JPH0576436B2 - - Google Patents
Info
- Publication number
- JPH0576436B2 JPH0576436B2 JP59158053A JP15805384A JPH0576436B2 JP H0576436 B2 JPH0576436 B2 JP H0576436B2 JP 59158053 A JP59158053 A JP 59158053A JP 15805384 A JP15805384 A JP 15805384A JP H0576436 B2 JPH0576436 B2 JP H0576436B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- liquid
- sensitive
- recording material
- water
- 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 - Fee Related
Links
- 239000000463 material Substances 0.000 claims description 25
- 238000004040 coloring Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 8
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 claims description 4
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 claims description 4
- 229960005222 phenazone Drugs 0.000 claims description 4
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 2
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 39
- 239000010410 layer Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000011161 development Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 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
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001454 recorded image Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007651 thermal printing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate 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
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
〔技術分野〕
本発明は感熱記録材料に関し、特に画像の信頼
性に優れかつ高感度な感熱記録材料に関する。
〔従来技術〕
近年、情報量の増大、省資源、省力化、無公害
化等の社会的要請に伴つて、情報記録分野におい
ても種々の記録方式の実用化や改良が進められて
いるが、中でも感熱記録材料を用いる感熱記録方
式は、(1)１次発色で現像工程が不要、(2)ハードが
簡単で且つコンパクトにできる上、メンテナンス
コストが安い、(3)普通紙に近い感触でしかもシー
ト自体も比較的安価等の特徴もあつて、コンピユ
ーターのアウトプツト、医療計測用レコーダー分
野、フアクシミリ分野、プリンター分野、POS
用ラベル、自動販売機用乗車券等への実用化がな
されている。このような方式に用いられる感熱記
録材料としては、支持体上にラクトン、ラクタ
ム、又はスピロピラン環を有する無色又は淡色の
ロイコ染料と酸性物質、例えば有機酸又はフエノ
ール性化合物を含有する感熱発色層を設けたもの
（特公昭43−4160号、45−14039号等）が公知であ
る。しかしながら、前記のようなロイコ系の感熱
記録材料の場合、記録画像の安定性が悪く、消色
しやすいという欠点を有している。例えば、油や
プラスチツクフイルム中の可塑剤（ジオクチルフ
タレート等）等と接触すると、その記録画像が消
色するという問題があり、この問題の解決がこの
種の記録材料における大き技術課題になつてい
る。
従来も、この問題解決を目的としたものがいく
つか提案されており、例えば、感熱発色層中に、
耐水及び耐薬品性の良い樹脂を大量に含有させて
感熱発色層の安定性を高めたものや、感熱発色層
中に熱又は光によつて硬化する樹脂を含有させて
感熱発色層の安定性を高めたものがある他、感熱
発色層の表面に樹脂保護層を形成して感熱発色層
を薬品や水の作用から保護したものなどがある。
一方、感圧紙の分野では、耐薬品の良い顕色剤を
用いたものが提案されているが（特開昭48−
51716号、特公昭51−25174号公報、この場合、特
定の顕色剤使用は感圧紙に関しては有効であつて
も、感熱記録紙に関しては有効でなく、可塑剤と
接触した場合に発色部は安定であるが、地色部
（非発色部）の発色が起るという問題がある。特
開昭59−11286号公報にも特定の顕色剤が示され
ているが、この顕色剤も感圧紙に適しているかも
知れないが、そのほとんどが感熱記録材料には不
適当である。すなわち、地色部の初期濃度が高く
（地肌カブリ）、極めて低品位の感熱記録材料しか
得ることができない。さらに、その多くのものは
前記感圧紙分野の顕色剤と同様に、可塑剤との接
触で地色部の発色が起つてしまう。
一方、近年、記録の高速化及び高密度化に対す
る要求が高まりつつあり、記録装置自体の高速化
は勿論、これに対応し得る記録材料の開発が強く
望まれている。この様の観点から、特開昭53−
39139号、特開昭53−26139号、特開昭53−5636
号、特開昭53−11036号公報等には、前述のよう
な感熱発色層中に各種ワツクス類、脂肪酸アミ
ド、アルキル化ビフエニル、置換ビフエニルアル
カン、クマリン類、ジフエニルアミン類等の低融
点の熱溶融性物質を増感剤（あるいは融点降下
剤）として添加したものが提案されているが、こ
の方式によつても充分満足し得る熱応答性は得ら
れず、高速記録に適するともに画像信頼性の高い
感熱記録材料の出現が強く望まれている。
〔目 的〕
本発明は、高速記録時の発色性に優れると共
に、水、油、可塑剤等との接触によつても発色部
の消色や、地肌部の発色がおこらない。高感度且
つ高画像信頼性の感熱記録材料を提供することを
目的とする。
〔構 成〕
本発明によれば、支持体上に、疎水性高分子微
粒子と水性エマルジヨン結着剤とを主成分として
含有するアンダーコート層を設け、その上に、ロ
イコ染料と顕色剤として式：
[Technical Field] The present invention relates to a heat-sensitive recording material, and particularly to a heat-sensitive recording material with excellent image reliability and high sensitivity. [Prior Art] In recent years, with the increase in the amount of information and social demands such as resource saving, labor saving, and pollution-free technology, various recording methods have been put into practical use and improved in the field of information recording. Among them, thermal recording methods that use thermal recording materials are: (1) Primary color development does not require a developing process, (2) The hardware is simple and compact, and maintenance costs are low, and (3) The feel is similar to that of plain paper. In addition, the sheet itself is relatively inexpensive, making it suitable for use in computer output, medical measurement recorder fields, facsimile fields, printer fields, and POS fields.
