JPS5949994A - Heat-sensitive recording type label - Google Patents
Heat-sensitive recording type labelInfo
- Publication number
- JPS5949994A JPS5949994A JP57161328A JP16132882A JPS5949994A JP S5949994 A JPS5949994 A JP S5949994A JP 57161328 A JP57161328 A JP 57161328A JP 16132882 A JP16132882 A JP 16132882A JP S5949994 A JPS5949994 A JP S5949994A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- color
- sensitive recording
- hydroxy
- leuco dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- 238000004040 coloring Methods 0.000 claims description 9
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000005997 Calcium carbide Substances 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- -1 Diethylamine phthalide Chemical compound 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid 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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer 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
- 235000010233 benzoic acid Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010040829 Skin discolouration Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000005562 fading 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
- 239000010419 fine particle Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 229960001553 phloroglucinol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は感熱記録型ラベルに関するものである。[Detailed description of the invention] The present invention relates to a heat-sensitive recording label.
従来、シート状支持体の表面に、ロイコ染料と、該ロイ
コ染料を熱時発色させる顕色性物質を含有する感熱記録
シートは知られておシ、この感熱記録シートをスーパー
マーケット等で使用されている値札ラベル等として利用
することが提案されている。このような感熱記録型ラベ
ルの場合、その印字方式はサーマルヘッドによるもので
あるため、従来のインクやインクリボンによる印字方式
に比して、簡単かつきれいに行い得るという利点を備え
ている。Hitherto, heat-sensitive recording sheets containing a leuco dye and a color-developing substance that causes the leuco dye to develop color when heated on the surface of a sheet-like support have been known. It has been proposed to use it as a price tag label, etc. In the case of such a heat-sensitive recording type label, since its printing method is based on a thermal head, it has the advantage that printing can be performed more easily and neatly than conventional printing methods using ink or ink ribbon.
しかしながら、このようなロイコ系の感熱記録シートの
ラベルを食品包装用等で使用する場合は、肉あるいは野
菜等の生餌食品の包装に用いられるポリ塩化ビニルなど
のプラスチックフィルムに含まれる可塑剤（ジオクチル
フタレート、ジオクチルアジ波−トなど）や、魚肉類の
油、水等との接触により、ラベル印字部が消色又は褪色
するという不都合が生じた。However, when using such leuco-based heat-sensitive recording sheet labels for food packaging, plasticizers ( There has been an inconvenience in that the printed portion of the label becomes discolored or fades due to contact with dioctyl phthalate, dioctyl azinate, etc.), fish oil, water, etc.
本発明者らは、感熱記録シートのラベルに見られるこの
ような欠点を解決すべく鋭意研究を重ねた結果、顕色性
物質として、４−ヒドロキシ−４′−クロルジフエニル
スルホンを用いるこトＫ 、Ｊ： ！Ｉｌｌ、前記欠点
が数珠されることを見出し、本発明を完成するに到った
。The inventors of the present invention have conducted extensive research in order to solve these drawbacks found in labels of heat-sensitive recording sheets, and as a result, they have discovered the use of 4-hydroxy-4'-chlorodiphenyl sulfone as a color developer. K, J: ! Ill discovered that the above-mentioned drawbacks could be overcome, and completed the present invention.
即ち、本発明によれば、支持体の表面に、ロイコ染料と
、該ロイコ染料を熱時発色させる顕色性物質とを含有す
る感熱発色層を設け、支持体の裏面に粘着加工を施した
感熱記録型ラベルにおいて該顕色性物質として、４−ヒ
ドロキシ−４′−クロルジフェニルスルホンを用いるこ
とを特徴とする感熱記録型ラベルが提供される。That is, according to the present invention, a heat-sensitive coloring layer containing a leuco dye and a color-developing substance that causes the leuco dye to develop color when heated is provided on the surface of the support, and an adhesive treatment is applied to the back surface of the support. A heat-sensitive recording label is provided, characterized in that 4-hydroxy-4'-chlordiphenyl sulfone is used as the color developing substance in the heat-sensitive recording label.
