WO2011036709A1 - 消去可能な液体インク - Google Patents
消去可能な液体インク Download PDFInfo
- Publication number
- WO2011036709A1 WO2011036709A1 PCT/JP2009/004829 JP2009004829W WO2011036709A1 WO 2011036709 A1 WO2011036709 A1 WO 2011036709A1 JP 2009004829 W JP2009004829 W JP 2009004829W WO 2011036709 A1 WO2011036709 A1 WO 2011036709A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- developer
- liquid ink
- solvent
- ink
- color
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000007641 inkjet printing Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000975 dye Substances 0.000 description 19
- 206010047571 Visual impairment Diseases 0.000 description 14
- -1 rhodamine B lactams Chemical class 0.000 description 12
- 238000007639 printing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- LQTIAFFVNAYEGV-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1.OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 LQTIAFFVNAYEGV-UHFFFAOYSA-N 0.000 description 1
- HUYKZYIAFUBPAQ-UHFFFAOYSA-N (2-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1O HUYKZYIAFUBPAQ-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ARWCZKJISXFBGI-UHFFFAOYSA-N (3,4-dihydroxyphenyl)-phenylmethanone Chemical compound C1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 ARWCZKJISXFBGI-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- FIXJGZDPCLYIFP-UHFFFAOYSA-N 1,1'-biphenyl 4-(4-hydroxyphenyl)phenol Chemical compound C1(=CC=C(C=C1)C1=CC=C(C=C1)O)O.C1=CC(=CC=C1)C=1C=CC=CC1 FIXJGZDPCLYIFP-UHFFFAOYSA-N 0.000 description 1
- OPAHUBUOHKIOOL-UHFFFAOYSA-N 1-butyl-2-methylindole Chemical compound C1=CC=C2N(CCCC)C(C)=CC2=C1 OPAHUBUOHKIOOL-UHFFFAOYSA-N 0.000 description 1
- YPTJKHVBDCRKNF-UHFFFAOYSA-N 2',6'-Dihydroxyacetophenone Chemical compound CC(=O)C1=C(O)C=CC=C1O YPTJKHVBDCRKNF-UHFFFAOYSA-N 0.000 description 1
- IXHBSOXJLNEOPY-UHFFFAOYSA-N 2'-anilino-6'-(n-ethyl-4-methylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(CC)C1=CC=C(C)C=C1 IXHBSOXJLNEOPY-UHFFFAOYSA-N 0.000 description 1
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WQXWIKCZNIGMAP-UHFFFAOYSA-N 3',5'-Dihydroxyacetophenone Chemical compound CC(=O)C1=CC(O)=CC(O)=C1 WQXWIKCZNIGMAP-UHFFFAOYSA-N 0.000 description 1
- HOUWRQXIBSGOHF-UHFFFAOYSA-N 3-[4-(diethylamino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=CC=CC=C2C(=O)O1 HOUWRQXIBSGOHF-UHFFFAOYSA-N 0.000 description 1
- ALVNKPZIBFHLEY-UHFFFAOYSA-N 3h-2-benzofuran-1-one;2-phenyl-1h-indole Chemical compound C1=CC=C2C(=O)OCC2=C1.N1C2=CC=CC=C2C=C1C1=CC=CC=C1 ALVNKPZIBFHLEY-UHFFFAOYSA-N 0.000 description 1
- RCVMSMLWRJESQC-UHFFFAOYSA-N 7-[4-(diethylamino)-2-ethoxyphenyl]-7-(1-ethyl-2-methylindol-3-yl)furo[3,4-b]pyridin-5-one Chemical compound CCOC1=CC(N(CC)CC)=CC=C1C1(C=2C3=CC=CC=C3N(CC)C=2C)C2=NC=CC=C2C(=O)O1 RCVMSMLWRJESQC-UHFFFAOYSA-N 0.000 description 1
- WXGMATMDAOFIIZ-UHFFFAOYSA-N C(C)C1=C(C(=O)O)C=C(C(=C1O)O)O.OC=1C=C(C(=O)OCC)C=C(C1O)O Chemical compound C(C)C1=C(C(=O)O)C=C(C(=C1O)O)O.OC=1C=C(C(=O)OCC)C=C(C1O)O WXGMATMDAOFIIZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical class C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002476 indolines Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QFVDKARCPMTZCS-UHFFFAOYSA-N methylrosaniline Chemical compound C1=CC(N(C)C)=CC=C1C(O)(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 QFVDKARCPMTZCS-UHFFFAOYSA-N 0.000 description 1
- 229960003926 methylrosaniline Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 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
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/18—Erasure; Erasable marking; Non-permanent marking
Definitions
- the present invention relates to a liquid ink capable of decoloring an image by heating or contact with a solvent.
