JP2007169319A - Water-erasable oily ink - Google Patents
Water-erasable oily ink Download PDFInfo
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- JP2007169319A JP2007169319A JP2005364692A JP2005364692A JP2007169319A JP 2007169319 A JP2007169319 A JP 2007169319A JP 2005364692 A JP2005364692 A JP 2005364692A JP 2005364692 A JP2005364692 A JP 2005364692A JP 2007169319 A JP2007169319 A JP 2007169319A
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- Prior art keywords
- water
- ethanol
- erasable
- oil
- resin
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 fatty acid ester Chemical class 0.000 claims abstract description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 13
- 229930195729 fatty acid Natural products 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 238000007127 saponification reaction Methods 0.000 claims abstract description 5
- 239000003599 detergent Substances 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 34
- 239000001993 wax Substances 0.000 description 15
- 235000019271 petrolatum Nutrition 0.000 description 8
- 239000000975 dye Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004264 Petrolatum Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000004200 microcrystalline wax Substances 0.000 description 3
- 235000019808 microcrystalline wax Nutrition 0.000 description 3
- 229940066842 petrolatum Drugs 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 235000019809 paraffin wax Nutrition 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- UWMZZSRDUVJJDP-UHFFFAOYSA-N sodium 4-[[9-(2-carboxyphenyl)-6-(2-methylanilino)xanthen-10-ium-3-yl]amino]-3-methylbenzenesulfonate Chemical compound [Na+].Cc1ccccc1Nc1ccc2c(-c3ccccc3C(O)=O)c3ccc(Nc4ccc(cc4C)S([O-])(=O)=O)cc3[o+]c2c1 UWMZZSRDUVJJDP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XKTMIJODWOEBKO-UHFFFAOYSA-M Guinee green B Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 XKTMIJODWOEBKO-UHFFFAOYSA-M 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- UMQAIKKJIZYHQC-UHFFFAOYSA-M Milling yellow 3G Chemical compound ClC=1C=CC(=C(C=1)S(=O)(=O)[O-])N1N=C(C(=C1O)N=NC1=CC=C(C=C1)OS(=O)(=O)C1=CC=C(C=C1)C)C.[Na+] UMQAIKKJIZYHQC-UHFFFAOYSA-M 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- SZYSLWCAWVWFLT-UTGHZIEOSA-N [(2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)-2-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxolan-2-yl]methyl octadecanoate Chemical compound O([C@@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@]1(COC(=O)CCCCCCCCCCCCCCCCC)O[C@H](CO)[C@@H](O)[C@@H]1O SZYSLWCAWVWFLT-UTGHZIEOSA-N 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- HKTCVYHTGCMMTJ-UHFFFAOYSA-O benzyl-[4-[[4-[benzyl(ethyl)amino]phenyl]-(5-hydroxy-2,4-disulfophenyl)methylidene]cyclohexa-2,5-dien-1-ylidene]-ethylazanium Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=CC=CC=2)C=2C(=CC(=C(O)C=2)S(O)(=O)=O)S(O)(=O)=O)C=CC=1N(CC)CC1=CC=CC=C1 HKTCVYHTGCMMTJ-UHFFFAOYSA-O 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011692 calcium ascorbate Substances 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- ZRYQXQUPWQNYSX-UHFFFAOYSA-L disodium;5-[(3-methyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]-2-[4-[(3-methyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]-2-sulfonatophenyl]benzenesulfonate Chemical compound [Na+].[Na+].CC1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C=C1S([O-])(=O)=O)=CC=C1C(C(=C1)S([O-])(=O)=O)=CC=C1N=NC(C1=O)C(C)=NN1C1=CC=CC=C1 ZRYQXQUPWQNYSX-UHFFFAOYSA-L 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 1
- MOYKHGMNXAOIAT-JGWLITMVSA-N isosorbide dinitrate Chemical compound [O-][N+](=O)O[C@H]1CO[C@@H]2[C@H](O[N+](=O)[O-])CO[C@@H]21 MOYKHGMNXAOIAT-JGWLITMVSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- AZLXCBPKSXFMET-UHFFFAOYSA-M sodium 4-[(4-sulfophenyl)diazenyl]naphthalen-1-olate Chemical compound [Na+].C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 AZLXCBPKSXFMET-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、熱可逆性記録シートなどに筆記可能であって、かつ、筆記線が水で容易に消去することができる水消去性油性インキに関するものである。 The present invention relates to a water-erasable oil-based ink that can be written on a thermoreversible recording sheet and the like, and the writing line can be easily erased with water.
