Patent Grant
9790386
The present invention relates to an ink composition and a two-pack curing ink composition set, that cure by light such as ultraviolet rays. More particularly, it relates to an ink composition and a two-pack curing ink composition set, having excellent film strength and additionally excellent curability. Furthermore, the present invention relates to a recording method and recorded matter, using the ink composition or the two-pack curing ink composition set.
Ink jet recording method is a printing method which conducts printing by flying small droplets of an ink composition and attaching the same to a recording medium such as papers. This ink jet recording method has the characteristic that high resolution and high definition image can be printed at high speed. In general, an ink composition used in an ink jet recording method comprises an aqueous solvent as a main component, and further contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.
On the other hand, where printing is conducted on recording media such as papers and clothes in which an aqueous ink composition is hard to penetrate, or materials such as metals and plastics, in which an aqueous ink composition does not penetrate, such as plates or films produced from phenol, melamine, vinyl chloride, acryl or polycarbonate, an ink composition is required to contain a component that a coloring material can stably be fixed to a recording medium.
To such a demand, a light curing ink jet ink comprising a coloring material, a light curing agent (racially polymerizable compound) and (photoradical) polymerization initiator is disclosed (for example, see Patent Document 1). It is described that this ink can prevent ink from bleeding into a recording medium, and can improve image quality.
Furthermore, to attempt improvement of film strength, chemical resistance, dispersion stability and the like, a light curing ink jet recording ink composition containing a coloring material, a urethane oligomer, a monomer having trifunctional or more reactive group, and an aqueous solvent is developed (see Patent Document 2).
Moreover, for the purpose of preventing separation of a pigment as a coloring material, improving scratch resistance and printing reliability, preventing bleeding after printing and enhancing drying properties of an ink, an ink jet recording ink comprising two components of an ink composition containing a coloring material, and a reaction liquid containing a polymerization initiator, and an ink jet recording method which prints on a recording medium using those two components are disclosed (for example, see Patent Document 3).
An ink jet recording ink comprising such two components is that a photopolymerization initiator and a light curing resin is contained in either of the ink composition or the reaction liquid. Thus, by separating into two components of the ink composition and the reaction liquid, dark reaction is suppressed, making it possible to store the ink composition and the reaction liquid over a long period of time and to obtain prints having excellent light resistance and heat resistance.
Patent Document 1: U.S. Pat. No. 5,623,001
Patent Document 2: JP-A-2000-336295
Patent Document 3: JP-A-8-218018
However, an ultraviolet curing ink composition using an aqueous solvent is that the aqueous medium does not contribute to curing. As a result, water bleeds upon curing, and due to the influence, a cured product does not have smooth edges, lacking in sharpness.
The present invention relates to an ultraviolet curing ink jet ink composition, which overcomes the disadvantages of the prior art, have excellent film strength, chemical resistance and dispersion stability and additionally excellent curability, and can form a clear image. Furthermore, the present invention relates to a recording method, using such ink composition.
As a result of the present inventors having made extensive and intensive investigations, the above objects are achieved by employing the following constitutions, and the present invention has been made.
The ultraviolet curing ink jet ink composition of the present invention contains at least a polymerizable compound and a photopolymerization initiator, and is free from an aqueous solvent, wherein the polymerizable compound comprises at least a urethane oligomer, and wherein the photopolymerization initiator comprises an acylphosphineoxide and α-hydroxyketone, wherein the polymerizable compound comprises an allyl compound and/or an N-vinyl compound. Owing to these features, an ink composition having excellent film strength and additionally excellent curability and capable of forming a clear image can be provided.
The ink composition of the present invention is described in detail below.
The ink composition of the present invention is an ink composition which contains at least a polymerizable compound, a photopolymerization initiator and a coloring material, and does not contain an aqueous solvent, wherein at least a urethane oligomer is contained as the polymerizable compound.
The urethane oligomer in the present invention means a urethane oligomer having at least one urethane bond and radically polymerizable unsaturated double bond in the molecule. The term “oligomer” as used in the present invention means a molecule of a medium size having a structure constituted by small number repetitions, generally from about 2 to 20, of units substantially or conceptually obtained from a molecule having a relative molecular mass (synonymous with a molecular weight).
The urethane oligomer in the present invention has at least one acryloyl group as a functional group, and therefore has the properties of inducing a polymerization reaction with a monomer or the like by ultraviolet irradiation or the like, thereby crosslinking and polymerizing.
The urethane oligomer used in the present invention includes a oligomer generated by an addition reaction of a polyol, a polyisocyanate and a polyhydroxy compound, and additionally includes a polyester type urethane acrylate, a polyether type urethane acrylate, a polybutadiene type urethane acrylate and a polyol type urethane acrylate, depending on a molecular structure constituting a skeleton.
The urethane oligomer used in the present invention has a molecular weight in a range of from about 500 to 20,000, and preferably from about 500 to 10,000.
The content of the urethane oligomer in the ink composition according to the present invention is in a range of from about 1 to 50% by weight, and preferably from about 3 to 30% by weight.
The ink composition according to the present invention preferably contains a photopolymerization initiator for radical polymerization or cationic polymerization as a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound which induces chemical change through action of light or interaction with electron excitation state of a sensitizing dye, thereby generating at least one of radical, acid and base.
The photopolymerization initiator can be used by appropriately selecting from compounds having sensitivity to active light irradiated, such as ultraviolet ray of 400 to 200 nm, far ultraviolet ray, g ray h ray, i ray, KrF excimer laser light, ArF excimer light, electron beam, X ray, molecular beam or ion beam.
Specific photopolymerization initiator can use the conventional initiators known to one skilled in the art, and is specifically described in, for example, Bruce M. Monroe et al., Chemical Revue, 93, 435 (1993); P. S. Davidson, Journal of Photochemistry and Biology A: Chemistry, 73. 81 (1993); J. P. Faussier, “Photoinitiated Polymerization-Theory and Applications”: Rapra Review vol. 9, Report, Rapra Technology (1998); and M. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996). Furthermore, many compounds used in chemical amplification photoresist and photocationic polymerization are described in The Japanese Research Association of Organic Electronics Materials, Imaging Organic Materials, pages 187-192 (1993), Bun-Shin Shuppan. Furthermore, compounds that oxidatively or reductively generate bond cleavage through interaction with electron excitation state of a sensitizing dye, as described in, for example, F. D. Saeva, Topics in Current Chemistry, 156, 59 (1990); G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993); H. B. Shuster et al., JACS, 112, 6329 (1990); and I. D. F. Eaton et al., JACS, 102, 3298 (1980) are known.
Preferable examples of the photopolymerization initiator include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) hexaaryl biimidazole compounds, (e) ketoxime ester compounds, (f) borate compounds, (g) adinium compounds, (h) metallocene compounds, (i) active ester compounds and (j) compounds having carbon-halogen bond.
Preferable examples of the aromatic ketones (a) include compounds having a benzophenone skeleton or a thioxanthone skeleton, described in “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY”, J. P. FOUASSIER, J. F. RABEK (1993), p 77 to 117.
More preferable aromatic ketones (a) include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, α-substituted benzoin compounds described in JP-B-47-22326, benzoin derivatives described in JP-B-47-23664, aroylphosphonic esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, benzoin ethers described in JP-B-60-26403 and JP-A-62-81345, α-aminobenzophenones described in JP-B-1-34242, U.S. Pat. No. 4,318,791 and EP 0284561 A1, p-di(dimethylaminobenzoyl)benzene described in JP-A-2-211452, thiosubstituted aromatic ketones described in JP-A-61-194062, acylphophine sulfides described in JP-B-2-9597, acylphosphines described in JP-B-2-9596, thioxanthones described in JP-B-63-61950 and coumalins described in JP-B-59-42864.
Examples of the aromatic onium salts (b) include elements of Groups V, VI and VII in the periodic table, specifically aromatic onium salts of N, P, As, Sb, Bi, O, S, Se, Te and I. For example, iodonium salts described in European Patent 104143, U.S. Pat. No. 4,837,124, JP-A-2-150848 and JP-A-2-96514; sulfonium salts described in European Patents 370693, 233567, 297443, 297442, 279210 and 422570, and U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760,013, 4,734,444 and 2,833,827; diazonium salts (such as benzene diazonium which may have a substituent); diazonium salt resins (such as formaldehyde resin of diazodiphneylamine); N-alkoxypyridinium salts (for example, described in U.S. Pat. No. 4,743,528, JP-A-63-138345, JP-A-63-142345, JP-A-63-142346 and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate and the like); and compounds described in JP-B-52-147277, 52-14278 and 52-14279 are preferably used.
The organic peroxides (c) include almost all of organic compounds having at least one oxygen-oxygen bond in the molecule, and preferred examples thereof include peroxide ester types such as 3,3′,4,4′-tetra-(t-butylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra-(t-amylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra-(t-hexylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra-(t-octylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra-(t-cumylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra-(t-isopropylcumylperoxycarbonyl)benzo-phenone, and di-t-butylperoxyisophthalate.