- a decoloring agent By adding a decoloring agent to a composition containing a leuco dye and a developer, a colored state is stably present at a temperature near room temperature, and the treatment with heat or a solvent causes long-term erasing at a practical temperature.
- An image forming material that fixes the color state has been proposed as an effective paper reuse technique.
- image forming materials have high stability in the coloring / decoloring state of images, and in addition, the material safety is high. It is compatible with electrophotographic toner, liquid ink, ink ribbon, and writing utensils, and has the advantage that large-scale erasure processing is possible.
- liquid ink a decolorable water-based ink having a uniform particle size, a dark color, and not fading is disclosed (for example, see Patent Document 1).
- the erasable water-based ink is a pigment particle dispersion (emulsion) ink and may cause nozzle clogging when applied to ink jet printing. Therefore, there has been a demand for water-soluble liquid ink that can be applied to ink jet printing and simultaneously satisfies the color developability of an image during printing and the image erasability during heating or solvent treatment.
- emulsion pigment particle dispersion
- the present invention provides a water-soluble erasable liquid ink that simultaneously satisfies the color developability of an image during printing and the image erasability during heating or solvent treatment and can be applied to inkjet printing. Objective.
- the erasable liquid ink according to the present invention contains a leuco dye, a developer and a solvent, and the developer is represented by the general formula [Chemical Formula 1] or [Chemical Formula 2].
- a water-soluble erasable liquid ink that can satisfy the color developability of an image at the time of printing and the image erasability at the time of heating or solvent treatment and can be applied to ink jet printing.
- the liquid ink 1 contains a leuco dye 2, a developer 3, a water-soluble organic solvent 4 and water 5 (hereinafter, the water-soluble organic solvent and water are collectively referred to as a solvent). is doing.
- the leuco dye 2 and the developer 3 are in a free state, the leuco dye 2 and the developer 3 are combined as shown in FIG. 1 (b) as the solvent is evaporated by printing or coating on paper or the like.
- Image 6 is formed. In order to obtain good color developability of the image 6, it is important that after printing or the like, the solvent is quickly evaporated, and the leuco dye 2 and the developer 3 are separated from the solvent and bonded to each other.
- the affinity between the leuco dye 2 and the developer 3 and the solvent can be controlled by their selection. That is, by selecting the leuco dye 2 and the developer 3 having a low affinity with the water 5, the leuco dye 2 and the developer 3 are quickly combined with each other to develop a color.
- the affinity between the developer 3 and the water 5 should be taken into consideration.
- the developer contained in the erasable liquid ink of the present invention has a specific structure represented by the general formula [Chemical Formula 1] or [Chemical Formula 2]. And is applicable to inkjet printing. This is because, as described above, the developer has a relatively low affinity with water, is itself colorless, and does not develop color upon heating.
- the content of the developer is preferably 15 mol equivalent or more with respect to the leuco dye. This is because the equilibrium reaction shown in [Equation 1] proceeds in the direction of color development according to the law of mass action. If it is less than 15 mol equivalent, a sufficient image density cannot be obtained, which is not preferable.
- the content of the developer is preferably less than the solubility in the solvent. This is because when the developer content reaches the solubility in the solvent, the developer precipitates when storing the liquid ink, thereby inducing a decrease in color developability and a decrease in ink discharge performance.