従来より一時的な画像表示が行なえ、不要となったときにはその画像の消去ができ、温度に依存して透明度が可逆的に変化する感熱層を有する熱可逆性記録シートが知られており、特開昭５５−１５４１９８号公報、特開平３−２０８９号公報、特開平６−２５５２４７号公報などが知られている。
これらの熱可逆性記録シートは、疎水性樹脂などでオーバーコートされているために水性インキを弾くので、熱可逆性記録シートに筆記する場合は、特公平８−２２９８７号公報記載の油性マーキングペンや特公平１−３８４２２号公報記載のクレヨンのような固形描画剤といった油性インキを使用していた。そして、油性インキは、基本的に水に不溶である為、筆記線を消去したい場合は油性系洗剤を使用して消去する必要があった。
しかし、消去する際に油性系洗剤を用いると、熱可逆性記録シートのオーバーコート層や感熱層を侵してしまい、熱可逆性記録シートの寿命を著しく短縮してしまう欠点があった。
A thermoreversible recording sheet having a heat-sensitive layer that can temporarily display an image and can erase the image when it is no longer needed and whose transparency changes reversibly depending on temperature is known. Japanese Laid-Open Patent Publication Nos. 55-154198, 3-2089, 6-255247 and the like are known.
Since these thermoreversible recording sheets repel water-based ink because they are overcoated with a hydrophobic resin or the like, when writing on the thermoreversible recording sheet, the oil-based marking pen described in JP-B-8-22987 And oil-based inks such as solid drawing agents such as crayons described in JP-B-1-38422. And since oil-based ink is fundamentally insoluble in water, when it was desired to erase the writing line, it was necessary to erase it using an oil-based detergent.
However, when an oil-based detergent is used for erasing, the overcoat layer and the heat-sensitive layer of the thermoreversible recording sheet are eroded and the life of the thermoreversible recording sheet is remarkably shortened.
そこで、本発明は疎水性樹脂でオーバーコートされた熱可逆性記録シートに筆記可能である油性インキであるが、油性系洗剤を用いなくても筆記線が消去できる油性インキを提供することを目的としている。 Accordingly, the present invention is an oil-based ink that can be written on a thermoreversible recording sheet that is overcoated with a hydrophobic resin, and an object thereof is to provide an oil-based ink that can erase the writing lines without using an oil-based detergent. It is said.
前記課題を解決する為に、少なくとも、水とエタノールに可溶である染料と、水とエタノールに可溶である樹脂と、エタノールとからなる水消去性油性インキ。当該水消去性油性インキに更に炭化水素系ワックス、酸化炭化水素系ワックス、糖脂肪酸エステルから選ばれる少なくとも１種を付加してなる水消去性油性インキ。また、水とエタノールに可溶である樹脂が、鹸化度が５０ｍｏｌ％以下の低鹸化ポリビニルアルコール樹脂である前記水消去性油性インキを提供する。 In order to solve the above problems, a water-erasable oil-based ink comprising at least a dye soluble in water and ethanol, a resin soluble in water and ethanol, and ethanol. A water-erasable oil-based ink obtained by further adding at least one selected from a hydrocarbon wax, an oxidized hydrocarbon wax, and a sugar fatty acid ester to the water-erasable oil-based ink. In addition, the water-erasable oil-based ink is provided in which the resin soluble in water and ethanol is a low-saponified polyvinyl alcohol resin having a saponification degree of 50 mol% or less.