Examples of the hexaaryl biimidazole include lophine dimers described in JP-B-45-37377 and JP-B-44-86516 such as 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(m-methoxyphenyl) biimidazole, 2,2′-bis(o,o′-dichlorophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o-nitrophenyl)-4,4′,5,5′-tetraphenyl biimidazole, 2,2′-bis(o-methylphenyl)-4,4′,5,5′-tetraphenyl biimidazole, and 2,2′-bis(o-trifluorophenyl)-4,4′,5,5′-tetraphenyl biimidazole.
Examples of the ketoxime ester include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propoinyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-toluenesulfonyloxyiminobutan-1-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
Examples of the borate salt (f) that is other example of the photopolymerization initiator in the present invention include compounds described in U.S. Pat. Nos. 3,567,453 and 4,343,891, and European Patents 109,772 and 109,773. Examples of the adinium salt compound (g) that is other example of the photopolymerization initiator include compounds having N—O bond described in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537 and JP-B-46-42363.
Examples of the metallocene compound (h) which is other example of the photopolymerization initiator include titanocene compounds described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249 and JP-A-2-4705, and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.
Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluoropheny-1-yl, di-cyclopentadienyl-Ti-2,6-difluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluoropheny-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro-pheny-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheny-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluoropheny-1-yl, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pry-1-yl)phenyl)-titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfone-amide)phenyl]titanium, and bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbiaroyl-amino)phenyl]titanium.
Examples of the active ester compound (i) include nitrobenzyl ester compounds described in European Patents 0290750, 046083, 156153, 271851 and 0388343, U.S. Pat. Nos. 3,901,710 and 4,181,531, JP-A-60-198538 and JP-A-53-133022; iminosulfonate compounds described in European Patents 0199672, 84515, 199672, 044115 and 0101122, U.S. Pat. Nos. 4,618,564, 4,371,605 and 4,431,774, JP-A-64-18143, JP-A-2-245756 and JP-A-4-365048; and compounds described in JP-B-62-6223, JP-B-63-14340 and JP-A-59-174831.
Preferable examples of the compound (j) having carbon-halogen bond include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent 1,388,492, compounds described in JP-A-53-133428, and compounds described in German Patent 3,337,024.
Further examples include compounds described in F. C. Schaefer et al., J. Org. Chem., 29, 1527 (1964), compounds described in JP-A-62-58241, and compounds described in JP-A-5-281728, and additionally include compounds described in German Patent 2,641,100, compounds described in German Patent 3,333,450, compounds described in German Patent 3,021,590, and compounds described in German Patent 3,021,599.
Photoradical polymerization initiators commercially available in trade names of Vicure 10 and 30 (products of Stauffer Chemical), Irgacure 127, 184, 500, 651, 2959, 907, 369, 379, 754, 1700, 1800, 1850, 819, OXE01, Darocur 1173, TPO, IXT (products of Ciba Specialty Chemicals), Quantacure CTX (a product of Aceto Chemical), Kayacure DETX-S (a product of Nippon Kayaku) and ESCURE KIP150 (a product of Lamberti) can also be used.
The photopolymerization initiator is contained in the ink composition according to the present invention in an amount of preferably from 1 to 20% by weight, and more preferably from 3 to 15% by weight. Use of the photopolymerization initiator in the above range exhibits the effect of holding curability without deterioration of cured film strength.
The polymerizable compound other than the urethane oligomer used in the ink composition according to the present invention is not particularly limited and can use any compound regardless of the species of a monomer, an oligomer and a polymer so long as it is a compound which induces polymerization reaction by giving any energy and cures. In particular, the conventional various polymerizable monomers known as photocationically polymerizable monomers and photoradically polymerizable monomers, that induce polymerization reaction by initiation species generated from a photopolymerization initiator are preferably used.
The polymerizable compound can be used alone or a mixture of two or more thereof for the purpose of adjusting reaction rate, ink properties, cured film properties and the like. Furthermore, the polymerizable compound may be a monofunctional compound or a multifunctional compound.
Examples of the cationically polymerizable compound used as the polymerizable compound in the present invention include epoxy compounds, vinyl ether compounds and oxetane compounds, described in, for example, JP-A-6-9714, 2001-31892, 2001-40068, 2001-55507, 2001-310938, 2001-310937 and 2001-220526.
The epoxy compound includes aromatic epoxides and alicyclic epoxides.
Examples of the monofunctional epoxy compound that can be used in the present invention include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-bitadiene monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide and 3-vinylcyclohexene oxide.
Examples of the multifunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclo-hexane carboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane and 1,2,5,6-diepoxycyclooctane.
Of those epoxy compounds, the aromatic epoxide and alicyclic epoxide are preferred from the standpoint of excellent curing rate, and the alicyclic epoxide is particularly preferred.
Examples of the monofunctional vinyl ether that can be used in the present invention include methylvinyl ether, ethylvinyl ether, propylvinyl ether, n-butylvinyl ether, t-butylvinyl ether, 2-ethylhexylvinyl ether, n-nonylvinyl ether, laurylvinyl ether, cyclohexylvinyl ether, cyclohexylmethylvinyl ether, 4-methylcyclohexylmethylvinyl ether, benzylvinyl ether, dicyclopentenylvinyl ether, 2-dicyclopentenoxyethylvinyl ether, methoxyethylvinyl ether, ethoxymethylvinyl ether, butoxyethylvinyl ether, methoxyethoxyethylvinyl ether, ethoxyethoxyethylvinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfurylvinyl ether, 2-hydroxyethylvinyl ether, 2-hydroxypropylvinyl ether, 4-hydroxybutylvinyl ether, 4-hydroxymethylcyclohexylmethylvinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethylvinyl ether, chlorobutylvinyl ether, chloroethoxyethylvinyl ether, phenylethylvinyl ether and phenoxypolyethylene glycol vinyl ether.
Examples of the multifunctional vinyl ether include divinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether and bisphenol F alkylene oxide divinyl ether; and multifunctional vinyl ethers such as trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol hexavinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
The vinyl ether compound is preferably a di- or trivinyl ether compound from the standpoints of curability, adhesion to a medium to be recorded, surface hardness of image formed, and the like, and a divinyl ether compound is particularly preferred.
The oxetane compound in the present invention means a compound having an oxetane ring, and the conventional oxetane compounds as described in JP-A-2001-220526, 2001-310937 and 2003-341217 can optionally be selected and used.
The compound having an oxetane ring that can be used in the present invention is preferably a compound having from 1 to 4 oxetane rings in its structure. Use of such a compound makes it easy to maintain a viscosity of an ink composition in a range of good handling properties, and can obtain high adhesion of ink after curing to a medium to be recorded.
Examples of the monofunctional oxetane used in the present invention include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether, isobornyloxyethyl(3-ethyl-3-oxetanylmethyl)ether, isobornyl(3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, ethyl diethylene glycol(3-ethyl-3-oxetanylmethyl)ether, dicyclopentadiene(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyloxyethyl(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl(3-ethyl-3-oxetanylmethyl)ether, tetrahydrofurfuryl(3-ethyl-3-oxetanylmethyl)ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tetrabromophenoxyethyl(3-ethyl-3-oxetanylmethyl)ether, tribromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tribromophenoxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, butoxyethyl(3-ethyl-3-oxetanylmethyl)ether, pentachlorophenyl(3-ethyl-3-oxetanylmethyl)ether, pentabromo(3-ethyl-3-oxetanylmethyl)ether, and bornyl(3-ethyl-3-oxetanylmethyl)ether.
Examples of the multifunctional oxetane include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3′-(1,3-(2-methylenyl)propanediylbis(oxymethylene)bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl)-ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)-ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether.
Such compounds having an oxetane ring are described in detail in JP-A-2003-341217, paragraphs 0021 to 0048, and the compounds described therein can suitably be used in the present invention.
Of the oxetane compounds used in the present invention, a compound having 1 to 2 oxetane rings is preferably used from the standpoints of viscosity and adhesion of an ink composition.
In the ink composition of the present invention, those polymerizable compounds may be used alone or as mixtures of two or more thereof, other than the urethane oligomer. From the standpoint of effectively suppressing shrinkage at the time of ink curing, at least one oxetane compound and at least one selected from an epoxy compound and a vinyl ether compound are preferably used together.
It is preferred in the present invention to use conventional various radically polymerizable compounds that induce polymerization reaction by initiation species generated from a photoradical initiator, as the polymerizable compound.
Examples of the radically polymerizable monomer include (meth)acrylates, (meth)acryl amides and aromatic vinyls. In the description, when both or any one of “acrylate” and “methacrylate” are intended, it is described “(meth)acrylate”, and when both or any one of “acryl” and “methacryl” are intended, it is described “(meth)acryl”.
The (meth)acrylate used in the present invention includes the following compounds.
