JPS63132087A - Heat-sensitive recording sheet - Google Patents
Heat-sensitive recording sheetInfo
- Publication number
- JPS63132087A JPS63132087A JP61278996A JP27899686A JPS63132087A JP S63132087 A JPS63132087 A JP S63132087A JP 61278996 A JP61278996 A JP 61278996A JP 27899686 A JP27899686 A JP 27899686A JP S63132087 A JPS63132087 A JP S63132087A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- recording sheet
- thermal
- composite particle
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 239000008119 colloidal silica Substances 0.000 claims abstract description 14
- 239000011246 composite particle Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 238000004040 coloring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 230000004043 responsiveness Effects 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract 3
- 230000002265 prevention Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- MTMKZABGIQJAEX-UHFFFAOYSA-N 4,4'-sulfonylbis[2-(prop-2-en-1-yl)phenol] Chemical compound C1=C(CC=C)C(O)=CC=C1S(=O)(=O)C1=CC=C(O)C(CC=C)=C1 MTMKZABGIQJAEX-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JJXVDRYFBGDXOU-UHFFFAOYSA-N dimethyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C=C1C(=O)OC JJXVDRYFBGDXOU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- -1 lactone compounds Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- WQFYAGVHZYFXDO-UHFFFAOYSA-N 2'-anilino-6'-(diethylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 WQFYAGVHZYFXDO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-UHFFFAOYSA-N 0.000 description 1
- ZWQBZEFLFSFEOS-UHFFFAOYSA-N 3,5-ditert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=C(O)C(C(C)(C)C)=C1 ZWQBZEFLFSFEOS-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical class O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NSDCINLDXHWOFO-UHFFFAOYSA-N 3-ethoxycarbonyl-5-hydroxybenzoic acid Chemical compound CCOC(=O)C1=CC(O)=CC(C(O)=O)=C1 NSDCINLDXHWOFO-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 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 1
- PLOYJEGLPVCRAJ-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid;styrene Chemical compound C=CC=C.OC(=O)C=C.C=CC1=CC=CC=C1 PLOYJEGLPVCRAJ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 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
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
（Ａ＞産業上の利用分野
本発明は、ロイコ染料と顕色剤との間の発色反応を利用
した感熱記録材料に関し、更に詳しくは記録時感熱材料
の熱溶融物がヘッドに転移する事によって起こるカスの
付＠量が少なく、固着によるスティッキングも小さい、
サーマルヘッド記録適性の優れた感熱記録シートに関す
るものである。Detailed Description of the Invention (A> Industrial Application Field The present invention relates to a heat-sensitive recording material that utilizes a color-forming reaction between a leuco dye and a color developer, and more specifically relates to a heat-sensitive recording material that utilizes a heat-melted material during recording. The amount of debris caused by the transfer of to the head is small, and the sticking caused by adhesion is also small.
The present invention relates to a heat-sensitive recording sheet with excellent thermal head recording suitability.
（Ｂ）従来の技術
無色または淡色のロイコ染料と該染料を熱時発色させ得
る顕色剤を利用した感熱記録シートは広く実用化され、
通常ロイコ染料とフェノール性物質等の顕色剤をそれぞ
れ別々に湿式磨砕機にかけて数−以下の微粒子にまで分
散粉砕した後、両者を混合し、これに結合剤、増感剤、
充填剤、滑剤、安定剤、分散剤、消泡剤などの助剤を添
加して塗液とし、紙、フィルム、合成紙等の支持体に塗
布したものであり、加熱により、ロイコ染料と顕色剤の
一方又は両方が溶融、接触して起こる化学反応により発
色記録を得るものである。この様な発色記録を得るには
、サーマルヘッドを内蔵したサーマルプリンター等が用
いられる。感熱記録は、直接発色方式で、他の記録方式
と比較して、記録時の騒音・臭気がない、装置の小形化
・軽但化が可能、現像・定着等の必要がない、操作が簡
単でメンテナンスが容易、感熱紙のコストが安いなどの
長所があり、ファクシミリ分野、コンピュータ−のアウ
トプット、電卓等のプリンター分野、医療計測用のレコ
ーダー分野、自動券売機分野、画像通信分野、ラベル（
ＰＯ３）分野等に広く用いられている。しかし、この様
なロイコ染料と顕色剤の組み合わせによる感熱記録シー
トは、（１）記録時サーマルヘッドにカスが付着する。(B) Prior art Thermal recording sheets that utilize a colorless or light-colored leuco dye and a color developer that can cause the dye to develop color when heated have been widely put into practical use.