本願発明者は鋭意研究の結果、前記課題を解決した消去性油性インキを見出すことに成功した。
すなわち、本発明の消去性油性インキを使用した筆記具や浸透印を用い、疎水性樹脂でオーバーコートされた熱可逆性記録シートに筆記・押印することができる。また、インキの揮発乾燥時間が早く、堅牢性も十分有るので、誤って触っても手指を汚さないし、筆記線や印影が崩れることが無い。
また、水に接触させるだけで筆記線や印影が容易に消去するので、特別な洗剤などを必要とせず、繰り返し使用される熱可逆性記録シートを傷めることが無い。
As a result of intensive studies, the present inventors have succeeded in finding an erasable oil-based ink that has solved the above problems.
That is, it is possible to write and seal on a thermoreversible recording sheet overcoated with a hydrophobic resin using a writing instrument or penetrating mark using the erasable oil-based ink of the present invention. In addition, the ink has a fast volatile drying time and is sufficiently robust, so that even if it is touched by mistake, the fingers are not soiled, and the writing lines and imprints are not broken.
In addition, since the writing lines and seals are easily erased simply by contacting with water, no special detergent or the like is required, and the thermoreversible recording sheet that is used repeatedly is not damaged.
以下、本発明を詳細に説明する。
本発明の油性インキは、筆記具や浸透印に用いられる水消去性油性インキであって、少なくとも、水とエタノールに可溶である染料と、水とエタノールに可溶である樹脂と、エタノールを必須構成要件としている。
Hereinafter, the present invention will be described in detail.
The oil-based ink of the present invention is a water-erasable oil-based ink used for writing instruments and penetrants, and at least a dye that is soluble in water and ethanol, a resin that is soluble in water and ethanol, and ethanol are essential. It is a configuration requirement.
本発明油性インキに用いられる染料としては、水とエタノール両方に可溶である染料を用いることができ、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ３６、同４０、同４２、同７３や、Ｃ．Ｉ．Ａｃｉｄ Ｏｒｅｎｇｅ ７、同２０や、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ４９、同５２、同８７、同８８、同９２、同９４、 同９５や、Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ９や、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ５、同９、同７４や、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ３などを例示することができる。
これらの染料は色合いを勘案しながら１又は２以上を選択して使用でき、インキ全量に対して０．０１〜２０重量％程度を使用することができる。
As the dye used in the oil-based ink of the present invention, a dye that is soluble in both water and ethanol can be used. I. Acid Yellow 36, 40, 42, 73, and C.I. I. Acid Orange 7, 20 and C.I. I. Acid Red 49, 52, 87, 88, 92, 94, 95, C.I. I. Acid Violet 9 and C.I. I. Acid Blue 5, 9 and 74, and C.I. I. Acid Green 3 etc. can be illustrated.
One or more of these dyes can be selected and used in consideration of the hue, and about 0.01 to 20% by weight can be used with respect to the total amount of ink.
本発明油性インキに用いられる樹脂としては、水とエタノールに可溶である樹脂を用いることができ、ポリビニルピロリドン樹脂、ポリビニルアルコール樹脂などを例示することができる。
これらの樹脂は染料を定着させ堅牢性を付与するために用いられ、１又は２以上混合して用いることができ、インキ全量に対して０．１〜７０重量％、好ましくは１〜３０重量％程度を使用することができる。
特に、ポリビニルアルコール樹脂であれば、水及びエタノールへの溶解性の見地から、鹸化度が５０ｍｏｌ％以下の低鹸化ポリビニルアルコール樹脂が好ましく用いられる。
As the resin used in the oil-based ink of the present invention, a resin that is soluble in water and ethanol can be used, and examples thereof include a polyvinyl pyrrolidone resin and a polyvinyl alcohol resin.
These resins are used for fixing dyes and imparting fastness, and can be used by mixing one or two or more, and are used in an amount of 0.1 to 70% by weight, preferably 1 to 30% by weight, based on the total amount of ink. The degree can be used.
In particular, in the case of a polyvinyl alcohol resin, a low saponified polyvinyl alcohol resin having a saponification degree of 50 mol% or less is preferably used from the viewpoint of solubility in water and ethanol.
本発明油性インキに用いられる溶剤は、エタノールである。
エタノールは、速乾性の見地から特に好ましく用いられ、インキ全量に対して５０〜９９重量％、好ましくは６０〜９５重量％程度を使用することができる
The solvent used for the oil-based ink of the present invention is ethanol.