Examples of the monofunctional (meth)acrylate include hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, tert-octyl(meth)acrylate, isoamyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, cyclohexyl(meth)acrylate, 4-n-butylcyclohexyl(meth)acrylate, bornyl(meth)acrylate, isobornyl(meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl diglycol(meth)acrylate, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, benzyl (meth)acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, alkoxymethyl (meth)acrylate, alkoxyethyl (meth)acrylate, 2-(2-methoxyethoxyl)ethyl (meth)acrylate, 2-(2-butoxyethoxyl)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H, 1H, 2H, 2H-perfluorodecyl(meth)acrylate, 4-butylphenyl(meth)acrylate, phenyl(meth)acrylate, 2,4,5-tetramethylphenyl(meth)acrylate, 4-chlorophenyl(meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, glycidyl(meth)acrylate, glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate, glycidyloxypropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, hydroxyalkyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acrylate, diethylaminopropyl(meth)acrylate, trimethoxysilylpropyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, polyethylene oxide monomethyl ether (meth)acrylate, oligoethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide (meth)acrylate, oligoethylene oxide (meth)acrylate, oligoethylene oxide monoalkyl ether (meth)acrylate, polyethylene oxide monoalkyl ether (meth)acrylate, dipropylene glycol(meth)acrylate, polypropylene oxide monoalkyl ether (meth)acrylate, oligopropylene oxide monoalkyl ether (meth)acrylate, 2-methacryloyloxythyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol(meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, EO-modified phenol(meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol(meth)acrylate, PO-modified nonylphenol(meth)acrylate, and EO-modified-2-ethylhexyl(meth)acrylate.
Examples of the bifunctional (meth)acrylate include 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl-1,5-pentanediol di(meth)acrylate, butyl ethyl propane di(meth)acrylate, ethoxylated cyclohexane methanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 2-ethyl-2-butyl-butanediol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, polypropylene glycol di(meth)acrylate, oligopropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, 1,9-nonane di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, and tricyclodecane di(meth)acrylate.
Examples of the trifunctional (meth)acrylate include trimethylolpropane(meth)acrylate, trimethylolethane (meth)acrylate, alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropane)ether, isocyanuric acid alkylene oxide-modified tri(meth)acrylate, propionic acid dipentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and ethoxylated glycerin triacrylate.
Examples of the tetrafunctional (meth)acrylate include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, propionic acid dipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.
Examples of the pentafunctional (meth)acrylate include sorbitol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate.
Examples of the hexa(meth)acrylate include dipentaerythritol hexa(methacrylate), sorbitol hexa(methacrylate), alkylene oxide-modified hexa(methacrylate) of phosphazene, and caprolacton-modified dipentaerythritol hexa(meth)acrylate.
Examples of the (meth)acrylamides used in the present invention include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl(meth)acrylamide, N-n-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and (meth)acryloyl morpholine.
Examples of the aromatic vinyls used in the present invention include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenylstyrene, 4-t-butoxycarbonylstyrene, 4-methoxystyrene and 4-t-butoxystyrene.
Examples of the radically polymerizable monomer in the present invention include vinyl esters (vinyl acetate, vinyl propionate, vinyl versatate and the like), allyl esters (allyl acetate and the like), halogen-containing monomers (vinylidene chloride, vinyl chloride and the like), vinyl ethers (methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyvinyl ether, 2-ethylhexylvinyl ether, methoxyethylvinyl ether, cyclohexylvinyl ether, chloroethylvinyl ether and the like), vinyl cyanate ((meth)acrylonitrile and the like), and olefins (ethylene, propylene and the like).
Of those, as the radically polymerizable monomers in the present invention, (meth)acrylates and (meth)acrylamides are preferred from the point of curing rate, and tetrafunctional or more (meth)acrylates are particularly preferred from the point of curing rate. Furthermore, it is preferred to use the multifunctional (meth)acrylates in combination with monofunctional or bifunctional (meth)acrylates, and (meth)acrylamide from the standpoint of viscosity of an ink composition.
It is suitable that the content of the polymerizable compound in an ink composition is from 50 to 95% by mass based on the total solid content of the composition. The content is in a range of preferably from 60 to 92% by weight, and more preferably from 70 to 90% by weight.
It is preferred that the monomer used in the present invention has PII value (Primary Irritation Index) of 2 or less.
Monofunctional monomers, bifunctional monomers and multifunctional monomers, having PII value of 2 or less used in the present invention are shown in Table 1 below.
Viscosity in the above Table is the measurement value at 25° C.
In the present invention, compounds having an allyl group and compounds having an N-vinyl group are preferably used as the polymerizable compound.
The compound having an allyl group as the polymerizable compound in the present invention is the generic name of compounds having a 2-propenyl structure (—CH2CH═CH2). The 2-propenyl group is called an allyl group, and is a common expression in IUPAC nomenclature system.
Examples of the compound having an allyl group include allyl glycol (a product of Nippon Nyukazai Co.); trimethylolpropane diallyl ether, pentaerythritol triallyl ether and glycerin monoallyl ether (products of Daiso Co.); and polyoxyalkylene compounds having an allyl group as trade names of UNIOX, UNIROOVE, POLYCERIN and UNISAFE (products of NOF Corporation).
In the present invention, examples of the compound having an N-vinyl group include N-vinyl formamide, N-vinyl carbazole, N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl caprolactam and their derivatives. N-vinyl formamide is particularly preferred.
Where the addition amount of the allyl group-containing compound and/or N-vinyl formamide is less than 20% by weight, there are problems on viscosity, dispersion stability, storage stability and the like of an ink composition. Where the addition amount exceeds 80% by weight, curability and film strength as an ink composition may be insufficient. Therefore, the addition amount is preferably from 20 to 80% by weight, and more preferably from 20 to 70% by weight.
The ink composition of the present invention may contain a polymerization accelerator.
The polymerization accelerator is not particularly limited, and examples thereof include Darocur EHA and EDB (products of Ciba Specialty Chemicals).
When the polymerizable compound is a radically polymerizable compound, the ink composition of the present invention preferably contains a heat radical polymerization inhibitor. Use of the inhibitor improves storage stability of the ink composition. The heat radical polymerization inhibitor includes Irgastab UV-10 (a product of Ciba Specialty Chemicals).
The ink composition of the present invention can use a surfactant. For example, as a silicone surfactant, it is preferred to use a polyester-modified silicone and a polyether-modified silicone, and it is particularly preferred to use a polyether-modified polydimethylsiloxane or a polyester-modified polydimethylsiloxane. Specific examples thereof include BYK-347, BYK-348, and BYK-UV3500, 3510, 3530 and 3570 (products of BYK-Chemie Japan)
The ink composition of the present invention contains a coloring material.
The coloring material used may be either of dyes and pigments, but use of pigments is advantageous from the point of durability of printed matters.
The dyes used in the present invention can use various dyes generally used in ink jet recording, such as direct dyes, acid dyes, edible dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes and reaction disperse dyes.
The pigments used in the present invention can use inorganic pigments and organic pigments without particular limitation.
The inorganic pigment can use titanium oxide and iron oxide, and additionally can use carbon black produced by the conventional methods such as contact method, furnace method and thermal method. The organic pigment that can be used includes azo pigments (including azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment and the like), polycyclic pigments (for example, phthalocyanine pigment, perylene pigment, perylone pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, thioindigo pigment, isoindolinone pigment and quinofuralone pigment), dye chelates (for example, basic dye chelate and acidic dye chelate), nitro pigments, nitroso pigments and aniline black.
As the specific examples of the pigments, examples of carbon black include C. I. pigment black 7; No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100 and No. 2200, products of Mitsubishi Chemical Corporation; Raven 5750, 5250, 5000, 3500, 1255 and 700, products of Colombian Chemicals; Regal 400R, 330R and 660R, Mogul L and 700, and Monarch 800, 880, 900, 1000, 1100, 1300 and 1400, products of Cabot Corporation; and Color Black FW1, FW2, FW2V, FW18 and FW200, Color Black 5150, S160 and 5170, Printex 35, U, V and 140U, and Special Black 6, 5, 4A and 4, products of Tegussa Co.
Examples of the pigment used in a yellow ink include C. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 180, 185 and 213.
Examples of the pigment used in a magenta ink include C. I. Pigment Red 5, 7, 12, 48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202 and 209, and Pigment Violet 19.
Examples of the pigment used in a cyan ink include C. I. Pigment Blue 1, 2, 3, 15:3, 15:4, 60, 16 and 22.
According to the preferred embodiment of the present invention, the pigment has an average particle diameter in a range of preferably from 10 to 200 nm, and more preferably from about 50 to 150 nm. The addition amount of the coloring material in the ink composition is in a range of preferably from 0.1 to 25% by mass, and more preferably from about 0.5 to 15% by mass.
According to the preferred embodiment of the present invention, those pigments are dispersed in a monomer medium with a dispersing agent or a surfactant to obtain a pigment dispersion, which may be used as an ink composition. Dispersing agents commonly used to prepare a pigment dispersion, for example, a polymer dispersing agent, can be used as the preferred dispersing agent.