Normally, a leuco dye and a color developer such as a phenolic substance are separately pulverized using a wet grinder to disperse and pulverize them to a few or less fine particles, and then the two are mixed, and a binder, a sensitizer,
A coating liquid is prepared by adding auxiliary agents such as fillers, lubricants, stabilizers, dispersants, and antifoaming agents, and is applied to a support such as paper, film, or synthetic paper. Color recording is obtained by a chemical reaction that occurs when one or both of the colorants melt and come into contact with each other. To obtain such color recording, a thermal printer or the like with a built-in thermal head is used. Thermal recording is a direct coloring method, and compared to other recording methods, there is no noise or odor during recording, the device can be made smaller and lighter, there is no need for development or fixing, and it is easy to operate. It has advantages such as easy maintenance and low cost of thermal paper, and is used in facsimile fields, computer output, printers such as calculators, medical measurement recorders, automatic ticket vending machines, image communication fields, labels (
PO3) is widely used in the field. However, in a heat-sensitive recording sheet using such a combination of a leuco dye and a color developer, (1) residue adheres to the thermal head during recording;
（２）固着によりスティッキングが起こる。（３）（１
）（２）により熱応答性が劣化し、発色濃度が低下する
という欠点を有する。(2) Sticking occurs due to adhesion. (3)(1
) (2) has the disadvantage that thermal responsiveness deteriorates and color density decreases.
（Ｃ）発明が解決しようとする問題点
ロイコ染料と顕色剤を主成分とする感熱発色層を支持体
上に形成した感熱記録シートを用いる感熱記録法におい
て、感熱発色時サーマルヘッドにカスがつかず、またヘ
ッドマツチング性の良い、熱応答性の優れた感熱記録シ
ートの開発が望ま机ている。(C) Problem to be solved by the invention In a heat-sensitive recording method using a heat-sensitive recording sheet in which a heat-sensitive coloring layer containing a leuco dye and a color developer as main components is formed on a support, scum is generated on the thermal head during heat-sensitive coloring. It is desired to develop a heat-sensitive recording sheet that does not stick, has good head matching properties, and has excellent thermal responsiveness.
（Ｄ）問題点を解決するための手段
本発明によれば、支持体上にロイコ染料と顕色剤を主成
分とする感熱発色層を、その上にオーバーコート図を設
けた感熱記録シートにおいて、オーバーコート層がコロ
イド性シリカ水不溶性樹脂に対して”１００重母重量上
の割合で含有し、かつガラス転移温度が１５℃以上であ
る複合粒子エマルジョンを主成分とする層であることに
よって、前記した様な感熱記録シートの欠点が改善され
る。(D) Means for Solving the Problems According to the present invention, in a heat-sensitive recording sheet in which a heat-sensitive color forming layer containing a leuco dye and a color developer as main components is provided on a support, and an overcoat pattern is provided thereon. , by the overcoat layer being a layer mainly composed of a composite particle emulsion containing colloidal silica in a proportion of 100% by weight to the water-insoluble resin and having a glass transition temperature of 15° C. or higher, The drawbacks of heat-sensitive recording sheets as described above are improved.
特にコロイド性シリカの重量％が、２００重間％以上で
ある時は、ガラス転移温度が１５℃程度の比較的低い領
域の場合でも効果が認められる。また１００〜２００重
１％の時は、３０〜５０’Ｃの比較的高いガラス転移温
度を持つ水性エマルジョンが有効である。In particular, when the weight percent of colloidal silica is 200 weight percent or more, the effect is recognized even when the glass transition temperature is in a relatively low range of about 15°C. When the content is 100 to 200% by weight, an aqueous emulsion having a relatively high glass transition temperature of 30 to 50'C is effective.
