JP2005185643A - Indicator ink composition that develops color by moisture and printing configuration using the same - Google Patents
Indicator ink composition that develops color by moisture and printing configuration using the same Download PDFInfo
- Publication number
- JP2005185643A JP2005185643A JP2003432649A JP2003432649A JP2005185643A JP 2005185643 A JP2005185643 A JP 2005185643A JP 2003432649 A JP2003432649 A JP 2003432649A JP 2003432649 A JP2003432649 A JP 2003432649A JP 2005185643 A JP2005185643 A JP 2005185643A
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- JP
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- Prior art keywords
- red
- ink composition
- moisture
- sheet
- colorant
- Prior art date
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- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000007639 printing Methods 0.000 title claims description 21
- 239000003086 colorant Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 9
- 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 claims description 12
- 150000002596 lactones Chemical group 0.000 claims description 11
- MQWPIYMKAKYEEQ-UHFFFAOYSA-L dipotassium 2,3,4,5-tetrachloro-6-(2,4,5,7-tetrabromo-3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [K+].[K+].[O-]C(=O)c1c(Cl)c(Cl)c(Cl)c(Cl)c1-c1c2cc(Br)c([O-])c(Br)c2oc2c(Br)c(=O)c(Br)cc12 MQWPIYMKAKYEEQ-UHFFFAOYSA-L 0.000 claims description 7
- 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 claims description 7
- 235000012732 erythrosine Nutrition 0.000 claims description 6
- ZYIBVBKZZZDFOY-UHFFFAOYSA-N phloxine O Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 ZYIBVBKZZZDFOY-UHFFFAOYSA-N 0.000 claims description 6
- UBVSIAHUTXHQTD-UHFFFAOYSA-N 2-n-(4-bromophenyl)-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(NC=2C=CC(Br)=CC=2)=N1 UBVSIAHUTXHQTD-UHFFFAOYSA-N 0.000 claims description 4
- ZDTNHRWWURISAA-UHFFFAOYSA-N 4',5'-dibromo-3',6'-dihydroxyspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C(Br)=C1OC1=C(Br)C(O)=CC=C21 ZDTNHRWWURISAA-UHFFFAOYSA-N 0.000 claims description 4
- AHSJNHONMVUMLK-UHFFFAOYSA-L disodium;4',5'-diiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC=C([O-])C(I)=C1OC1=C(I)C([O-])=CC=C21 AHSJNHONMVUMLK-UHFFFAOYSA-L 0.000 claims description 4
- 229960001483 eosin Drugs 0.000 claims description 4
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 4
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 claims description 4
- GVKCHTBDSMQENH-UHFFFAOYSA-L phloxine B Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 GVKCHTBDSMQENH-UHFFFAOYSA-L 0.000 claims description 4
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 claims description 3
- OOYIOIOOWUGAHD-UHFFFAOYSA-L disodium;2',4',5',7'-tetrabromo-4,5,6,7-tetrachloro-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [Na+].[Na+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(Br)=C([O-])C(Br)=C1OC1=C(Br)C([O-])=C(Br)C=C21 OOYIOIOOWUGAHD-UHFFFAOYSA-L 0.000 claims description 3
- UWBXIFCTIZXXLS-UHFFFAOYSA-L disodium;2,3,4,5-tetrachloro-6-(2,4,5,7-tetraiodo-3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 UWBXIFCTIZXXLS-UHFFFAOYSA-L 0.000 claims description 2
- DBZJJPROPLPMSN-UHFFFAOYSA-N bromoeosin Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 DBZJJPROPLPMSN-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 210000002700 urine Anatomy 0.000 abstract description 6
- 238000010030 laminating Methods 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 51
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
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- 239000000463 material Substances 0.000 description 6
- -1 sodium hydrocarbon Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920001800 Shellac Polymers 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000027939 micturition Effects 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229940113147 shellac Drugs 0.000 description 5
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 4
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- 239000004208 shellac Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910000147 aluminium phosphate 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
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- 239000005456 alcohol based solvent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
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- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
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- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 description 1
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 description 1
- 229960004555 rutoside Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Orthopedics, Nursing, And Contraception (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
【課題】 尿や水分用のインジケーターとして着色剤が流出せず、色調が目立つものを提供する。
【解決手段】 少なくともインキバインダー、水分の存在下で塩基性物質からなる顕色剤の働きかけで発色する着色剤及びpH調整剤を含有する水分インジケーターインキ組成物を、該顕色剤を含有するシートに印刷することを特徴とするシートへのインキ組成物の積層方法。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide an indicator for urine and moisture, in which a colorant does not flow out and a color tone is conspicuous.
A water indicator ink composition containing at least an ink binder, a colorant that develops color by the action of a developer composed of a basic substance in the presence of moisture, and a pH adjuster, and a sheet containing the developer A method for laminating an ink composition on a sheet, wherein the ink composition is printed on a sheet.