Where the ink composition contains a coloring material, the ink composition containing the coloring material may comprise plural ink compositions of respective colors. For example, where in addition to four fundamental colors of yellow, magenta, cyan and black, dark color and/or light color of the same color series are to be added for the respective color, examples thereof include light magenta (light color) and red (dark color) for magenta, light cyan (light color) and blue (dark color) for cyan, and gray and light black (light colors) and mat black (dark color) for black.
Wetting agents, penetrating agents, pH regulators, preservatives, mildewcides and the like may be added to the ink composition of the present invention as conventional other components that can be used in an ink.
Besides, leveling additives, matte agents, and polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins and waxes for adjusting film properties can be added according to need.
When the ink composition of the present invention is used in an ink jet recording method, it is preferred in use that the ink composition has viscosity of 10 mPa·s or less at 25° C.
When the ink composition of the present invention is a light curing ink composition, curing reaction is conducted by light irradiation. When the ink composition of the present invention is an ultraviolet curing ink composition, the ink composition is discharged on a recording medium, and is then irradiated with ultraviolet rays.
When the two-pack curing ink composition set of the present invention is a light curing ink composition set, curing reaction is conducted by mixing an ink composition containing a coloring material and a reaction liquid containing a photopolymerization initiator, and then irradiating with light (preferably ultraviolet rays). Mixing may be conducted before or after printing so long as it is before curing reaction. Specifically, the mixing and printing may have the embodiment that the ink composition containing a coloring material and the reaction liquid containing a photopolymerization initiator are deposited on a recording medium at the same position, or may have the embodiment that the ink composition containing a coloring material and the reaction liquid containing a photopolymerization initiator are mixed, and then deposited on a recording medium.
The two-pack curing ink composition set of the present invention does not have any particular limitation on the formation of the ink composition containing a coloring material and the reaction liquid containing a photopolymerization initiator so long as, in the state of mixing the ink composition containing a coloring material and the reaction liquid containing a photopolymerization initiator, such a mixture is the ink composition according to the present invention as described above (that is, an ink composition that contains at least a polymerizable compound, a photopolymerization initiator and a coloring material, and that does not contain an aqueous solvent, wherein at least a urethane oligomer is contained as the polymerizable compound).
Irradiation light source is not particularly limited, but the irradiation light source is preferably light having a wavelength of from 350 to 450 nm.
Irradiation amount of ultraviolet rays is in a range of from 10 to 20,000 mJ/cm2, and preferably from 50 to 15,000 mJ/cm2. Ultraviolet irradiation amount in a range of such a degree enables curing reaction to sufficiently conduct.
Ultraviolet irradiation is conducted with lamps, and examples of the lamp include metal halide lamp, xenon lamp, carbon arc lamp, chemical lamp, low pressure mercury lamp and high pressure mercury lamp. For example, commercially available lamps such as H lamp, D lamp and V lamp, products of Fusion System, can be used.
Furthermore, ultraviolet irradiation can be conducted with ultraviolet light-emitting semiconductor elements such as ultraviolet light-emitting diode (ultraviolet LED) and ultraviolet light-emitting semiconductor laser.
The recording method of the ink composition and two-pack curing composition set according to the present invention are suitably used in ink jet, UV flexo printing, UV gravure printing and the like, and can form a clear image having excellent film strength and additionally excellent curability.
The present invention will be illustrated in greater detail by reference to the following Examples, but the invention should not be construed as being limited thereto.
(Preparation of Pigment Dispersion)
In the Examples and Comparative Examples, the pigment dispersion was prepared by the following method.
Allyl glycol (a product of Nippon Nyukazai Co.) as a monomer was added to 15% by weight of C. I. Pigment Black 7 (carbon black) as a coloring material and 3.5% by weight of DISCOL N-509 (a product of Dainichiseika Color & Chemicals Mfg. Co.) to make the whole 100% by weight, followed by mixing and stirring to obtain a mixture. This mixture was subjected to dispersion treatment together with zirconia beads (diameter 1.5 mm) for 6 hours using a sand mill (a product of Yasukawa Seisakusho).
Thereafter, zirconia beads were separated with a separator to obtain a black pigment dispersion.
Pigment dispersions corresponding to the respective colors, specifically cyan pigment dispersion 4 (C. I. Pigment Blue 15:3), magenta pigment dispersion (C. I. Pigment Violet 19) and yellow pigment dispersion (C. I. Pigment Yellow 155), were prepared in the same manner as above.
(Preparation of Ink Composition)
In the Examples and the Comparative Examples, a polymerizable compound, a photoradical polymerization initiator and a dispersing agent were mixed and completely dissolved to prepare an ink composition. The above-described pigment dispersion was gradually added dropwise to an ink solvent of the ink composition while stirring the pigment dispersion. After completion of the dropwise addition, the resulting mixture was mixed and stirred at ordinary temperature for 1 hour to obtain an ink composition. The respective ink composition was filtered with a membrane filter of 5 μm to obtain the desired ink composition. Ink compositions of the Examples (Examples 1 to 12) and the Comparative Examples (Comparative Examples 1 to 8) are shown in Tables 2 to 6 (the numerical values in the Tables are “% by weight”).
(Film Characteristic Test)
The above ink composition was put in drops on a glass substrate, and irradiated with ultraviolet rays having a wavelength of 365 nm under the conditions such that irradiation intensity is 17 mW/cm2, irradiation time is 6 seconds and cumulative light amount is 102 mJ/cm2 to cure the ink composition. The ink composition of the Comparative Examples was put in drops as it is on a glass substrate, and subjected to the ultraviolet irradiation and curing treatment.
Visual evaluation of surface state and the like was conducted by the following indexes.
A: Scratches are not formed with nail scrubbing.
B: Curing is not sufficient, and film is peeled with nail scrubbing.
(Bleeding Characteristic Evaluation)
In the above visual evaluation, bleeding characteristic evaluation was conducted on the ink compositions of the Examples and the Comparative Examples by the following indexes.
A: Edge portion is sharply cured.
B: Bleeding out is generated, and edge portion is jagged.
As is apparent from Tables 7 to 11, each ink composition of each Example according to the present invention obtains the satisfactory results in the film characteristic evaluation and the bleeding characteristic evaluation, and can sufficiently be used as an ink composition having excellent film strength and additionally excellent curability.
(Preparation of Pigment Dispersion)
In the Examples and the Comparative Examples, the pigment dispersion was prepared by the following method.
Allyl glycol (a product of Nippon Nyukazai Co.) as a monomer was added to 15% by weight of C. I. Pigment Black 7 (carbon black) as a coloring material and 3.5% by weight of Discol N-509 (a product of Dainichiseika Color & Chemicals Mfg. Co.) to make the whole 100% by weight, followed by mixing and stirring to obtain a mixture. This mixture was subjected to dispersion treatment together with zirconia beads (diameter 1.5 mm) for 6 hours using a sand mill (a product of Yasukawa Seisakusho).
Thereafter, zirconia beads were separated with a separator to obtain a black pigment dispersion.
Pigment dispersions corresponding to the respective colors, specifically cyan pigment dispersion 4 (C. I. Pigment Blue 15:3), magenta pigment dispersion (C. I. Pigment Violet 19) and yellow pigment dispersion (C. I. Pigment Yellow 155), were prepared in the same manner as above.
(Preparation of Two-Pack Light Curing Ink Composition Set)
[Preparation of Reaction Liquid A1-4]
Allyl glycol, tripropylene glycol diacrylate and a photoradical polymerization initiator (Irgacure 819 and 127) were mixed in the formulation (wt %) shown in Table 12 below to completely dissolving those. The resulting mixture was filtered with a membrane filter of 5 μm to obtain reaction liquid A1-4.
[Preparation of Ink Composition B1-4]
Allyl glycol, a urethane oligomer and a dispersing agent were mixed in the formulation (wt %) shown in Table 12 below to completely dissolving those. The above-prepared pigment dispersion (Pigment Black 7, Pigment Blue 15:3, Pigment Violet 19 and Pigment Yellow 155) was added dropwise to the mixture obtained above while stirring (the addition amounts are shown in Table 12 below). After completion of the dropwise addition, the resulting mixture was mixed and stirred at ordinary temperature for 1 hour. The mixture was then filtered with a membrane filter of 5 μm to obtain ink composition B1-4.
Two-pack light curing ink composition sets of Examples 13 to 16 are shown in Table 12.
(Film Characteristic Test)
The reaction liquid (kind A) and the ink composition (kind B) as the two-pack curing ink composition set prepared above were put in drops on a glass substrate and then mixed, and the resulting mixture was irradiated with ultraviolet rays having a wavelength of 365 nm under the conditions such that irradiation intensity is 17 mW/cm2, irradiation time is 6 seconds and cumulative light amount is 102 mJ/cm2 to cure the mixed ink composition. Visual evaluation of surface state and the like was conducted in the same manner as in Example 1. The results are shown in Table 13.
