WO1991005668A1 - Thermal recording medium - Google Patents

Thermal recording medium Download PDF

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Publication number
WO1991005668A1
WO1991005668A1 PCT/JP1989/001056 JP8901056W WO9105668A1 WO 1991005668 A1 WO1991005668 A1 WO 1991005668A1 JP 8901056 W JP8901056 W JP 8901056W WO 9105668 A1 WO9105668 A1 WO 9105668A1
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WO
WIPO (PCT)
Prior art keywords
heat
paper
conductive
recording medium
support
Prior art date
Application number
PCT/JP1989/001056
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroyuki Harada
Katsumi Moronuki
Original Assignee
Honshu Paper Co., Ltd.
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Honshu Paper Co., Ltd. filed Critical Honshu Paper Co., Ltd.
Publication of WO1991005668A1 publication Critical patent/WO1991005668A1/en

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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
    • 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
    • B41M5/41—Base layers supports or substrates

Definitions

  • the present invention relates to a heat-sensitive recording medium, and more particularly, to prevent a paper passing trap or the like generated due to electrification of a heat-sensitive recording medium, and to achieve a natural paper texture. Thermal recording paper that does not impair the performance.
  • thermosensitive recording medium in which a heat-sensitive coloring layer containing a color-forming substance and a color-developing substance that reacts with the color-forming substance upon heating to form a color is provided on a support.
  • Such a thermal recording medium is easy to maintain, has no odor or noise during recording, and has a primary color.
  • -It is widely used as a recording medium.
  • thermosensitive recording media using a synthetic paper or a synthetic resin film, which does not generate paper dust, as a support.
  • Such a thermal recording medium does not generate paper dust and has high smoothness, so that dot reproducibility is excellent, high speed and halftone reproducibility are excellent, and water resistance is high. Has the advantage of good 0
  • synthetic paper or synthetic resin film has a higher electric resistance value, especially a higher volume resistance value, than paper, and is used as a heat-sensitive material. Recording media have the disadvantage that they are prone to paper-feed problems due to their charging properties.
  • thermosensitive recording medium In general, ion conductive substances and electron conductive substances are used as conductive agents.However, if ion conductive substances are used, the dependence on environmental humidity is sufficient for dogs. To achieve the antistatic effect, a considerable amount of coating is required, and stickiness and blocking occur at high humidity. Occurs. On the other hand, The use of such an electronically conductive substance causes a problem that the coloration of the non-environmental humidity-dependent one is remarkable, and that the resulting thermosensitive recording medium is damaged externally.
  • the purpose of the present invention is to describe the various problems described above.
  • thermal recording medium that has no wet stickiness or blocking when wet, has good paper-passing properties, and has a natural paper feel. To do so. Disclosure of the invention
  • a heat-sensitive coloring layer containing a coloring material and a coloring material which reacts with the coloring material by heating to form a color is provided on at least one surface of a support.
  • the surface of the support on which the heat-sensitive layer is coated and / or the surface where the heat-sensitive layer is not coated is coated with potassium titanate or carbonized carbon ( S i C), ⁇ zone see Na (a ⁇ 2 0 3), nitride Ke i (S i 3 N 4 ⁇ office mosquitoes such as zinc oxide - Table 3 ⁇ 4 of conductive material that Do is coated
  • a heat-sensitive recording material characterized by having an antistatic layer containing a conductive material as a main component.
  • tin oxide and antimony oxide are used, and a prevention layer is formed together with a binder and other components.
  • each of Japanese Patent Application Laid-Open Nos. 63-34180 and 633-176158 are coated with an antimony-doped oxide oxide. Use the force to remove the paper feed trouble of the thermal recording medium.
  • the present invention is characterized in that a conductive whisker is used as a conductive material.
  • the reason why the conductive disc is used as the conductive material in the present invention is as follows.
  • the conductive My force coated with the above-mentioned antimony-doped oxide tin has a flat plate shape, and does not exhibit conductivity unless the entire support is covered. .
  • the drawbacks are that the amount of coating increases, the color increases, and the cost is high.
  • the whisker it is sufficient for the whisker to cover the surface of the support in a mesh-like manner, and the coating amount is small compared to the My force, so that the color is difficult to obtain.
  • a conductive material in which a small amount of antimony oxide is mixed with tin oxide is of the order of ⁇ m in size due to its particle shape, whereas the conductive material of the present invention has a size of ⁇ m.
  • the conductive material that covers Iska is very thin and orderly.
  • the conductive disk of the present invention is more efficient, and the color is not conspicuous because of its small thickness.
  • Antimony oxide is black, and cannot provide sufficient conductivity to particulate oxide so that it cannot be mixed in large quantities.
  • the surface resistance of the antistatic layer is 20 and less than X 0 12 ⁇ in an atmosphere of 15% RH