[Selection figure] None
Description
本発明は水分インジケーター機能を有する積層シートの製造法に関し、特に視認による水分(尿)インジケーター機能を有する例えば紙おむつ等に用いるインキ組成物及びそれを用いた印刷構成方法に関する。 The present invention relates to a method for producing a laminated sheet having a moisture indicator function, and more particularly, to an ink composition having a moisture (urine) indicator function by visual recognition, such as a paper diaper, and a printing composition method using the same.
生活水準の向上、衛生へのより一層の配慮の下、紙おむつや病人用のシートにも尿等の水分インジケーター付きのものが用いられるようになっている。さて、このためのインジケーターインキには、インキ中の着色剤が流れ出すことによって図柄がぼやける、消え去る、あるいは変色する等のものがある。例えば以下の特許文献1、同2には尿による消色性のインジケータ用インキが開示されている。
しかしながら、これらのタイプのインジケーターインキは、流れた着色剤のため紙おむつ等が汚れた様に見えてしまうことがある。特に、着色剤の流出によって変色するタイプのインジケーターインキでは、変色前後の色に差を持たせるために、どうしても流出する着色剤の量が多くなり、その結果汚れが目立ちやすくなる。また、変色後の色が変色前の色よりも薄くなるため、色調によっては水分による変色が目立ち難い。また、他の衣料品を着色したりすることもある。また、消色型の場合も目立ち難いことがある。 However, these types of indicator inks may appear to be dirty on paper diapers due to the flowing colorant. In particular, in the type of indicator ink that changes color due to the outflow of the colorant, the amount of colorant that flows out inevitably increases in order to give a difference in the color before and after the color change. In addition, since the color after the color change becomes lighter than the color before the color change, the color change due to moisture is hardly noticeable depending on the color tone. In addition, other clothing items may be colored. In the case of a decoloring type, it may be difficult to stand out.
このため、消色或いは変色後に流出した着色剤による汚染や、変色後の色が変色前の色と比べて淡いことによる視認性の不足の少ない、そして当然人体への害のない水分(尿)インジケーター機能を有するシート及び該シートを用いた紙おむつの実現が望まれていた。 For this reason, moisture (urine) that is less contaminated by colorant that has flowed out after decoloring or discoloration, and lack of visibility due to the color after discoloration being lighter than the color before discoloration, and naturally harming the human body Realization of a sheet having an indicator function and a paper diaper using the sheet has been desired.
本発明は、以上の課題を解決するためになされたものであり、着色剤、インキベースとなる樹脂(インキバインダー)、着色剤のpHによる色相の変化、顕色剤として最適な塩基性の物質を種々検討し、また着色剤は染料や顔料等がpHによってどのように発色状態が変化するかを確認し、更にpHの調整剤の安全性、効果等を考慮し、更にまたインキバインダーとなる樹脂は好ましくは水またはアルコール系の溶剤に溶解し且つ乾燥した塗膜が水に対する耐性(耐性は完全でなくてもよい。水に対して半溶解か膨潤してもよい)を持つ様な物を選定して本発明を完成したものである。 The present invention has been made in order to solve the above-described problems, and is a basic material that is optimal as a colorant, an ink-based resin (ink binder), a hue change due to pH of the colorant, and a developer. In addition, the coloring agent is used to confirm how the coloring state of dyes and pigments changes depending on the pH, and further considering the safety and effect of the pH adjusting agent, and further becomes an ink binder. The resin is preferably dissolved in water or an alcohol-based solvent, and the dried coating has resistance to water (resistance may not be complete; it may be semi-dissolved or swelled in water). This completes the present invention.