Ethanol is particularly preferably used from the standpoint of quick-drying, and can be used in an amount of 50 to 99% by weight, preferably about 60 to 95% by weight, based on the total amount of ink.
油性インキを用いた筆記具や浸透印は、キャップを外したまま放置しておくとペン先や印面が乾燥して樹脂等が硬化し、筆記・押印不可能となる欠点があった。いわゆるドライアップである。本発明では、そのドライアップを防止するためのドライアップ防止剤を前記油性インキに付加することができる。
本発明油性インキに付加することができるドライアップ防止剤としては、炭化水素系ワックス、酸化炭化水素系ワックス、糖脂肪酸エステルから選ばれる少なくとも１種が使用できる。
炭化水素系ワックスは、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムワックス、ポリエチレンワックス等を用いることができ、例えば、パラフィンワックス１１５・１２５・１３５・１５０、ＮＨＰ−３・５・９・１１・１４Ｇ、ＳＰ−０１４５・０１６０・１０３５・１０４０、Ｈｉ−Ｍｉｃ−１０７０・１０８０・２０４５・２０６５・３０９０（以上、日本精蝋（株）製）等を使用することができる。
酸化炭化水素系ワックスは、酸化パラフィンワックス、酸化マイクロクリスタリンワックス、酸化ペトロラタムワックス、酸化ポリエチレンワックス、酸化サゾールワックス等を用いることができる。これらは、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムワックス、ポリエチレンワックス等の炭化水素系ワックスを空気酸化して製造され、アルコール、酸、エステル、ケトンの混合物として存在しているものであって、例えば、ネオワックスＥ，Ｅ−２０(以上ヤスハラケミカル社製)、ペトロライトＣ−７５００，Ｃ−８５００，Ｃ−９５００，ペトロナウバＣ，カーディス３６，３１４，３１９，３２０，３７０(以上東洋ペトロライト社製)、Ｆ−Ｔ合成ワックスＢ−１２０，Ｃ−２０，Ｃ−６０Ｃ−４６０，Ｅ−３０２，Ｅ−３２１，Ｅ−４２１Ｒ，Ｈ１１１ＥＭ，Ｊ３２４ＡＭ，Ｊ３２４ＳＴ，ポリエチレンワックスＡＸ９５９，ＡＸ１５３９，ＡＶ１５５０，ＡＶ１５５１，ＡＷ１０５０，ＰＥ２０（以上加藤洋行社製）、ＯＸ−１７４９，ＯＸ−０１５３，ＯＸ−２６１ＢＮ，ＮＰＳ−９２１０，ＮＰＳ−９１２５，ＯＸ−１９４９，ＯＸ−０２０Ｔ，ＮＰＳ−８０７０，ＮＰＳ−ＬＳ−７０（以上日本精蝋社製）等を使用することができる。
糖脂肪酸エステルは、糖の水酸基を脂肪酸で置換したエステルをさし、グルコース、フルクトース等、及び、これらを還元したソルビット等の単糖類、麦芽糖、ラクトース等のマルトース型二糖類、トレハロース、ショ糖等のトレハロース型二糖類の水酸基のうち１〜３個を、酢酸・プロピオン酸・酪酸・カプロン酸・カプリル酸・カプリン酸・ラウリン酸・ミリスチン酸・パルミチン酸・ステアリン酸・ベヘン酸等の脂肪酸でエステル化して置換させた糖脂肪酸モノエステル・糖脂肪酸ジエステル・糖脂肪酸トリエステルを例示することができる。ここで、置換数が４以上のものは本発明の溶剤に対する溶解度が低いため完全に溶解せず、インキが経時的に不安定で析出する欠点があるので好ましくない。但し、置換数が４〜８の糖脂肪酸エステルの本発明インキ中における存在を全く否定するものではなく、前記置換数１〜３の糖脂肪酸エステルの不純物として本発明インキ中に若干量存在していても本発明の効果を低下させるものではない。また、ＨＬＢ１０未満のものはペン先表面での被膜形成力が比較的弱いので、ＨＬＢ１０以上の糖脂肪酸エステルが特に好ましく用いられる。
本発明では、前記ドライアップ防止剤は、単独又は２以上を併用して用いることができ、インキ全量に対して０．０１重量％〜１０重量％の範囲で添加するとドライアップ防止効果を発揮し、特に０．１重量％〜５重量％の範囲が最も好ましい結果を示す。
Writing instruments and penetrating marks using oil-based inks have the drawback that if the cap is left with the cap removed, the pen tip and the marking surface dries and the resin hardens, making writing and stamping impossible. This is so-called dry-up. In the present invention, a dry-up preventing agent for preventing the dry-up can be added to the oil-based ink.
