素を下記Dye(3)
に変えた以外は同様の組成及び手段により感熱転
写記録媒体Ｃを、及び熱溶融性化合物をカルナバ
ロウに変えた以外は同様の組成及び手段により感
熱転写記録媒体Ｄを、各々作製した。
また比較例として感熱転写記録媒体Ａ〜Ｃから
熱溶融性層を除いたものを作製し、感熱転写記録
媒体Ｅ，Ｆ，Ｇとした。
次いで前記の感熱転写記録媒体Ａ〜Ｇの塗布面
を普通紙に重ね合わせ、表面温度150℃のサーマ
ルプレート（４cm×１cm）を１秒間押しつけ普通
紙上に転写画像を得た。この結果を第１表に示す
（同表の転写濃度の項参照）。
上記の結果、本発明の記録媒体Ａ〜Ｄは比較例
Ｅ〜Ｇに比べて高濃度の転写画像が得られた。
次に被転写紙を80℃の温度で１週間放置した結
果、感熱転写記録媒体Ａ〜Ｃを用いた転写画像は
濃度の減少が少ししか認められなかつたが、Ｆ〜
Ｇでは濃度が著しく減少した。
次に放置前後のλmaxによる光学濃度を（放置
前Do1、放置後D1）測定し、Ｄ／Do×100（％）
を残存率とし画像の熱安定性をテストした。
この結果を第１表に示す。
同表に示す通り、本発明の感熱転写記録媒体Ａ
〜Ｄを用いた感熱転写記録方式では、熱溶融性層
を含まない比較例の感熱転写記録媒体Ｅ〜Ｇを用
いた感熱転写記録方式に比べて、転写濃度、熱安
定性（定着性）ともに非常に優れていることがわ
かる。
以上本発明の好ましい実施例について、即ちサ
ーマルヘツドの発熱体を当てて加熱し、感熱転写
媒体より色素を転写させる場合について説明した
が、これに限定されず、例えば、支持体側からヘ
リウム−ネオンレーザー、炭酸ガスレーザー、
YAGレーザー等のレーザー光を照射し、感熱転
写媒体を発熱させ、色素を転写させて画像を形成
させてもよい。
[Industrial Application Field, etc.] The present invention relates to a thermal transfer recording medium and a thermal transfer recording method capable of forming a dye image by thermally transferring a sublimable dye. More specifically, it is a thermal transfer recording medium that can produce a dye image with high sharpness and multi-gradation properties that is stable against heat, light, etc. on a recording sheet such as plain paper through a thermal transfer process using a sublimable dye. and a thermal transfer recording method. [Prior Art] Conventionally, methods have been known in which thermal paper is colored and images are recorded using a thermal head composed of thick-film resistors, thin-film resistors, semiconductor resistors, etc., or a heat source such as a laser or a xenon lamp. Since these methods use thermal paper, there are problems with the stability of the image against heat and light, and there are also disadvantages of high manufacturing costs.Furthermore, for colorization, it is necessary to have multiple coloring layers, so it is necessary to use only two colors. The drawback was that there was a limit. A thermal recording method that solves the above-mentioned drawbacks is, for example, as described in Japanese Patent Application Laid-open No. 15446/1982, in which a coloring material that is solid or semi-solid at room temperature is deposited on a support such as paper or resin film. The coloring material on the support is brought into contact with the recording sheet, and the coloring material on the support is heated by a heat source controlled according to image information to selectively form the recording sheet. A thermal transfer method that performs recording is known. The thermal transfer process in this method uses a coloring material mixed with a dye in a solvent with a low melting point and small heat capacity, and a melt transfer type that thermally transfers the dye together with the solvent, and a melt transfer type that uses a sublimable dye as the coloring material and uses a dye alone. A sublimation transfer type that performs sublimation transfer is known. Among these, the melt transfer type has the disadvantage that if a certain amount of thermal energy or more is applied, all the coloring material is transferred, making it difficult to obtain gradation of the image. On the other hand, in the sublimation transfer type, the dye is transferred depending on the amount of thermal energy applied, so it is a desirable method for obtaining gradation. However, in the sublimation transfer type, sublimable dyes are used for image formation, so there are problems with image fixability and storage stability due to re-sublimation of the dyes, especially when transferring to plain paper.