本発明の請求項1の発明は、少なくともインキバインダー、水分の存在下で塩基性物質からなる顕色剤の働きかけで発色する着色剤及びpH調整剤を含有する水分インジケーターインキ組成物を、該顕色剤を有するシートに印刷することを特徴とするシートへのインキ組成物の印刷構成方法であり、請求項2の発明は、前記顕色剤として充填剤を用いることを特徴とする請求項1に記載のシートへのインキ組成物の印刷構成方法であり、請求項3の発明は、前記着色剤として、フルオラン、エリスロシン(赤色3号)(C.1.45430)、フロキシンB(赤色104−1号)(C.1.45410)、ローズベンガル(赤色105−1号)(C.1.45440)、テトラクロルテトラブロムフルオレセイン(赤色218号)(C.1.45410)、テトラブロムフルオレセイン(赤色223号)(C.1.45380)、エオシンYS(赤色230−1号)(C.1.45380)、ジブロムフルオレセイン(橙色201号)(C.1.45370)、フルオレセイン(黄色201号)(C.1.45350)、ウラニン(黄色202−1号)(C.1.45350)、エオシンYSK(赤色203−2号)(C.1.45380)、フロキシンBK(赤色231号)(C.1.45410)、ローズベンガルK(赤色232号)(C.1.45440)、ジヨードフルオレセイン(橙色206号)(C.1.45425A)、エリスロシン黄NA(橙色207号)(C.1.45425)、ウラニンK(黄色202−2号)(C.1.45350)、ビオラミンR(赤色401号)(C.1.45190)からなる群から選ばれたラクトン環を有するもしくはPH調整でラクトン環を形成することができる染料を用いることを特徴とする請求項1又は請求項2に記載のシートへのインキ組成物の印刷構成方法であり、請求項4の発明は、塩基性物質からなる顕色剤を有するシートの印刷用水分インジケーターインキ組成物であって、少なくともインキバインダー、水分の存在下で該塩基性物質からなる顕色剤の働きかけで発色する着色剤及びpH調整剤を含有することを特徴とする水分インジケーターインキ組成物であり、請求項5の発明は、前記着色剤として、フルオラン、エリスロシン(赤色3号)(C.1.45430)、フロキシンB(赤色104−1号)(C.1.45410)、ローズベンガル(赤色105−1号)(C.1.45440)、テトラクロルテトラブロムフルオレセイン(赤色218号)(C.1.45410)、テトラブロムフルオレセイン(赤色223号)(C.1.45380)、エオシンYS(赤色230−1号)(C.1.45380)、ジブロムフルオレセイン(橙色201号)(C.1.45370)、フルオレセイン(黄色201号)(C.1.45350)、ウラニン(黄色202−1号)(C.1.45350)、エオシンYSK(赤色203−2号)(C.1.45380)、フロキシンBK(赤色231号)(C.1.45410)、ローズベンガルK(赤色232号)(C.1.45440)、ジヨードフルオレセイン(橙色206号)(C.1.45425A)、エリスロシン黄NA(橙色207号)(C.1.45425)、ウラニンK(黄色202−2号)(C.1.45350)、ビオラミンR(赤色401号)(C.1.45190)からなる群から選ばれたラクトン環を有するもしくはPH調整でラクトン環を形成することができる染料を用いることを特徴とする請求項4に記載の水分インジケーターインキ組成物である。 According to the first aspect of the present invention, there is provided a moisture indicator ink composition containing at least an ink binder, a colorant that develops color by the action of a developer composed of a basic substance in the presence of moisture, and a pH adjuster. It is a printing constitution method of an ink composition on a sheet characterized by printing on a sheet having a colorant, and the invention of claim 2 is characterized in that a filler is used as the developer. The invention according to claim 3 is a method for printing an ink composition on a sheet according to claim 3, wherein the colorant includes fluoran, erythrosin (red No. 3) (C. 1.45430), Phloxine B (red 104- 1) (C. 1.45410), Rose Bengal (Red 105-1) (C. 1.45440), Tetrachlorotetrabromofluorescein (Red 218) (C.1. 5410), tetrabromofluorescein (red 223) (C.1.4380), eosin YS (red 230-1) (C.1.4380), dibromofluorescein (orange 201) (C.1.45370). ), Fluorescein (yellow 201) (C.1.4350), uranin (yellow 202-1) (C.1.4350), eosin YSK (red 202-2) (C.1.4380), phloxine BK (Red 231) (C. 1.45410), Rose Bengal K (Red 232) (C. 1.44540), Diiodofluorescein (Orange 206) (C. 1.45425A), Erythrosine Yellow NA ( Orange No. 207) (C. 1.45425), Uranine K (Yellow No. 202-2) (C. 1.45350), Violamine R (Red) A dye having a lactone ring selected from the group consisting of (No. 01) (C. 1.45190) or capable of forming a lactone ring by pH adjustment is used. According to the invention, the ink composition for printing on a sheet having a developer composed of a basic substance, the water indicator ink composition for printing on a sheet, comprising at least an ink binder and a water content. A moisture indicator ink composition comprising a colorant that develops color under the action of a developer composed of the basic substance and a pH adjuster in the presence, and the invention according to claim 5 provides the colorant as the colorant. Fluoran, erythrosine (red No. 3) (C. 1.45430), Phloxine B (red No. 104-1) (C. 1.45410), rose bengal (red Color 105-1) (C.I. 1.44540), tetrachlorotetrabromofluorescein (red 218) (C. 1.45410), tetrabromofluorescein (red 223) (C. 145380), eosin YS (red 230-1) (C 1.45380), dibromofluorescein (orange 201) (C.1.45370), fluorescein (yellow 201) (C.1.4350), uranin (yellow 202-1) (C.1.4350) ), Eosin YSK (Red No. 203-2) (C. 1.45380), Phloxine BK (Red No. 231) (C. 1.45410), Rose Bengal K (Red No. 232) (C. 1.45440), Diiodofluorescein (orange 206) (C. 1.45425A), erythrosine yellow NA (orange 207) (C. 1.45) 25), having a lactone ring selected from the group consisting of Uranine K (Yellow 202-2) (C.1.45350), Violamine R (Red 401) (C.1.45190), or lactone by adjusting the pH The moisture indicator ink composition according to claim 4, wherein a dye capable of forming a ring is used.