It has been put to practical use in travel labels, tickets for vending machines, etc. The heat-sensitive recording material used in such a method includes a heat-sensitive coloring layer containing a colorless or light-colored leuco dye having a lactone, lactam, or spiropyran ring and an acidic substance, such as an organic acid or a phenolic compound, on a support. Those provided (Japanese Patent Publication No. 43-4160, No. 45-14039, etc.) are known. However, in the case of the above-mentioned leuco-based heat-sensitive recording material, the stability of the recorded image is poor and the color is easily erased. For example, there is a problem in that the recorded image fades when it comes into contact with oil or plasticizers (dioctyl phthalate, etc.) in plastic films, and solving this problem is a major technical challenge for this type of recording material. . In the past, several methods have been proposed to solve this problem. For example, in the heat-sensitive coloring layer,
The stability of the thermosensitive coloring layer can be improved by containing a large amount of resin with good water resistance and chemical resistance, or by containing a resin that hardens by heat or light in the thermosensitive coloring layer. In addition to those that have a higher coloring layer, there are also those that have a resin protective layer formed on the surface of the thermosensitive coloring layer to protect it from the effects of chemicals and water.
On the other hand, in the field of pressure-sensitive paper, one using a color developer with good chemical resistance has been proposed (Japanese Unexamined Patent Application Publication No. 1989-1999).
No. 51716, Japanese Patent Publication No. 51-25174, in this case, although the use of a specific color developer is effective for pressure-sensitive paper, it is not effective for heat-sensitive recording paper, and when it comes into contact with a plasticizer, the color developing area Although it is stable, there is a problem that color development occurs in the ground color area (non-color development area). JP-A-59-11286 also discloses certain color developers, which may be suitable for pressure-sensitive papers, but most of them are unsuitable for heat-sensitive recording materials. . That is, the initial density of the background color portion is high (background fog), and only an extremely low-quality heat-sensitive recording material can be obtained. Furthermore, many of them, like the color developers used in the pressure-sensitive paper field, develop color in the background color when they come into contact with plasticizers. On the other hand, in recent years, there has been an increasing demand for higher speed and higher density recording, and there is a strong desire not only to increase the speed of the recording apparatus itself, but also to develop recording materials that can meet this demand. From this point of view, JP-A-53-
No. 39139, JP-A-53-26139, JP-A-53-5636