  • Binders used together with the conductive substance include polyvinyl alcohol, and if they are suitable for the purpose of the present invention, they are water-soluble and solvents.
  • the binder used for the heat-sensitive layer side is not particularly limited, and it is preferable that the binder be water- or water-resistant.
  • Conventional methods can be used to apply a heat-sensitive paint to the support and obtain a heat-sensitive recording medium.
  • the synthetic paper in the present invention includes a synthetic resin film having a paper-like appearance and physical properties, a synthetic fiber formed by wet or dry synthetic paper, and the like. It is.
  • synthetic paper in which a synthetic resin film is given an appearance and physical properties like paper is particularly preferable.
  • Such synthetic paper is manufactured by coating a white pigment on the surface of the synthetic resin film, or by adding a filler or foaming agent to the synthetic resin film.
  • There is a method of making the material opaque by adding a compound, and any of them can be used as the support of the present invention.
  • the synthetic resin film used as a support in the present invention may be a conventionally known synthetic resin film such as a polystyrene film or a polyolefin film. Reinforth finolems, cellulosic finolems, polyamide finolems, etc. one
  • Conductive whisker (trade name: WK-200 made by Otsuka Chemical) 7 parts Polyvinyl alcohol 12% aqueous solution 130 ⁇ 15 Water 60 parts Conductive whiskers used here The powder is a mixture of ultrafine tin oxide and antimony oxide (antioxidant doped with antimony oxide). )).
  • the above composition was stirred and mixed to obtain a coating liquid for conductive treatment.
  • This coating solution is applied to one side of a commercially available synthetic paper (trade name: UPO FPGI80, manufactured by Oji Yuka Synthetic Paper) so as to have a solid content of about 4 g Znf, and dried to form an antistatic layer. A support was obtained.
  • This heat-sensitive coating liquid was applied to the support not coated with the conductive treatment liquid so as to have a solid content of about 7 g non-nf and dried to obtain a heat-sensitive recording material of the present invention.
  • Example 1 The heat-sensitive coating of Example 1 was applied on the side of the support obtained in Example 1 on which the conductive processing liquid was applied to one side thereof, on the side to which the conductive processing liquid was applied, so as to have a solid content of about 7 g / nf. After drying, a thermosensitive recording medium was obtained.
  • Example 3 9/05668 PCT / JP89 / 01056
  • synthetic resin finolem, polystyrene film thermoplastic polyethylene
  • Example 1 was repeated except that a conductive oxide tin (trade name: SEO-200, manufactured by Nihon Kagaku Sangyo) was used in place of the conductive disk used in Example 1. In the same way, a thermosensitive recording body was obtained.
  • a conductive oxide tin trade name: SEO-200, manufactured by Nihon Kagaku Sangyo
  • Example 2 was completely different from Example 2 except that conductive oxide tin (trade name: SEO-200, manufactured by Nihon Kagaku Sangyo) was used in place of the conductive disk. In the same manner, a thermosensitive recording medium was obtained.
  • conductive oxide tin trade name: SEO-200, manufactured by Nihon Kagaku Sangyo
  • the synthetic paper used in Example 1 was prepared by adding a commercially available ion conductive paint (trade name: SKYITAF T-505, manufactured by Achilles) to a solid content of 1.0 g / irf. Then, the heat-sensitive paint used in Example 1 was applied to the opposite surface to a solid content of 7 g / nf and dried to obtain a heat-sensitive recording material.
  • a commercially available ion conductive paint trade name: SKYITAF T-505, manufactured by Achilles
  • Example 1 The thermal paper used in Example 1 was applied to the synthetic paper used in Example 1 so as to have a solid content of 7 g Zrrf and dried to obtain a thermal recording medium. Comparative Example 5
  • Example 1 was completely different from Example 1 except that the conductive whisker used in Example 1 was replaced by a conductive wick (trade name: MEC-200, manufactured by Teikoku Chemicals Co., Ltd.). In the same manner, a thermal recording body was obtained.
  • a conductive whisker used in Example 1 was replaced by a conductive wick (trade name: MEC-200, manufactured by Teikoku Chemicals Co., Ltd.). In the same manner, a thermal recording body was obtained.
  • Measurements were made with an applied voltage of 100 V using a 4329 A and resistance measurement box 16008A.
  • Continuous printing is performed with a high-speed thermal printer using a fixed head, and the recording paper sticks to the main unit and the recording paper sticks to each other due to static electricity.
  • the thing was X and the thing without trouble was ⁇ .
  • the stickiness was sensory tested by touching it with a finger in an atmosphere of 20 ° C and 65% RH.
  • the surface of the heat-sensitive layer was visually observed, and a colorless natural paper feeling was designated as ⁇ , and a slightly colored one was designated X.
  • the heat-sensitive recording material of the present invention is better than the conventional heat-sensitive recording material of this kind in paper passing property, appearance, and appearance. It is clear that all points are clean
  • the heat-sensitive recording medium of the present invention does not generate stickiness or blocking at high humidity, and has improved paper-passing traveling performance, as compared with a heat-sensitive recording medium using a conventional conductive material. Almost immediately, it has a natural paper texture.