本発明の印刷構成方法によって得られる積層シートは、水分の存在下で、発色若しくは変色して該水分の存在を目視で確認することが可能であり、乳幼児等の排尿の的確な認識が容易となり、且つ着色剤の流出による変化(変色)でないため、汚れが目立たなくて済む。また、本発明の印刷構成方法によって得られる積層シートは、変色前の色調より、乳幼児等の排尿による変色後の色調を濃くすることが可能であり、乳幼児等の排尿の的確な視認性に優れており、紙おむつ等の尿(水分)インジケーターとして優れている。 The laminated sheet obtained by the printing composition method of the present invention can be colored or discolored in the presence of moisture to visually confirm the presence of the moisture, facilitating accurate recognition of urination of infants and the like. In addition, since there is no change (discoloration) due to the outflow of the colorant, dirt is not noticeable. Further, the laminated sheet obtained by the printing composition method of the present invention can darken the color tone after discoloration due to urination of infants and the like than the color tone before discoloration, and is excellent in accurate visibility of urination of infants and the like. It is excellent as a urine (moisture) indicator for paper diapers.
本発明の、色相の変化の1例を示すと、シート(フィルム)に印刷されたインキ層中の色素(着色剤)はpH調整剤の作用で殆ど無色のままであるが、水分や尿などによって、例えば、フィルム中の顕色剤(充填剤)として用いた炭酸カルシウムをインキ層中の色素が溶解し、その過程で、色素のラクトン環が開裂して、カルシウム塩となり積層シートは、強烈な色相に変化する。 An example of the change in hue according to the present invention is as follows. The coloring matter (coloring agent) in the ink layer printed on the sheet (film) remains almost colorless by the action of the pH adjusting agent. For example, the calcium carbonate used as a developer (filler) in the film dissolves the pigment in the ink layer, and in the process, the lactone ring of the pigment is cleaved to form a calcium salt. Changes to a different hue.
以下、本発明をその最良の実施の形態に基づいて説明する。 Hereinafter, the present invention will be described based on the best mode.
本発明は、塩基性物質からなる顕色剤の作用で発色する着色剤、適切なpH調整剤及び最終的には水に不溶(難溶)となるインキバインダーを少なくとも含有するインキ組成物を、該顕色剤を有するシート上に印刷(積層)する方法であり、本発明の印刷構成方法により、尿等の水分によって発色する水分インジケーター機能を有する積層シートを作製することができる。 The present invention comprises an ink composition comprising at least an ink binder that develops color by the action of a developer composed of a basic substance, an appropriate pH adjuster, and finally an insoluble (insoluble) water. This is a method of printing (laminating) on a sheet having the developer, and a laminated sheet having a moisture indicator function that develops color by moisture such as urine can be produced by the printing composition method of the present invention.
水分によって直接あるいは間接的に着色剤に働きかける塩基性物質からなる顕色剤としては、例えばアンモニア、炭化水素ナトリウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸アルミン酸マグネシウム、酸化マグネシウム、酸化カルシウム、水酸化カルシウム、水酸化マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム及びそれらの共沈物質が挙げられ、特に限定されるものではない。本発明では、顕色剤として、従来充填剤として用いられているものを好適に用いることが出来る。 Examples of the developer made of a basic substance that directly or indirectly acts on the colorant by moisture include ammonia, sodium hydrocarbon, calcium carbonate, magnesium carbonate, magnesium silicate aluminate, magnesium oxide, calcium oxide, and calcium hydroxide. , Magnesium hydroxide, calcium silicate, magnesium silicate, and coprecipitates thereof are not particularly limited. In the present invention, those conventionally used as fillers can be suitably used as the developer.