No. 53-11036, etc., the heat-sensitive coloring layer described above contains various waxes, fatty acid amides, alkylated biphenyl, substituted biphenylalkanes, coumarins, diphenylamines, etc. with low melting points. A method in which a melting substance is added as a sensitizer (or melting point depressant) has been proposed, but even with this method, a sufficiently satisfactory thermal response cannot be obtained, and while it is suitable for high-speed recording, image reliability is There is a strong desire for the emergence of a heat-sensitive recording material with high heat resistance. [Purpose] The present invention has excellent color development during high-speed recording, and does not cause decoloring of the colored areas or color development of the background areas even when in contact with water, oil, plasticizers, etc. The purpose is to provide a heat-sensitive recording material with high sensitivity and high image reliability. [Structure] According to the present invention, an undercoat layer containing hydrophobic polymer fine particles and an aqueous emulsion binder as main components is provided on a support, and a leuco dye and a color developer are added thereon. formula:
本発明の感熱記録材料は、高速記録時の発色性
に優れると共に、水、油、可塑剤等の接触によつ
ても画像部の消色や地肌部の発色が抑制され、高
感度高信頼性の感熱記録材料である。
〔実施例〕
参考例
硫酸亜鉛（ZnSO4・7H2O）14.5ｇとチオシア
ン酸カリウム29.2ｇを水200mlに溶かす。アンチ
ピリン18.8ｇを水200mlに溶かした溶液を上記溶
液に撹拌下に滴下すると直ちに白色沈殿が生ず
る。この沈殿を濾別し水洗後乾燥する。乾燥した
白色粉末を水−エタノールの混合溶媒で再結晶
し、融点118〜120℃のチオシアン酸亜鉛のアンチ
ピリン錯体の白色結晶24.2ｇを得た。
実施例 １
ポリスチレン樹脂の40％分散液 75.0重量部
スチレン／ブタジエン共重合体 6.3 〃
エマルジヨン48％液
水 18.7 〃
上記成分からなる混合物をアジターで撹拌して
アンダーコート液を調製し、これを坪量50ｇ／m2
の上質紙上に乾燥時付着量が3.0ｇ／m2となる様
塗布乾燥してアンダーコート層を設けた。なお、
アンダーコート塗布液の含まれる粒子の体積平均
粒子径は約1.8μmである。
〔Ａ 液〕
３−Ｎ−メチルシクロヘキシルアミノ
−６−メチル−７−フエニルアミノ
フルオラン 10重量部
ヒドロキシエチルセルロース
10％水溶液 10重量部
水 30 〃
上記組成物をアトライターで20時間分散し〔Ａ
液〕とする。
〔Ｂ 液〕
チオシアン酸亜鉛のアンチピリン
錯体 10重量部
メチルセルロース５％水溶液 10 〃
水 30 〃
上記組成物をアトライターで15時間分散し〔Ｂ
液〕とする。
〔Ｃ 液〕
炭酸カルシウム 15重量部
メチルセルロース５％水溶液 15 〃
水 20 〃
上記組成物をアトライターで３時間分散し〔Ｃ
液〕とする。
〔Ｄ 液〕
ステアリン酸アミド 10重量部
メチルセルロース５％水溶液 20 〃
水 20 〃
上記組成物をアトライターで10時間分散し〔Ｄ
液〕とする。
以上のようにして調製した〔Ａ液〕〜〔Ｄ液〕
を用い、下記組成の感熱発色層塗布液を調製し、
これを前記アンダーコート層上に乾燥時付着量が
５ｇ／m2となるよう塗布乾燥して感熱発色層を形
成し本発明の感熱記録材料を得た。
〔感熱発色層塗液〕
〔Ａ液〕 10重量部
〔Ｂ液〕 40 〃
〔Ｃ液〕 15 〃
〔Ｄ液〕 20 〃
スチレン／ブタジエン共重合体 ３ 〃
エマルジヨン48％液
実施例 ２
〔Ｅ 液〕
Ｎ−オクタデシル−カルバモイル−ｐ−
メトキシカルボニルベンゼン 10重量部
メチルセルロース５％液 10 〃
水 30重量部
上記組成物をアトライターで15時間分散し〔Ｅ
液〕とする。
〔Ｆ 液〕
カルボキシ変成ポリビニルアルコール
10％水溶液 50重量部
尿素／ホルマリン樹脂 10 〃
耐水化剤 12 〃
水 40 〃
上記組成物をアトライターで５時間分散し〔Ｆ
液〕とする。
実施例１で調製したアンダーコート層塗液を坪
量50ｇ／m2の上質紙上に乾燥時付量が5.5ｇ／m2
となるよう塗布乾燥しアンダー層を設け、その上
に下記組成の感熱発色層塗液を調製後乾燥時付着
量が6.0ｇ／m2となるよう塗布乾燥して感熱発色
層を形成後、更にその上に〔Ｆ液〕を乾燥時付着
量が1.5ｇ／m2となるよう塗布乾燥し保護層を形
成し本発明の感熱記録材料を得た。
〔感熱発色層塗液〕
〔Ａ液〕 10重量部
〔Ｂ液〕 40 〃
〔Ｃ液〕 10 〃
〔Ｅ液〕 20 〃
ポリ酢酸ビニルエマルジヨン40％液 ４ 〃
比較例 １
実施例１の〔Ｂ液〕の替りに下記〔Ｇ液〕を、
またスチレン／ブタジエン共重合体エマルジヨン
のかわりにポリビニルアルコール10％水溶液を使
用して感熱発色層塗液を調製し、これを坪量50
ｇ／m2の上質紙上に乾燥時付着量が５ｇ／m2とな
るよう塗布乾燥し感熱発色層を形成し比較用の感
熱記録材料を得た。
〔Ｇ 液〕
チオシアン酸亜鉛のイミダゾール 10重量部
錯体（融点143〜145℃）
メチルセルロース５％水溶液 10 〃
水 30 〃
上記組成物をアトライターで15時間分散し〔Ｇ
液〕とする。
比較例 ２
実施例１の〔Ｂ液〕の替りに下記〔Ｈ液〕を、
またスチレン／ブタジエン共重合体エマルジヨン
のかわりに酸化デンプン20％水溶液を使用して感
熱発色層塗液を調製し、これを坪量50ｇ／m2の上
質紙上に乾燥時付着量が5.5ｇ／m2となるよう塗
布乾燥して感熱発色層を設け、その上に前記〔Ｆ
液〕を乾燥時付着量が1.5ｇ／m2となるよう塗布
乾燥し保護層を形成し比較用の感熱記録材料を得
た。
〔Ｈ 液〕
ビスフエノールＡ 15重量部
ヒドロキシエチルセルロース 15 〃
水 20 〃
上記組成物をアトライターで15時間分散し〔Ｈ
液〕とする。
以上のようにして得られた本発明及び比較用の
感熱記録材料をキヤレンダーにて表面処理した
後、熱傾斜試験機（東洋精機製）にて圧力２Kg／
cm2、接触時間１秒間で150℃で印字した。以上の
印字した感熱記録材料の印字部に綿実油を塗布し
40℃dry条件下に15時間放置した後、変化の状態
を調べたところ実施例１及び２のものは印字部の
消色及び非印字部の発色は見られなかつたが、比
較例１及び２については非印字部の発色はなかつ
たものの印字部に消色がみられた。
次に耐可塑剤テストとして同様に印字し印字部
を中心にポリ塩化ビニルフイルム（信越ポリマー
