JPS62244693A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS62244693A JPS62244693A JP61089048A JP8904886A JPS62244693A JP S62244693 A JPS62244693 A JP S62244693A JP 61089048 A JP61089048 A JP 61089048A JP 8904886 A JP8904886 A JP 8904886A JP S62244693 A JPS62244693 A JP S62244693A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- coloring layer
- recording material
- sensitive
- titanium oxide
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000004040 coloring Methods 0.000 claims abstract description 46
- 239000010410 layer Substances 0.000 claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000011882 ultra-fine particle Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000011241 protective layer Substances 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- -1 malachite green lactone Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CTCWYLTZEXJDHK-UHFFFAOYSA-N 2,4-dihydroxy-3-methoxybenzophenone Natural products COC1=C(O)C=CC(C(=O)C=2C=CC=CC=2)=C1O CTCWYLTZEXJDHK-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- YHDJCBWJTOHJQT-UHFFFAOYSA-N (2,4-dihydroxy-5-methylphenyl)-phenylmethanone Chemical compound C1=C(O)C(C)=CC(C(=O)C=2C=CC=CC=2)=C1O YHDJCBWJTOHJQT-UHFFFAOYSA-N 0.000 description 1
- HJPCUVKFCLZYFR-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2-methylphenyl)methanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=C(O)C=C1O HJPCUVKFCLZYFR-UHFFFAOYSA-N 0.000 description 1
- OCLYELQBMFRPIL-UHFFFAOYSA-N (2-hydroxyphenyl)-(3-hydroxyphenyl)methanone Chemical compound OC1=CC=CC(C(=O)C=2C(=CC=CC=2)O)=C1 OCLYELQBMFRPIL-UHFFFAOYSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- SIYOADGKTUWNLJ-UHFFFAOYSA-N (3-hydroxy-4-methylphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=C(O)C(C)=CC=C1C(=O)C1=CC=C(O)C=C1 SIYOADGKTUWNLJ-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 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
- 229940107698 malachite green Drugs 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は感熱記録材料に関し、特に加熱することによ
って発色する感熱発色層を有する感熱記録材料に関する
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material having a heat-sensitive coloring layer that develops color when heated.
（従来技術）
第２図は従来の感熱記録材料の一例を示す断面図である
。この感熱記録材料ｌは、シート基材２を含み、シート
基材２の表面には、加熱することによって発色する感熱
発色層３が形成されている。(Prior Art) FIG. 2 is a sectional view showing an example of a conventional heat-sensitive recording material. This heat-sensitive recording material 1 includes a sheet base material 2, and a heat-sensitive coloring layer 3 that develops color when heated is formed on the surface of the sheet base material 2.
したがって、この感熱記録材料ｌは、その感熱発色層３
を加熱することによって、その加熱された部分を発色す
ることができる。Therefore, this heat-sensitive recording material 1 has its heat-sensitive coloring layer 3
By heating the area, the heated area can develop color.
（発明が解決しようとする問題点）
ところが、このような従業の感熱記録材料は、太陽、蛍
光灯などの光の下では、感熱発色層の発色された部分が
脱色されたり、非発色の部分が変色されたりし易いため
、長期間の使用には耐え得らない。このように、脱色あ
るいは変色されるのは、感熱発色層のロイコ染料が光（
紫外線）によって分解されるためと考えられる。(Problem to be Solved by the Invention) However, in such heat-sensitive recording materials, when exposed to sunlight, fluorescent light, or other light, the colored portions of the heat-sensitive coloring layer may be bleached, or the non-colored portions may be discolored. It cannot withstand long-term use because it is easily discolored. In this way, the leuco dye in the heat-sensitive coloring layer is bleached or discolored by light (
This is thought to be because it is decomposed by ultraviolet light).
そこで、紫外線吸収剤を使用した感熱記録紙が考え出さ
れた。このような感熱記録紙は、たとえば特開昭５４−
１８７５２号公報に開示されている。Therefore, heat-sensitive recording paper using ultraviolet absorbers was devised. Such thermal recording paper is known, for example, from Japanese Patent Application Laid-Open No. 1987-
It is disclosed in Japanese Patent No. 18752.
