Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
  • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
  • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
  • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
  • B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
• • 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
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

• the present invention relates to a liquid composition, an ink jet recording method, ink jet recording apparatus and a recorded image.
• An ink jet recorded image in particular, a recorded image formed with an aqueous ink involves a problem on fastness properties such as water fastness and scratch resistance. As measures to solve this problem, it has been known in recent years to use an ink jet ink containing an emulsion.
• a technique for forming a fast image is mentioned a technique of using an aqueous liquid composition containing a water-insoluble polymer present in a state of an emulsion.
• a water-insoluble polymer present in the state of the emulsion in the liquid composition hereinafter also referred to as a polymer emulsion
• the polymer emulsion aggregates to form a film as the water around the emulsion decreases.
• the film formed can protect an image formed on the recording medium to improve the fastness of the image.
• the above-described technique has caused the following problems in some cases.
• the polymer held in the state of the emulsion in an aqueous medium has caused in some cases destruction of the emulsion structure due to storage under a severe environment (high temperature, vibration), long-term storage or an influence by the pH of a coloring material upon addition of the coloring material into the liquid composition to cause deposition of polymer components.
• the liquid composition containing the polymer emulsion has been applied to a recording medium, in some cases, the filming (aggregation) of the polymer emulsion has rapidly progressed to make the film formed uneven, and consequently the quality of the resulting image has become insufficient, and the fastness has not been sufficiently improved.
• WO01/057145 describes a technique for improving the fastness of an image with a liquid composition containing acroylmorpholine.
• an object of the present invention to provide an aqueous liquid composition curable by irradiation of active energy rays, also suitably usable as an ink containing a coloring material, excellent in stability, and capable of forming a uniform film and imparting high fastness to an image.
• Another object of the present invention is to provide an ink jet recording method and an ink jet recording apparatus using the liquid composition, and a recorded image.
• an aqueous liquid composition comprising a water-soluble monomer, a photopolymerization initiator and an aqueous medium and further comprising a polymer emulsion, wherein the water-soluble monomer is a monomer that has two or more ethylenically unsaturated bonds and is curable with an active energy ray.
• an ink jet recording method and an ink jet recording apparatus using the liquid composition and a recorded image formed by the ink jet recording method.
• an aqueous liquid composition curable by irradiation of active energy rays also suitably usable as an ink containing a coloring material, excellent in stability, and capable of forming a uniform film and imparting high fastness to an image.
• an ink jet recording method and an ink jet recording apparatus using the liquid composition, and a recorded image are also provided.
• aqueous liquid composition containing a polymer emulsion and a water-soluble monomer that has two or more ethylenically unsaturated bonds and is curable with an active energy ray is excellent in the following respects, thus leading to completion of the present invention.
• the liquid composition can form a uniform film on an image obtained by irradiation of active energy rays, is excellent in fastness such as the crosslinking degree of a cured product of the water-soluble monomer and adhesion between the cured product and a film formed by the polymer emulsion and also satisfies the level of low viscosity required in ink jet recording applications.
• the liquid composition is excellent in long-term storage stability and ejection stability (also referred to as stability merely) required in aqueous liquid compositions in particular.
• the reason why the liquid composition according to the present invention, which contains the above-described specific water-soluble monomer, can form a uniform film and achieves excellent results in curing performance and stability is not clearly known.
• the present inventors speculate as follows.
• the monomer used in the present invention has a hydroxyl group or an ethylene oxide group and thus exhibits specific water-solubility (hydrophilicity). Accordingly, the water-soluble monomer can hold water in the liquid composition like a high-boiling alcoholic solvent.
• the water-soluble monomer can gradually release the water held upon formation of a film formed by the polymer emulsion, so that it is supposed that the monomer can function as an ideal aid agent to inhibit the rapid aggregation of the polymer emulsion so as to gradually form a film.
• the mechanism with which the curing performance of the liquid composition according to the present invention is improved is presumed to be as follows.
• the water-soluble monomer used in the present invention is cured in a film formed by the emulsion upon irradiation of active energy rays unlike a conventional aid agent liable to remain in a liquid state in the film, so that the fastness of the film obtained from the emulsion can be improved.
• the water-soluble monomer can form the film together with the polymer emulsion, so that an extremely fast film can be formed compared with the case where the water-soluble monomer alone or the polymer emulsion alone is used.
• the active energy ray used in the present invention may be used ultraviolet rays or electron rays. Description is given below taking a liquid composition of such a type that radical polymerization take place by ultraviolet rays to be cured, as a typical example. However, the application range of the present invention is not limited by this example at all.
• the liquid composition according to the present invention can exhibit a particularly marked effect on a recording medium which has liquid absorbability but is hard to improve the color of a pigment and scratch resistance, such as plain paper.