シートに有される上述の塩基性物質からなる顕色剤の作用で変色をする機構を持つ着色剤としては、直接染料等の合成水溶性染料、合成食用染料、天然色素や無機顔料、有機顔料等のうち、pHによって色相、明度等の色調が変化する物を使用する。特に色調が大きく変化するものが好ましく、用途によっては水に難溶のものが好ましい。さらに好ましくは、フルオラン、エリスロシン(赤色3号)(C.1.45430)、フロキシンB(赤色104−1号)(C.1.45410)、ローズベンガル(赤色105−1号)(C.1.45440)、テトラクロルテトラブロムフルオレセイン(赤色218号)(C.1.45410)、テトラブロムフルオレセイン(赤色223号)(C.1.45380)、エオシンYS(赤色230−1号)(C.1.45380)、ジブロムフルオレセイン(橙色201号)(C.1.45370)、フルオレセイン(黄色201号)(C.1.45350)、ウラニン(黄色202−1号)(C.1.45350)、エオシンYSK(赤色203−2号)(C.1.45380)、フロキシンBK(赤色231号)(C.1.45410)、ローズベンガルK(赤色232号)(C.1.45440)、ジヨードフルオレセイン(橙色206号)(C.1.45425A)、エリスロシン黄NA(橙色207号)(C.1.45425)、ウラニンK(黄色202−2号)(C.1.45350)、ビオラミンR(赤色401号)(C.1.45190)からなる群から選ばれたラクトン環を有するもしくはPH調整でラクトン環を形成することができる染料を用いられる。但し、これら以外の着色剤の使用や併用を本発明の効果を害さない限り、排除するものではない。本発明の「シートに有される」とは、シートに含有されていてもよく、また、シートに色素(着色剤)とは別に塗布されていてもよい。そして、色素は重ねてもよく、また、近傍にあってもよい。 Examples of the colorant having a mechanism that changes color by the action of the above-described basic substance in the sheet include synthetic water-soluble dyes such as direct dyes, synthetic food dyes, natural and inorganic pigments, and organic pigments. Among them, a substance whose hue such as hue and brightness changes depending on pH is used. In particular, those whose color tone changes greatly are preferred, and those which are hardly soluble in water are preferred depending on the application. More preferably, fluoran, erythrosine (Red No. 3) (C.1.4545), Phloxine B (Red No. 104-1) (C.1.445410), Rose Bengal (Red No. 105-1) (C.1) .45440), tetrachlorotetrabromofluorescein (red 218) (C. 1.45410), tetrabromofluorescein (red 223) (C. 145380), eosin YS (red 230-1) (C.I. 1.45380), dibromofluorescein (orange 201) (C.1.45370), fluorescein (yellow 201) (C.1.445350), uranin (yellow 202-1) (C.1.4350) Eosin YSK (Red No. 203-2) (C.1.45380), Phloxine BK (Red No. 231) (C.1.4541) ), Rose Bengal K (Red No. 232) (C. 1.45440), Diiodofluorescein (Orange 206) (C. 1.45425A), Erythrosine Yellow NA (Orange 207) (C. 1.45425), It has a lactone ring selected from the group consisting of uranin K (yellow 202-2) (C.1.445350), violamine R (red 401) (C.1.45190), or forms a lactone ring by adjusting the pH Dyes that can be used are used. However, the use or combination of colorants other than these is not excluded unless the effects of the present invention are impaired. The “contained in the sheet” of the present invention may be contained in the sheet, or may be applied to the sheet separately from the pigment (colorant). And a pigment | dye may be piled up and may exist in the vicinity.
顕色剤を有するシートへ印刷(積層)された状態のインキ組成物が空気中の湿気等で発色しないように(初期着色を抑制)、印刷されたインキ組成物やその周囲のpHを一定の範囲に(特に多少酸性に)保持するためのpH調整剤としては、無機酸、有機酸等を用いる。例えば酸としてはギ酸、酢酸、リン酸、こはく酸、フマル酸、フタル酸、テレフタル酸、安息香酸、P−ヒドロキシ安息香酸、DL−リンゴ酸、マレイン酸、サリチル酸、シュウ酸、グルコン酸、クエン酸、アジピン酸、酒石酸、ソルビン酸、L(+)アスコルビン酸、ルチン、フィチン酸を挙げられる。 Keep the printed ink composition and the surrounding pH constant so that the ink composition printed (laminated) on the sheet having the developer does not develop color due to moisture in the air (suppressing initial coloring). An inorganic acid, an organic acid, or the like is used as a pH adjuster for maintaining the range (particularly somewhat acidic). For example, formic acid, acetic acid, phosphoric acid, succinic acid, fumaric acid, phthalic acid, terephthalic acid, benzoic acid, P-hydroxybenzoic acid, DL-malic acid, maleic acid, salicylic acid, oxalic acid, gluconic acid, citric acid , Adipic acid, tartaric acid, sorbic acid, L (+) ascorbic acid, rutin, phytic acid.
インキバインダーとしては、従来水分インジケータ用インキ組成物に用いられているものと特に相違はなく、例えばアクリル樹脂、ウレタン樹脂、酪酢酸繊維素系樹脂、硝化綿、ポリアミド系樹脂、ガムコパール、ガムロジン、セラック、塩ビ酢ビ共重合樹脂等が挙げられる。但し、他の材料、高分子結着剤の使用や併用も可能である。インキバインダーとしては、好ましくはアルコール系の溶剤に溶解し、且つ塗膜になった場合に、水に対する耐水性をもつ樹脂である。
本発明の顕色剤、着色剤等の成分は、マイクロカプセル化して含有させることが可能である。
The ink binder is not particularly different from those conventionally used in ink compositions for moisture indicators, such as acrylic resin, urethane resin, butyric acetate fiber resin, nitrified cotton, polyamide resin, gum copearl, gum rosin, shellac. And vinyl chloride vinyl acetate copolymer resin. However, other materials and polymer binders can be used or used together. The ink binder is preferably a resin that dissolves in an alcohol-based solvent and has water resistance when formed into a coating film.