Abstract

The invention relates to a thermal recording medium which comprises a support formed of synthetic paper or synthetic resin film and an antistatic layer containing conductive whiskers as the major component and being provided on the surface of a heat-sensitive layer and/or a heat-insensitive layer. This medium gives a hand of natural paper, causes neither sticking nor blocking in a high-moisture atmosphere, and shows improved travelling properties.

Description

明 細 発 明 の 名 称  Name of the invention
感 熱 記 録 体  Thermal recording body
技 術 分 野  Technical field
本発明 は感熱記録体 に関 し 、 更に詳 し く は感熱記 録体の帯電が原因 と な つ て発生す る 通紙 ト ラ プ ル等 を防止 し 、 し か も 自 然紙の風合を損な わ な い 感熱記 録紙に関す る 。  The present invention relates to a heat-sensitive recording medium, and more particularly, to prevent a paper passing trap or the like generated due to electrification of a heat-sensitive recording medium, and to achieve a natural paper texture. Thermal recording paper that does not impair the performance.
背 景 技 術  Background technology
従来 よ り 発色性物質 と 該発色性物質を熱時反応 し て発色せ し め る 顕色性物質 と を含有す る 感熱発色層 を支持体上 に設けて な る 感熱記録体 は良 く 知 ら れて い る o  It is well known that a thermosensitive recording medium in which a heat-sensitive coloring layer containing a color-forming substance and a color-developing substance that reacts with the color-forming substance upon heating to form a color is provided on a support. O
かか る 感熱記録体 は メ ィ ン テ ナ ン ス が容易、 記録 時 に臭気、 騒音がな い 、 一次発色であ る な どの理由 に よ り 、 フ ァ ク シ ミ リ 、 プ リ ン タ ー な どの記録媒体 と し て広 く 利用 さ れて い る 。  Such a thermal recording medium is easy to maintain, has no odor or noise during recording, and has a primary color. -It is widely used as a recording medium.
こ れ ら の感熱紙の支持体 と し て は従来 よ り 主 と し て紙が使用 さ れて い た。 し 力、 し な 力《 ら 、 最近で は感 熱紙の使用 さ れ る 範囲が広が り 、 ク リ 一 ン ルー ム等 で も 使用 さ れ る 様に な っ た。 こ の よ う な 用途 に従来 の紙を支持体 と し た感熱紙を使用す る と 紙粉が発生 し 、 わず力、な チ リ に も 好 ま し く な い ク リ ー ン ルー ム で は使用 出来な い。 そ こ で紙粉の発生 し な い 合成紙 又は合成樹脂 フ ィ ル ム を支持体 と し た感熱記録体が 種 々 考え ら れて い る 。 Conventionally, paper has been mainly used as a support for these thermal papers. In recent years, the range of use of thermal paper has expanded, and it has also been used in clean rooms and the like. When using thermal paper with conventional paper as a support for such applications, paper dust is generated and the clean room is not suitable for short-term or poor cleaning. It cannot be used with. There are various types of thermosensitive recording media using a synthetic paper or a synthetic resin film, which does not generate paper dust, as a support.
こ の よ う な 感熱記録体 は紙粉が発生 し な い上 に平 滑性が高い た め、 ド ッ ト の再現性が良 く 、 高速性及 び中間調再現性 に優れ、 耐水性が良い と い う 長所が あ る 0  Such a thermal recording medium does not generate paper dust and has high smoothness, so that dot reproducibility is excellent, high speed and halftone reproducibility are excellent, and water resistance is high. Has the advantage of good 0
し 力、 し な 力 ら 合成紙又は合成樹脂 フ ィ ル ム は一般 的 に紙に比較 し て電気抵抗値特 に体積抵抗値が高 く . こ れ ら を支持体 と し て用 い た感熱記録体 は、 そ の帯 電性の た め に通紙 ト ラ ブルを起 し やすい と い う 欠点 があ る 。  In general, synthetic paper or synthetic resin film has a higher electric resistance value, especially a higher volume resistance value, than paper, and is used as a heat-sensitive material. Recording media have the disadvantage that they are prone to paper-feed problems due to their charging properties.
従来特開昭 5 7 - 1 5 6 2 9 2 号、 同 5 7 - 1 7 0 7 9 4 号、 同  Conventionally, JP-A-57-15692, JP-A-57-170794, JP
5 7 - 1 9 9 6 8 7 号、 同 5 9 - 1 4 8 6 9 3 号、 各公報等 に お いて 帯電に よ る 通紙 ト ラ ブルを解消す る た め の提案がな さ れて い る 。 確か に上記の提案に よ れば通紙 ト ラ ブ ル は解消 さ れ る も の の 、 一般に使用 さ れ る 導電剤を 使用 し た場合 に は以下の新た な 問題が発生す る 。 In the publications of 57-196, 967 and 59-149648, each of the publications, proposals were made to eliminate paper-feed problems due to charging. ing . Certainly, although the paper-feeding problem is solved according to the above proposal, the following new problems occur when a commonly used conductive agent is used.
一般に導電剤 と し て は、 イ オ ン導電性の物質 と 電 子導電性の物質が使用 さ れ る が、 イ オ ン導電性物質 を用 い た場合、 環境湿度依存性が犬で十分な帯電防 止効果を得 る た め に は、 かな り の塗工量が必要であ る 事お よ び高湿度時にベ タ ツ キ、 ブ ロ ッ キ ン グが発 生す る と い う 問題が生 じ る 。 一方、 従来当業界で知 ら れた電子導電性物質を用 い る と 環境湿度依存性 は な い も の の着色が著 し く 、 得 ら れ る 感熱記録体の外 損な わ れ る と い う 問題が生 し 。 In general, ion conductive substances and electron conductive substances are used as conductive agents.However, if ion conductive substances are used, the dependence on environmental humidity is sufficient for dogs. To achieve the antistatic effect, a considerable amount of coating is required, and stickiness and blocking occur at high humidity. Occurs. On the other hand, The use of such an electronically conductive substance causes a problem that the coloration of the non-environmental humidity-dependent one is remarkable, and that the resulting thermosensitive recording medium is damaged externally.
そ こ で 本発明の 目 的 は上記 し た各種の 問題点を 走記  Therefore, the purpose of the present invention is to describe the various problems described above.
解決 し た 湿時のベ タ ツ キ、 ブ ロ ッ キ ン グが発生せ ず、 通紙 行性 にす ぐ れ、 し か も 自 然紙の風合を有 す る 感熱 録体を提供す る こ と に め る 。 発 明 の 開 示 To provide a thermal recording medium that has no wet stickiness or blocking when wet, has good paper-passing properties, and has a natural paper feel. To do so. Disclosure of the invention
本発明 は発色性物質 と 、 該発色性物質を熱時反応 し て発色せ し め る 顕色性物質 と を含有す る 感熱発色 層を支持体の少な く と も 一方の面上 に設 けて な る 感 熱記録体 に お いて、 支持体の 感熱層を塗工す る 面お よ び / ま た は塗工 し な い面 に、 チ タ ン酸 カ リ ウ ム 、 炭化ケ ィ ( S i C ) 、 ァ ゾレ ミ ナ （ A ί 2 0 3 ) 、 窒化ケ ィ ( S i 3 N 4 酸化亜鉛等の ゥ ィ ス カ ―の表 ¾ 、 導電性物質が被覆 さ れて な る 導電素材 を主成分 と す る 帯電防止層を設 け た事を特徴 と す る 感熱記録体 に関す る も のであ る Ο According to the present invention, a heat-sensitive coloring layer containing a coloring material and a coloring material which reacts with the coloring material by heating to form a color is provided on at least one surface of a support. In the case of a heat-sensitive recording medium, the surface of the support on which the heat-sensitive layer is coated and / or the surface where the heat-sensitive layer is not coated is coated with potassium titanate or carbonized carbon ( S i C), § zone see Na (a ί 2 0 3), nitride Ke i (S i 3 N 4 © office mosquitoes such as zinc oxide - Table ¾ of conductive material that Do is coated A heat-sensitive recording material characterized by having an antistatic layer containing a conductive material as a main component.
本発明 用 い る 導電性物質 と し て は、 酸化 ス ズ と 酸化ァ ン チ モ ン が用 い ら れ、 結着剤そ の他の成分 と 共に 防止層を形成す る 。  As the conductive substance used in the present invention, tin oxide and antimony oxide are used, and a prevention layer is formed together with a binder and other components.
な お 、 近特開昭 6 3 - 3 4 1 8 0号 、 同 6 3 - 1 7 6 1 5 8 号各 公報 に ァ ン チ モ ン を ドープ し た酸化ス ズで被覆 し た 性マ ィ 力 を用 い て感熱記録体の通紙 ト ラ ブルを - -In addition, the properties of each of Japanese Patent Application Laid-Open Nos. 63-34180 and 633-176158 are coated with an antimony-doped oxide oxide. Use the force to remove the paper feed trouble of the thermal recording medium. --
PCT/JP89/01056 防止す る 提案が さ れて い る が、 本発明 は導電素材 と し て導電性 ウ イ ス カ ーを用 い る 点に特徴があ る 。 PCT / JP89 / 01056 Although prevention has been proposed, the present invention is characterized in that a conductive whisker is used as a conductive material.
本発明で導電性素材 と し て導電性 ゥ ィ ス カ 一 を用 い た理由 は大要次の と お り であ る  The reason why the conductive disc is used as the conductive material in the present invention is as follows.
前記の ア ン チ モ ン を ド ー プ し た酸化ス ズで被覆 し た導電性マ イ 力 は、 平板状であ り 、 支持体全面を被 覆 し な い と 導電性が発現 し な い。 こ の た め塗工量が 多 く な り 、 色がつ く 上、 コ ス ト も高い と い う 難点力 あ る 。  The conductive My force coated with the above-mentioned antimony-doped oxide tin has a flat plate shape, and does not exhibit conductivity unless the entire support is covered. . The drawbacks are that the amount of coating increases, the color increases, and the cost is high.
こ れに対 し 、 ウ イ ス カ 一 は支持体表面を網 目 状に 被覆すれば充分で、 マ イ 力 と 比較 し て被覆量が少な く てすむので、 色がつ き に く く 、 自 然紙風にで き 、 し 力、 も 低 コ ス ト でで き る と い う メ リ ッ ト カ あ る 。  On the other hand, it is sufficient for the whisker to cover the surface of the support in a mesh-like manner, and the coating amount is small compared to the My force, so that the color is difficult to obtain. Some of the benefits are that they can be made naturally like paper and have low cost.
ま た 、 酸化ス ズ に酸化ア ン チ モ ン を少量混合 し た 導電性物質 は、 粒子状の た め大 き さ は ^ m オ ー ダ ー であ る の に対 し 、 本発明の ウ イ ス カ — を被覆す る 導 電性物質 は き わ めて薄 く オ ー ダ — で あ る 。  In addition, a conductive material in which a small amount of antimony oxide is mixed with tin oxide is of the order of ^ m in size due to its particle shape, whereas the conductive material of the present invention has a size of ^ m. The conductive material that covers Iska is very thin and orderly.
こ の た め本発明 の導電性ゥ ィ ス カ — の方が効率が 良い上、 厚 さ が薄い の で色が 目 立た な い の で あ る 。  For this reason, the conductive disk of the present invention is more efficient, and the color is not conspicuous because of its small thickness.
酸化ア ン チ モ ン は 黒色で 、 粒子状 の酸化ス ズ に は 大量に混合す る こ と がで き な い ので導電性が十分 に 与え ら れな い。  Antimony oxide is black, and cannot provide sufficient conductivity to particulate oxide so that it cannot be mixed in large quantities.
帯電防止層の表面抵抗値は 2 0て 、 1 5 % R Hの雰囲気 下で X 0 1 2 Ω 以下であ る 前記導電性物質 と 共 に用 い ら れ る 結着剤 は ポ リ ビ ニ ルア ル コ ールを は じ め、 本発明 の 目 的 にかな う も の であ れば水溶性であ れ溶剤系であ れ特 に制限 さ れ な いが、 感熱層側 に用 い る 結着剤は耐水性又は耐水 化出来 る も の が好ま し い。 The surface resistance of the antistatic layer is 20 and less than X 0 12 Ω in an atmosphere of 15% RH Binders used together with the conductive substance include polyvinyl alcohol, and if they are suitable for the purpose of the present invention, they are water-soluble and solvents. The binder used for the heat-sensitive layer side is not particularly limited, and it is preferable that the binder be water- or water-resistant.
支持体 に 感熱塗料を塗布 し 、 感熱記録体を得 る に は通常行わ れて い る 方法が使用 出来 る 。  Conventional methods can be used to apply a heat-sensitive paint to the support and obtain a heat-sensitive recording medium.
本発明 に用 い ら れ る 支持体 は 、 合成紙、 合成樹脂 フ ィ ル ム な どが用 い ら れ る 。  As the support used in the present invention, synthetic paper, synthetic resin film, and the like are used.
本発明 に お け る 合成紙に は 合成樹脂 フ ィ ル ム に紙 の よ う な外観や物性を与え た も の や、 合成繊維を湿 式又 は乾式で抄造 し た も の な どが含ま れ る 。  The synthetic paper in the present invention includes a synthetic resin film having a paper-like appearance and physical properties, a synthetic fiber formed by wet or dry synthetic paper, and the like. It is.
こ れ ら の支持体 の 中 で合成樹脂 フ ィ ル ム に 紙の よ う な 外観や物性を与え た合成紙が特に好 ま し い。 こ の よ う な 合成紙の製造法 に は合成樹脂 フ ィ ル ム の表 面 に 白色顔料の コ ーテ ィ ン グを行 っ た り 、 合成樹脂 フ ィ ル ム 中 に充填剤や発泡剤を添加 し て不透明 化を 行 う 方法な どがあ り 、 い ずれ も 本発明 の支持体 と し て使用す る こ と が出来 る 。  Among these supports, synthetic paper in which a synthetic resin film is given an appearance and physical properties like paper is particularly preferable. Such synthetic paper is manufactured by coating a white pigment on the surface of the synthetic resin film, or by adding a filler or foaming agent to the synthetic resin film. There is a method of making the material opaque by adding a compound, and any of them can be used as the support of the present invention.
ま た本発明 に支持体 と し て用 い ら れ る 合成樹脂 フ イ ル ム は 、 従来公知の合成樹脂 フ ィ ル ム た と え ば ポ リ エ ス テ ノレ フ ィ ル ム 、 ポ リ オ レ フ イ ン フ イ ノレ ム 、 セ ル ロ ー ス 系 フ イ ノレ ム 、 ポ リ ア ミ ド フ イ ノレ ム等力 あ げ ら れ る 一 The synthetic resin film used as a support in the present invention may be a conventionally known synthetic resin film such as a polystyrene film or a polyolefin film. Reinforth finolems, cellulosic finolems, polyamide finolems, etc. one
91/05668 PCT/JP89/01056 発明 を実施す る た め の最良の形態 91/05668 PCT / JP89 / 01056 Best mode for carrying out the invention
以下本発明 を実施例及び比較例を あ げて更 に詳細 に説明す る 。 な お、 説明中の 「部」 及び 「％」 は特 に断 ら な い 限 り 、 そ れぞれ 「重量部」 お よ び 「重量 %」 を示す。  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the description, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.
実施例 1 Example 1
① 帯電防止層 の形成  ① Formation of antistatic layer
導電性 ウ イ ス カ ー （商品名 ： WK-200 大塚化 学製） 7 部 ポ リ ビニ ル ア ル コ ー ル 12 %水溶液 130咅 15 水 60部 こ こ に 用 い た導電性ウ イ ス カ 一 はチ タ ン 酸 カ リ ゥ ム ウ イ ス カ ー の微粉末表面を超微粒子酸化ス ズ と 酸化 ア ン チ モ ン の混合物 （酸化ア ン チ モ ン を ド ― プ し た 酸化ス ズ） で被覆 し た も の で あ る 。  Conductive whisker (trade name: WK-200 made by Otsuka Chemical) 7 parts Polyvinyl alcohol 12% aqueous solution 130 咅 15 Water 60 parts Conductive whiskers used here The powder is a mixture of ultrafine tin oxide and antimony oxide (antioxidant doped with antimony oxide). )).
上記の組成物を撹拌混合 し 、 導電処理用 の塗液 と し た。 こ の塗液を市販の合成紙 （商品名 ： ュ ポ FPGI80. 王子油化合成紙製） の片面 に約 4 g Z nf 固 形分に な る よ う に塗布乾燥 し 、 帯電防止層を有す る 支持体を得た。  The above composition was stirred and mixed to obtain a coating liquid for conductive treatment. This coating solution is applied to one side of a commercially available synthetic paper (trade name: UPO FPGI80, manufactured by Oji Yuka Synthetic Paper) so as to have a solid content of about 4 g Znf, and dried to form an antistatic layer. A support was obtained.
② A液調成  ② Preparation of liquid A
ク リ ス タ ノレ く ィ ォ レ ツ ト ラ ク ト ン 5 部 ス テ ア リ ン 酸亜鉛 10部 炭酸 カ ル シ ウ ム 27部 ポ リ ア ク リ ル酸 ソ 一ダ 1 0 %水溶液 5 部 ポ リ ビニ ル ア ル コ ー ル 1 2 %水溶液 3 0部 水 5 0部 こ の組成物をペ イ ン ト シ ヱ イ 力 一で 1 2時間分散 し た c 5 parts of crystal clear tracton zinc stearate 10 parts of calcium carbonate 27 parts Sodium polyacrylate 10% aqueous solution 5 parts Polyvinyl alcohol 12% aqueous solution 30 parts Water 50 parts Paint composition in 1 2 hours distributed c
③ B 液調成 ③ B liquid preparation
4 , 4 ' — イ ソ プ ロ ピ リ デ ン ジ フ ヱ ノ ー ル 1 5部 炭酸カ ル シ ウ ム 2 7部 ポ リ ア ク リ ル酸 ソ 一 ダ 1 0 %水溶液 5 部 ポ リ ビニ ル ア ル コ ー ル 1 2 %水溶液 3 0部 水 5 0部 こ の組成物をペイ ン ト シ ヱ イ 力 一で 1 2時間分散 し た， 4, 4 '— Isopropylidene divinyl 1 5 parts Calcium carbonate 2 7 parts Sodium polyacrylate 10% aqueous solution 5 parts Polyvinyl Rualcoal 12% aqueous solution 30 parts Water 50 parts This composition was dispersed for 12 hours with a paint dryer.
④ 記録層の形成 の Formation of recording layer
別 々 に分散 し た A 液、 B 液を混合 し 、 更に ポ リ ビ ニ ル ア ル コ ー ル 1 2 %水溶液 6 5部を加え、 感熱塗料を 作成 し た。  Separately dispersed solution A and solution B were mixed and further added with 65 parts of a 12% aqueous solution of polyvinyl alcohol to prepare a heat-sensitive paint.
こ の感熱塗液を前記支持体の導電処理液を塗布 し て い な い側 に、 約 7 g ノ nf 固形分 に な る よ う に塗布 乾燥 し 、 本発明の感熱記録体を得た。  This heat-sensitive coating liquid was applied to the support not coated with the conductive treatment liquid so as to have a solid content of about 7 g non-nf and dried to obtain a heat-sensitive recording material of the present invention.
実施例 2  Example 2
実施例 1 で得た片面 に導電処理液を塗布 し た支持 体の導電処理液を塗布 し た側に、 実施例 1 の 感熱塗 料を約 7 g / nf 固形分 に な る よ う に塗布、 乾燥 し 、 感熱記録体を得た。  The heat-sensitive coating of Example 1 was applied on the side of the support obtained in Example 1 on which the conductive processing liquid was applied to one side thereof, on the side to which the conductive processing liquid was applied, so as to have a solid content of about 7 g / nf. After drying, a thermosensitive recording medium was obtained.
実施例 3 - - 91/05668 PCT/JP89/01056 実施例 1 で用 い た支持体 · 合成紙 に代えて、 合成 樹脂 フ イ ノレ ム · ポ リ エ ス テ ル フ ィ ルム （熱可塑性 ポ リ エ チ レ ン テ レ フ 夕 レ ー ト フ イ ノレ ム ） を 用 い た以外 は実施例 1 と 全 く 同様 に し て感熱記録体を得た。 Example 3 --91/05668 PCT / JP89 / 01056 Instead of the support and synthetic paper used in Example 1, synthetic resin finolem, polystyrene film (thermoplastic polyethylene) A heat-sensitive recording medium was obtained in exactly the same manner as in Example 1 except that the intermediate recording medium was used.
比較例 1 Comparative Example 1
実施例 1 で用 い た導電性 ゥ イ ス カ ー に代え て、 導 電性酸化ス ズ （商品名 ： SEO-200 、 日 本化学産業製） を用 い た以外 は、 実施例 1 と 全 く 同様に し て感熱記 録体を得た。  Example 1 was repeated except that a conductive oxide tin (trade name: SEO-200, manufactured by Nihon Kagaku Sangyo) was used in place of the conductive disk used in Example 1. In the same way, a thermosensitive recording body was obtained.
比較例 2 Comparative Example 2
実施例 2 に お い て、 導電性 ゥ イ ス カ ー に代え て、 導電性酸化ス ズ （商品名 ： SEO-200 、 日 本化学産業 製） を用 い た以外 は実施例 2 と 全 く 同様に し て感熱 記録体を得た。  Example 2 Example 2 was completely different from Example 2 except that conductive oxide tin (trade name: SEO-200, manufactured by Nihon Kagaku Sangyo) was used in place of the conductive disk. In the same manner, a thermosensitive recording medium was obtained.
比較例 3 Comparative Example 3
実施例 1 で用 い た合成紙 に、 市販の イ オ ン導電性 塗料 （商品名 ： ス カ イ タ フ T- 505 、 ア キ レ ス 製） を 1.0 g / irf 固形分 に な る よ う に塗工 し 、 反対面 に実 施例 1 で用 い た感熱塗料を 7 g / nf 固形分に な る よ う に塗布、 乾燥 し 、 感熱記録体を得た。  The synthetic paper used in Example 1 was prepared by adding a commercially available ion conductive paint (trade name: SKYITAF T-505, manufactured by Achilles) to a solid content of 1.0 g / irf. Then, the heat-sensitive paint used in Example 1 was applied to the opposite surface to a solid content of 7 g / nf and dried to obtain a heat-sensitive recording material.
比較例 4  Comparative Example 4
実施例 1 で用 い た合成紙に 、 実施例 1 で用 い た感 熱塗料を 7 g Z rrf 固形分 に な る よ う に塗布、 乾燥 し 、 感熱記録体を得た。 比較例 5 The thermal paper used in Example 1 was applied to the synthetic paper used in Example 1 so as to have a solid content of 7 g Zrrf and dried to obtain a thermal recording medium. Comparative Example 5
実施例 1 で用 い た導電性 ウ イ ス カ ー の代わ り に 、 導電性マ イ 力 （商品名 ： MEC- 200 帝国化工 （株） 製） を使用 し た以外 は実施例 1 と 全 く 同様 に し て感熱記 録体を得た。  Example 1 was completely different from Example 1 except that the conductive whisker used in Example 1 was replaced by a conductive wick (trade name: MEC-200, manufactured by Teikoku Chemicals Co., Ltd.). In the same manner, a thermal recording body was obtained.