(株)製、ポリラツプＶ−300）を３枚重ね40℃dry
条件下に荷重150ｇ／cm2をかけ15時間放置後、変
化状態ぐ調べたところ実施例１及び２の感熱記録
材料は非印字部の発色がなく、また印字部の消色
も少ないのに対し、比較例１及び２のものは、非
印字部の発色はなかつたものの印字部の消色が甚
しかつた。更に、同様にして印字したサンプルを
水に浸漬し15時間放置後、印字部の変化をみたと
ころ実施例のものは変化が小さかつたのに対し比
較例のものは大きな濃度変化があつた。以上の結
果を表−１に示す。
The heat-sensitive recording material of the present invention has excellent color development during high-speed recording, and also suppresses decolorization in the image area and color development in the background area even when in contact with water, oil, plasticizer, etc., and has high sensitivity and high reliability. It is a heat-sensitive recording material. [Example] Reference Example Dissolve 14.5 g of zinc sulfate (ZnSO 4.7H 2 O) and 29.2 g of potassium thiocyanate in 200 ml of water. When a solution of 18.8 g of antipyrine dissolved in 200 ml of water is added dropwise to the above solution while stirring, a white precipitate immediately forms. This precipitate is separated by filtration, washed with water, and then dried. The dried white powder was recrystallized from a mixed solvent of water and ethanol to obtain 24.2 g of white crystals of an antipyrine complex of zinc thiocyanate having a melting point of 118 to 120°C. Example 1 40% dispersion of polystyrene resin 75.0 parts by weight Styrene/butadiene copolymer 6.3 Emulsion 48% liquid water 18.7 A mixture of the above components was stirred in an agitator to prepare an undercoat liquid, and the basis weight 50g/ m2
An undercoat layer was provided by coating and drying on high-quality paper such that the dry weight was 3.0 g/m 2 . In addition,
The volume average particle diameter of the particles contained in the undercoat coating liquid is approximately 1.8 μm. [Liquid A] 3-N-Methylcyclohexylamino-6-methyl-7-phenylaminofluorane 10 parts by weight Hydroxyethylcellulose 10% aqueous solution 10 parts by weight Water 30 The above composition was dispersed with an attritor for 20 hours [A
liquid]. [Liquid B] Antipyrine complex of zinc thiocyanate 10 parts by weight Methyl cellulose 5% aqueous solution 10 Water 30 Disperse the above composition with an attritor for 15 hours [B
liquid]. [Liquid C] Calcium carbonate 15 parts by weight Methyl cellulose 5% aqueous solution 15 Water 20 The above composition was dispersed with an attritor for 3 hours [C
liquid]. [Liquid D] Stearic acid amide 10 parts by weight Methyl cellulose 5% aqueous solution 20 Water 20 Disperse the above composition with an attritor for 10 hours [D
liquid]. [Liquid A] to [Liquid D] prepared as above
A heat-sensitive color forming layer coating solution having the following composition was prepared using
This was coated and dried on the undercoat layer so that the dry weight was 5 g/m 2 to form a heat-sensitive coloring layer, thereby obtaining the heat-sensitive recording material of the present invention. [Thermosensitive coloring layer coating liquid] [Liquid A] 10 parts by weight [Liquid B] 40 [Liquid C] 15 [Liquid D] 20 [Liquid D] 20 [Styrene/butadiene copolymer 3] Emulsion 48% liquid Example 2 [Liquid E] [E
liquid]. [F solution] Carboxy-modified polyvinyl alcohol 10% aqueous solution 50 parts by weight Urea/formalin resin 10 Water resistant agent 12 Water 40 Disperse the above composition with an attritor for 5 hours [F