Components such as a developer and a colorant of the present invention can be contained in microcapsules.
本発明のインキ組成物に用いられる溶剤としては、主としてアルコール系の溶剤を用いる。アルコール系の溶剤としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、n−プロピルアルコール、n−ブチルアルコール、sec−ブチルアルコール、イソブチルアルコール等を挙げられる。勿論、エステル類脂肪族炭化水素、ケトン類等のこれら以外の溶剤を使用したり併用してもよい。なお、それらと併用する際、アルコール類の濃度は特に限定されない。従って、従来溶剤としてインキ組成物に用いられるものと特に大きな相違はない。 As the solvent used in the ink composition of the present invention, an alcohol solvent is mainly used. Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol and the like. Of course, other solvents such as esters aliphatic hydrocarbons and ketones may be used or used in combination. In addition, when using together with them, the density | concentration of alcohol is not specifically limited. Therefore, it is not particularly different from those conventionally used in ink compositions as solvents.
その他、用途に応じて本発明のインキ組成物に、消泡剤、増粘剤、可塑剤、分散剤、乳化剤、酸化防止剤、防腐剤等を適量含有するようにしても良い。また、本発明のインキ組成物に、消色インキ組成物或いはインジケータ機能を有しない通常のインキ組成物を混合することも可能である。 In addition, the ink composition of the present invention may contain an appropriate amount of an antifoaming agent, a thickener, a plasticizer, a dispersant, an emulsifier, an antioxidant, an antiseptic, or the like depending on the application. Moreover, it is also possible to mix the decoloring ink composition or the normal ink composition which does not have an indicator function with the ink composition of this invention.
本発明のインキ組成物は、上述の着色剤を0、1〜20重量部、インキバインダーを5〜50重量部、pH調整剤、溶剤を適量混合して得る。なお、この比率は用途等に応じて適量変更しても良い。 The ink composition of the present invention is obtained by mixing 0 to 1 to 20 parts by weight of the above-described colorant, 5 to 50 parts by weight of an ink binder, a pH adjuster, and an appropriate amount of a solvent. Note that this ratio may be changed in an appropriate amount depending on the application.
本発明に用いられる塩基性物質からなる顕色剤を有するシートとしては、例えば紙おむつに使用されるポリエチレン等の合成樹脂等に上述の炭酸カルシウム等の顕色剤を多量に混練し、延伸することにより、微細な穴(透湿性)を有する顕色剤含有シート(合成樹脂フィルム)を挙げることができる。また、本発明に用いられる塩基性物質からなる顕色剤を含有するシートは、シートの上に塩基性物質からなる顕色剤をコーティングすることにより得ることが出来る。合成樹脂フィルムの他、紙、合成紙、または不織布等を用いることも可能である。 As a sheet having a developer composed of a basic substance used in the present invention, for example, a large amount of the developer such as calcium carbonate described above is kneaded in a synthetic resin such as polyethylene used for a paper diaper and then stretched. Can include a developer-containing sheet (synthetic resin film) having fine holes (moisture permeability). Moreover, the sheet | seat containing the developer which consists of a basic substance used for this invention can be obtained by coating the developer which consists of a basic substance on a sheet | seat. In addition to the synthetic resin film, paper, synthetic paper, nonwoven fabric, or the like can be used.
水分の存在下で塩基物質からなる顕色剤の働きかけで発色する着色剤、インキバインダー、及びpH調整剤物質を少なくとも含有するインキ組成物を、該顕色剤を含有するシートに印刷(積層)する方法としては、特に限定されず、グラビア印刷方式やフレキソ印刷方式やシルクスクリーン方式等が、インキ組成物の組成やその濃度や使用される被印刷体(シート)の加工の段階等に応じて、適宜選択することができる。また、被印刷体(シート)であるが、上述したように、特には限定されず、例えば紙、合成紙、合成樹脂フィルム、不織布等を挙げられる。 Printing (lamination) an ink composition containing at least a colorant, an ink binder, and a pH adjuster substance that develops color by the action of a developer composed of a base substance in the presence of moisture on a sheet containing the developer. The method of performing is not particularly limited, and a gravure printing method, a flexographic printing method, a silk screen method, and the like, depending on the composition of the ink composition, its concentration, the stage of processing of the printed material (sheet) to be used, etc. Can be appropriately selected. Moreover, although it is a to-be-printed body (sheet), as mentioned above, it is not specifically limited, For example, paper, a synthetic paper, a synthetic resin film, a nonwoven fabric etc. are mentioned.