As is apparent from Table 13, according to the two-pack light curing ink composition set according to the present invention, it became possible to form a clear image having excellent film strength and additionally excellent curability.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-323892 | Nov 2006 | JP | national |
| 2007-223824 | Aug 2007 | JP | national |
This application is a continuation of, and claims priority under 35 U.S.C. §120 on, U.S. application Ser. No. 14/095,270, filed Dec. 3, 2013, which is a continuation of application Ser. No. 13/197,174, filed Aug. 3, 2011, now U.S. Pat. No. 8,673,994, which is a continuation of application Ser. No. 11/998,469, filed Nov. 29, 2007, abandoned, which claims priority under 35 U.S.C. §119 on Japanese patent application no. 2007-223824, filed Aug. 30, 2007 and Japanese patent application no. 2006-323892, filed Nov. 30, 2006. The content of each such related application is incorporated by reference herein in its entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3582487 | Fuhr et al. | Jun 1971 | A |
| 3607693 | Heine et al. | Sep 1971 | A |
| 3720635 | Metzner et al. | Mar 1973 | A |
| 3929693 | Hochberg | Dec 1975 | A |
| 4007144 | Sanders et al. | Feb 1977 | A |
| 4129486 | Deutsch et al. | Dec 1978 | A |
| 4133793 | Lewis et al. | Jan 1979 | A |
| 4190602 | Brunisholz et al. | Feb 1980 | A |
| 4233195 | Mills | Nov 1980 | A |
| 4239866 | Reitel et al. | Dec 1980 | A |
| 4239966 | Wang | Dec 1980 | A |
| 4308400 | Felder et al. | Dec 1981 | A |
| 4315807 | Felder et al. | Feb 1982 | A |
| 4318791 | Felder et al. | Mar 1982 | A |
| 4320186 | Kato et al. | Mar 1982 | A |
| 4321118 | Felder et al. | Mar 1982 | A |
| 4347111 | Gehlhaus et al. | Aug 1982 | A |
| 4370379 | Kato et al. | Jan 1983 | A |
| 4450279 | Shirosaki et al. | May 1984 | A |
| 4477681 | Gehlhaus et al. | Oct 1984 | A |
| 4507466 | Tomalia et al. | Mar 1985 | A |
| 4522693 | Henne et al. | Jun 1985 | A |
| 4558120 | Tomalia et al. | Dec 1985 | A |
| 4568737 | Tomalia et al. | Feb 1986 | A |
| 4587329 | Tomalia et al. | May 1986 | A |
| 4631337 | Tomalia et al. | Dec 1986 | A |
| 4694064 | Tomalia et al. | Sep 1987 | A |
| 4721734 | Gehlhaus et al. | Jan 1988 | A |
| 4830902 | Plantenga et al. | May 1989 | A |
| 4922004 | Kohler et al. | May 1990 | A |
| 5041516 | Frechet et al. | Aug 1991 | A |
| 5077402 | Desobry et al. | Dec 1991 | A |
| 5212212 | Fonda | May 1993 | A |
| 5221334 | Ma et al. | Jun 1993 | A |
| 5281682 | Cornforth et al. | Jan 1994 | A |
| 5370976 | Williamson et al. | Dec 1994 | A |
| 5453121 | Nicholls et al. | Sep 1995 | A |
| 5479193 | Shimoda et al. | Dec 1995 | A |
| 5504512 | Shimoda et al. | Apr 1996 | A |
| 5609671 | Nagasawa | Mar 1997 | A |
| 5623001 | Figov | Apr 1997 | A |
| 5662736 | Sakai et al. | Sep 1997 | A |
| 5662738 | Schmid et al. | Sep 1997 | A |
| 5690723 | Sano et al. | Nov 1997 | A |
| 5846306 | Kubota et al. | Dec 1998 | A |
| 5903290 | Nicoloff, Jr. et al. | May 1999 | A |
| 5928419 | Uemura et al. | Jul 1999 | A |
| 5952401 | Kimura et al. | Sep 1999 | A |
| 5958121 | Lin | Sep 1999 | A |
| 5976233 | Osumi et al. | Nov 1999 | A |
| 6030441 | Kubota et al. | Feb 2000 | A |
| 6087416 | Pearlstine et al. | Jul 2000 | A |
| 6114404 | Deeken et al. | Sep 2000 | A |
| 6117606 | Macholdt et al. | Sep 2000 | A |
| 6123759 | Mise et al. | Sep 2000 | A |
| 6136286 | Okuyama et al. | Oct 2000 | A |
| 6179415 | Okazaki et al. | Jan 2001 | B1 |
| 6187897 | Kawashima et al. | Feb 2001 | B1 |
| 6300388 | Verdonck et al. | Oct 2001 | B1 |
| 6322188 | Sano | Nov 2001 | B1 |
| 6331111 | Cao | Dec 2001 | B1 |
| 6332291 | Flosbach et al. | Dec 2001 | B1 |
| 6341841 | Shimada et al. | Jan 2002 | B1 |
| 6395079 | Sano | May 2002 | B1 |
| 6419733 | Sano et al. | Jul 2002 | B1 |
| 6428662 | Woodruff et al. | Aug 2002 | B1 |
| 6433038 | Tanabe et al. | Aug 2002 | B1 |
| 6444019 | Zou et al. | Sep 2002 | B1 |
| 6488751 | Takemoto | Dec 2002 | B1 |
| 6491748 | Watanabe | Dec 2002 | B2 |
| 6518370 | Abuelyaman et al. | Feb 2003 | B2 |
| 6558460 | Walker et al. | May 2003 | B1 |
| 6558753 | Ylitalo et al. | May 2003 | B1 |
| 6602333 | Miyabayashi | Aug 2003 | B2 |
| 6637850 | Shimada et al. | Oct 2003 | B2 |
| 6653367 | Miyabayashi | Nov 2003 | B2 |
| 6654367 | Kaufman | Nov 2003 | B1 |
| 6664306 | Gaddam et al. | Dec 2003 | B2 |
| 6726756 | Zou et al. | Apr 2004 | B1 |
| 6793313 | Adachi et al. | Sep 2004 | B1 |
| 6793318 | Saksa | Sep 2004 | B2 |
| 6846074 | Hirai | Jan 2005 | B2 |
| 6846851 | Nakhmanovich et al. | Jan 2005 | B2 |
| 6849110 | Sano | Feb 2005 | B2 |
| 6869470 | Kato | Mar 2005 | B2 |
| 6877851 | Watanabe | Apr 2005 | B2 |
| 6890049 | Shimada et al. | May 2005 | B2 |
| 6924327 | Sano et al. | Aug 2005 | B2 |
| 6989054 | Tanabe et al. | Jan 2006 | B2 |
| 7008475 | Randler et al. | Mar 2006 | B2 |
| 7025449 | Simons et al. | Apr 2006 | B2 |
| 7040747 | Kubota et al. | May 2006 | B2 |
| 7064153 | Bruck | Jun 2006 | B2 |
| 7156909 | Oyanagi et al. | Jan 2007 | B2 |
| 7259100 | Zurcher et al. | Aug 2007 | B2 |
| 7285592 | Harz et al. | Oct 2007 | B2 |
| 7296883 | Kanaya et al. | Nov 2007 | B2 |
| 7303619 | Oyanagi | Dec 2007 | B2 |
| 7348128 | Yamada et al. | Mar 2008 | B2 |
| 7384472 | Schweikart et al. | Jun 2008 | B2 |
| 7419255 | Kawaguchi et al. | Sep 2008 | B2 |
| 7438405 | Ichizawa et al. | Oct 2008 | B2 |
| 7513945 | Nakano et al. | Apr 2009 | B2 |
| 7538144 | Vanmaele et al. | May 2009 | B2 |
| 7581829 | Oyanagi et al. | Sep 2009 | B2 |
| 7591889 | Stoffel et al. | Sep 2009 | B2 |
| 7604693 | Oyanagi et al. | Oct 2009 | B2 |
| 7619015 | Oyanagi et al. | Nov 2009 | B2 |
| 7670418 | Kato et al. | Mar 2010 | B2 |
| 7732505 | Kito et al. | Jun 2010 | B2 |
| 7753514 | Nakano et al. | Jul 2010 | B2 |
| 7790245 | Oyanagi et al. | Sep 2010 | B2 |
| 7795324 | Loccufier et al. | Sep 2010 | B2 |
| 7850280 | Oyanagi et al. | Dec 2010 | B2 |
| 7854798 | Udagawa et al. | Dec 2010 | B2 |
| 7855041 | Weber et al. | Dec 2010 | B2 |
| 7866807 | Makuta et al. | Jan 2011 | B2 |
| 7893127 | Nagvekar et al. | Feb 2011 | B2 |