本発明による複合粒子エマルジョンとは、コア・シェル
型の異名構造を持つ様な水性エマルジョンを示しており
、詳しくは直径０．１ｐｎ程度の水不溶性樹脂の粒子の
表面にコロイド性シリカが反応し吸着する事によって擬
似カプセルが形成される様な水性エマルジョンを示すも
のである。The composite particle emulsion according to the present invention refers to an aqueous emulsion having a core-shell type structure, and more specifically, colloidal silica reacts and adsorbs on the surface of water-insoluble resin particles with a diameter of about 0.1 pn. This indicates an aqueous emulsion in which pseudocapsules are formed by
また複合粒子エマルジョンは、水不溶性樹脂系エマルジ
ョンとコロイド性シリカを単に混合したものに比べてフ
レキシビリティが大きく、耐水性、フィルムの耐熱性な
どに優れている。これらのエマルジョンを、感熱発色層
上に絶乾で、３．０〜３゜５ｇ／Ｔｒｔ塗布する事によ
りフィルムを形成させると、ヘッドのカス付着防止、ヘ
ッドマツチング性の向上が見られ、かつ十分な発色濃度
が得られる。Moreover, the composite particle emulsion has greater flexibility and is superior in water resistance, film heat resistance, etc., compared to a simple mixture of a water-insoluble resin emulsion and colloidal silica. When a film is formed by applying these emulsions on the heat-sensitive coloring layer in an absolute dry state at 3.0 to 3.5 g/Trt, it is observed that the adhesion of residue on the head is prevented and the head matching property is improved. Sufficient color density can be obtained.
次に水不溶性樹脂の具体例としては、ポリスチレン、ポ
リアクリル酸エステル、ポリウレタン、ポリ酢酸ビニル
、スチレン−ブタジェン−アクリル酸共重合体等が挙げ
られる。Specific examples of the water-insoluble resin include polystyrene, polyacrylic ester, polyurethane, polyvinyl acetate, styrene-butadiene-acrylic acid copolymer, and the like.
一方、ロイコ染料と顕色剤を支持体上に結合支持させる
ための結合剤としては、ポリビニルアルコール（ＰＶＡ
） 、カルボキシメチルセルロース、ヒドロキシエチル
セルロース、メトキシセルロース、カルボキシ変性ポリ
ビニルアルコール、ポリアクリルアミド、ポリアクリル
酸、デンプン及びその誘導体、カゼイン、ゼラチン、ス
チレン−無水マイレン酸共重合体のアルカリ塩等の水溶
性高分子化合物および前記水不溶性樹脂の水性エマルジ
ョン等が挙げられる。On the other hand, polyvinyl alcohol (PVA
), water-soluble polymer compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, methoxy cellulose, carboxy-modified polyvinyl alcohol, polyacrylamide, polyacrylic acid, starch and its derivatives, casein, gelatin, and alkali salts of styrene-maleic anhydride copolymers. and aqueous emulsions of the water-insoluble resins.
ロイコ染料は、分子内にラクトン環を有するラクトン系
と、非ラクトン系に分けられ、通常感熱記録紙にはトリ
フェニルメタン系およびフルオラン系のラクトン化合物
が使用されているが、その具体例を示す。Leuco dyes are divided into lactone-based dyes, which have a lactone ring in the molecule, and non-lactone-based dyes.Tiphenylmethane-based and fluoran-based lactone compounds are usually used in thermal recording paper, but specific examples are shown below. .