しかしながら、このような感熱記録紙でも、まだ、十分
な耐光性を得るには至っていない。However, even such heat-sensitive recording paper has not yet achieved sufficient light resistance.
それゆえに、この発明の主たる目的は、耐光性を向上さ
せた、感熱記録材料を提供することである。Therefore, the main object of this invention is to provide a heat-sensitive recording material with improved light resistance.
（問題点を解決するための手段）
この発明は、シート基材と、このシート基材の表面に形
成され、°ロイコ染料が含有され加熱することによって
発色する感熱発色層と、この感熱発色層の表面に形成さ
れ、超微粒子状の酸化チタンが含有された被覆層とを含
む、感熱記録材料である。(Means for Solving the Problems) The present invention includes a sheet base material, a thermosensitive coloring layer formed on the surface of the sheet base material that contains a leuco dye and develops color when heated, and a thermosensitive coloring layer that is This is a heat-sensitive recording material comprising a coating layer formed on the surface of the substrate and containing ultrafine titanium oxide particles.
（作用）
被覆層の超微粒子状の酸化チタンによって、外部の紫外
線が、反射される。(Function) External ultraviolet rays are reflected by the ultrafine titanium oxide particles in the coating layer.
（発明の効果）
この発明によれば、外部の紫外線が、反射されるので、
外部の紫外線によって、感熱発色層の発色された部分が
脱色されにくく、かつ、非発色の部分が変色されにくく
なる。したがって、感熱記録材料の耐光性を向上するこ
とができる。(Effect of the invention) According to this invention, since external ultraviolet rays are reflected,
The colored portions of the thermosensitive coloring layer are less likely to be bleached by external ultraviolet rays, and the non-colored portions are less likely to be discolored. Therefore, the light resistance of the heat-sensitive recording material can be improved.
この発明の上述の目的、その他の目的、特徴および利点
は、図面を参照して行う以下の実施例の詳細な説明から
一層明らかとなろう。The above objects, other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings.
（実施例）
、 第１図はこの発明の一実施例を示す断面図で
ある。この感熱記録材料ｌＯは、シート基材１２を含む
。このシート基材１２は、たとえば紙９合成樹脂などの
シート材で形成される。(Embodiment) FIG. 1 is a sectional view showing an embodiment of the present invention. This thermosensitive recording material IO includes a sheet base material 12. This sheet base material 12 is formed of a sheet material such as paper 9 synthetic resin.
シート基材１２の表面には、加熱することによって発色
する感熱発色層１４が形成される。この感熱発色層１４
は、シート基材１２の表面に、たとえば、ロイコ染料、
顕色剤および結着剤の混合物を塗布乾燥することに・よ
って形成される。A thermosensitive coloring layer 14 that develops color when heated is formed on the surface of the sheet base material 12 . This thermosensitive coloring layer 14
For example, leuco dye,
It is formed by applying and drying a mixture of a color developer and a binder.
この場合、ロイコ染料としては、たとえば、クリスタル
バイオレットラクトン、マラカイトグリーンラクトン、
３．３−ビス（パラジメチルアミノフェニル）−６−ア
ミノフタリド、３．３−ビス（パラジメチルアミノフェ
ニル）−６−（パラトルエンスホンアミド）フタリド、
３−ジエチルアミノ−７−（Ｎ−メチル−ｐ−）ルイジ
ン）フルオラン、３−ジエチルアミノ−７−クロルフル
オラン、３−シクロヘキシルアミノ−６−クロルフルオ
ラン、Ｎ−フェニルローダミンＢラクタム、アシッドロ
ーダミンＢサルトン、ベンゾ−β−ナフトスピロピラン
、１．３．３−トリメチル−６′−クロロ−８′−メト
キシ−インドリノベンゾスピロピランなどが挙げられる
。In this case, examples of leuco dyes include crystal violet lactone, malachite green lactone,
3.3-bis(paradimethylaminophenyl)-6-aminophthalide, 3.3-bis(paradimethylaminophenyl)-6-(para-toluenesphonamide) phthalide,
3-diethylamino-7-(N-methyl-p-)luidine) fluorane, 3-diethylamino-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, N-phenylrhodamine B lactam, acidrhodamine B sultone , benzo-β-naphthospiropyran, 1.3.3-trimethyl-6'-chloro-8'-methoxy-indolinobenzospiropyran, and the like.