か く し て、 得 ら れた 8種類の感熱記録体 に つ い て、 以下の評価試験を行い 、 そ の結果を表 に示 し た。  The following evaluation tests were performed on the eight types of thermal recording media thus obtained, and the results are shown in the table.
( 1 ) 表面抵抗測定法  (1) Surface resistance measurement method
ヒ ュ レ ツ ト パ ッ カ ー ド社製高抵抗測定器  Hurette Packard High Resistance Measuring Instrument
4329 A お よ び抵抗測定箱 16008Aを用 い 、 印加電圧 100Vで測定 し た。  Measurements were made with an applied voltage of 100 V using a 4329 A and resistance measurement box 16008A.
(2) 帯電性評価法  (2) Electrification evaluation method
宍戸商会製ス タ チ ッ ク ォネ ス ト メ 一 タ を用 い 、 14誦の距離力、 ら 6 KVの コ ロ ナ チ ャ ー ジ を行い 、 感 熱記録体の両面が帯電 し な い も の を 〇 と し 、 片面 又 は両面が帯電 し た も の を X と し た。  Using a static gonometer made by Shishido Shokai Co., Ltd., a corona charge of 14 KV and a distance of 6 KV was performed, and both surfaces of the thermal recording material were not charged. The sample was designated as 〇, and the sample with one or both surfaces charged was designated as X.
(3) 通紙性  (3) Paper passage
固定へ ッ ドを使用 し た高速感熱プ リ ン タ ーで連 続印字 し 、 記録紙が本体にへば り つ い た り 、 記録 紙が静電気の為 に互い に く つ つ い た り し た も の を X と し 、 ト ラ ブルの無い も の を 〇 と し た。  Continuous printing is performed with a high-speed thermal printer using a fixed head, and the recording paper sticks to the main unit and the recording paper sticks to each other due to static electricity. The thing was X and the thing without trouble was 〇.
(1) 〜 （3) は 20°C、 15% RHの雰囲気下で測定 し た c (1) to (3) c was measured in an atmosphere of RH 20 ° C, 15%
(4) (5) 地肌濃度の測定 (4) (5) Measurement of background density
感熱記録面お よ びそ の裏面の地肌濃度を マ ク ベ - - 91/05668 PCT/JP89/01056 ス 濃度計 RD-514で測定 し た。 測定値が 0.10以上の 場合外観不良 と 判定 し た。 Measure the thermal recording surface and the density of the background on the back. --91/05668 PCT / JP89 / 01056 Measured with densitometer RD-514. When the measured value was 0.10 or more, it was judged as poor appearance.
(6) 裏面のベ タ ツ キ  (6) Sticky back
20°C、 65% RHの雰囲気下で指で触れて、 そ のべ タ ツ キを官能テ ス ト し た。  The stickiness was sensory tested by touching it with a finger in an atmosphere of 20 ° C and 65% RH.
〇ベ タ ツ キ な し 、 X ベ タ ツ キ あ り  〇 No stickiness, X sticky
(7) 自 然紙の風合  (7) Natural paper texture
感熱層の表面を 目 視 し 、 着色がな く 自 然紙感が あ る も の を〇、 わずかで も 着色 し て い る も の を X と し た。 The surface of the heat-sensitive layer was visually observed, and a colorless natural paper feeling was designated as 〇, and a slightly colored one was designated X.
(1)支 の表面抵抗 (Ω) (2) 纏 体 (3) mm^ (4) 感執言 ¾1面の (5) 麵の (6)麵の (7) 自然紙 感熱 J1紅側 感熱層非塗工側 の 帯電 性 地 肌 濃 度 ベタツキ 風 合 雄例 1 1.41X1011 7.5 xlO8以下 Ο 〇 0.05 0.06 〇 O(1) Surface resistance of the branch (Ω) (2) Body (3) mm ^ (4) Impression (1) (5) 麵 (6) 麵 (7) Natural paper Thermal J1 Red side Thermal layer Non-coating side Chargeable background Concentration Stickiness Wind case Male 1 1.41X10 11 7.5 xlO 8 or less Ο 〇 0.05 0.06 〇 O
2 7.5 xlO8 1.2 XI 010 Ο o 0.07 0.05 〇 〇2 7.5 xlO 8 1.2 XI 0 10 Ο o 0.07 0.05 〇
3 .3.7 X 1011 1.3 X 1010 〇 〇 0.05 0.03 〇 〇 比铰例 1 4.2 1014 8.7 X 1010 Ο 0 0.05 0.32 0 〇3.3.7 X 10 11 1.3 X 10 10 〇 〇 0.05 0.03 〇 〇 Comparative example 1 4.2 10 14 8.7 X 10 10 Ο 0 0.05 0.32 0 〇
' 2 8.7 lO10 4.2 X I 014 〇 〇 0.16 0.03 〇 X'2 8.7 lO 10 4.2 XI 0 14 〇 〇 0.16 0.03 〇 X
3 4.2 xlO14 5.8 X 1012 X X 0.05 0.04 X 〇3 4.2 xlO 14 5.8 X 10 12 XX 0.05 0.04 X 〇
4 4.2 xlO14 4.2 XI 014 X X 0.05 0.03 〇 O4 4.2 xlO 14 4.2 XI 0 14 XX 0.05 0.03 〇 O
5 3.8 1014 2.8 1012 X X 0.05 0.08 〇 X 5 3.8 10 14 2.8 10 12 XX 0.05 0.08 〇 X
一 - 91/05668 PCT/JP89/01056 表に示 さ れた結果か ら本発明の感熱記録体 は従来 の こ の種の感熱記録体よ り 通紙性、 外観お よ びべ 夕 ツ キ等すベての点です ぐ れて い る 事が明 ら かであ る 1-91/05668 PCT / JP89 / 01056 From the results shown in the table, the heat-sensitive recording material of the present invention is better than the conventional heat-sensitive recording material of this kind in paper passing property, appearance, and appearance. It is clear that all points are clean
産業上の利用可能性 Industrial applicability
本発明の感熱記録体は、 従来の導電性物質を用 い た感熱記録体に比較 し て、 高湿度時のベ タ ツ キ、 プ ロ ッ キ ン グを発生せず、 通紙走行性に す ぐ れ、 し か も 自 然紙の風合を有す る 。  The heat-sensitive recording medium of the present invention does not generate stickiness or blocking at high humidity, and has improved paper-passing traveling performance, as compared with a heat-sensitive recording medium using a conventional conductive material. Almost immediately, it has a natural paper texture.

Claims

3 Three
PCT/JP89/01056 特許請求の範囲 PCT / JP89 / 01056 Claims
. 発色性物質 と 該発色性物質を熱時反応 し て発色 せ し め る 顕色性物質 と を含有す る 感熱発色層を支 持体の少な く と も 一方の面上に設け て な る 感熱記 録体に お い て、 支持体の感熱層を塗工す る 面お よ び / ま た は塗工 し な い面 に 、 導電性 ゥ イ ス カ ーを 主成分 と す る 帯電防止層を設けた事を特徴 と す る 感熱記録体。  A heat-sensitive color-developing layer containing a color-forming substance and a color-developing substance that reacts with heat to develop a color when heated is provided on at least one surface of the support. In thermal recording media, antistatic mainly composed of conductive loudspeakers on the surface of the support where the thermal layer is coated and / or the surface that is not coated. Thermal recording medium characterized by having a layer.
2 . 導電性 ゥ イ ス カ ーが ウ イ ス カ ーの微粉末表面を 超微粒子酸化ス ズ と 酸化ア ン チ モ ン で被覆 し た導 電性 ウ イ ス カ ーであ る 請求項 1 記載の 感熱記録体 2. The conductive whisker is a conductive whisker in which the surface of the whisker's fine powder is coated with ultrafine oxide oxide and antimony oxide. Thermal recording medium described
3 . ウ イ ス カ 一 力《 チ タ ン酸カ リ ウ ム 、 炭化ゲ イ 素、 ア ル ミ ナ 、 窒化ゲ イ 素、 酸化亜鉛か ら 選ばれ る ゥ ィ ス カ ー であ る 請求項 1 記載の感熱記録体。 3. Whisker strength <Claim that the whisker is a disc selected from the group consisting of potassium titanate, silicon carbide, aluminum, silicon nitride, and zinc oxide. 1. The heat-sensitive recording material according to 1.
4 . 帯電防止層の表面抵抗値が 1 X 1 0 1 2 Ω 以下で あ る 請求項 1 記載の感熱記録体。 4. The heat-sensitive recording material according to claim 1, wherein the surface resistance value of the antistatic layer is 1 × 10 12 Ω or less.
5 . 支持体が合成紙、 合成樹脂 フ ィ ル ム か ら 選ばれ る 支持体であ る 請求項 1 記載の 感熱記録体。  5. The heat-sensitive recording material according to claim 1, wherein the support is a support selected from a synthetic paper and a synthetic resin film.
PCT/JP1989/001056 1988-09-13 1989-10-13 Thermal recording medium WO1991005668A1 (en)

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JPS6334180A (en) * 1986-07-29 1988-02-13 Honshu Paper Co Ltd Thermal recording material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5719016A (en) * 1996-11-12 1998-02-17 Eastman Kodak Company Imaging elements comprising an electrically conductive layer containing acicular metal-containing particles
EP1008618A1 (en) * 1997-08-27 2000-06-14 Otsuka Kagaku Kabushiki Kaisha Printing sheets
EP1008618A4 (en) * 1997-08-27 2000-10-25 Otsuka Kagaku Kk Printing sheets
US6713164B1 (en) 1997-08-27 2004-03-30 Otsuka Kagaku Kabushiki Kaisha Printing sheets
US5939243A (en) * 1998-05-04 1999-08-17 Eastman Kodak Company Imaging element comprising an electrically-conductive layer containing mixed acicular and granular metal-containing particles and a transparent magnetic recording layer
US6074807A (en) * 1998-10-15 2000-06-13 Eastman Kodak Company Imaging element containing an electrically-conductive layer containing acicular metal-containing particles and a transparent magnetic recording layer

Also Published As

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JPH0276782A (en) 1990-03-16

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