フルオラン系化合物として、２−アニリノ−３−メチル
−６−ジエチルアミノフルオラン、２−アニリノ−３−
メチル−６−（メチルシクロヘキシルアミノ）−フルオ
ラン、２ニアニリノ−３−メチル−６−（エチルイソベ
ンジルアミノ）フルオラン、２−アニリノ−３−メチル
−６−シブチルアミノフルオラン、２−（Ｐ−クロロア
ニリノ〉−３−メチル−６−ジニチルアミノフルオラン
、２−（Ｐ−フルオロアニリノ）−３−メチル−６−ジ
ニチルアミノフルオラン、２−アニリノ−３−メチル−
６−（Ｐ−トルイジノエチルアミノ）フルオラン、２−
（Ｐ−トルイジノ）−３−メチル−６−ジニチルアミノ
フルオラン、２− （０−クロロアニリノ）−６−シブ
チルアミノフルオラン、２−（Ｏ−フルオロアニリノ）
−６−ジニチルアミノフルオラン、２−（Ｏ−フルオロ
アニリノ）−６−シブチルアミノフルオラン、２−アニ
リノ−３−メチル−６−ピペリジノフルオラン、２−ア
ニリノ−３−メチル−６−ピロリジノフルオラン、２−
エトキシエチルアミノ−３−クロロ−６−ジエチルアミ
ノフルオラン、２−アニリノ−３−クロロ−６−ジエチ
ルアミノフルオラン、２−クロロ−６−ジエチルアミノ
フルオラン、２−メチル−６−ジエチルアミノフルオラ
ン等が挙げられ、トリアリールメタン系化合物としては
、３．３−ビス（Ｐ−ジメチルアミノフェニル）−６−
シメチルアミノフタリド（別名：クリスタルバイオレッ
トラクトン）、３，３−ビス−（Ｐ−ジメチルアミノフ
ェニル）フタリド、３＝ （Ｐ−ジメチルアミノフェニ
ル）−３−（１，２−ジメチルアミンインドール−３−
イル）フタリド等が挙げられ、これらのロイコ染料は単
独もしくは混合して用いられる。As fluoran compounds, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-
Methyl-6-(methylcyclohexylamino)-fluorane, 2-anilino-3-methyl-6-(ethylisobenzylamino)fluorane, 2-anilino-3-methyl-6-sibutylaminofluorane, 2-(P- Chloroanilino>-3-methyl-6-dinithylaminofluorane, 2-(P-fluoroanilino)-3-methyl-6-dinithylaminofluorane, 2-anilino-3-methyl-
6-(P-toluidinoethylamino)fluoran, 2-
(P-toluidino)-3-methyl-6-dinithylaminofluorane, 2-(0-chloroanilino)-6-sibutylaminofluorane, 2-(O-fluoroanilino)
-6-dinithylaminofluorane, 2-(O-fluoroanilino)-6-sibutylaminofluorane, 2-anilino-3-methyl-6-piperidinofluorane, 2-anilino-3-methyl -6-pyrrolidinofluorane, 2-
Examples include ethoxyethylamino-3-chloro-6-diethylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2-chloro-6-diethylaminofluorane, 2-methyl-6-diethylaminofluoran, etc. As a triarylmethane compound, 3,3-bis(P-dimethylaminophenyl)-6-
Dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis-(P-dimethylaminophenyl)phthalide, 3= (P-dimethylaminophenyl)-3-(1,2-dimethylamine indole-3 −
yl) phthalide, etc., and these leuco dyes can be used alone or in combination.
又、顕色剤としては、Ｐ−オクチルフェノール、Ｐ −
ｔｅｒｔ−ブチルフェノール、１，１−ビス（Ｐ−ヒド
ロキシフェニル）プロパン、２．２−ビス−（Ｐ−ヒド
ロキシフェニル）プロパン、１，１−ビス（Ｐ−ヒドロ
キシフェニル）シクロヘキサン、４．４′−チオビスフ
ェノール、４，４′−スルホニルジフェノール、ビス−
（３−アリル−４−ヒドロキシフェニル）−スルホン、
ノボラック型フェノール樹脂、Ｐ−ヒドロキシ安息香酸
エステル、４−ヒドロキシフタル酸ジメチル、５−ヒド
ロキシイソフタル酸エチル、３，５−ジーｔｅｒｔ−ブ
チルサリチル酸、３，５−ジ−α−メチルベンジルサリ
チル酸等及び芳香族カルボン酸に於てはその多価全屈塩
が挙げられる。In addition, as a color developer, P-octylphenol, P-
tert-butylphenol, 1,1-bis(P-hydroxyphenyl)propane, 2,2-bis-(P-hydroxyphenyl)propane, 1,1-bis(P-hydroxyphenyl)cyclohexane, 4,4'-thio Bisphenol, 4,4'-sulfonyldiphenol, bis-
(3-allyl-4-hydroxyphenyl)-sulfone,
Novolak type phenolic resin, P-hydroxybenzoic acid ester, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-tert-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, etc., and aroma Examples of the group carboxylic acids include their polyvalent total salts.