- leuco dye examples of the leuco dye contained in the erasable liquid ink of the present invention include electron-donating organic substances such as diarylphthalides, polyarylcarbinols, rhodamine B lactams, indolines, spiropyrans, and fluorans. .
- crystal violet lactone (hereinafter referred to as CVL), 2-anilino-6- (N-cyclohexyl-N-methylamino) -3-methylfluorane, 2-anilino-3-methyl-6- (N-methyl-N-propylamino) fluorane, 3- [4- (4-phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluorane, 2-anilino-6- (N-methyl- N-isobutylamino) -3-methylfluorane, 2-anilino-6- (dibutylamino) -3-methylfluorane, 3-chloro-6- (cyclohexylamino) fluorane, 2-chloro-6- (diethylamino) Fluorane, 7- (N, N-dibenzylamino) -3- (N, N-diethylamino) fluorane, 3,6-bis (diethylamino
- leuco dyes can be used alone or in combination of two or more. Appropriate selection of leuco dyes enables easy color handling since various color development states can be obtained.
- particularly suitable materials are triphenylmethane, fluoran, and phenylindole-phthalide leuco dyes.
- the solvent contained in the liquid ink of the present invention includes a water-soluble organic solvent and water.
- water-soluble organic solvent examples include alcohols, glycols, glycol monoalkyl ethers, and glycol dialkyl ethers.
- alcohols and glycol monoalkyl ethers are particularly preferable from the viewpoint of image color developability, and more specifically, ethanol, propylene glycol monomethyl ether, propanol, ethylene glycol-n-butyl ether, ethylene glycol-t. -Butyl ether is preferred.
- the water content is desirably 10 wt% or more and 40 wt% or less with respect to the entire solvent. This is because if it is less than 10 wt%, the ink ejection stability in ink jet printing is clearly reduced. Further, if it exceeds 40 wt%, the image density is remarkably lowered.
- a compound such as a surfactant and glycol ether can be appropriately added as necessary from the viewpoint of ejection stability and storage stability.
- Example 1 In a screw vial (20 mL) with a magnetic stirring bar, 50 mg (0.12 mmol) of crystal violet lactone (hereinafter referred to as CVL) as a leuco dye and 2,4′-dihydroxy as a developer Add 546 mg (2.7 mmol) of diphenylmethane (2.7 mmol), 3 g of pure water, and 6 g of propylene glycol monomethyl ether (hereinafter referred to as PGMME) as a water-soluble organic solvent, and stir well at room temperature for 1 hour. did. The resulting suspension was filtered to give a colorless solution.
- CVL crystal violet lactone
- PGMME propylene glycol monomethyl ether
- the image density of the obtained image was calculated as follows.
- the reflectance of a solid image was measured using a color difference meter (CR-300; manufactured by Konica Minolta), and this was converted into an image density using the following [Equation 2].
- the image density thus obtained was as high as 0.40 (including background density: 0.091).
- the image was heated in a thermostatic bath at 130 ° C. for 60 minutes, and the color difference with respect to the background color of the obtained afterimage was calculated.
- the color difference is a distance in a color space of the La * b * color system of two colors, and is obtained by the following equation (3).
- a clear correlation is established between the color difference of the afterimage with respect to the background color and the degree of visual recognition of the afterimage. For this reason, the color difference of the afterimage with respect to the background color was used as an index of erasability.
- the afterimage color difference calculated from the following [Equation 3] was as small as 0.28, and the afterimage was visually unrecognizable.
- Example 2 The same operation as in Example 1 was carried out except that the developer was changed to 500 mg (2.3 mmol) of 2,4-dihydroxybenzophenone (2,4-dihydroxybenzophenone). The resulting solution was light blue.
- Examples 3 to 7 The same operation as in Example 1 was performed using 4-a-cumylphenol, bisphenol F, bisphenol A, HDP-24, and 3,5-dihydroxyacetophenone as the developer. As shown in Table 1, the obtained liquid ink was confirmed to have high values for both color developability and erasability.