It had the disadvantage that the color density was low and that the color density decreased significantly due to re-sublimation of the dye over time. Therefore, in order to obtain multi-tone image recording, there is a strong desire to develop a thermal transfer recording medium and a thermal transfer recording method that use advantageous sublimable dyes and can form stable images on plain paper or the like. [Object of the Invention] The present invention has been made to satisfy the above-mentioned requirements, and its purpose is to provide a thermal transfer method capable of obtaining a dye image with high transfer density, high sharpness, and multi-gradation on plain paper, etc. An object of the present invention is to provide a recording medium and a thermal transfer recording method. [Structure of the Invention] In the present invention, the sublimable layer contains a dye that is solid at room temperature and can be sublimated and transferred by heating (hereinafter referred to as sublimable dye), and a heat-fusible layer provided on the sublimable layer. contains a heat-melting compound. Examples of the sublimable dyes include dyes that sublimate at 60° C. to 300° C., such as azo dyes, anthraquinone dyes, xanthene dyes, azomethane dyes, triphenylmethane dyes, nitro dyes, and quinoline dyes. . The heat-melting compound is preferably a low-melting compound, that is, a colorless or white compound having a melting point of 65°C to 130°C, such as waxes such as carnauba wax, beeswax, and canteri wax, and higher fatty acids such as stearic acid and behenic acid. , alcohols such as xylitol, amides such as acetamide and benzamide, ureas such as phenylurea and diethylurea, and the like. In addition, a polymer having excellent dye retention properties such as polyvinylpyrrolidone, polyvinyl butyral, and saturated polyester may be added to the heat-melting layer containing the heat-melting compound. As for the method for producing the thermal transfer recording medium of the present invention, it is preferable that it be produced by coating a sublimable layer and a heat-fusible layer in this order on a support.
Specifically, a sublimation-transferable dye is coated onto a support using a suitable binder, or only the dye is coated onto a support to form a sublimable layer, and a heat-melting compound is applied on top of the sublimable layer. With a suitable binder,
Alternatively, the heat-fusible compound itself may also serve as a binder to form a heat-fusible layer by coating. Note that a suitable intermediate layer may be provided between the sublimable layer and the heat-fusible layer. Furthermore, it is also optional to provide an overcoat layer, an undercoat layer, and the like. As the coating method, the compound of the present invention can be heated and hot-melt coated. As the coating means, wire bar coating, roll coating, gravure roll coating, etc. are used.
It can also be dissolved in a solvent such as toluene or xylene and applied using a similar application method. As the binder, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polystyrene, styrene-butadiene copolymer, cellulose esters such as ethyl cellulose, acrylic resins such as methyl methacrylate, gelatin, etc. can be used. As the support, a support having heat resistance strength and high smoothness is desirable. Heat resistance strength is required to maintain the toughness of the support without softening or plasticization due to the heating temperature of the thermal head, and smoothness is sufficient to ensure that each layer on the support exhibits a good transfer rate. A good level of smoothness is desired. Smoothness was determined by smoothness test using a Beck tester (JIS
P8119), 200 sec or more is sufficient, and 300 sec or more will yield images with good transfer rate and reproducibility. Materials include, for example, paper such as plain paper, synthetic paper, and laminated paper, or polyethylene,
Resin films such as polystyrene, polypropylene, polyimide, and paper-resin film composites are all suitably used. The thickness of the support is preferably about 60 μm or less in order to obtain good thermal conductivity. A condition for obtaining a good image is that each layer of the heat-sensitive transfer recording medium produced as described above has a thickness of about 1 to 20 μm. Preferably one layer
The suitable thickness is 15 μm or less, more preferably about 2 μm to 8 μm. A method for thermal transfer recording using the thermal transfer recording medium of the present invention having the following configuration will be described below. That is, when energy is applied to the heat-sensitive transfer recording medium from the support side in accordance with image information, the heat-fusible layer is transferred to the recording paper by applying energy of a certain value or more. The dye is sublimated and transferred from the sublimable layer according to the amount of energy, and an image made of the sublimable dye is obtained on recording paper (plain paper, etc.) in a form dissolved in the heat-fusible layer. In the present invention, the dye coated on the support is transferred to the recording paper and fixed on the recording sheet as described above because the thermofusible layer containing the thermofusible compound is transferred onto the recording paper by heat. At the same time or later, the sublimable dye is transferred onto the recording paper onto which the heat-fusible compound has been transferred, or after the sublimable dye is transferred to the heat-fusible layer, the sublimable dye is transferred to the heat-fusible layer. This is because the sublimable dye is retained on the recording paper in a state dissolved in the heat-fusible layer by transferring the heat-fusible dye contained therein. Therefore, as described above, the sublimable layer containing a sublimation transferable dye and the heat-fusible layer are preferably coated on the support in this order. The image obtained as described above has a high transfer density, high sharpness and multi-tone property, and is also excellent in fixability. Therefore, plain paper may be used as the recording paper, and dye images can be applied not only to paper but also to various plastic films, cloth, and the like. [Example] Preferred examples of the present invention are shown below, but the present invention is not limited to these examples. First, about the means for producing a thermal transfer recording medium.
This will be explained based on the diagram. First, apply the following composition to a polyethylene terephthalate film base 1 with a thickness of 6 μm.
Apply using a wire bar to give a thickness of 59.4μ.
It was dried to form a sublimable layer 2. Cellulose diacetate Sublimable dye (1) Acetone 0.6g 0.3g 20ml Subsequently, the following composition was coated on the sublimable layer to a wet film thickness of 27.4μ, and dried to form the meltable layer 3.
was formed to produce a thermal transfer recording medium A. Permarin PN (manufactured by Sanyo Kasei) H 2 O 2% anionic activator 10ml 10ml 0.3ml Next, a thermal transfer recording test using the thermal transfer recording medium A described above will be described. Thermal transfer recording test (1) The coated surface of the thermal transfer recording medium A and white plain paper 4 were stacked facing each other, and the thermal head 5 was used to transfer the paper from the support 1 side of the thermal transfer recording medium A through the heating element 6. A transfer recording test was conducted by heating and transferring Dye 7. In this test, the temperature of the thermal head 5 and the time of voltage application were varied. The situation of the change is shown in Figs. 2 and 3. Figure 2 shows the relationship between temperature and transfer density (at this time, the voltage application time is
It was set to 0.8msec. ), Figure 3 shows the relationship between application time and transfer density (at this time, the temperature of the thermal head is
The temperature was 150℃. ). As shown in the figure, it has been found that according to the present invention, by a simple operation of changing the temperature of the thermal head 5 or the application time, multi-gradation of an image can be obtained corresponding to each change. Thermal transfer recording test (2) The thermal transfer recording medium A and the sublimable dye are as follows.
Thermal transfer recording medium B was prepared using the same composition and method except that Dye (2) was used, and the sublimation dye was changed to Dye (3) below.
A thermal transfer recording medium C was prepared using the same composition and method except that carnauba wax was used as the heat-melting compound, and a thermal transfer recording medium D was prepared using the same composition and method except that carnauba wax was used as the heat-melting compound. Further, as comparative examples, heat-sensitive transfer recording media A to C from which the heat-fusible layer was removed were prepared as heat-sensitive transfer recording media E, F, and G. Next, the coated surfaces of the thermal transfer recording media A to G were placed on plain paper, and a thermal plate (4 cm x 1 cm) having a surface temperature of 150° C. was pressed for 1 second to obtain a transferred image on the plain paper. The results are shown in Table 1 (see the section on transfer density in the same table). As a result of the above, recording media A to D of the present invention provided transferred images with higher density than those of Comparative Examples E to G. Next, as a result of leaving the transfer paper at a temperature of 80°C for one week, only a slight decrease in density was observed in the transferred images using thermal transfer recording media A to C, but F to
In G, the concentration decreased significantly. Next, measure the optical density according to λmax before and after leaving (Do 1 before leaving, D 1 after leaving), and calculate D/Do x 100 (%).
The thermal stability of the image was tested using the residual rate. The results are shown in Table 1. As shown in the table, thermal transfer recording medium A of the present invention
In the thermal transfer recording method using ~D, both the transfer density and thermal stability (fixing property) are improved compared to the thermal transfer recording method using comparative example thermal transfer recording media E~G that do not contain a heat-fusible layer. It turns out that it is very good. A preferred embodiment of the present invention has been described above, in which a heating element of a thermal head is applied to heat the dye and the dye is transferred from the heat-sensitive transfer medium. However, the present invention is not limited to this. , carbon dioxide laser,
An image may be formed by irradiating a laser beam such as a YAG laser to generate heat in the heat-sensitive transfer medium to transfer the dye.
上記実施例から明らかなように、本発明によれ
ば普通紙に転写濃度の高い、かつ熱安定性に優れ
た多階調性を有する色素画像を得ることができ
る。
As is clear from the above examples, according to the present invention, it is possible to obtain a multi-gradation dye image with high transfer density and excellent thermal stability on plain paper.
第１図は本発明に係る感熱転写記録媒体の作製
手段を示す説明図、第２図はサーマルヘツドの温
度と転写濃度の関係を示すグラフ、第３図は電圧
印加時間と転写濃度の関係を示すグラフである。
FIG. 1 is an explanatory diagram showing the means for producing a thermal transfer recording medium according to the present invention, FIG. 2 is a graph showing the relationship between the temperature of the thermal head and the transfer density, and FIG. 3 is a graph showing the relationship between the voltage application time and the transfer density. This is a graph showing.
Claims (1)
昇華転写可能な色素を含有する昇華性層を設け、
該昇華性層の上に熱溶融性化合物を含有する熱溶
融性層を設けたことを特徴とする感熱転写記録媒
体。 支持体上に、常温では固体であり加熱により昇
華転写可能な色素を含有する昇華性層を設け、該
昇華性層の上に熱溶融性化合物を含有する熱溶融
性層を設けてなる感熱転写記録媒体と、記録紙を
重ね合わせ、該感熱転写記録媒体と支持体側より
画像の情報に応じて熱エネルギーを与え、前記記
録紙上に色素による画像を形成させることを特徴
とする感熱転写記録方法。[Claims] 1. A sublimable layer containing a dye that is solid at room temperature and can be sublimated and transferred by heating is provided on a support,
A heat-sensitive transfer recording medium characterized in that a heat-fusible layer containing a heat-fusible compound is provided on the sublimation layer. A heat-sensitive transfer in which a sublimable layer containing a dye that is solid at room temperature and capable of sublimation transfer by heating is provided on a support, and a heat-fusible layer containing a heat-fusible compound is provided on the sublimable layer. 1. A thermal transfer recording method, which comprises overlapping a recording medium and a recording paper, and applying thermal energy according to image information from the thermal transfer recording medium and support side to form a dye image on the recording paper.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57217063A JPS59106997A (en) | 1982-12-13 | 1982-12-13 | Thermal transfer recording medium and recording method |
| US06/688,741 US4585688A (en) | 1982-10-04 | 1985-01-02 | Thermographic transfer recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57217063A JPS59106997A (en) | 1982-12-13 | 1982-12-13 | Thermal transfer recording medium and recording method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59106997A JPS59106997A (en) | 1984-06-20 |
| JPH0441075B2 true JPH0441075B2 (en) | 1992-07-07 |
Family
ID=16698245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57217063A Granted JPS59106997A (en) | 1982-10-04 | 1982-12-13 | Thermal transfer recording medium and recording method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59106997A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0761744B2 (en) * | 1985-06-21 | 1995-07-05 | 大日本印刷株式会社 | Thermal transfer sheet |
| JP2549846B2 (en) * | 1986-09-12 | 1996-10-30 | 大日本印刷株式会社 | Transfer sheet |
| JPS63168394A (en) * | 1986-12-29 | 1988-07-12 | Victor Co Of Japan Ltd | Ink sheet |
| JP2918228B2 (en) * | 1987-09-07 | 1999-07-12 | 株式会社リコー | Sublimation type thermal transfer media |
| JPH0225388A (en) * | 1988-07-15 | 1990-01-26 | Ricoh Co Ltd | Sublimation-type thermal transfer recording method |
| EP0625429B1 (en) * | 1989-07-14 | 1998-12-16 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
| JPH0449141U (en) * | 1990-08-28 | 1992-04-24 | ||
| JP3004104B2 (en) * | 1991-11-01 | 2000-01-31 | コニカ株式会社 | Image recording method and image recording apparatus |
| JPH07214920A (en) * | 1995-01-17 | 1995-08-15 | Dainippon Printing Co Ltd | Thermal transfer sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5343538B2 (en) * | 1976-08-20 | 1978-11-21 | ||
| JPS56109789A (en) * | 1980-02-01 | 1981-08-31 | Ricoh Co Ltd | Stencil paper for electronic recording |
| JPS57150600A (en) * | 1981-03-13 | 1982-09-17 | Fuji Xerox Co Ltd | Recording medium for thermal transfer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5842637Y2 (en) * | 1976-09-20 | 1983-09-27 | 東芝熱器具株式会社 | Fuel pumping device for combustion appliances |
-
1982
- 1982-12-13 JP JP57217063A patent/JPS59106997A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5343538B2 (en) * | 1976-08-20 | 1978-11-21 | ||
| JPS56109789A (en) * | 1980-02-01 | 1981-08-31 | Ricoh Co Ltd | Stencil paper for electronic recording |
| JPS57150600A (en) * | 1981-03-13 | 1982-09-17 | Fuji Xerox Co Ltd | Recording medium for thermal transfer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59106997A (en) | 1984-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0216715B2 (en) | ||
| US4617224A (en) | Thermal transfer recording medium | |
| JPS58219086A (en) | Heat-sensitive transfer recording medium | |
| JPH0441075B2 (en) | ||
| JPS60225793A (en) | Thermal transfer recording method | |
| US4585688A (en) | Thermographic transfer recording medium | |
| JPH0545435B2 (en) | ||
| JPS60104394A (en) | Thermal transfer recording medium | |
| JPH041717B2 (en) | ||
| JPS59194892A (en) | Thermal transfer recording medium | |
| JPS58219087A (en) | Heat-sensitive transfer recording medium | |
| JPS60165291A (en) | Thermal heat transfer recording medium | |
| JPS6078777A (en) | Thermal transfer ink ribbon | |
| JPH0333515B2 (en) | ||
| JPH0377796B2 (en) | ||
| JPS60104395A (en) | Thermal transfer recording medium | |
| JPH0461793B2 (en) | ||
| JPH0415117B2 (en) | ||
| JPH0377794B2 (en) | ||
| JPS60132791A (en) | Thermal transfer recording medium and manufacture thereof | |
| JPS60994A (en) | Thermal transfer paper and preparation thereof | |
| JPS6046296A (en) | Thermal transfer recording medium | |
| JPH024590A (en) | Thermal transfer recording medium | |
| JPH0671836B2 (en) | Melt transfer type image receiving sheet for thermal transfer | |
| JPS61114891A (en) | Thermal transfer recording medium |