As the dry-up preventing agent that can be added to the oil-based ink of the present invention, at least one selected from hydrocarbon waxes, oxidized hydrocarbon waxes, and sugar fatty acid esters can be used.
As the hydrocarbon wax, paraffin wax, microcrystalline wax, petrolatum wax, polyethylene wax and the like can be used. For example, paraffin wax 115 · 125 · 135 · 150, NHP-3 · 5 · 9 · 11 · 14G, SP -0145 · 0160 · 1035 · 1040, Hi-Mic-1070 · 1080 · 2045 · 2065 · 3090 (manufactured by Nippon Seiwa Co., Ltd.) and the like can be used.
As the oxidized hydrocarbon wax, oxidized paraffin wax, oxidized microcrystalline wax, oxidized petrolatum wax, oxidized polyethylene wax, oxidized sazol wax and the like can be used. These are produced by air-oxidizing hydrocarbon waxes such as paraffin wax, microcrystalline wax, petrolatum wax, polyethylene wax, etc., and exist as a mixture of alcohol, acid, ester, ketone, for example, Neowax E, E-20 (above Yashara Chemical Co., Ltd.), Petrolite C-7500, C-8500, C-9500, Petronauba C, Cardis 36, 314, 319, 320, 370 (above Toyo Petrolite) FT synthetic wax B-120, C-20, C-60C-460, E-302, E-321, E-421R, H111EM, J324AM, J324ST, polyethylene wax AX959, AX1539, AV1550, AV1551, AW1050, PE20 (More Manufactured by Fujiyo Co., Ltd.), OX-1749, OX-0153, OX-261BN, NPS-9210, NPS-9125, OX-1949, OX-020T, NPS-8070, NPS-LS-70 (manufactured by Nippon Seiwa Co., Ltd.) ) Etc. can be used.
Sugar fatty acid ester refers to an ester in which the hydroxyl group of sugar is substituted with a fatty acid, such as glucose, fructose, etc., and monosaccharides such as sorbitol, maltose disaccharides such as maltose, lactose, trehalose, sucrose, etc. 1 to 3 of the hydroxyl groups of trehalose-type disaccharides with fatty acids such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid Examples thereof include sugar fatty acid monoesters, sugar fatty acid diesters, and sugar fatty acid triesters that have been substituted. Here, those having a substitution number of 4 or more are not preferable because the solubility in the solvent of the present invention is low so that they are not completely dissolved and the ink is unstable and precipitates with time. However, it does not completely deny the presence of sugar fatty acid esters having 4 to 8 substitutions in the ink of the present invention, and is present in a slight amount in the ink of the present invention as an impurity of the sugar fatty acid esters having 1 to 3 substitutions. However, the effect of the present invention is not reduced. Also, sugar fatty acid esters of HLB10 or higher are particularly preferably used since those having a HLB of less than 10 have a relatively weak film forming ability on the nib surface.
In the present invention, the anti-dry-up agent can be used alone or in combination of two or more. When added in the range of 0.01% by weight to 10% by weight with respect to the total amount of the ink, the anti-dry-up effect is exhibited. In particular, a range of 0.1% to 5% by weight shows the most preferable result.
以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
（実施例１）
Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ９ ０．５重量％
ポリビニルピロリドン樹脂 ７．５重量％
エタノール ９２．０重量％
以上の物質を混合し、粘度４．０ｍＰａ・ｓ（２５℃・６０ｒｐｍ）の紫色インキを得た。
Example 1
C. I. Acid Violet 9 0.5% by weight
Polyvinylpyrrolidone resin 7.5% by weight
Ethanol 92.0% by weight
The above substances were mixed to obtain a purple ink having a viscosity of 4.0 mPa · s (25 ° C. · 60 rpm).