- Example 1 The same operation as in Example 1 was performed except that 500 mg (2.5 mmol) of 2,4-dihydroxydiphenylmethane was used as the developer. The resulting solution was light orange.
- the inkjet dischargeability was stable.
- the resulting image density was as high as 0.43 (including background density: 0.084).
- Example 2 The same operation as in Example 1 was performed except that the color developer was changed to 500 mg (2.7 mmol) of 4,4′-biphenyl (4,4′-biphenol). The resulting solution was light blue.
- the inkjet dischargeability was stable.
- the obtained image density was as low as 0.11 (including background density: 0.086).
- Example 3 The same operation as in Example 1 was performed except that the color developer was changed to 500 mg (2.5 mmol) of ethyl-3,4,5-trihydroxybenzoate (ethyl-3,4,5-trihydroxybenzoate). The resulting solution was blue.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
まず、本発明の液体インクの発色のメカニズムについて説明する。図1(a)のように液体インク1は、ロイコ色素2、顕色剤3、水溶性有機溶剤4および水5(以下、この水溶性有機溶剤および水を併せて溶媒と記載する)を含有している。ロイコ色素2と顕色剤3は遊離した状態にあるが、紙などに印刷または塗布され溶媒が蒸発するに従い、図1(b)のように、ロイコ色素2と顕色剤3は結合して画像6を形成する。画像6が良好な発色性を得るためには、印刷等をしたのち、溶媒を速やかに蒸発させ、ロイコ色素2と顕色剤3を溶媒から分離し、互いに結合させることが重要である。
本発明の消色可能な液体インクに含有するロイコ色素には、ジアリールフタリド類、ポリアリールカルビノール類、ローダミンBラクタム類、インドリン類、スピロピラン類、フルオラン類などの電子供与性有機物が挙げられる。具体的には、クリスタルバイオレットラクトン(以下、CVLと記載する)、2-アニリノ-6-(N-シクロヘキシル-N-メチルアミノ)-3-メチルフルオラン、2-アニリノ-3-メチル-6-(N-メチル-N-プロピルアミノ)フルオラン、3-[4-(4-フェニルアミノフェニル)アミノフェニル]アミノ-6-メチル-7-クロロフルオラン、2-アニリノ-6-(N-メチル-N-イソブチルアミノ)-3-メチルフルオラン、2-アニリノ-6-(ジブチルアミノ)-3-メチルフルオラン、3-クロロ-6-(シクロヘキシルアミノ)フルオラン、2-クロロ-6-(ジエチルアミノ)フルオラン、7-(N,N-ジベンジルアミノ)-3-(N,N-ジエチルアミノ)フルオラン、3,6-ビス(ジエチルアミノ)フルオラン-γ-(4’-ニトロ)アニリノラクタム、3-ジエチルアミノベンゾ[a]-フルオラン、3-ジエチルアミノ-6-メチル-7-アミノフルオラン、3-ジエチルアミノ-7-キシリジノフルオラン、3-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリド、3-(4-ジエチルアミノフェニル)-3-(1-エチル-2-メチルインドール-3-イル)フタリド、3-ジエチルアミノ-7-クロロアニリノフルオラン、3-ジエチルアミノ-7,8-ベンゾフルオラン、3,3-ビス(1-n-ブチル-2-メチルインドール-3-イル)フタリド、3,6-ジメチルエトキシフルオラン、3-ジエチルアミノ-6-メトキシ-7-アミノフルオラン、DEPM、ATP、ETAC、2-(2-クロロアニリノ)-6-ジブチルアミノフルオラン、クリスタルバイオレットカルビノール、ローダミンBラクタム、2-(フェニルイミノエタンジリデン)-3,3-ジメチルインドリン、N-3,3-トリメチルインドリノベンゾスピロピラン、8’-メトキシ-N-3,3-トリメチルインドリノベンゾスピロピラン、3-ジエチルアミノ-6-メチル-7-クロロフルオラン、3-ジエチルアミノ-7-メトキシフルオラン、3-ジエチルアミノ-6-ベンジルオキシフルオラン、1,2-ジベンゾ-6-ジエチルアミノフルオラン、3,6-ジ-p-トルイジノ-4,5-ジメチルフルオラン、フェニルヒドラジド-γ-ラクタム、3-アミノ-5-メチルフルオランなどが挙げられる。これらは1種または2種以上を混合して用いることが可能である。ロイコ色素を適宜選択すれば多様な色の発色状態が得られることからカラー対応も容易である。これらの中で、特に適している材料は、トリフェニルメタン系、フルオラン系、フェニルインドール-フタリド系のロイコ色素である。