また、各種の必要な耐性や性能を得るためには、このインキ組成物のシートへの印刷に際してオーバーコートやアンダーコートを行っても良い。これらオーバーコートやアンダーコートに使用する物質は、用途例えば、多少酸性を持たせて発色を少し遅らせるようにする、或いは少し厚くして耐汗性を持たせる等に応じて適切なものが選定される。 In addition, in order to obtain various necessary durability and performance, overcoating or undercoating may be performed when printing the ink composition on a sheet. The materials used for these overcoats and undercoats are selected appropriately depending on the application, for example, to give a little acidity to delay the color development a little, or to make it a little thicker to give sweat resistance. The
以下、本発明の印刷構成方法をその実施例を基に具体的に説明する。 Hereinafter, the printing configuration method of the present invention will be specifically described based on the embodiments.
着色剤として赤色染料218号(テトラクロルテトラブロムフルオレセイン)を4重量部、インキバインダーとしてセラック{(株)岐阜セラック製造所社製}を10重量部、またpH調整剤として燐酸を10重量部、更に残量としてエチルアルコールを加えて100重量部とし、これらの混合液を全体が均一になるように撹拌し、無色のインキ組成物を得た。 4 parts by weight of red dye 218 (tetrachlorotetrabromofluorescein) as a colorant, 10 parts by weight of shellac {manufactured by Gifu Shellac Manufacturing Co., Ltd.} as an ink binder, and 10 parts by weight of phosphoric acid as a pH adjuster, Furthermore, ethyl alcohol was added as a remaining amount to make 100 parts by weight, and these mixed liquids were stirred so as to be uniform throughout to obtain a colorless ink composition.
次に、得られた無色のインキ組成物を炭酸カルシウムを含有する透湿性ポリエチレンフィルムに印刷(積層)して無色の印刷物(積層シート)を得、以下の発色試験を行った。 Next, the obtained colorless ink composition was printed (laminated) on a moisture-permeable polyethylene film containing calcium carbonate to obtain a colorless printed matter (laminated sheet), and the following color development test was performed.
印刷物(積層シート)の印刷面(インキ組成物層)に2つ折りのティッシュペーパーを2枚重ねて水を2ml滴下して3分間静置した。その後、ティッシュペーパーを取り除いた。無色の印刷物(積層シート)は、ピンク色に発色していた。 Two folded tissue papers were stacked on the printed surface (ink composition layer) of the printed material (laminated sheet), and 2 ml of water was dropped on the printed surface (ink composition layer) and allowed to stand for 3 minutes. Thereafter, the tissue paper was removed. The colorless printed matter (laminated sheet) was colored pink.
着色剤として赤色染料218号(テトラクロルテトラブロムフルオレセイン)を4重量部、Cyanine Blue 4034{山陽色素(株)社製}を10重量部、インキバインダーとしてセラック{(株)岐阜セラック製造所社製}を10重量部、またpH調整剤として燐酸を10重量部加え更に残量としてメチルアルコールを加えて100重量部とし、これらの混合液を全体が均一になるように撹拌し、青色のインキ組成物を得た。 4 parts by weight of red dye 218 (tetrachlorotetrabromofluorescein) as a colorant, 10 parts by weight of Cyanine Blue 4034 (manufactured by Sanyo Dye Co., Ltd.), and shellac (manufactured by Gifu Shellac Co., Ltd.) as an ink binder } And 10 parts by weight of phosphoric acid as a pH adjuster, and methyl alcohol as a remaining amount to 100 parts by weight. The mixture is stirred so that the whole is uniform, and the blue ink composition I got a thing.
次に、得られた青色のインキ組成物を、炭酸マグネシウムを含有する透湿性ポリエチレンフィルムに印刷する積層方法により、青色の印刷物(積層シート)を得た。
得られた青色の印刷物を用いて、以下の試験を行った。
青色の印刷物(積層シート)の印刷面(インキ組成物層)に2つ折りのティッシュペーパーを2枚重ねて水を2ml滴下して3分間静置したその後に、ティッシュペーパーを取り除いた。青色の印刷物が紫色に変色していた。
Next, a blue printed matter (laminated sheet) was obtained by a laminating method in which the obtained blue ink composition was printed on a moisture-permeable polyethylene film containing magnesium carbonate.
The following tests were performed using the obtained blue printed matter.
Two sheets of folded tissue paper were stacked on the printing surface (ink composition layer) of the blue printed material (laminated sheet), and 2 ml of water was dropped and allowed to stand for 3 minutes, and then the tissue paper was removed. The blue printed product had turned purple.
次に、実際に排尿等のインジケータへの使用を想定しての実験を行った。すなわち、使い捨てのおむつ用の炭酸カルシウムを含有するシートに上記実施例1のインキ組成物を印刷し、更にその上面、赤ん坊の皮膚側へ防湿用のシートをかぶせて乳幼児に装着した。この場合、排尿があれば確実に発色したが、数時間の発汗による水分では発色はなかった。 Next, an experiment was conducted assuming that it was actually used for indicators such as urination. That is, the ink composition of Example 1 was printed on a sheet containing calcium carbonate for disposable diapers, and a moisture-proof sheet was put on the upper surface of the baby's skin side and attached to an infant. In this case, if there was urination, the color was surely developed.
以上、本発明をその好ましい実施の形態に基づいて説明してきたが、本発明は何もそれらに限定されないのは勿論である。すなわち、例えば以下のようにしていてもよい。 As mentioned above, although this invention has been demonstrated based on the preferable embodiment, of course, this invention is not limited to them at all. That is, for example, it may be as follows.
(1)老人や長期療養者用のシーツに使用するため、水分の存在で発色するイン
キ層を挟んで上下に各一層ずつ保護層と塩基性物質(顕色剤)のコーティング層を設け、発汗等での着色は防止している。
(1) For use in sheets for elderly people and long-term care patients, a protective layer and a coating layer of basic substance (developer) are provided on the top and bottom of the ink layer that develops color in the presence of moisture. Coloring with etc. is prevented.
(2)上記(1)にも関係するが、空気中の水分、着用者の発汗等で徐々に発色
するようにし、それにより使用期間の終期や交換時期を知る目安となるようにすることも可能である。またこのため、pH調整剤の含有量や透湿性シートの透湿度も季節、使用期間等を考慮の上定められることとなる。更には複数の場所に異なる種類のインジケータインキ組成物を付着させたり、pH調整剤の配合率、オーバーコートの厚さ等を変化させ、各場所での着色の有無や程度を変えることも可能である。
(2) Although related to (1) above, it is possible to gradually develop color due to moisture in the air, sweating by the wearer, etc., so that it becomes a guide to know the end of the period of use and the replacement period Is possible. For this reason, the content of the pH adjusting agent and the moisture permeability of the moisture permeable sheet are also determined in consideration of the season, period of use, and the like. In addition, it is possible to attach different types of indicator ink compositions to multiple locations, change the blending ratio of pH adjuster, thickness of overcoat, etc., and change the presence or degree of coloring in each location. is there.
Claims (5)
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| JP2003432649A JP2005185643A (en) | 2003-12-26 | 2003-12-26 | Indicator ink composition that develops color by moisture and printing configuration using the same |
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| JP2003432649A JP2005185643A (en) | 2003-12-26 | 2003-12-26 | Indicator ink composition that develops color by moisture and printing configuration using the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011016872A (en) * | 2009-07-07 | 2011-01-27 | Pilot Ink Co Ltd | Granule whose color is changed with water and laminate whose color is changed with water using the same |
| JP2012506915A (en) * | 2008-07-03 | 2012-03-22 | ボスティック インコーポレイテッド | Hot-melt wettability indicating adhesive composition containing an ultraviolet fluorescent agent |
| JP2012170482A (en) * | 2011-02-17 | 2012-09-10 | Seiji Kawashima | Disposable diaper |
| JP2015530448A (en) * | 2012-09-26 | 2015-10-15 | ザ プロクター アンド ギャンブルカンパニー | Liquid activated formulation with solvent-based binding matrix |
| JP2021522093A (en) * | 2018-04-24 | 2021-08-30 | エルカーヴェー エスエー | Manufacturing method of printed non-woven film laminate |
| WO2023026311A1 (en) | 2021-08-21 | 2023-03-02 | 株式会社松井色素化学工業所 | Color change materials and color-changing colorant |
-
2003
- 2003-12-26 JP JP2003432649A patent/JP2005185643A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012506915A (en) * | 2008-07-03 | 2012-03-22 | ボスティック インコーポレイテッド | Hot-melt wettability indicating adhesive composition containing an ultraviolet fluorescent agent |
| JP2011016872A (en) * | 2009-07-07 | 2011-01-27 | Pilot Ink Co Ltd | Granule whose color is changed with water and laminate whose color is changed with water using the same |
| JP2012170482A (en) * | 2011-02-17 | 2012-09-10 | Seiji Kawashima | Disposable diaper |
| US9018435B2 (en) | 2011-02-17 | 2015-04-28 | Kiyoharu Kawashima | Paper diaper |
| JP2015530448A (en) * | 2012-09-26 | 2015-10-15 | ザ プロクター アンド ギャンブルカンパニー | Liquid activated formulation with solvent-based binding matrix |
| JP2021522093A (en) * | 2018-04-24 | 2021-08-30 | エルカーヴェー エスエー | Manufacturing method of printed non-woven film laminate |
| WO2023026311A1 (en) | 2021-08-21 | 2023-03-02 | 株式会社松井色素化学工業所 | Color change materials and color-changing colorant |
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