| 7968621 | Oyanagi et al. | Jun 2011 | B2 |
| 8044116 | Idemura et al. | Oct 2011 | B2 |
| 8097075 | Oyanagi et al. | Jan 2012 | B2 |
| 8105429 | Oyanagi et al. | Jan 2012 | B2 |
| 8215764 | Sano et al. | Jul 2012 | B2 |
| 20030003296 | Dries et al. | Jan 2003 | A1 |
| 20030017353 | Yamaguchi et al. | Jan 2003 | A1 |
| 20030050379 | Shih et al. | Mar 2003 | A1 |
| 20030085948 | Sekiya | May 2003 | A1 |
| 20030089271 | Hirano et al. | May 2003 | A1 |
| 20030144377 | Sano et al. | Jul 2003 | A1 |
| 20030153649 | Bromberg | Aug 2003 | A1 |
| 20030157356 | Tamura et al. | Aug 2003 | A1 |
| 20030176566 | Wight et al. | Sep 2003 | A1 |
| 20030222959 | Yamanouchi et al. | Dec 2003 | A1 |
| 20030231234 | Ushirogouchi et al. | Dec 2003 | A1 |
| 20040021753 | Yoshihiro et al. | Feb 2004 | A1 |
| 20040069183 | Kamoto et al. | Apr 2004 | A1 |
| 20040099170 | Takabayashi | May 2004 | A1 |
| 20040257419 | Iinuma et al. | Dec 2004 | A1 |
| 20040266907 | Sugita et al. | Dec 2004 | A1 |
| 20050039631 | Best et al. | Feb 2005 | A1 |
| 20050129638 | Dumousseaux | Jun 2005 | A1 |
| 20050158524 | Sloat et al. | Jul 2005 | A1 |
| 20050159501 | Kiefer-Liptak | Jul 2005 | A1 |
| 20050176841 | Krohn | Aug 2005 | A1 |
| 20050176847 | Cagle | Aug 2005 | A1 |
| 20050197418 | Graziano et al. | Sep 2005 | A1 |
| 20050197419 | Graziano et al. | Sep 2005 | A1 |
| 20050282930 | Fu et al. | Dec 2005 | A1 |
| 20060009546 | Brown | Jan 2006 | A1 |
| 20060014849 | Vanmaele et al. | Jan 2006 | A1 |
| 20060014850 | Vanmaele et al. | Jan 2006 | A1 |
| 20060014851 | Loccufier et al. | Jan 2006 | A1 |
| 20060036001 | Oyanagi et al. | Feb 2006 | A1 |
| 20060078695 | Sen et al. | Apr 2006 | A1 |
| 20060092254 | Claes et al. | May 2006 | A1 |
| 20060158493 | Nakano et al. | Jul 2006 | A1 |
| 20060160917 | Oyanagi et al. | Jul 2006 | A1 |
| 20060187285 | Oyanagi et al. | Aug 2006 | A1 |
| 20060189712 | Kondo | Aug 2006 | A1 |
| 20060211788 | Krohn | Sep 2006 | A1 |
| 20060229382 | Schweikart et al. | Oct 2006 | A1 |
| 20060268084 | Nishizaki et al. | Nov 2006 | A1 |
| 20070002119 | Abrott | Jan 2007 | A1 |
| 20070017415 | Oyanagi et al. | Jan 2007 | A1 |
| 20070022547 | O'Brien | Feb 2007 | A1 |
| 20070027239 | Weber et al. | Feb 2007 | A1 |
| 20070031615 | Nair et al. | Feb 2007 | A1 |
| 20070037961 | Oyanagi et al. | Feb 2007 | A1 |
| 20070044684 | Nakano et al. | Mar 2007 | A1 |
| 20070046720 | Konno et al. | Mar 2007 | A1 |
| 20070060670 | Ellis | Mar 2007 | A1 |
| 20070076069 | Edwards et al. | Apr 2007 | A1 |
| 20070120926 | Doumaux et al. | May 2007 | A1 |
| 20070129457 | Nakano et al. | Jun 2007 | A1 |
| 20070142501 | Oyanagi et al. | Jun 2007 | A1 |
| 20070148585 | Kaneko et al. | Jun 2007 | A1 |
| 20070182789 | Sekiya | Aug 2007 | A1 |
| 20070199478 | Schlegl et al. | Aug 2007 | A1 |
| 20070222811 | Yanagi | Sep 2007 | A1 |
| 20070224345 | Metz et al. | Sep 2007 | A1 |
| 20070249750 | Oyanagi et al. | Oct 2007 | A1 |
| 20070281141 | Kohlweyer | Dec 2007 | A1 |
| 20080022893 | Mizutani | Jan 2008 | A1 |
| 20080024577 | Nakano et al. | Jan 2008 | A1 |
| 20080028980 | Aoki et al. | Feb 2008 | A1 |
| 20080090931 | Nagvekar et al. | Apr 2008 | A1 |
| 20080096998 | Oyanagi et al. | Apr 2008 | A1 |
| 20080098928 | Oyanagi et al. | May 2008 | A1 |
| 20080125511 | Nakano et al. | May 2008 | A1 |
| 20080132599 | Nakano et al. | Jun 2008 | A1 |
| 20080145628 | Oyanagi et al. | Jun 2008 | A1 |
| 20080152825 | Mukai et al. | Jun 2008 | A1 |
| 20080152828 | Mukai et al. | Jun 2008 | A1 |
| 20080152877 | Mukai et al. | Jun 2008 | A1 |
| 20080173214 | Oyanagi et al. | Jul 2008 | A1 |
| 20080182083 | Oyanagi et al. | Jul 2008 | A1 |
| 20080182085 | Oyanagi et al. | Jul 2008 | A1 |
| 20080186355 | Sekiya | Aug 2008 | A1 |
| 20080207805 | Blease et al. | Aug 2008 | A1 |
| 20080210570 | Schuster et al. | Sep 2008 | A1 |
| 20080213518 | Oyanagi et al. | Sep 2008 | A1 |
| 20080233362 | Kato et al. | Sep 2008 | A1 |
| 20080250970 | Oyanagi et al. | Oct 2008 | A1 |
| 20080308004 | Deroover et al. | Dec 2008 | A1 |
| 20090053415 | Isobe | Feb 2009 | A1 |
| 20090075036 | Itano et al. | Mar 2009 | A1 |
| 20090081367 | Makuta et al. | Mar 2009 | A1 |
| 20090110827 | Nakano et al. | Apr 2009 | A1 |
| 20090142555 | Sano et al. | Jun 2009 | A1 |
| 20090169834 | Sano et al. | Jul 2009 | A1 |
| 20090208651 | Oyanagi et al. | Aug 2009 | A1 |
| 20090214833 | Oyanagi et al. | Aug 2009 | A1 |
| 20090220695 | Oyanagi et al. | Sep 2009 | A1 |
| 20090233064 | Yatake et al. | Sep 2009 | A1 |
| 20090246479 | Mukai et al. | Oct 2009 | A1 |
| 20090280265 | Oyanagi et al. | Nov 2009 | A1 |
| 20090289973 | Makuta et al. | Nov 2009 | A1 |
| 20090295847 | Mukai et al. | Dec 2009 | A1 |
| 20100009136 | Oyanagi et al. | Jan 2010 | A1 |
| 20100086690 | Aoki | Apr 2010 | A1 |
| 20100086691 | Mukai et al. | Apr 2010 | A1 |
| 20100092674 | Mukai et al. | Apr 2010 | A1 |
| 20100092675 | Aoki | Apr 2010 | A1 |
| 20110014440 | Itano et al. | Jan 2011 | A1 |
| 20110036266 | Oyanagi et al. | Feb 2011 | A1 |
| 20110183124 | Aoki et al. | Jul 2011 | A1 |
| 20110183125 | Aoki et al. | Jul 2011 | A1 |
| 20120006224 | Oyanagi et al. | Jan 2012 | A1 |
| Number | Date | Country |
|---|---|---|
| 1060995 | May 1992 | CN |
| 1086637 | Jun 2002 | CN |
| 1398724 | Feb 2003 | CN |
| 1721462 | Jan 2006 | CN |
| 1771307 | May 2006 | CN |
| 10 2005021160 | Nov 2006 | DE |
| 0 284 561 | Sep 1988 | EP |
| 0 333 224 | Sep 1989 | EP |
| 0 352 821 | Jan 1990 | EP |
| 0 372 778 | Jun 1990 | EP |
| 0 822 011 | Feb 1998 | EP |
| 0 894 835 | Feb 1999 | EP |
| 0 997 507 | May 2000 | EP |
| 1 045 013 | Oct 2000 | EP |
| 1 260 563 | Nov 2002 | EP |
| 1 295 916 | Mar 2003 | EP |
| 1 422 072 | May 2004 | EP |
| 1 445 290 | Aug 2004 | EP |
| 1 452 569 | Sep 2004 | EP |
| 1 566 419 | Aug 2005 | EP |
| 1 614 730 | Jan 2006 | EP |
| 1 616 920 | Jan 2006 | EP |
| 1 616 921 | Jan 2006 | EP |
| 1 666 545 | Jun 2006 | EP |
| 1 674 499 | Jun 2006 | EP |
| 1 752 504 | Feb 2007 | EP |
| 1 806 387 | Jul 2007 | EP |
| 1 815 978 | Aug 2007 | EP |
| 1 837 381 | Sep 2007 | EP |