本発明の液体インクに含有する溶媒は、水溶性有機溶剤と水を含む。
磁気攪拌子を付したスクリューバイアル(20mL)に、ロイコ色素としてクリスタルヴァイオレットラクトン(Crystal Violet Ractone;以下、CVLと記載する)を50mg(0.12 mmol)、顕色剤として2,4’-ジヒドロキシジフェニルメタン(2,4’-dihydroxydiphenylmethane)546mg(2.7mmol)、純水3g、および水溶性有機溶剤としてプロピレングリコールモノメチルエーテル(propylenegrycholmonomethylrther ;以下、PGMMEと記載する)6gを入れ、室温で1時間良く攪拌した。得られた懸濁液を濾過すると、無色の溶液が得られた。
顕色剤を2,4-ジヒドロキシベンゾフェノン(2,4-dihydroxybenzophenone)500mg(2.3mmol)とした以外は、実施例1と同様の操作を行った。得られた溶液は淡青色であった。
顕色剤として、4-a-クミルフェノール、ビスフェノールF、ビスフェノールA、HDP-24、3,5-dihydroxyacetophenoneをそれぞれ用い、実施例1と同様の操作を行った。得られた液体インクは表1のように発色性および消去性ともに高い値が確認された。
顕色剤を2,4-ジヒドロキシジフェニルメタン(2,4-dihydroxydiphenylmethane)500mg(2.5mmol)とした以外は、実施例1と同様の操作を行った。得られた溶液は淡橙色であった。
顕色剤を4、4’-ビフェニル(4,4’-biphenol)500mg(2.7mmol)とした以外は、実施例1と同様の操作を行った。得られた溶液は淡青色であった。
顕色剤をエチル-3,4,5-トリヒドロキシベンゾエート(ethyl-3,4,5-trihydroxybenzoate)500mg(2.5mmol)とした以外は、実施例1と同様の操作を行った。得られた溶液は青色であった。
2 ロイコ色素
3 顕色剤
4 水溶性有機溶剤
5 水
6 画像
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CN200980161573XA CN102549084A (zh) | 2009-09-24 | 2009-09-24 | 可消色的液体油墨 |
JP2011532793A JP5398840B2 (ja) | 2009-09-24 | 2009-09-24 | 消去可能な液体インク |
PCT/JP2009/004829 WO2011036709A1 (ja) | 2009-09-24 | 2009-09-24 | 消去可能な液体インク |
US13/428,167 US8506696B2 (en) | 2009-09-24 | 2012-03-23 | Erasable liquid ink |
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WO (1) | WO2011036709A1 (ja) |
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CN102558952A (zh) * | 2012-01-06 | 2012-07-11 | 浙江大学 | 不可逆热致消色油墨及其调制方法 |
JP2012224789A (ja) * | 2011-04-21 | 2012-11-15 | Toshiba Corp | 消去可能インクジェットインク |
JP2013028727A (ja) * | 2011-07-28 | 2013-02-07 | Toshiba Corp | 消去可能な液体インク |
CN104024350A (zh) * | 2011-12-31 | 2014-09-03 | 桑福德有限合伙人公司 | 不可逆热致变色墨水组合物 |
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Also Published As
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JP5398840B2 (ja) | 2014-01-29 |
US8506696B2 (en) | 2013-08-13 |
US20120227623A1 (en) | 2012-09-13 |
CN102549084A (zh) | 2012-07-04 |
JPWO2011036709A1 (ja) | 2013-02-14 |
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