充填剤としては、炭酸カルシウム、炭酸マグネシウム、
酸化チタン、酸化亜鉛、シリカ、水酸化アルミニウム、
水酸化亜鉛、硫酸バリウム、クレー、タルク、表面処理
したカルシウムヤシリカの無機系微粉末の他、尿素−ホ
ルマリン樹脂、ポリスチレン樹脂等の有機系微粉末を挙
げることができる。As fillers, calcium carbonate, magnesium carbonate,
titanium oxide, zinc oxide, silica, aluminum hydroxide,
In addition to inorganic fine powders such as zinc hydroxide, barium sulfate, clay, talc, and surface-treated calcium silica, organic fine powders such as urea-formalin resin and polystyrene resin can be used.
その伯の添加物質としては、ステアリン酸亜鉛、ステア
リン酸カルシウム、ステアリン酸アマイド等の滑剤、各
種の界面活性剤、消泡剤等が必要に応じて加えられる。As additional substances, lubricants such as zinc stearate, calcium stearate, and stearamide, various surfactants, antifoaming agents, and the like are added as necessary.
感熱発色層を設ける支持体としては、紙、合成紙、フィ
ルム等が用いられる。Paper, synthetic paper, film, etc. are used as the support on which the thermosensitive coloring layer is provided.
（Ｅ）実施例 次に本発明を実施例により、ざらに詳細に説明する。(E) Example Next, the present invention will be roughly explained in detail with reference to Examples.
尚、以下に示す部及び％はいずれも重量基準でおる。Note that all parts and percentages shown below are based on weight.
実施例１
（Ａ）
２−７ニリノー３−メチル−６−
（メチルシクロへキシルアミノ）−フルオラン１０部
１０％ヒドロキシエチルセルロース水溶液５部
水 １５
部ＣＢ）
ビス（３−アリル−４−ヒドロキシフェニル）スルホン
２５部１、１．３−トリス（
３−ｔｅｒｔ−ブチル−４−ヒドロキシ−６−メチルフ
ェニル）
ブタン １０部１０％ポリビニ
ルアルコール水溶液 ２０部水
４５部（Ｃ）
ステアリン酸亜鉛 １０部炭酸カルシ
ウム ４０部５％メチルセルロース
水溶液 ５０部水
５０部上記組成からなる混合物のうち
、Ａ〜Ｃ液をそれぞれ平均粒径２ＩＩｆｔ以下となるよ
うに、サンドミルで分散してＡ液、Ｂ液及びＣ液を調製
した。Example 1 (A) 2-7 Nilino-3-methyl-6-(methylcyclohexylamino)-fluoran 10 parts 10% hydroxyethyl cellulose aqueous solution 5 parts Water 15
Part CB) Bis(3-allyl-4-hydroxyphenyl)sulfone 25 parts 1,1,3-tris(
(3-tert-butyl-4-hydroxy-6-methylphenyl) Butane 10 parts 10% polyvinyl alcohol aqueous solution 20 parts Water
45 parts (C) Zinc stearate 10 parts Calcium carbonate 40 parts 5% methylcellulose aqueous solution 50 parts Water
50 parts Among the mixtures having the above composition, Solutions A to C were dispersed using a sand mill so that the average particle size was 2IIft or less to prepare Solutions A, B, and C.
次にＡ液を６部、Ｂ液を２０部、Ｃ液を３０部、１０％
ポリビニルアルコール水溶液を７０部及び２０％ステア
リン酸アマイドエマルジョン（中東油脂製、商品名ハイ
ドリンＭ−７）を２５部混合攪拌して感熱塗液を調節し
、粒子ｆ１５５ ｇ／ｍの市販上質紙に乾燥塗布ｍが６
９ ／ ７７［になる様にワイヤーバーで塗布・乾燥し
、感熱発色層を得た。Next, 6 parts of liquid A, 20 parts of liquid B, 30 parts of liquid C, 10%
A heat-sensitive coating solution was prepared by mixing and stirring 70 parts of a polyvinyl alcohol aqueous solution and 25 parts of a 20% stearamide emulsion (manufactured by Middle East Yushi Co., Ltd., trade name Hydrin M-7), and dried on commercially available high-quality paper with particles f155 g/m. Application m is 6
It was coated with a wire bar and dried to obtain a heat-sensitive coloring layer.
次いで、コロイド性シリカをポリマーに対して２００重
母％含み、またガラス転移点が１５℃であるコロイド性
シリカ／アクリル複合粒子エマルジョン（大日本インキ
製、商品名ボンコートＤＶ−８０３）を主成分とするオ
ーバーコート層の塗目方が絶乾で３．０〜３．５９／ｍ
となる様に設け、本発明の感熱記録シートを得た。Next, a colloidal silica/acrylic composite particle emulsion (manufactured by Dainippon Ink, trade name Boncoat DV-803) containing 200% colloidal silica based on the polymer and having a glass transition point of 15° C. was used as the main component. The coating pattern of the overcoat layer is 3.0 to 3.59/m when completely dry.
A heat-sensitive recording sheet of the present invention was obtained.
実施例２
実施例１で形成した感熱発色層上に、コロイド性シリカ
を樹脂に対して１００重ｉ％含み、ガラス転移点が４５
℃である様なコロイド性シリカ／アクリル複合粒子エマ
ルジョン（大日本インキ製、商品名ボンコートＤＶ−９
９３）を主成分とするオーバーコート層を実施例１と同
様にして設けて、本発明の感熱記録シートを得た。Example 2 On the thermosensitive coloring layer formed in Example 1, colloidal silica was contained at 100% by weight based on the resin, and the glass transition point was 45.
Colloidal silica/acrylic composite particle emulsion (manufactured by Dainippon Ink, trade name Boncoat DV-9)
An overcoat layer containing 93) as a main component was provided in the same manner as in Example 1 to obtain a heat-sensitive recording sheet of the present invention.
比較例１〜２
本発明の感熱記録シート（紙）との比較用として、コロ
イド性シリカを３０重量％（対樹脂分）含み、ガラス転
移点が１５℃であるコロイド性シリカ／アクリル複合粒
子エマルジョン（大日本インキ製、商品名ボンコートＤ
Ｖ−７５９）を主成分とするオーバーコート層を実施例
１と同様にして設けたちのく比較例１）と、コロイド性
シリカを３０重１％含み、ガラス転移点が一２℃でおる
コロイド性シリカ／アクリル複合粒子エマルジョン（大
日本インキ製、商品名ボンコートＤＶ−７６７）を主成
分とするオーバーコート層を実施例１と同様にして設け
たもの（比較例２）とを用いて性能試験を実施したその
結果を表１に示す。Comparative Examples 1 to 2 For comparison with the heat-sensitive recording sheet (paper) of the present invention, a colloidal silica/acrylic composite particle emulsion containing 30% by weight (based on resin) of colloidal silica and having a glass transition point of 15°C (Manufactured by Dainippon Ink, product name Boncoat D
An overcoat layer containing V-759) as the main component was prepared in the same manner as in Example 1, and a colloid containing 30% by weight of colloidal silica and having a glass transition temperature of -2°C was used. A performance test was conducted using an overcoat layer containing a synthetic silica/acrylic composite particle emulsion (manufactured by Dainippon Ink, trade name Boncoat DV-767) in the same manner as in Example 1 (Comparative Example 2). The results are shown in Table 1.
熱板を用いて１５０℃、５秒間記録シートを押圧した時
の発色濃度をマクベス濃度計ＲＤ−５’１４（ラッテン
Ｎα１０６）で測定した。The color density when the recording sheet was pressed for 5 seconds at 150° C. using a hot plate was measured using a Macbeth densitometer RD-5'14 (Wratten Nα106).
ＭＦ−１（松下電子部品工業Ｕ製）でパルス巾を変化さ
せ、印字した時のカス付着を肉眼で判定した。またラベ
ル印字機（行田ハカリ（ｉｎ＞を用いて印字した時のカ
ス付着についても同様に測定した。なお、比較例１，２
については、高粘着性のため、ラベル印字機での印字は
不可能であった。The pulse width was varied using MF-1 (manufactured by Matsushita Electronic Components Co., Ltd.), and the adhesion of residue when printing was visually determined. In addition, the adhesion of residue when printing using a label printing machine (Gyoda Hakari (in)) was similarly measured. Comparative Examples 1 and 2
Due to its high tackiness, it was impossible to print with a label printing machine.
（ステツキング）
ＭＦ−１とラベル印字機で、ヘッドマツチング性を判定
した。(Sticking) Head matching performance was determined using MF-1 and a label printing machine.
（Ｆ）効果
実施例から明らかな様に、本発明の感熱記録シートは、
記録時のヘッドへのカス付着がなく、固着によるスティ
ッキングも起こさない熱応答性の優れたもので、感熱記
録シートの品質向上に大いに寄与するものである。(F) As is clear from the effect examples, the heat-sensitive recording sheet of the present invention:
It does not adhere to the head during recording, does not cause sticking due to adhesion, has excellent thermal responsiveness, and greatly contributes to improving the quality of heat-sensitive recording sheets.
Claims (1)
る顕色剤を主成分とする感熱発色層を、該感熱発色層上
にオーバーコート層を設けた感熱記録シートにおいて、
該オーバーコート層がコロイド性シリカを水不溶性樹脂
に対して１００重量％以上の割合いで含有し、かつ、ガ
ラス転移温度が１５℃以上である複合粒子エマルジョン
を主成分とする層であることを特徴とする感熱記録シー
ト。(1) A heat-sensitive recording sheet in which a heat-sensitive color-forming layer containing a leuco dye and a color developer capable of coloring the dye as main components is provided on a support, and an overcoat layer is provided on the heat-sensitive color-forming layer,
The overcoat layer contains colloidal silica in a proportion of 100% by weight or more based on the water-insoluble resin, and is mainly composed of a composite particle emulsion having a glass transition temperature of 15° C. or higher. A heat-sensitive recording sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61278996A JPH0688456B2 (en) | 1986-11-22 | 1986-11-22 | Thermal recording sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61278996A JPH0688456B2 (en) | 1986-11-22 | 1986-11-22 | Thermal recording sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63132087A true JPS63132087A (en) | 1988-06-04 |
| JPH0688456B2 JPH0688456B2 (en) | 1994-11-09 |
Family
ID=17604947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61278996A Expired - Lifetime JPH0688456B2 (en) | 1986-11-22 | 1986-11-22 | Thermal recording sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688456B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0326964A2 (en) * | 1988-01-30 | 1989-08-09 | Kanzaki Paper Manufacturing Co., Ltd. | Heat sensitive recording material |
| JPH0276066U (en) * | 1988-11-28 | 1990-06-11 | ||
| JPH0276065U (en) * | 1988-11-28 | 1990-06-11 | ||
| JPH02274589A (en) * | 1989-04-18 | 1990-11-08 | Nippon Kayaku Co Ltd | Thermal recording sheet |
-
1986
- 1986-11-22 JP JP61278996A patent/JPH0688456B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0326964A2 (en) * | 1988-01-30 | 1989-08-09 | Kanzaki Paper Manufacturing Co., Ltd. | Heat sensitive recording material |
| JPH0276066U (en) * | 1988-11-28 | 1990-06-11 | ||
| JPH0276065U (en) * | 1988-11-28 | 1990-06-11 | ||
| JPH02274589A (en) * | 1989-04-18 | 1990-11-08 | Nippon Kayaku Co Ltd | Thermal recording sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0688456B2 (en) | 1994-11-09 |
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