liquid]. The undercoat layer coating solution prepared in Example 1 was coated on high-quality paper with a basis weight of 50 g/m 2 at a dry weight of 5.5 g/m 2
After coating and drying to form an under layer, prepare a heat-sensitive coloring layer coating solution with the following composition on top of it, apply and dry to form a heat-sensitive coloring layer with a dry coating weight of 6.0 g/ m2 , and then [Liquid F] was coated thereon so that the dry weight was 1.5 g/m 2 and dried to form a protective layer to obtain the heat-sensitive recording material of the present invention. [Thermosensitive coloring layer coating liquid] [Liquid A] 10 parts by weight [Liquid B] 40 [Liquid C] 10 [Liquid E] 20 [Liquid E] 20 [Polyvinyl acetate emulsion 40% liquid] 4 [Comparative example 1] Example 1 [Liquid] Instead of [Liquid B], use [Liquid G] below.
In addition, a heat-sensitive coloring layer coating solution was prepared using a 10% polyvinyl alcohol aqueous solution instead of the styrene/butadiene copolymer emulsion, and this was coated with a basis weight of 50%.
A heat-sensitive recording material for comparison was obtained by coating and drying the mixture on a high-quality paper of g/m 2 to give a dry adhesion weight of 5 g/m 2 to form a heat-sensitive coloring layer. [Liquid G] 10 parts by weight imidazole complex of zinc thiocyanate (melting point 143-145°C) 5% aqueous solution of methylcellulose 10 〃 Water 30 〃 The above composition was dispersed with an attritor for 15 hours [G
liquid]. Comparative Example 2 The following [Liquid H] was used instead of [Liquid B] in Example 1.
In addition, a heat-sensitive coloring layer coating solution was prepared using a 20% aqueous oxidized starch solution instead of the styrene/butadiene copolymer emulsion, and this was coated on high-quality paper with a basis weight of 50 g/m 2 to a dry weight of 5.5 g/m2. 2 and dry it to form a heat-sensitive coloring layer, and then apply the above [F
A heat-sensitive recording material for comparison was obtained by applying and drying a protective layer to form a protective layer. [H solution] Bisphenol A 15 parts by weight Hydroxyethylcellulose 15 Water 20 The above composition was dispersed with an attritor for 15 hours [H
liquid]. The heat-sensitive recording materials of the present invention and comparative heat-sensitive recording materials obtained as described above were subjected to surface treatment using a calender, and then tested using a thermal gradient tester (manufactured by Toyo Seiki) at a pressure of 2 kg/kg.
cm 2 , 1 second contact time and 150°C. Apply cottonseed oil to the printed area of the heat-sensitive recording material printed above.
After being left under dry conditions at 40°C for 15 hours, we examined the state of change and found that Examples 1 and 2 showed no decoloring in the printed areas and no color development in the non-printed areas, but Comparative Examples 1 and 2 Although there was no color development in the non-printed areas, discoloration was observed in the printed areas. Next, as a plasticizer resistance test, print in the same way and place polyvinyl chloride film (Shin-Etsu Polymer
Polylap V-300 (manufactured by Co., Ltd.) is stacked in three layers and dried at 40℃.