本発明で用いる顕色剤４−ヒドロキシ−４′−クロルジ
フェニルスルホンは顕色性物質として単独で用いる必要
はなく、必要に応じて他の顕色性物質を併用することも
可能である。本発明で用いる４−ヒドロキシ−４′−ク
ロルジフェニルスルホンは、ロイコ染料１重量部に対し
、１〜８重量部、好ましくは２〜６重量部の割合である
。また、他の顕色性物質を併合する場合、その量は、４
−ヒドロキシ−４′−クロルジフェニルスルホン１重量
部に対して、９重量部以下、好ましくは４重量部以下の
割合にするのがよい。The color developer 4-hydroxy-4'-chlordiphenylsulfone used in the present invention does not need to be used alone as a color developer, and it is also possible to use other color developer in combination as necessary. The amount of 4-hydroxy-4'-chlordiphenylsulfone used in the present invention is 1 to 8 parts by weight, preferably 2 to 6 parts by weight, per 1 part by weight of the leuco dye. In addition, when other color developing substances are combined, the amount should be 4
The proportion is preferably 9 parts by weight or less, preferably 4 parts by weight or less, per 1 part by weight of -hydroxy-4'-chlordiphenylsulfone.
なお、本発明における感熱記録型ラベルとは、その表面
に対する印字や画像の記録を加熱方式により行うことが
でき、かつその裏面を固体表面に対して接着することの
できるシート状物を意味し、番号札、値札、薬ビン札な
どの各種ラベル又はレツテルの他、ネームプレート、シ
ール等も包含される。In addition, the heat-sensitive recording type label in the present invention means a sheet-like material whose surface can be printed or an image can be recorded by heating, and whose back surface can be adhered to a solid surface. In addition to various labels or labels such as number tags, price tags, medicine bottle tags, etc., name plates, stickers, etc. are also included.
本発明で用いる感熱発色層は、ロイコ染料、顕色性物質
、結合剤などを含むものであるが、次にこれらの成分に
ついて具体的に示す。The thermosensitive color forming layer used in the present invention contains a leuco dye, a color developing substance, a binder, etc. These components will be specifically described below.
囚 ロイコ染料
ロイコ染料゛としては、通常無色又は淡色の下記に示す
種々の染料のロイコ休が楠用される。Leuco dye As the leuco dye, leuco dyes of various colorless or light-colored dyes shown below are usually used.
殊に、トリフェニルメタン系、フルオラン系、フェノチ
アノン系、オーラミン系、スピロピラン系の染料のロイ
コ休の使用が好ましい。In particular, it is preferable to use triphenylmethane-based, fluoran-based, phenothianone-based, auramine-based, and spiropyran-based dyes in the form of leucolytic dyes.
３．３−ビス（ｐ 、）メチルアミノフェニル）−６−
ノメチルアミノフタリド
３’、３７ビス（ｐ 、、；メチルアミノフェニル）フ
タリド
３．３−ビス（ｐ−）メチルアミノフェニル）−６−、
ジエチルアミンフタリド
３．３−ビス（ｐ 、；メチルアミノフェニル）−６−
クロロフタリド
３−（Ｎ−’ｐ−）ツルーＮ−エチルアミノ）−６−メ
チル−７−（Ｎ−フェニルアミノ）フルオラン
３−）エチルアミノ−７−クロロフルオランベンゾイル
ロイコメチレンブルー
６′−クロロ−８′−メトキシ−ベンゾインＩＦ リノ
ービリロスピラン
６′−フロモー８′−メトキシ−ベンゾイントリノーピ
リロスビラン
２−（３，６−ビス（ジエチルアミノ）−９−（０−り
０ロアニリノ）キサンチル〕安息香酸ラクタム。3.3-Bis(p,)methylaminophenyl)-6-
Nomethylaminophthalide 3',37bis(p,, ;methylaminophenyl)phthalide 3,3-bis(p-)methylaminophenyl)-6-,
Diethylamine phthalide 3.3-bis(p,; methylaminophenyl)-6-
Chlorophthalide 3-(N-'p-)True N-ethylamino)-6-methyl-7-(N-phenylamino)fluoran 3-)ethylamino-7-chlorofluoran Benzoylleucomethylene blue 6'-chloro-8 '-Methoxy-benzoin IF Rinopyrylospiran 6'-Flomo8'-Methoxy-benzoin Trinopyrylosviran 2-(3,6-bis(diethylamino)-9-(0-ri0loanilino)xanthyl]benzoic acid lactam.