（実施例２）
Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ８７ ０．５重量％
ポリビニルピロリドン樹脂 ７．０重量％
エタノール ９２．０重量％
酸化パラフィンワックス ０．５重量％
以上の物質を混合し、粘度４．５ｍＰａ・ｓ（２５℃・６０ｒｐｍ）の赤色インキを得た。
(Example 2)
C. I. Acid Red 87 0.5% by weight
Polyvinylpyrrolidone resin 7.0% by weight
Ethanol 92.0% by weight
Oxidized paraffin wax 0.5% by weight
The above substances were mixed to obtain a red ink having a viscosity of 4.5 mPa · s (25 ° C. · 60 rpm).
（実施例３）
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ９ ０．５重量％
ポリビニルアルコール樹脂（鹸化度４５） ５．０重量％
エタノール ９２．０重量％
ＤＫエステル Ｆ−１１０ ０．５重量％
（第一工業製薬株式会社製ショ糖ステアリン酸エステル）
以上の物質を混合し、粘度３．５ｍＰａ・ｓ（２５℃・６０ｒｐｍ）の青色インキを得た。
(Example 3)
C. I. Acid Blue 9 0.5% by weight
Polyvinyl alcohol resin (degree of saponification 45) 5.0% by weight
Ethanol 92.0% by weight
DK ester F-110 0.5% by weight
(Daiichi Kogyo Seiyaku Co., Ltd. sucrose stearate)
The above substances were mixed to obtain a blue ink having a viscosity of 3.5 mPa · s (25 ° C. · 60 rpm).
（比較例１）
Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ３６ ３．０重量％
ポリビニルピロリドン樹脂 １０．０重量％
エタノール ５０．０重量％
水 ３７．０重量％
以上の物質を混合し、黄色インキを得た。
(Comparative Example 1)
C. I. Acid Yellow 36 3.0% by weight
Polyvinylpyrrolidone resin 10.0% by weight
Ethanol 50.0% by weight
37.0% by weight of water
The above substances were mixed to obtain a yellow ink.
（比較例２）
Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ４４ １．０重量％
ケトン樹脂 ５．０重量％
エタノール ９４．０重量％
以上の物質を混合し、青色インキを得た。
(Comparative Example 2)
C. I. Acid Blue 44 1.0% by weight
Ketone resin 5.0% by weight
Ethanol 94.0% by weight
The above substances were mixed to obtain a blue ink.
（筆記性試験）
オーバーコートされた熱可逆性記録シートに、実施例及び比較例のインキを充填したマーキングペンで筆記し、筆記線を弾くか否かを調べた。
＜評価＞ ○：筆記線を弾かない。 ×：筆記線を弾く。
（堅牢性試験）
筆記性試験で筆記した熱可逆性記録シートの筆記線を乾いた布で擦っても剥がれないか否かを調べた。
＜評価＞ ○：剥がれない。 ×：剥がれる。
（消去性試験）
筆記性試験で筆記した熱可逆性記録シートに、水を数滴垂らし、筆記線が消去するか否かを調べた。
＜評価＞ ○：完全に消去する。 ×：筆記線が残る。
(Writing test)
The overcoated thermoreversible recording sheet was written with a marking pen filled with the inks of Examples and Comparative Examples, and it was examined whether or not the writing line was repelled.
<Evaluation> ○: The writing line is not played. X: Play a writing line.
(Robustness test)
It was examined whether or not the writing line of the thermoreversible recording sheet written in the writing test could be peeled off even when rubbed with a dry cloth.
<Evaluation> ○: Not peeled off. X: Peel off.
(Eraseability test)
A few drops of water were dropped on the thermoreversible recording sheet written in the writing test, and it was examined whether or not the writing line was erased.
<Evaluation> ○: Completely erased. X: A writing line remains.