After being left under the conditions for 15 hours under a load of 150 g/cm 2 , the state of change was examined and found that the heat-sensitive recording materials of Examples 1 and 2 showed no color development in the non-printed areas and less discoloration in the printed areas. In Comparative Examples 1 and 2, there was no color development in the non-printed areas, but the printed areas were severely discolored. Furthermore, when samples printed in the same manner were immersed in water and left for 15 hours, changes in the printed area were observed.The changes in the printed area were small in the examples, but there were large changes in density in the comparative examples. The above results are shown in Table-1.
【表】
次に熱応答性をテストするために、実施例及び
比較例の感熱記録材料を薄膜ヘツド（松下電子部
品(株)製）を有する穴熱印字実験装置にてヘツド電
力0.5W／ドツト、１ライン記録時間20msec／
、走査線密度８×3.85／mmの条件でパルス幅を
1.6、2.0、2.4msecで印字しその印字濃度をマク
ベス濃度計RD−514（フイルターＷ−106）で測
定した。その結果を表−２に示す。[Table] Next, in order to test thermal responsiveness, the thermal recording materials of Examples and Comparative Examples were tested using a hole thermal printing experimental device with a thin film head (manufactured by Matsushita Electronic Components Co., Ltd.) at a head power of 0.5 W/dot. , 1 line recording time 20msec/
, pulse width under the condition of scanning line density 8 x 3.85/mm.
Printing was performed at 1.6, 2.0, and 2.4 msec, and the print density was measured using a Macbeth densitometer RD-514 (filter W-106). The results are shown in Table-2.
【表】
以上の結果から、本発明の感熱記録材料は、
油、可塑剤、水等の接触において発色部の消色や
地肌部の発色といつた欠点がなく、しかも高速記
録時の発色性も良い極めて優れた感熱記録材料で
あることがわかる。[Table] From the above results, the heat-sensitive recording material of the present invention has
It can be seen that it is an extremely excellent heat-sensitive recording material that does not have the disadvantages of decoloring of colored areas or coloring of background areas when it comes into contact with oil, plasticizer, water, etc., and also has good color development during high-speed recording.
Claims (1)
ルジヨン結着剤とを主成分として含有するアンダ
ーコート層を設け、その上に、ロイコ染料と顕色
剤として式： 【化】 で表わされるチオシアン酸亜鉛のアンチピリン錯
体と水性エマルジヨン結着剤とを主成分として含
有する感熱発色層を設けたことを特徴とする感熱
記録材料。[Claims] 1. An undercoat layer containing hydrophobic polymer fine particles and an aqueous emulsion binder as main components is provided on a support, and a leuco dye and a color developer containing the formula: [ 1. A heat-sensitive recording material comprising a heat-sensitive coloring layer containing as main components an antipyrine complex of zinc thiocyanate represented by the following formula and an aqueous emulsion binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59158053A JPS6135283A (en) | 1984-07-27 | 1984-07-27 | heat sensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59158053A JPS6135283A (en) | 1984-07-27 | 1984-07-27 | heat sensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6135283A JPS6135283A (en) | 1986-02-19 |
| JPH0576436B2 true JPH0576436B2 (en) | 1993-10-22 |
Family
ID=15663259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59158053A Granted JPS6135283A (en) | 1984-07-27 | 1984-07-27 | heat sensitive recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6135283A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2863924B2 (en) * | 1988-12-28 | 1999-03-03 | 株式会社リコー | Thermal recording material |
| JPH04209875A (en) * | 1990-12-05 | 1992-07-31 | Toyobo Co Ltd | Dyed knitted fabric of alternating knitting and its production |
| JPH0648020A (en) * | 1992-07-30 | 1994-02-22 | Brother Ind Ltd | Color transfer sheet for image transfer |
| CN1089821C (en) | 1997-02-13 | 2002-08-28 | 旭化成株式会社 | Elastic polyurethane fiber and process for producing same |
| US6406788B1 (en) | 1998-08-10 | 2002-06-18 | Asahi Kasei Kabushiki Kaisha | Elastic polyurethane fiber |
| JP5688601B2 (en) | 2011-06-23 | 2015-03-25 | 東レ・オペロンテックス株式会社 | Polyurethane yarn and fabric and swimsuit using the same |
-
1984
- 1984-07-27 JP JP59158053A patent/JPS6135283A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6135283A (en) | 1986-02-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |