JPH0355318B2 - - Google Patents
Info
- Publication number
- JPH0355318B2 JPH0355318B2 JP55104388A JP10438880A JPH0355318B2 JP H0355318 B2 JPH0355318 B2 JP H0355318B2 JP 55104388 A JP55104388 A JP 55104388A JP 10438880 A JP10438880 A JP 10438880A JP H0355318 B2 JPH0355318 B2 JP H0355318B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- surface layer
- color
- casein
- 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
- 239000002344 surface layer Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000005018 casein Substances 0.000 claims description 11
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 11
- 235000021240 caseins Nutrition 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 3
- -1 phenolic compounds Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
【発明の詳細な説明】
本発明は加熱により発色剤と顕色剤が反応して
画像が記録される感熱記録体に関し、さらに詳細
には発色画像の保存安定性を改良した感熱記録体
を得ることを目的とする。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-sensitive recording material in which an image is recorded by the reaction between a color forming agent and a color developer by heating, and more specifically, to obtain a heat-sensitive recording material with improved storage stability of colored images. The purpose is to
従来、感熱記録体としては例えば、米国特許第
271250号あるいは同第2730457号明細書に記載さ
れているクリスタルバイオレツトラクトン（Ｃ・
Ｖ・Ｌ・）、等のロイコ染料とフエノール性化合
物の如き有機酸との組み合せよりなるものが公知
である。 Conventionally, as a heat-sensitive recording medium, for example, U.S. Patent No.
Crystal violet lactone (C.
A combination of a leuco dye such as V.L.) and an organic acid such as a phenolic compound is known.
しかし、従来のこの種の感熱記録体は感熱発色
部がポリ塩化ビニルなどのプラスチツクと接触す
ると、プラスチツク中に含まれている可塑剤や安
定剤、添加剤、等により発色像が退色し消えてし
まつたり、また未発色部が接触した場合には発色
しなくなる等の欠点があつた。例えば感熱記録体
の上にプラスチツク消しゴムを置いておくと数時
間程度で発色画像が消えてしまつたり、発色記録
した感熱記録体をポリ塩化ビニル製のカードケー
ス中や皮サイフ中で長期間保存した場合には発色
画像が消えてしまう等の不都合が生じた。 However, in conventional heat-sensitive recording materials of this type, when the heat-sensitive color forming part comes into contact with plastic such as polyvinyl chloride, the color image fades and disappears due to the plasticizers, stabilizers, additives, etc. contained in the plastic. There were drawbacks such as clumping and failure to develop color when uncolored areas came into contact with each other. For example, if you place a plastic eraser on a heat-sensitive recording material, the colored image will disappear within a few hours, or the colored heat-sensitive recording material may be stored for a long time in a polyvinyl chloride card case or leather wallet. In this case, problems such as the colored image disappearing occurred.
そこで、本発明者らは従来の感熱記録体に用い
られている感熱記録材料がプラスチツクに用いら
れている可塑剤や皮製品に含まれている柔軟剤等
に対して不安定である原因を種々検討した結果、
従来顕色剤として使用されているフエノール性化
合物の如き有機酸は、プラスチツクの可塑剤等と
の相溶性が良いためにロイコ染料との発色反応が
起りにくくなり、また発色している部分をも消し
てしまうことをつきとめ、その対策を検討した結
果、感熱記録層の上に表面層を設けることによ
り、感熱記録体と可塑剤等との接触をさまたげ、
発色画像の保存安定性を改良した感熱記録体を得
たものである。 Therefore, the present inventors investigated various reasons why the heat-sensitive recording materials used in conventional heat-sensitive recording bodies are unstable against plasticizers used in plastics and softeners contained in leather products. As a result of consideration,
Organic acids such as phenolic compounds, which are conventionally used as color developers, have good compatibility with plasticizers, etc. of plastics, making it difficult for color reactions to occur with leuco dyes, and also to remove colored areas. As a result of investigating the countermeasures, we found that by providing a surface layer on the heat-sensitive recording layer, we can prevent contact between the heat-sensitive recording material and the plasticizer, etc.
A heat-sensitive recording material with improved storage stability of colored images is obtained.
すなわち本発明は、紙あるいはプラスチツクフ
イルムなどの支持体上に形成された感熱記録層の
上にカゼインとヒドロキシエチルセルロース、ヒ
ドロキシプロピルセルロース、イソブチレン−無
水マレイン酸共重合体、ポリ酢酸ビニル、酢酸ビ
ニル−アクリル共重合体、変性ポリアクリルアミ
ド、ポリビニルアルコールから成る群から選ばれ
た樹脂の少なくとも１種以上を主成分とした表面
層を設けた感熱記録体に係るものであり、前記表
面層を設けることにより感熱記録層への可塑剤等
の浸透を防止し、発色画像の保存安定性を改良し
たものである。 That is, the present invention provides casein, hydroxyethyl cellulose, hydroxypropyl cellulose, isobutylene-maleic anhydride copolymer, polyvinyl acetate, vinyl acetate-acrylic on a heat-sensitive recording layer formed on a support such as paper or plastic film. This relates to a heat-sensitive recording material provided with a surface layer mainly composed of at least one resin selected from the group consisting of copolymer, modified polyacrylamide, and polyvinyl alcohol. This prevents plasticizers from penetrating the recording layer and improves the storage stability of colored images.
本発明の感熱記録体を製造するには、まずロイ
コ染料、顕色剤、結着剤、助剤としてのワツクス
類、酸化亜鉛・酸化チタン・炭酸カルシウム・炭
酸マグネシウム・クレー・タルク、等の顔料およ
びその他の任意成分からなる水系感熱塗料を調整
し、この塗料を支持体上に塗布、乾燥して感熱記
録層を形成する。 To produce the heat-sensitive recording material of the present invention, first, a leuco dye, a color developer, a binder, waxes as auxiliaries, pigments such as zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, clay, talc, etc. A water-based heat-sensitive paint consisting of the following components and other optional components is prepared, and this paint is applied onto a support and dried to form a heat-sensitive recording layer.
本発明に使用されるロイコ染料としては、Ｃ・
Ｖ・Ｌ・等のラクトン系染料、ローダミンＢラク
タム等のラクタム系染料、７−ジエチルアミノ−
３−クロロフルオラン、３−ジエチルアミノ−６
−メチル−７−アニリノフルオラン等のフルオラ
ン系染料、Ｎ−ハロフエニルロイコオーラミン、
Ｎ−２，４，５−トリクロロフエニルロイコオー
ラミン等のオーラミン系染料、ベンゾ−β−ナフ
トスピロピラン等のスピロピラン系染料が挙げら
れるが、これらに限定されるものではない。 The leuco dyes used in the present invention include C.
Lactone dyes such as V.L., lactam dyes such as Rhodamine B lactam, 7-diethylamino-
3-chlorofluorane, 3-diethylamino-6
-Fluoran dyes such as methyl-7-anilinofluorane, N-halophenylleucoolamine,
Examples include, but are not limited to, auramine dyes such as N-2,4,5-trichlorophenylleucoauramine, and spiropyran dyes such as benzo-β-naphthospiropyran.
上記のロイコ染料を熱時発色させる顕色剤とし
ては、ビスフエノールＡ等のフエノール性化合物
や有機酸もしくはその塩などが使用できる。 As a color developer that causes the above-mentioned leuco dye to develop color when heated, a phenolic compound such as bisphenol A, an organic acid or a salt thereof, etc. can be used.
結着剤としては、水溶性の高分子が用いられ、
例えばポリビニルアルコール、ヒドロキシエチル
セルロース、メチルセルロース、デンプン、カゼ
イン、スチレン−無水マレイン酸共重合体、ある
いはスチレン−ブタジエンラテツクス等が用いら
れる。 A water-soluble polymer is used as the binder.
For example, polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, starch, casein, styrene-maleic anhydride copolymer, or styrene-butadiene latex can be used.
その他、必要に応じて白色顔料、ワツクス類、
分散剤、消泡剤を用いてもよい。 In addition, white pigments, waxes, etc. as necessary.
A dispersant and an antifoaming agent may also be used.
次に上記の如くして形成された感熱記録層の上
にカゼインとヒドロキシエチルセルロース、ヒド
ロキシプロピルセルロース、イソブチレン−無水
マレイン酸共重合体、ポリ酢酸ビニル、酢酸ビニ
ル−アクリル共重合体、変性ポリアクリルアミ
ド、ポリビニルアルコールから選ばれた樹脂の少
なくとも１種以上を主成分とした水性塗料を塗布
して表面層を設ける。表面層には必要に応じて感
熱記録材料として用いられる顔料やワツクス類を
添加することもできる。表面層は、可塑剤等との
相溶性の悪いカゼインやポリ酢酸ビニルにより可
塑剤等の浸透剤等の浸透を防止して発色画像の退
色を防ぐことができる。特にカゼインは、ポリ酢
酸ビニルに比較して発色を阻外することが少ない
ために主成分として使用している。カゼイン、ポ
リ酢酸ビニル以外の樹脂は、感熱記録層との接着
性や記録特性を良くするために加えることができ
るが、カゼインやポリ酢酸ビニルにくらべて、可
塑剤等の浸透を防止しにくい。また表面層に添加
できる顔料やワツクスは、記録特性を良くするこ
とができ、特にステイツキングを少なくすること
ができる。表面層を形成する樹脂は、表面層固形
分の50重量％以上、顔料は50重量％未満、ワツク
ス類は30重量％未満が良い。樹脂を50重量％未満
にした場合には可塑剤の浸透が容易になり、発色
画像が消えやすくなる。好ましくは、樹脂分は表
面層固形分の75％以上が良い。 Next, on the heat-sensitive recording layer formed as described above, casein, hydroxyethyl cellulose, hydroxypropyl cellulose, isobutylene-maleic anhydride copolymer, polyvinyl acetate, vinyl acetate-acrylic copolymer, modified polyacrylamide, A surface layer is provided by applying a water-based paint containing at least one resin selected from polyvinyl alcohol as a main component. Pigments and waxes used as heat-sensitive recording materials can also be added to the surface layer, if necessary. The surface layer is made of casein and polyvinyl acetate, which have poor compatibility with plasticizers, etc., and can prevent penetration of penetrants such as plasticizers, thereby preventing fading of colored images. In particular, casein is used as the main component because it inhibits color development less than polyvinyl acetate. Resins other than casein and polyvinyl acetate can be added to improve adhesion to the heat-sensitive recording layer and recording properties, but compared to casein and polyvinyl acetate, they are less likely to prevent penetration of plasticizers and the like. Furthermore, pigments and waxes that can be added to the surface layer can improve the recording properties, and in particular can reduce staking. The resin forming the surface layer should preferably be at least 50% by weight of the solid content of the surface layer, the pigment should be less than 50% by weight, and the wax should be less than 30% by weight. If the resin content is less than 50% by weight, the plasticizer will penetrate easily and the colored image will easily disappear. Preferably, the resin content is 75% or more of the surface layer solid content.
次に実施例により本発明を具体的に説明する。 Next, the present invention will be specifically explained with reference to Examples.
実施例 １
炭酸カルシウム10重量部とポリビニルアルコー
ル（10％水溶液）20重量部をペイントコンデイシ
ヨナーにて２時間分散した後、カゼインのアンモ
ニウム溶液（５％水溶液）300重量部と混合した
塗料をビスフエノールＡを用いた一般の感熱記録
紙（例えば巴川製紙所製感熱記録紙FB−04）の
上に乾燥後の塗布量が3g／m2となるよう塗布し
て表面層を形成した。Example 1 After dispersing 10 parts by weight of calcium carbonate and 20 parts by weight of polyvinyl alcohol (10% aqueous solution) in a paint conditioner for 2 hours, the paint mixed with 300 parts by weight of casein ammonium solution (5% aqueous solution) was mixed with a paint conditioner. A surface layer was formed by coating on a general thermal recording paper using phenol A (for example, thermal recording paper FB-04 manufactured by Tomoekawa Paper Mills) so that the coating amount after drying was 3 g/m 2 .
実施例 ２
ステアリン酸亜鉛10重量部とドデシルベンゼン
スルホン酸ナトリウム（２％水溶液）40重量部を
ボールミルに入れて48時間粉砕した分散液10重量
部に対してカゼインのアンモニウム水溶液（５
％）50重量部とイソブチレン−無水マレイン酸共
重合体のアンモニウム塩水溶液（５％）50重量部
を加えて十分混合した塗料を実施例１で用いた一
般の感熱記録紙の上に乾燥後の塗布量が3g／m2
となるよう塗布して表面層を形成した。Example 2 10 parts by weight of a dispersion of 10 parts by weight of zinc stearate and 40 parts by weight of sodium dodecylbenzenesulfonate (2% aqueous solution) were ground in a ball mill for 48 hours.
%) and 50 parts by weight of an ammonium salt aqueous solution (5%) of isobutylene-maleic anhydride copolymer were added and thoroughly mixed, and the paint was coated on the general heat-sensitive recording paper used in Example 1 after drying. Application amount is 3g/ m2
A surface layer was formed by applying the following.
実施例 ３
実施例２で用いたステアリン酸亜鉛分散液10重
量部に対してカゼインのアンモニウム水溶液（５
％）50重量部、イソブチレン−無水マレイン酸共
重合体のアンモニウム塩水溶液（５％）50重量
部、ポリ酢酸ビニルエマルジヨン（50％）５重量
部を加えて十分混合した塗料を実施例１で用いた
一般の感熱記録紙の上に乾燥後の塗布量が3g／
m2となるよう塗布して表面層を形成した。Example 3 An ammonium aqueous solution of casein (5 parts by weight) was added to 10 parts by weight of the zinc stearate dispersion used in Example 2.
%), 50 parts by weight of an ammonium salt aqueous solution of isobutylene-maleic anhydride copolymer (5%), and 5 parts by weight of polyvinyl acetate emulsion (50%) were added and thoroughly mixed. The coating amount after drying was 3g/on the general thermal recording paper used.
A surface layer was formed by applying the solution to a thickness of m 2 .
比較例 １ 実施例１で用いた一般の感熱記録紙。Comparative example 1 General thermal recording paper used in Example 1.
比較例 ２
実施例１で用いた一般の感熱記録紙の上にポリ
ビニルアルコール（５％水溶液）を乾燥後の塗布
量が3g／m2となるよう塗布して表面層を形成し
た。Comparative Example 2 A surface layer was formed by coating polyvinyl alcohol (5% aqueous solution) on the general thermal recording paper used in Example 1 so that the coating amount after drying was 3 g/m 2 .
上記の実施例ならびに比較例の感熱記録体を感
熱記録装置（パナフアツクス7000）で発色記録
し、発色部の上にプラスチツク消しゴムをのせ、
500gの圧力を加えて２時間放置して消色テスト
を行なつた。この時の発色記録濃度と消色テスト
後の濃度を下表に示す。尚濃度の測定はマクベス
濃度計（RD−100R型）で測定した。 The heat-sensitive recording materials of the above Examples and Comparative Examples were color-recorded using a heat-sensitive recording device (Panafax 7000), and a plastic eraser was placed on the colored portion.
A color eradication test was performed by applying 500 g of pressure and leaving it for 2 hours. The recorded color density at this time and the density after the color erasure test are shown in the table below. The concentration was measured using a Macbeth densitometer (model RD-100R).
記録濃度 消色テスト後の濃度
実施例１ 0.82 0.82
実施例２ 0.90 0.88
実施例３ 0.95 0.95
比較例１ 0.90 0.20
比較例２ 0.92 0.58
以上の実施例、比較例から明らかなごとく、本
発明の感熱記録体の記録画像はプラスチツクの可
塑剤に対して消色性が著るしく改善されたもので
ある。従来の感熱記録紙では記録部で可塑剤を含
むプラスチツク材料を押しつけた場合には、１〜
２時間程度で記録がほとんど消色してしまうが、
本発明の場合には１〜２時間ではほとんど消える
ことがなく、24時間後でも充分に記録が確認でき
る。また記録層の耐水性、耐湿性も改良される。 Recording density Density after decolorization test Example 1 0.82 0.82 Example 2 0.90 0.88 Example 3 0.95 0.95 Comparative example 1 0.90 0.20 Comparative example 2 0.92 0.58 As is clear from the above examples and comparative examples, the thermal recording of the present invention The recorded image of the body has significantly improved color erasing properties compared to plasticizers in plastics. With conventional thermal recording paper, when a plastic material containing a plasticizer is pressed in the recording section, the
Most of the recording will fade after about 2 hours, but
In the case of the present invention, the recording hardly disappears within 1 to 2 hours, and the recording can be clearly confirmed even after 24 hours. Furthermore, the water resistance and humidity resistance of the recording layer are also improved.
Claims (1)
と該発色性染料を熱時発色させる顕色剤及び結着
剤を含有する感熱記録層を設け、さらにこの感熱
記録層の上にカゼインとヒドロキシエチルセルロ
ース、ヒドロキシプロピルセルロース、イソブチ
レン−無水マレイン酸共重合体、ポリ酢酸ビニ
ル、酢酸ビニル−アクリル共重合体、変性ポリア
クリルアミド、ポリビニルアルコールから成る群
から選ばれた樹脂の少なくとも一種以上を主成分
とした表面層を設けてなる感熱記録体。 ２ 前記表面層がカゼインとヒドロキシエチルセ
ルロース、ヒドロキシプロピルセルロース、イソ
ブチレン−無水マレイン酸共重合体、ポリ酢酸ビ
ニル、酢酸ビニル−アクリル共重合体、変性ポリ
アクリルアミド、ポリビニルアルコールから成る
群から選ばれた樹脂の少なくとも一種を主体とし
て顔料および／またはワツクスを含む特許請求の
範囲第１項記載の感熱記録体。 ３ 前記表面層に含まれる樹脂分が表面層固形分
の50重量％以上である特許請求の範囲第１項記載
の感熱記録体。[Scope of Claims] 1. A heat-sensitive recording layer containing a normally colorless or light-colored color-forming dye and a color developer and a binder that develop color when heated is provided on a support, and further, this heat-sensitive recording layer Casein and at least one resin selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, isobutylene-maleic anhydride copolymer, polyvinyl acetate, vinyl acetate-acrylic copolymer, modified polyacrylamide, and polyvinyl alcohol. A heat-sensitive recording material provided with a surface layer containing the above as main components. 2. The surface layer is made of casein and a resin selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, isobutylene-maleic anhydride copolymer, polyvinyl acetate, vinyl acetate-acrylic copolymer, modified polyacrylamide, and polyvinyl alcohol. The heat-sensitive recording material according to claim 1, which mainly contains at least one type of pigment and/or wax. 3. The heat-sensitive recording material according to claim 1, wherein the resin content contained in the surface layer is 50% by weight or more of the solid content of the surface layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10438880A JPS5729491A (en) | 1980-07-31 | 1980-07-31 | Preservation improved thermosensitive recording substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10438880A JPS5729491A (en) | 1980-07-31 | 1980-07-31 | Preservation improved thermosensitive recording substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5729491A JPS5729491A (en) | 1982-02-17 |
| JPH0355318B2 true JPH0355318B2 (en) | 1991-08-22 |
Family
ID=14379359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10438880A Granted JPS5729491A (en) | 1980-07-31 | 1980-07-31 | Preservation improved thermosensitive recording substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5729491A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58208091A (en) * | 1982-05-28 | 1983-12-03 | Ricoh Co Ltd | Heat sensitive recording sheet |
| JPS599091A (en) * | 1982-07-09 | 1984-01-18 | Ricoh Co Ltd | Heat-sensitive recording sheet |
| JPS5945191A (en) * | 1982-09-08 | 1984-03-13 | Oji Paper Co Ltd | Heat sensitive recording sheet improved in preservability |
| JPS5967082A (en) * | 1982-10-08 | 1984-04-16 | Tomoegawa Paper Co Ltd | Heat sensitive recording sheet |
| JPS60193693A (en) * | 1984-03-15 | 1985-10-02 | Oji Paper Co Ltd | Heat-sensitive recording sheet |
| JPS60245590A (en) * | 1984-05-22 | 1985-12-05 | Oji Paper Co Ltd | Thermal recording material |
| US4641159A (en) * | 1985-04-18 | 1987-02-03 | Ncr Corporation | Protective barrier and method of providing same for thermosensitive sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4830437A (en) * | 1971-08-23 | 1973-04-21 | ||
| JPS54128347A (en) * | 1978-03-27 | 1979-10-04 | Hitachi Maxell | Heattsensitive record |
| JPS54143153A (en) * | 1978-04-28 | 1979-11-08 | Honshu Paper Co Ltd | Thermosensitive recording material |
-
1980
- 1980-07-31 JP JP10438880A patent/JPS5729491A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4830437A (en) * | 1971-08-23 | 1973-04-21 | ||
| JPS54128347A (en) * | 1978-03-27 | 1979-10-04 | Hitachi Maxell | Heattsensitive record |
| JPS54143153A (en) * | 1978-04-28 | 1979-11-08 | Honshu Paper Co Ltd | Thermosensitive recording material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5729491A (en) | 1982-02-17 |
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