以下、試験結果を表にする。
（表１）
┌──────┬─────┬─────┬─────┐
│ ｜筆記性試験｜堅牢性試験｜消去性試験｜
├──────┼─────┼─────┼─────┤
｜ 実施例１ ｜ ○ ｜ ○ ｜ ○ ｜
├──────┼─────┼─────┼─────┤
｜ 実施例２ ｜ ○ ｜ ○ ｜ ○ ｜
├──────┼─────┼─────┼─────┤
｜ 実施例３ ｜ ○ ｜ ○ ｜ ○ ｜
├──────┼─────┼─────┼─────┤
｜ 比較例１ ｜ × ｜ ○ ｜ ○ ｜
├──────┼─────┼─────┼─────┤
｜ 比較例２ ｜ ○ ｜ ○ ｜ × ｜
└──────┴─────┴─────┴─────┘
The test results are tabulated below.
(Table 1)
┌──────┬─────┬─────┬─────┐
│ | Writability test | Fastness test | Erasability test |
├──────┼─────┼─────┼─────┤
Example 1 | ○ | | ○ | ○ |
├──────┼─────┼─────┼─────┤
Example 2 | ○ | | ○ | ○ |
├──────┼─────┼─────┼─────┤
Example 3 | ○ | | ○ | ○ |
├──────┼─────┼─────┼─────┤
Comparative Example 1 | × | | ○ | ○ |
├──────┼─────┼─────┼─────┤
Comparative Example 2 | ○ | | ○ | × |
└──────┴─────┴─────┴─────┘
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005364692A JP4953625B2 (en) | 2005-12-19 | 2005-12-19 | Water-erasable oil-based ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005364692A JP4953625B2 (en) | 2005-12-19 | 2005-12-19 | Water-erasable oil-based ink |
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| Publication Number | Publication Date |
|---|---|
| JP2007169319A true JP2007169319A (en) | 2007-07-05 |
| JP4953625B2 JP4953625B2 (en) | 2012-06-13 |
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|---|---|---|---|
| JP2005364692A Active JP4953625B2 (en) | 2005-12-19 | 2005-12-19 | Water-erasable oil-based ink |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014167052A (en) * | 2013-02-28 | 2014-09-11 | Zebra Pen Corp | Ink composition and marking pen |
| JP2015040251A (en) * | 2013-08-21 | 2015-03-02 | ゼブラ株式会社 | Water-erasable aqueous ink composition, and marking pen |
| JP2018159040A (en) * | 2017-03-23 | 2018-10-11 | シヤチハタ株式会社 | Water-color ink for skin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239064A (en) * | 1991-01-09 | 1992-08-26 | Brother Ind Ltd | Ink composition |
| JP2002129085A (en) * | 2000-10-30 | 2002-05-09 | Pilot Ink Co Ltd | Water erasable marker for toys and figure toy set using the same |
| JP2007016095A (en) * | 2005-07-06 | 2007-01-25 | Sakura Color Prod Corp | Water-erasable ink composition |
| JP2007023212A (en) * | 2005-07-20 | 2007-02-01 | Sakura Color Prod Corp | Coloring material composition erasable by washing |
-
2005
- 2005-12-19 JP JP2005364692A patent/JP4953625B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04239064A (en) * | 1991-01-09 | 1992-08-26 | Brother Ind Ltd | Ink composition |
| JP2002129085A (en) * | 2000-10-30 | 2002-05-09 | Pilot Ink Co Ltd | Water erasable marker for toys and figure toy set using the same |
| JP2007016095A (en) * | 2005-07-06 | 2007-01-25 | Sakura Color Prod Corp | Water-erasable ink composition |
| JP2007023212A (en) * | 2005-07-20 | 2007-02-01 | Sakura Color Prod Corp | Coloring material composition erasable by washing |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014167052A (en) * | 2013-02-28 | 2014-09-11 | Zebra Pen Corp | Ink composition and marking pen |
| JP2015040251A (en) * | 2013-08-21 | 2015-03-02 | ゼブラ株式会社 | Water-erasable aqueous ink composition, and marking pen |
| JP2018159040A (en) * | 2017-03-23 | 2018-10-11 | シヤチハタ株式会社 | Water-color ink for skin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4953625B2 (en) | 2012-06-13 |
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