| 1 852 477 | Nov 2007 | EP |
| 1 892 105 | Feb 2008 | EP |
| 1 942 157 | Jul 2008 | EP |
| 1 942 158 | Jul 2008 | EP |
| 2 210 743 | Apr 2011 | EP |
| 1 276 369 | Jun 1972 | GB |
| 1 547 283 | Jun 1979 | GB |
| 2029433 | Mar 1980 | GB |
| 2 172 655 | Sep 1986 | GB |
| 2 367 299 | Apr 2002 | GB |
| 47-3981 | Feb 1972 | JP |
| 47-6416 | Feb 1972 | JP |
| 47-22326 | Jun 1972 | JP |
| 47-23664 | Jul 1972 | JP |
| 56-028256 | Mar 1981 | JP |
| 57-30704 | Feb 1982 | JP |
| 59-42864 | Oct 1984 | JP |
| 60-26403 | Jun 1985 | JP |
| 60-26483 | Jun 1985 | JP |
| 61-194062 | Aug 1986 | JP |
| 62-1426 | Jan 1987 | JP |
| 62-81345 | Apr 1987 | JP |
| 63-61950 | Nov 1988 | JP |
| 01-34242 | Jul 1989 | JP |
| 01-238656 | Sep 1989 | JP |
| 02-009596 | Mar 1990 | JP |
| 02-009597 | Mar 1990 | JP |
| 2-211452 | Aug 1990 | JP |
| 3-56573 | Mar 1991 | JP |
| 3-79678 | Apr 1991 | JP |
| 3-160068 | Jul 1991 | JP |
| 03-216379 | Sep 1991 | JP |
| 4-18462 | Jan 1992 | JP |
| 05-186725 | Jul 1993 | JP |
| 07-258578 | Oct 1995 | JP |
| 08-003498 | Jan 1996 | JP |
| 08-218018 | Aug 1996 | JP |
| 08-283596 | Oct 1996 | JP |
| 08-295836 | Nov 1996 | JP |
| 10-043675 | Feb 1998 | JP |
| 10-110110 | Apr 1998 | JP |
| 10-110111 | Apr 1998 | JP |
| 10-110114 | Apr 1998 | JP |
| 10-120956 | May 1998 | JP |
| 10-120958 | May 1998 | JP |
| 10-195331 | Jul 1998 | JP |
| 10-195360 | Jul 1998 | JP |
| 10-237349 | Sep 1998 | JP |
| 10-287035 | Oct 1998 | JP |
| 10-330665 | Dec 1998 | JP |
| 11-011002 | Jan 1999 | JP |
| 11-138863 | May 1999 | JP |
| 11-165420 | Jun 1999 | JP |
| 11-193316 | Jul 1999 | JP |
| 11-202558 | Jul 1999 | JP |
| 11-343436 | Dec 1999 | JP |
| 2000-044858 | Feb 2000 | JP |
| 2000-044861 | Feb 2000 | JP |
| 2000-336295 | Dec 2000 | JP |
| 2000-345080 | Dec 2000 | JP |
| 2000-355667 | Dec 2000 | JP |
| 2001-348519 | Dec 2001 | JP |
| 2002-038063 | Feb 2002 | JP |
| 2002-179960 | Jun 2002 | JP |
| 2002-225414 | Aug 2002 | JP |
| 2002-249165 | Sep 2002 | JP |
| 2002-256189 | Sep 2002 | JP |
| 2002-529572 | Sep 2002 | JP |
| 2002-292775 | Oct 2002 | JP |
| 2002-332436 | Nov 2002 | JP |
| 2002-348513 | Dec 2002 | JP |
| 2003-012971 | Jan 2003 | JP |
| 2003-055463 | Feb 2003 | JP |
| 2003-055563 | Feb 2003 | JP |
| 2003-096337 | Apr 2003 | JP |
| 2003-147233 | May 2003 | JP |
| 2003-182113 | Jul 2003 | JP |
| 2003-253148 | Sep 2003 | JP |
| 2003-292836 | Oct 2003 | JP |
| 2003-292857 | Oct 2003 | JP |
| 2003-306625 | Oct 2003 | JP |
| 2003-311945 | Nov 2003 | JP |
| 2003-342499 | Dec 2003 | JP |
| 2004-009359 | Jan 2004 | JP |
| 2004-009360 | Jan 2004 | JP |
| 2004-018716 | Jan 2004 | JP |
| 2004-059857 | Feb 2004 | JP |
| 2004-066817 | Mar 2004 | JP |
| 2004-099796 | Apr 2004 | JP |
| 2004-131645 | Apr 2004 | JP |
| 2004-161852 | Jun 2004 | JP |
| 2004-174971 | Jun 2004 | JP |
| 2004-175906 | Jun 2004 | JP |
| 2004-195797 | Jul 2004 | JP |
| 2004-196838 | Jul 2004 | JP |
| 2004-197055 | Jul 2004 | JP |
| 2004-216654 | Aug 2004 | JP |
| 2004-250659 | Sep 2004 | JP |
| 2004-263139 | Sep 2004 | JP |
| 2004-264435 | Sep 2004 | JP |
| 2004-291604 | Oct 2004 | JP |
| 2004-535506 | Nov 2004 | JP |
| 2004-535508 | Nov 2004 | JP |
| 2004-359960 | Dec 2004 | JP |
| 2005-007577 | Jan 2005 | JP |
| 2005-008690 | Jan 2005 | JP |
| 2005-015813 | Jan 2005 | JP |
| 2005-023284 | Jan 2005 | JP |
| 2005-023299 | Jan 2005 | JP |
| 2005-036079 | Feb 2005 | JP |
| 2005-060411 | Mar 2005 | JP |
| 2005-060419 | Mar 2005 | JP |
| 2005-068251 | Mar 2005 | JP |
| 2005-068252 | Mar 2005 | JP |
| 2005-068439 | Mar 2005 | JP |
| 2005-096194 | Apr 2005 | JP |
| 2005-096254 | Apr 2005 | JP |
| 2005-134738 | May 2005 | JP |
| 2005-161583 | Jun 2005 | JP |
| 2005-187659 | Jul 2005 | JP |
| 2005-220352 | Aug 2005 | JP |
| 2005-290362 | Oct 2005 | JP |
| 2005-298757 | Oct 2005 | JP |
| 2005-314655 | Nov 2005 | JP |
| 2005-350551 | Dec 2005 | JP |
| 2005-536375 | Dec 2005 | JP |
| 2006-070255 | Mar 2006 | JP |
| 2006-117795 | May 2006 | JP |
| 2006-117931 | May 2006 | JP |
| 2006-123529 | May 2006 | JP |
| 2006-123542 | May 2006 | JP |
| 2006-137183 | Jun 2006 | JP |
| 2006-176734 | Jul 2006 | JP |
| 2006-199929 | Aug 2006 | JP |
| 2006-206688 | Aug 2006 | JP |
| 2006-206875 | Aug 2006 | JP |
| 2006-241194 | Sep 2006 | JP |
| 2006-257302 | Sep 2006 | JP |
| 2006-257303 | Sep 2006 | JP |
| 2006-265524 | Oct 2006 | JP |
| 2006-272933 | Oct 2006 | JP |
| 2006-274025 | Oct 2006 | JP |
| 2006-274029 | Oct 2006 | JP |
| 2006-281538 | Oct 2006 | JP |
| 2006-281568 | Oct 2006 | JP |
| 2006-281570 | Oct 2006 | JP |
| 2006-282822 | Oct 2006 | JP |
| 2006-282823 | Oct 2006 | JP |
| 2006-283017 | Oct 2006 | JP |
| 2006-523762 | Oct 2006 | JP |
| 2006-312711 | Nov 2006 | JP |
| 2007-016103 | Jan 2007 | JP |
| 2007-023161 | Feb 2007 | JP |
| 2007-045989 | Feb 2007 | JP |
| 2007-046034 | Feb 2007 | JP |
| 2007-055084 | Mar 2007 | JP |
| 2007-505177 | Mar 2007 | JP |
| 2007-100053 | Apr 2007 | JP |
| 2007-100054 | Apr 2007 | JP |
| 2007-112970 | May 2007 | JP |
| 2007-131741 | May 2007 | JP |
| 2007-138084 | Jun 2007 | JP |
| 2007-154087 | Jun 2007 | JP |
| 2007-169306 | Jul 2007 | JP |
| 2007-169307 | Jul 2007 | JP |
| 2007-169308 | Jul 2007 | JP |
| 2007-169451 | Jul 2007 | JP |
| 2007-191613 | Aug 2007 | JP |
| 2007-211036 | Aug 2007 | JP |
| 2007-254735 | Oct 2007 | JP |
| 2007-262272 | Oct 2007 | JP |
| 2007-269017 | Oct 2007 | JP |
| 2007-270085 | Oct 2007 | JP |
| 2007-297586 | Nov 2007 | JP |
| 2008-138045 | Jun 2008 | JP |
| 2008-155523 | Jul 2008 | JP |
| 2008-155524 | Jul 2008 | JP |
| 2009-113494 | May 2009 | JP |
| 2009-114454 | May 2009 | JP |
| 2009-242441 | Oct 2009 | JP |
| 2010-006062 | Jan 2010 | JP |
| 2010-018651 | Jan 2010 | JP |
| 2010-090270 | Apr 2010 | JP |
| 2010-090271 | Apr 2010 | JP |
| 2010-094809 | Apr 2010 | JP |
| 2010-094852 | Apr 2010 | JP |
| 2012-092252 | May 2012 | JP |
| 9321235 | Oct 1993 | WO |
| 9905230 | Feb 1999 | WO |
| 0052530 | Sep 2000 | WO |
| 0108895 | Feb 2001 | WO |
| 0238687 | May 2002 | WO |
| 02076764 | Oct 2002 | WO |
| 2004018197 | Mar 2004 | WO |
| 2004031308 | Apr 2004 | WO |
| 2004052947 | Jun 2004 | WO |
| 2004087816 | Oct 2004 | WO |
| 2004094534 | Nov 2004 | WO |
| 2004104051 | Dec 2004 | WO |
| 2005047405 | May 2005 | WO |
| 2005061566 | Jul 2005 | WO |
| 2005089957 | Sep 2005 | WO |
| 2005095006 | Oct 2005 | WO |
| 2006041004 | Apr 2006 | WO |
| 2006085992 | Aug 2006 | WO |
| 2006087930 | Aug 2006 | WO |
| 2006098676 | Sep 2006 | WO |
| 2006112031 | Oct 2006 | WO |
| 2007026355 | Mar 2007 | WO |
| 2007026366 | Mar 2007 | WO |
| 2007060264 | May 2007 | WO |
| Entry |
|---|
| European Search Report dated Apr. 21, 2008, EP Application No. 07024545.1-2102. |
| BYK Additives & Instruments, Data Sheet S212, Issue 07/08, BYK-UV 3500 BYK-UV 3510 BYK-UV 3530 BYK-UV 3570, “Surface Additives for Radiation Curable Systems”. |
| CIBA®, ®Ciba Specialty Chemicals Coating Effects, “Ciba® Darocur® EDB Photoinitiator”, Edition Feb. 20, 2003. |
| CIBA®, ®Ciba Secialty Chemicals, “Ciba® IRGASTAB® UV 22”, Coating Effects, 2006. |
| Herbst, et al., Industrial Organic Pigments, Productiion, Properties, Applications, Wiley, Jan. 2004, pp. 572-573. |
| Hawker, C., et al., “Preparation of Polymers with Controlled Molecular Architecture. A New Convergent Approach to Dendritic Macromolecules”, Journal of American Chemistry Society, 1990, 112, pp. 7638-7647. |
| SYSMEX Corporation, Operators Manual, “Flow Particle Image Analyzer FPIA-3000/FPIA-3000S”, Aug. 2010. |
| Eckart “Metalic Effect Pigments, Fundamentals and Applications”, Vicentz Network GmbH & Co KG, 2006. |
| Mimaki, JV3S Series Operation Manual, Mimaki Engineering Co., Ltd., 2003. |
| ONYX Graphics Inc., RIP Software Manual and Users Guide, 1994-2006. |
| Ohta, N., et al. “Color Desktop Printer Technology”, Taylor & Francis Group, Published in 2006, CRC Press. |
| Petition of the Patentee filed in the opposition procedure of EP1942158, dated Sep. 9, 2014. |
| Decision revoking EP1942158, dated Oct. 29, 2014. |
| Saeva, F. D., et al., Topics in Current Chemistry 156, Photoinduced Electron Transfer (PET) Bond Cleavage Reactions, 1990. |
| Final Office Action, U.S. Appl. No. 12/228,193, dated Oct. 14, 2011. |
| Maslak, P., et al., Topics in Current Chemistry, 168, Fragmentations by Photoinduced Electron Transfer Fundamentals and Practical Aspects, 1993. |
| Chatterjee, S., et al., “Photochemistry of Carbocyanine Alkyltriphenylborate Salts: Intra-Ion-Pair Electron Transfer and the Chemistry of Boranyl Radicals”, J. Am. Chem. Soc., 112, pp. 6329-6338, 1990. |
| Eaton, D., et al., “One-electron oxidation of benzyltrialkylstannanes. 1. Cation radical fragmentation by dual modes”, J. Am. Chem. Soc., 1981, 102 (9), pp. 3278-3280 Publication Date: Apr. 1980. |
| Fouassier, J.P., “Photoinitiated Polymerisation—Theory and Applications”, Rapra Review Report, vol. 9, No. 4, 1998. |
| Shiraj, M., et al., “Photoacid and Photobase Generators: Chemistry and Applications to Polymeric Materials”, Prog. Polm. Sci., vol. 21, No. 1, 1996. |
| Office Action, U.S. Appl. No. 12/228,193 dated Jun. 2, 2011. |
| Davidson, R.S., “The chemistry of photoinitiators—some recent developments”, J. Photochem: Photobiol., A: Chem, 73. pp. 81-96, 1993. |
| Fouassier, J.P., et al., Radiation Curing in Polymer Science and Technology, vol. 1, fundamentals and methods, pp. 76-117, 1993. |
| EP Search Report for Application No. 08016440.3, dated Dec. 29, 2008. |
| Search Report for PCT/JP2008/064126 dated Sep. 16, 2008. |
| The Japanese Research Association for Organic Electronics Materials for Imaging, Bunshin Publishing Co., pp. 187-192, 1993. |
| Notice of Allowance, U.S. Appl. No. 12/228,224 dated Oct. 20, 2011. |
| Office Action, U.S. Appl. No. 12/228,224, dated Jun. 2, 2011. |
| Supplemental Notice of Allowance, U.S. Appl. No. 12/228,224, dated Jun. 28, 2012. |
| Step, E.N., et al., “Mechanism of Polymer Stabilization by Hindered-Amine Light Stabilizers (HALS). Model Investigations of the Interaction of Peroxy Radicals with HALS Amines and Amino Ethers”, Macromolecules, American Chemical Society, 27, pp. 2529-2539, 1994. |
| Final Office Action, U.S. Appl. No. 12/894,423, dated May 29, 2012. |
| Office Action, JP2007-304874 dated May 25, 2011, English Translation. |
| Office Action, U.S. Appl. No. 12/394,336, dated Apr. 26, 2012. |
| Shima, K., “2.6 Ink-jet Dyes”, Prospects of Markets of Functional Dyes and Their Applications (Z129), CMC Publishing Co., Ltd., Mar. 5, 1998. |
| European Search Report dated Nov. 2, 2011, Application No. 11177753.8. |
| Office Action, U.S. Appl. No. 12/894,423, dated Nov. 10, 2011. |
| Office Action, U.S. Appl. No. 13/240,667, dated Dec. 12, 2011. |
| Office Action, U.S. Appl. No. 12/228,193, dated Mar. 8, 2012. |
| CIBA, ® Ciba Specialty Chemicals Inc., Coating Effects Segment, Ciba ® IRGACURE ® 819, Photoinitiator, Edition Aug. 30, 2001. |
| Ciba® Ciba Specialty Chemicals Inc., Coating Effects Segment, IRGACURE ® 127, Photoinitiator, Edition Apr. 9, 2004. |
| Kim, Y., “Highly Branched Aromatic Polymers Prepared by Single Step Syntheses”, Macromol. Symp. pp. 21-33, 1994. |
| Hawker, C., et al., “Hyperbranched Poly(ethylene glycol)s: A New Class of Ion-Conducting Materials”, Macromolecules, vol. 29, pp. 3831-3838, 1996. |
| EP Search Report for Application No. 11152226.4, dated May 11, 2011. |
| Ciba® IRGACURE® 369 Photoinitiator, Ciba Specialty Chemicals Coating Effects Segment, Edition Sep. 4, 2001. |
| Final Office Action, U.S. Appl. No. 12/074,308 dated Jun. 8, 2012. |
| Office Action, CN Application No. 200910004654.0, dated Nov. 30, 2010, with English Translation. |
| Office Action, JP Application No. 2007-316368, dated Mar. 9, 2011, with English Translation. |
| Dispersion definition from Hawley's Condensed Chemical Dictionary. |
| Dispersion (chemistry) Wikipedia Definition, Wikipedia the free encyclopedia, Oct. 25, 2010. |
| Monroe, B., et al., “Photoinitiators for Free-Radical-Initiated Photoimaging Systems”, American Chemical Society, Chemical Rev. 93, pp. 435-448, 1993. |
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|---|---|---|---|
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