（Ｂ） 顕色性物質
本発明における顕色性物質としては、前記しｆｃ、 ４
− ヒｆロキシー４′−クロルジフェニルスルホンが必
須成分として用いられるが、他の顕色性物質と併用する
ことができる。この場合に併用される顕色性物質として
は、例えば以下に示すようなものが挙げられる。(B) Color-developing substance The color-developing substance in the present invention includes the aforementioned fc, 4
- Hifroxy 4'-chlordiphenyl sulfone is used as an essential component, but it can be used in combination with other color developing substances. Examples of the color developing substance used in combination in this case include those shown below.
ホウ酸、シュウ酸、マレイン酸、酒石酸、（Ｃ）クエン
酸、コハク酸、安息香酸、ステアリン酸、没食子酸、サ
リチル酸、ｌ−ヒドロキシ−２−ナフトエ酸、０−ヒド
ロキシ安息香酸、ｎｌ−ヒドロキシ安息香酸、２−ヒド
ロキシ−ｐ−）ルイル酸、３，５−キシレノール、チモ
ール、ｐ−ｔｅｒｔ−ブチルフェノール、４−ヒドロキ
シフェノキシド、メチル−４−ヒドロキシベンゾエート
、４−ヒＩＳロキンアセトフエノン、α−ナフト−ル、
β−ナフト−ル、カテコール、レゾルシン、ヒドロキノ
ン、４−ｔｅｒｔ−オクチノール、２，２′−ジヒドロ
キシジフェニル、２ 、２’−メチレンビス（４−メチ
ル−６ｔｅｒｔ−ブチルフェノール）、２．２−ビス（
４−ヒドロキシフェニル）フロノξン、４．４−イソゾ
ロビリデン−ビス（２−ｔｅｒｔ−ブチルフェノール）
、４，４−ｓｅｃ−ブチリデン・ノフェノール、ビロガ
ロール、フロログルシン、フロログルタ／カルボン酸
。Boric acid, oxalic acid, maleic acid, tartaric acid, (C) citric acid, succinic acid, benzoic acid, stearic acid, gallic acid, salicylic acid, l-hydroxy-2-naphthoic acid, 0-hydroxybenzoic acid, nl-hydroxybenzoic acid Acid, 2-hydroxy- p- naphthol,
β-naphthol, catechol, resorcinol, hydroquinone, 4-tert-octinol, 2,2'-dihydroxydiphenyl, 2,2'-methylenebis(4-methyl-6tert-butylphenol), 2,2-bis(
4-Hydroxyphenyl) furonon, 4,4-isozolobylidene-bis(2-tert-butylphenol)
, 4,4-sec-butylidene nophenol, birogallol, phloroglucin, phlorogluta/carboxylic acid.
結合剤
感熱発色層を支持体上に結合支持さる結合剤としでは下
記に示すような種々のものが適用される。Binders As binders for bonding and supporting the thermosensitive coloring layer on the support, various binders as shown below can be used.
ポリビニルアルコール、メトキシセルロース、ヒドロキ
シエチルセルロース、カルゼキシメチルセルロース、ポ
リビニルピロリドン、；１？ＩＪ ７クリルアミド、ぼ
りアクリル酸、デンプン、ゼラチンなどのような水溶性
のもの、あるいはポリスチレン、塩化ビニル−酢酸ビニ
ル共重合体、ポリジチルメタクリレートなどのような水
性エマルジョンのものを結合剤として用いることができ
る。Polyvinyl alcohol, methoxycellulose, hydroxyethylcellulose, calxoxymethylcellulose, polyvinylpyrrolidone; 1? IJ 7 Water-soluble materials such as acrylamide, acrylic acid, starch, gelatin, etc., or water-based emulsion materials such as polystyrene, vinyl chloride-vinyl acetate copolymer, polydityl methacrylate, etc. can be used as binders. can.
まだ、感熱発色層中には、必要に応じ、さらに慣用の補
助添加剤、例えば、炭酸カルシウム、／リカ、アルミナ
、マグネシア、タルク、チタニア、硫酸バリウム、ステ
アリン酸アルミニウムなどの微粉末を添加し、発色画像
の鮮明性を向」ニさせることができる。また、感熱度増
加剤、例えば、高級脂肪酸アミドなどを含有させること
ができる。Furthermore, if necessary, conventional auxiliary additives such as fine powders of calcium carbonate, lyca, alumina, magnesia, talc, titania, barium sulfate, aluminum stearate, etc. may be added to the heat-sensitive coloring layer. The clarity of colored images can be improved. Further, a heat sensitivity increasing agent such as a higher fatty acid amide can be included.
本発明の感熱記録型ラベルにおいて、耐薬品性をさらに
高めるために、感熱記録層の表面、支持体と感熱発色層
との間、及び／又は支持体と粘着加工層との間に水溶性
高分子層（・ζリヤ一層）を設けることができる。この
場合の水溶性高分子としては、例えば、ポリビニルアル
コール、メチルセルロース、エチルセルロース、カルボ
キソメチルセルロース、ポリビニルピロリドン、デンプ
ン、ゼラチン、メトキシセルロース、ポリアクリル°ア
ミド等が挙げられる。また、この水溶性高分子層には、
無機又は有機系の微粒子を添加することができるし、慣
用の耐水化剤を添加することもできる。まだ、水溶性高
分子層には前記水溶性高分子と併用して疎水性高分子の
水性エマルジョンの使用もできる。このような水性エマ
ルジョントシテは、ポリ酢酸ビニル、塩化ビニル／酢酸
ビニル共重合体、ポリウレタン、ポリアクリル酸エステ
ル、スチレン／シタ・ジエン／アクリル系共重合体、ポ
リエステル等を挙げることができる。In the heat-sensitive recording label of the present invention, in order to further improve the chemical resistance, a water-soluble high A molecular layer (・ζ rear layer) can be provided. Examples of water-soluble polymers in this case include polyvinyl alcohol, methylcellulose, ethylcellulose, carboxomethylcellulose, polyvinylpyrrolidone, starch, gelatin, methoxycellulose, and polyacrylamide. In addition, this water-soluble polymer layer has
Inorganic or organic fine particles can be added, as well as conventional waterproofing agents. However, an aqueous emulsion of a hydrophobic polymer can also be used in the water-soluble polymer layer in combination with the water-soluble polymer described above. Examples of such aqueous emulsions include polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, polyurethane, polyacrylic acid ester, styrene/silica diene/acrylic copolymer, polyester, and the like.
次に本発明を実施例によりさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
下記成分をそれぞれＮ −Ｌ ミルを用いて２４時間粉
砕分散して分散液Ａ、Ｂ、Ｃを調製した後、分散ａＡ及
びＢをさらに混合して感熱発色層形成液を調製した。Example 1 Dispersions A, B, and C were prepared by pulverizing and dispersing the following components for 24 hours using an N-L mill, and then dispersions aA and B were further mixed to prepare a thermosensitive coloring layer forming liquid.
分散液Ａ：
炭酸カルシウム １．０
〃２０％酸化デンゾン水溶液 ５．
ｏ〃水
４２５ 〃分散液Ｂ：
２０係ポリビニルアルコール ８．
Ｏｔｔｔｔ水
３６．０／／分散液Ｃ：
炭酸カルシウム ５．０
重量部２０係ポリビニルアルコールｉｏ
２５．０’ ｔｔ前記のようにして調製した感熱発色
層形成液を上質紙（約５０Ｓ４／ｎｆ）の表面に塗布乾
燥して付着量がｓｙ／ｍｌ（、固形分）の感熱発色層を
形成せしめた感熱シート（１）と、さらに該感熱発色層
」二にＣ液を塗布乾燥して付着量が４ Ｙ ／ ｍ”
（固形分）になる様・すりア層を乾燥させた感熱シート
（ＩＩ）を得た。Dispersion A: Calcium carbonate 1.0
〃20% Denzone oxide aqueous solution 5.
o water
425 Dispersion B: 20 polyvinyl alcohol 8.
Ottt water
36.0//Dispersion C: Calcium carbonate 5.0
Weight part: 20 Polyvinyl alcohol io
25.0' ttThe thermosensitive coloring layer forming liquid prepared as above was applied to the surface of high-quality paper (approximately 50S4/nf) and dried to form a thermosensitive coloring layer with an adhesion amount of sy/ml (solid content). Liquid C was applied to the heat-sensitive sheet (1) and the heat-sensitive coloring layer (2) and dried until the adhesion amount was 4 Y/m.
(solid content) A heat-sensitive sheet (II) was obtained in which the abrasion layer was dried.
次に、上質紙（ｓ ’Ｏｆｌ−７ｍ”）上にシリコーン
樹脂を塗工して形成した剥離台紙に接着層を形成させ、
その接着剤層の表面と前記感熱ノー ト（１）及び（ｊ
ｌ）の裏面とを貼合せて感熱記録型ラベル（ザンプルＥ
−１’及びＥ−２）を得た。Next, an adhesive layer was formed on a release mount formed by coating silicone resin on high-quality paper (s 'Ofl-7m''),
The surface of the adhesive layer and the heat-sensitive notebook (1) and (j
1) and the back side of the heat-sensitive recording label (Sample E).
-1' and E-2) were obtained.
比較例１
分散液Ｂの４−ヒ１こロキシー４′−クロルジフェニル
スルホンの代すニヒスフェノールＡ ５． （１＠ ｍ
部を用い他の条件は実施例１のザンプルＥ−１と同様に
して感熱記録型ラベル（ザンプルＢ−１）を得た。Comparative Example 1 Nihisphenol A replaced by 4-H-1-choxy 4'-chlordiphenyl sulfone of Dispersion B 5. (1@m
A heat-sensitive recording type label (Sample B-1) was obtained in the same manner as Sample E-1 of Example 1 using the following conditions.
一１１］ヨーセＶ＝づｔ−ｍ＝−４Ｊ−一一ニメーてｔ
−ブシー；クフーーａ嘴−ブレ□プるーブレ一対重１シ
ー□（−４七ト華を・中計引刊≠１〒用キイ酬鋤Ｕ牛市
ト突→制積トド（トサ゛ −一比口中２〜５
分散液Ｂの４ヒドロキシ−４′−クロルジフェニルフル
ホンの替シに４−ヒド口中シ−４′−フルオルジフエニ
ルスルホンＤＩｚ較例２） 及Ｕ： ４−ヒＦロキシー
４′−メチルジフェニルスルホン（比較例３）及び４−
ヒドロキシ−４′−クロル−３′−メチルジフェニルス
ルホン（比較ｆｌＪ４ ） 及ヒ４−４ トロキシジフ
ェニルスルホン（比較例５）を用いた以外は実施例１の
サンプルＥ−１と同様にして感熱記録型ラベルＢ−２、
Ｂ−３、Ｂ−４、Ｂ−５を得た。111] Yose V=zutm=-4J-11nimetet
- Bushy; Kufuu a beak - Bree □ Puruble 1 pair heavy 1 Sea □ (-4 Seven Toka ・ Medium-term plan publication ≠ 1 〒 Key exchange plow U Ugyuichi Totsu → Pressure accumulation sea lion (Tosa ゛ - One ratio Mouth 2 to 5 In place of 4-hydroxy-4'-chlordiphenylsulfone in dispersion B, 4-hydroxy-4'-fluorodiphenylsulfone DIz Comparative Example 2) and U: 4-hydroxy-4'-fluorodiphenylsulfone were used. '-Methyldiphenylsulfone (Comparative Example 3) and 4-
Hydroxy-4'-chloro-3'-methyldiphenylsulfone (Comparative flJ4) and 4-4 Thermosensitive recording was carried out in the same manner as Sample E-1 of Example 1, except that troxydiphenylsulfone (Comparative Example 5) was used. Type label B-2,
B-3, B-4, and B-5 were obtained.
次に以上の様にして得だ本発明品（Ｅ−１，Ｅ−２）及
び比較品（Ｂ−１、Ｂ−２、Ｂ−３、Ｂ−４，Ｂ−５）
を熱傾斜試験機で１５０℃Ｘ２ＫＳｌ！／ｃａＸ １
ｓｅｃ の条件で発色させ発色部にポリ塩化ビニルラッ
プフィルム（信越ポリマー社製、ポリマラップ）、綿実
油、水をそれぞれ接触させた後、発色部の濃度をマクベ
ス濃度計で測定し褪色の度合を比較した。また、保存時
の地肌発色の代用！［イ性として耐熱性も合せて試験し
た。表−１に上記試験の結果を示し、本発色の有意性を
示す。尚参考として表−２に詳細な試験法を示す。Next, the products of the present invention (E-1, E-2) and comparative products (B-1, B-2, B-3, B-4, B-5) obtained as described above.
with a thermal gradient tester at 150℃ x 2KSl! /caX 1
After coloring under the conditions of sec and contacting the colored area with polyvinyl chloride wrap film (manufactured by Shin-Etsu Polymer Co., Ltd., Polymer Wrap), cottonseed oil, and water, the density of the colored area was measured with a Macbeth densitometer and the degree of fading was compared. . Also, a substitute for skin coloring during storage! [Heat resistance was also tested. Table 1 shows the results of the above test and shows the significance of this color development. For reference, detailed test methods are shown in Table 2.
表−２（試験法）Table-2 (Test method)
Claims (1)
熱時発色させる顕色性物質とを含有する感熱発色層を設
け、支持体の裏面に粘着加工を施した感熱記録型ラベル
において、該顕色性物質トシて、４−ヒドロキシ−４′
−クロルジフェニルスルホンを用いることを特徴とする
感熱記録型ラベル。(1) In a heat-sensitive recording label in which a heat-sensitive coloring layer containing a leuco dye and a color-developing substance that causes the leuco dye to develop color when heated is provided on the surface of the support, and an adhesive is applied to the back surface of the support. , the color developing substance is 4-hydroxy-4'
- A heat-sensitive recording label characterized by using chlordiphenyl sulfone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57161328A JPS5949994A (en) | 1982-09-16 | 1982-09-16 | Heat-sensitive recording type label |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57161328A JPS5949994A (en) | 1982-09-16 | 1982-09-16 | Heat-sensitive recording type label |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5949994A true JPS5949994A (en) | 1984-03-22 |
Family
ID=15732993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57161328A Pending JPS5949994A (en) | 1982-09-16 | 1982-09-16 | Heat-sensitive recording type label |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5949994A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6141594A (en) * | 1984-08-03 | 1986-02-27 | Oji Paper Co Ltd | Thermal recording material for label |
| JPS6449566U (en) * | 1987-09-18 | 1989-03-28 |
-
1982
- 1982-09-16 JP JP57161328A patent/JPS5949994A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6141594A (en) * | 1984-08-03 | 1986-02-27 | Oji Paper Co Ltd | Thermal recording material for label |
| JPH0430919B2 (en) * | 1984-08-03 | 1992-05-25 | ||
| JPS6449566U (en) * | 1987-09-18 | 1989-03-28 |
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