また、顕色剤としては、たとえば、３．４’−ジヒドロ
キシ−４−メチルベンゾフェノン、３゜４−ジヒドロキ
シ−２′−メチルベンゾフェノン、２．３−ジヒドロキ
シベンゾフェノン、２．４−ジヒドロキシベンゾフェノ
ン、２，４−ジヒドロキシ−３−メトキシベンゾフェノ
ン、２．６−ジヒドロキシベンゾフェノン、３．４−ジ
ヒドロキシベンゾフェノン、３．５−ジヒドロキシベン
ゾフェノン、２，４−ジヒドロキシ−５−メチルベンゾ
フェノン、２．４’−ジヒドロキシベンゾフェノン、３
．３’−ジヒドロキシベンゾフェノン、２．３′−ジヒ
ドロキシベンゾフェノン、２．４−ジヒドロキシ−２′
−メチルベンゾフェノン、３．４．５−トリヒドロキシ
ベンゾフェノンなどが挙げられる。In addition, examples of the color developer include 3,4'-dihydroxy-4-methylbenzophenone, 3'4-dihydroxy-2'-methylbenzophenone, 2,3-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2, 4-dihydroxy-3-methoxybenzophenone, 2.6-dihydroxybenzophenone, 3.4-dihydroxybenzophenone, 3.5-dihydroxybenzophenone, 2,4-dihydroxy-5-methylbenzophenone, 2.4'-dihydroxybenzophenone, 3
．． 3'-dihydroxybenzophenone, 2,3'-dihydroxybenzophenone, 2,4-dihydroxy-2'
-methylbenzophenone, 3.4.5-trihydroxybenzophenone, and the like.
さらに、結着剤としては、たとえば、ポリビニルアルコ
ール、メチルセルロース、メトキシセルロース、ヒドロ
キシエチルセルロース、カルボキシルメチルセルロース
、変性でんぷん、ポリビニルピロリドン、ポリアクリル
アミド、アルキッド樹脂、石油樹脂、マレイン酸樹脂、
エポキシ樹脂、ポリエステル樹脂、塩素化ポリプロピレ
ン、アクリル酸エステル、ポリアクリルアミドなどが挙
げられる。Furthermore, as a binder, for example, polyvinyl alcohol, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxylmethylcellulose, modified starch, polyvinylpyrrolidone, polyacrylamide, alkyd resin, petroleum resin, maleic acid resin,
Examples include epoxy resin, polyester resin, chlorinated polypropylene, acrylic ester, and polyacrylamide.
したがって、この感熱発色層１４は、それを加熱するこ
とによって、発色できる。Therefore, this thermosensitive coloring layer 14 can develop color by heating it.
なお、感熱発色層１４を形成するための混合物の中に、
必要に応じて、感熱発色層１４に任意に着色を行うため
に、無機填料および有機填料などの填料や、感熱発色層
１４の熱に対する感度を高めるために、増悪剤などを添
加してもよい。In addition, in the mixture for forming the thermosensitive coloring layer 14,
If necessary, fillers such as inorganic fillers and organic fillers may be added in order to arbitrarily color the thermosensitive coloring layer 14, and an aggravating agent may be added in order to increase the sensitivity of the thermosensitive coloring layer 14 to heat. .
この場合、無機填料としては、たとえば、水酸化アルミ
ニウム、重質炭酸カルシウム、軽質炭酸カルシウム、酸
化チタン、硫酸バリウム、シリカゲル、活性白土、タル
ク、クレー、カオリナイト、ケイソウ土、炭酸マグネシ
ウム、アルミナ、酸化アルミニウムなどが挙げられ、有
機填料としては、たとえば、ポリスチレン樹脂粒子、尿
素−ホルマリン樹脂粒子、ポリオレフィン粒子などが挙
げられる。In this case, examples of inorganic fillers include aluminum hydroxide, heavy calcium carbonate, light calcium carbonate, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, kaolinite, diatomaceous earth, magnesium carbonate, alumina, Examples of the organic filler include polystyrene resin particles, urea-formalin resin particles, and polyolefin particles.
また、増感剤としては、たとえば、ステアリン酸アマイ
ド、パルミチン酸アマイド、オレイン酸アマイド、ラウ
リン酸アマイド、エチレンビスステアロアマイド、メチ
レンビスステアロアマイドおよびメチロールステアロア
マイドなどのアマイド、パラフィンワックス、高級アル
コールなどが挙げられる。Examples of sensitizers include amides such as stearamide, palmitamide, oleic acid amide, lauric acid amide, ethylene bis stearamide, methylene bis stearamide, and methylol stearamide, paraffin wax, and Examples include alcohol.
さらに、感熱発色層１４の材料となる混合物には、その
混合物中の結着剤をはやく硬化させるための硬化剤や、
感熱発色層１４の表面を滑らかにするための滑剤部どを
添加してもよい。Furthermore, the mixture serving as the material for the thermosensitive coloring layer 14 includes a curing agent for quickly curing the binder in the mixture,
A lubricant or the like may be added to make the surface of the heat-sensitive coloring layer 14 smooth.
この感熱発色層１４の表面には、保護層１６が形成され
る。この保護層１６は、感熱発色層１４の表面に、たと
えば、超微粒子状の酸化チタンおよび結着剤の混合物を
塗布乾燥することによって形成される。A protective layer 16 is formed on the surface of this thermosensitive coloring layer 14. The protective layer 16 is formed by, for example, applying a mixture of ultrafine titanium oxide and a binder to the surface of the heat-sensitive coloring layer 14 and drying it.
この保護層１６中の超微粒子状の酸化チタンは、外部の
光（紫外線）を反射するためのものであって、好ましく
は、その粒径が０．５μｍ以下の超微粒子状の酸化チタ
ンが用いられ、さらに好ましくは、その粒径が０．０５
μｍ以下の超微粒子状の酸化チタンが用いられる。The ultrafine titanium oxide in the protective layer 16 is for reflecting external light (ultraviolet light), and preferably ultrafine titanium oxide with a particle size of 0.5 μm or less is used. more preferably, the particle size is 0.05
Titanium oxide in the form of ultrafine particles of μm or less is used.
また、結着剤としては、上述の感熱発色Ｊｉ１４の成分
となる結着剤、すなわち、たとえば、ポリビニルアルコ
ール、メチルセルロース、メトキシセルロース、ヒドロ
キシエチルセルロース、カルボキシルメチルセルロース
、変性でんぷん、ポリビニルピロリドン、ポリアクリル
アミド、アルキッド樹脂、石油樹脂、マレイン酸樹脂、
エポキシ樹脂、ポリエステル樹脂、塩素化ポリプロピレ
ン、アクリル酸エステル、ポリアクリルアミドなどが用
いられる。In addition, as the binder, binders that are components of the above-mentioned heat-sensitive coloring Ji14, such as polyvinyl alcohol, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxylmethylcellulose, modified starch, polyvinylpyrrolidone, polyacrylamide, alkyd resin , petroleum resin, maleic acid resin,
Epoxy resin, polyester resin, chlorinated polypropylene, acrylic ester, polyacrylamide, etc. are used.
したがって、この保護層１６によって、感熱発色層１４
は外部の光（紫外線）から保護される。Therefore, this protective layer 16 protects the heat-sensitive coloring layer 14.
is protected from external light (ultraviolet light).
そのため、この感熱記録材料１０は、それを太陽、蛍光
灯などの光の下に長期間放置した場合でも、感熱発色層
１４の発色された部分が脱色されたり、感熱発色層１４
の非発色の部分が変色されたりしにくく、したがって、
その耐光性を向上できる。Therefore, even if this heat-sensitive recording material 10 is left under light such as the sun or a fluorescent lamp for a long period of time, the colored portion of the heat-sensitive coloring layer 14 may be bleached or the heat-sensitive coloring layer 14 may be bleached.
The non-colored parts are less likely to change color, therefore,
Its light resistance can be improved.
なお、この感熱記録材料１０では、その保護層１６の超
微粒子状の酸化チタンの間の結着剤などが可視光線を通
過させることができるため、感熱発色層１４の発色され
た部分を、保護層１６を通して外部から見ることができ
る。In this heat-sensitive recording material 10, since the binder between the ultrafine titanium oxide particles in the protective layer 16 allows visible light to pass through, the colored portion of the heat-sensitive coloring layer 14 can be protected. Visible from the outside through layer 16.
さらに、上述の実施例では、超微粒子状の酸化チタンを
保護層１６に配合したが、この超微粒子状の酸化チタン
をさらに感熱発色層１４に配合してもよい。このように
、超微粒子状の酸化チタンを、保護層１６および感熱発
色層１４に配合しても、感熱記録材料ｌＯの耐光性を向
上することができる。Further, in the above-described embodiment, ultrafine titanium oxide particles were blended into the protective layer 16, but the ultrafine titanium oxide particles may be further blended into the heat-sensitive coloring layer 14. In this way, even when ultrafine titanium oxide is blended into the protective layer 16 and the heat-sensitive coloring layer 14, the light resistance of the heat-sensitive recording material IO can be improved.
実験例
まず、下記成分のＡ液、Ｂ液およびＣ液を、それぞれ、
ボールミルで２４時間粉砕分散して調製した。Experimental example First, the following components of liquid A, liquid B, and liquid C were prepared, respectively.
It was prepared by pulverization and dispersion in a ball mill for 24 hours.
Ａ液
・３−（Ｎ−メチル−Ｎ−
シクロへキシルアミノ）
−６−メチル−７＝
アニリノフルオラン ５部・５％ヒドロ
キシエチル
セルロース水溶液 ５０部・水
２５部
Ｂ液
・４．４′−イソプロピリデンジ
フェノール １５部・５％ヒドロ
キシエチル
セルロース水溶液 ６０部・ステアリン
酸アマイド １５部・水
１０部
Ｃ液
・軽質炭酸カルシウム ４０部・１０％ポ
リビニル
アルコール水溶液 ４０部・水
２０部
次に、上述のＡ液を１０部、Ｂ液を３３部、Ｃ液を４９
部および１０％ポリビニルアルコール水溶液を３０部混
合して、感熱発色層の材料となる混合物を調製した。Solution A・3-(N-methyl-N-cyclohexylamino)-6-methyl-7=anilinofluorane 5 parts・5% hydroxyethylcellulose aqueous solution 50 parts・water
25 parts Solution B・15 parts of 4.4'-isopropylidenediphenol・5% hydroxyethyl cellulose aqueous solution 60 parts・Stearamide 15 parts・Water
10 parts Liquid C/Light calcium carbonate 40 parts/10% polyvinyl alcohol aqueous solution 40 parts/Water
20 parts Next, add 10 parts of the above-mentioned liquid A, 33 parts of liquid B, and 49 parts of liquid C.
and 30 parts of a 10% polyvinyl alcohol aqueous solution were mixed to prepare a mixture serving as a material for a heat-sensitive coloring layer.
さらに、比較例１．比較例■およびサンプルとなる３枚
の上質紙を準備した。Furthermore, Comparative Example 1. Comparative Example (1) and three sheets of high-quality paper as samples were prepared.
そして、上述の混合物を、乾燥塗布量が６ｇ／ｄになる
ように、３枚の上質紙の表面に、それぞれ、塗布乾燥し
て、感熱発色層を形成した。このように、上質紙の表面
に感熱発色層が形成されたものの１つを、比較例■とし
た。Then, the above-mentioned mixture was applied and dried on the surfaces of three pieces of high-quality paper so that the dry coating amount was 6 g/d, respectively, to form a heat-sensitive coloring layer. One of the high-quality papers in which a heat-sensitive coloring layer was formed on the surface was designated as Comparative Example (2).
次に、１０％ポリビニルアルコール水溶液を準備し、そ
れを残りの一方の感熱発色層の表面に、乾燥塗布量が３
ｇ／ｎｒになるように乾燥塗布して、比較例■とした。Next, prepare a 10% polyvinyl alcohol aqueous solution and apply it to the surface of the remaining heat-sensitive coloring layer until the dry coating amount is 3.
Comparative Example (2) was prepared by dry coating so as to give g/nr.
さらに、１０％ポリビニルアルコール水溶液を１００部
および超微粒子状の酸化チタンを５部ボールミルで２４
時間分散させて、被覆層の材料となる混合物を調製した
。そして、この混合物を、残りの感熱発色層の表面に、
乾燥塗布量がＩｇ／ｄになるように乾燥塗布して、サン
プルとした。Furthermore, 100 parts of 10% polyvinyl alcohol aqueous solution and 5 parts of ultrafine titanium oxide were added in a ball mill for 24 hours.
A mixture serving as a material for the coating layer was prepared by dispersing the mixture over time. Then, apply this mixture to the surface of the remaining heat-sensitive coloring layer.
A sample was prepared by dry coating so that the dry coating amount was Ig/d.
なお、この超微粒子状の酸化チタンとしては、たとえば
帝国化工株式会社製の超微粒子状の酸化チタンＭＴ−１
００３（商品名）が用いられた。The ultrafine titanium oxide may be, for example, ultrafine titanium oxide MT-1 manufactured by Teikoku Kako Co., Ltd.
003 (trade name) was used.
そして、比較例！、比較例■およびサンプルに、５．０
００Ｌｕｘの蛍光灯の光を１週間照射して、それらの感
熱発色層の変化を調べた。And a comparative example! , Comparative example ■ and sample, 5.0
The samples were irradiated with 00 Lux fluorescent light for one week to examine changes in their thermosensitive coloring layers.
その結果、比較例！および比較例■では、その感熱発色
層が黄変したが、サンプルでは、その感熱発色層が変色
しなかった。As a result, a comparative example! In Comparative Example (3), the heat-sensitive coloring layer turned yellow, but in the sample, the heat-sensitive coloring layer did not change color.
この実験結果から、サンプルは比較例！および比較例■
に比べて、その感熱発色層の耐光性がよいということが
わかる。Based on this experimental result, the sample is a comparative example! and comparative example ■
It can be seen that the heat-sensitive coloring layer has better light resistance compared to the above.
このように、この発明によれば、感１熱発色記録材料の
耐光性を向上させることができる。As described above, according to the present invention, it is possible to improve the light resistance of a thermochromic recording material.
第１図はこの発明の一実施例を示す断面図である。
第２図は従来の感熱記録材料の一例を示す断面図である
。
図において、１０は感熱記録材料、１２はシート基材、
１４は感熱発色層、１６は保護層を示す。FIG. 1 is a sectional view showing an embodiment of the present invention. FIG. 2 is a sectional view showing an example of a conventional heat-sensitive recording material. In the figure, 10 is a heat-sensitive recording material, 12 is a sheet base material,
14 is a heat-sensitive coloring layer, and 16 is a protective layer.
Claims (1)
れ加熱することによって発色する感熱発色層、および 前記感熱発色層の表面に形成され、超微粒子状の酸化チ
タンが含有された被覆層を含む、感熱記録材料。 ２ 前記超微粒子状の酸化チタンは、その粒径が０．５
μｍ以下の酸化チタンを含む、特許請求の範囲第１項記
載の感熱記録材料。 ３ 前記被覆層の材料は結着剤を含む、特許請求の範囲
第１項または第２項記載の感熱記録材料。 ４ 前記結着剤はポリビニルアルコールを含む、特許請
求の範囲第３項記載の感熱記録材料。 ５ 前記結着剤はヒドロキシエチルセルロースを含む、
特許請求の範囲第３項記載の感熱記録材料。 ６ 前記結着剤はカルボキシルメチルセルロースを含む
、特許請求の範囲第３項記載の感熱記録材料。 ７ 前記感熱発色層の材料は顕色剤を含む、特許請求の
範囲第１項ないし第６項のいずれかに記載の感熱記録材
料。 ８ 前記感熱発色層の材料は結着剤を含む、特許請求の
範囲第１項ないし第７項のいずれかに記載の感熱記録材
料。[Scope of Claims] 1. A sheet base material, a heat-sensitive coloring layer formed on the surface of the sheet base material, containing a leuco dye and developing color when heated, and a heat-sensitive coloring layer formed on the surface of the heat-sensitive coloring layer, containing ultrafine particles. A heat-sensitive recording material comprising a coating layer containing titanium oxide. 2 The ultrafine titanium oxide particles have a particle size of 0.5
The heat-sensitive recording material according to claim 1, which contains titanium oxide having a particle size of less than μm. 3. The heat-sensitive recording material according to claim 1 or 2, wherein the material of the coating layer contains a binder. 4. The heat-sensitive recording material according to claim 3, wherein the binder contains polyvinyl alcohol. 5. The binder includes hydroxyethyl cellulose.
A heat-sensitive recording material according to claim 3. 6. The heat-sensitive recording material according to claim 3, wherein the binder contains carboxymethyl cellulose. 7. The heat-sensitive recording material according to any one of claims 1 to 6, wherein the material of the heat-sensitive coloring layer contains a color developer. 8. The heat-sensitive recording material according to any one of claims 1 to 7, wherein the material of the heat-sensitive coloring layer contains a binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089048A JPS62244693A (en) | 1986-04-16 | 1986-04-16 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089048A JPS62244693A (en) | 1986-04-16 | 1986-04-16 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62244693A true JPS62244693A (en) | 1987-10-26 |
Family
ID=13959996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61089048A Pending JPS62244693A (en) | 1986-04-16 | 1986-04-16 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62244693A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169292A (en) * | 1988-12-23 | 1990-06-29 | Ricoh Co Ltd | Thermal recording material |
| JPH02175281A (en) * | 1988-12-28 | 1990-07-06 | Ricoh Co Ltd | Heat sensitive recording material |
| FR2642704A1 (en) * | 1989-02-06 | 1990-08-10 | Osaka Sealing Label Print | HEAT-SENSITIVE RECORDING PAPER |
| JPH0355289A (en) * | 1989-07-24 | 1991-03-11 | Mitsubishi Paper Mills Ltd | Thermosensitive recording sheet |
| US5256619A (en) * | 1990-07-05 | 1993-10-26 | Nippon Shokubai Co., Ltd. | Heat-sensitive recording material |
| JPH06219047A (en) * | 1993-01-29 | 1994-08-09 | Sliontec:Kk | Reversible thermal recording sheet |
| US5804529A (en) * | 1996-05-10 | 1998-09-08 | Mitsubishi Paper Mills Ltd. | Heat-sensitive recording material and process for the production thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835874A (en) * | 1981-08-27 | 1983-03-02 | Kao Corp | Chemical cell |
| JPS59174389A (en) * | 1983-03-23 | 1984-10-02 | Ricoh Co Ltd | Thermal recording material |
| JPS6255189A (en) * | 1985-09-03 | 1987-03-10 | Fuji Photo Film Co Ltd | Thermal recording material |
-
1986
- 1986-04-16 JP JP61089048A patent/JPS62244693A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835874A (en) * | 1981-08-27 | 1983-03-02 | Kao Corp | Chemical cell |
| JPS59174389A (en) * | 1983-03-23 | 1984-10-02 | Ricoh Co Ltd | Thermal recording material |
| JPS6255189A (en) * | 1985-09-03 | 1987-03-10 | Fuji Photo Film Co Ltd | Thermal recording material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169292A (en) * | 1988-12-23 | 1990-06-29 | Ricoh Co Ltd | Thermal recording material |
| JPH02175281A (en) * | 1988-12-28 | 1990-07-06 | Ricoh Co Ltd | Heat sensitive recording material |
| FR2642704A1 (en) * | 1989-02-06 | 1990-08-10 | Osaka Sealing Label Print | HEAT-SENSITIVE RECORDING PAPER |
| JPH0355289A (en) * | 1989-07-24 | 1991-03-11 | Mitsubishi Paper Mills Ltd | Thermosensitive recording sheet |
| US5256619A (en) * | 1990-07-05 | 1993-10-26 | Nippon Shokubai Co., Ltd. | Heat-sensitive recording material |
| JPH06219047A (en) * | 1993-01-29 | 1994-08-09 | Sliontec:Kk | Reversible thermal recording sheet |
| US5804529A (en) * | 1996-05-10 | 1998-09-08 | Mitsubishi Paper Mills Ltd. | Heat-sensitive recording material and process for the production thereof |
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