• a recording medium with low liquid absorbability of the aqueous liquid composition or a non-absorbent recording medium made of a metal or plastic may also be used.
• the liquid composition according to the present invention contains a polymer emulsion.
• the polymer emulsion means a water-insoluble polymer present in a state of an emulsion in the liquid composition.
• the water-insoluble polymer means a polymer having a solubility of 1% by mass or less in water under normal conditions (ordinary temperature, ordinary pressure, ordinary humidity).
• the polymer emulsion used in the present invention is favorably made up by a thermoplastic resin capable of forming a film.
• the weight average molecular weight (Mw) of the polymer is favorably within a range of 5,000 or more and 10,000 or less.
• a monomer usable for obtaining the polymer emulsion according to the present invention No particular limitation is imposed on a monomer usable for obtaining the polymer emulsion according to the present invention.
• the following monomer may be suitably used.
• Specific examples thereof include styrene, acrylic esters such as methyl acrylate and ethyl acrylate, vinyl chloride, vinyl acetate, acrylic acid, and methacrylic acid.
• the average particle size of the polymer emulsion is favorably within a range of 0.01 ⁇ m or more and 2 ⁇ m or more.
• the average particle size of the polymer emulsion can be determined by measuring its d50 particle diameter that is a median diameter by means of a laser light scattering type particle size measuring apparatus.
• the polymer making up the polymer emulsion is favorably a polymer of a structure having a plurality of groups polymerizable by irradiation of active energy rays.
• the polymer emulsion according to the present invention may also be used a commercially available polymer emulsion.
• Examples of the commercially available polymer emulsion include VINYBLAN 277 (emulsion of a vinyl chloride-acrylic ester copolymer, available from Nisshin Chemical Industries Co., Ltd.), JONCRYL 537J (emulsion of a styrene-acrylic acid copolymer, available from BASF Japan Ltd.) and UCECOAT 7655 (polymer emulsion having a plurality of groups polymerizable by irradiation of active energy rays, available from DAICEL-CYTEC COMPANY LTD.).
• VINYBLAN 277 emulsion of a vinyl chloride-acrylic ester copolymer, available from Nisshin Chemical Industries Co., Ltd.
• JONCRYL 537J emulsion of a styrene-acrylic acid copolymer, available from BASF Japan Ltd.
• UCECOAT 7655 polymer emulsion having a plurality of groups polymerizable by
• the polymer emulsion used in the present invention is favorably contained in a content range of 1.0% by mass or more and 40.0% by mass or less based on the total mass of the liquid composition.
• the monomer used in the present invention is water-soluble.
• the water-solubility in the water-soluble monomer means that the monomer is dissolved in water in an amount of 5% by mass or more under normal conditions (ordinary temperature, ordinary pressure, ordinary humidity). Accordingly, the water-solubility in the present invention means the so-called hydrophilicity. When a monomer exhibits the hydrophilicity of this extent, it can be present stably in the aqueous liquid composition.
• the monomer exhibiting the water-solubility is favorably used a monomer having one or more hydroxyl groups.
• a monomer achieving the water-solubility by another group alone than the hydroxyl group such as a monomer having an ethylene oxide group, is used when the monomer achieving the water-solubility by the hydroxyl group is used, so that higher fastness can be imparted to the resulting image.
• the water-soluble monomer used in the present invention is a monomer having two or more ethylenically unsaturated bonds in its structure and curable with active energy rays.
• Examples of the monomer having ethylenically unsaturated bonds and curable with active energy rays include monomers having functional groups such as a (meth)acryl group and a (meth)acrylamide group.
• the water-soluble monomer according to the present invention has two or more ethylenically unsaturated bonds and thus has two or more such functional groups as described above.
• the liquid composition according to the present invention contains the above-described specific water-soluble monomer and may further contain any other monomer than this monomer.
• the water-soluble monomer used in the present invention favorably has a molecular structure satisfying the relationship of the following expression (1)
• the expression (1) means the proportion of molecules making up the ethylenically unsaturated bonds in the water-soluble monomer.
• a group making up an ethylenically unsaturated bond means CR 1 R 2 ⁇ CR 3 R 4 (R 1 to R 4 being arbitrary groups)
• R 1 to R 4 being arbitrary groups
• the lowest molecular weight of the groups making up the ethylenically unsaturated bond i.e., the molecular weight (28.05) of ethylene, in which R 1 to R 4 are all H, was used to calculate the proportion of molecules considered to substantially contribute to the ethylenically unsaturated bonds in the water-soluble monomer.
• the water-soluble monomer satisfies the relationship of the expression (1), whereby the strength of the film cured can be strengthened.
• the water-soluble monomer according to the present invention may further have any other functional group than the hydroxyl group, the ethylene oxide group and the group having the unsaturated double bond in its structure.
• a functional group include a carboxyl group, a sulfonic group, a phosphoric group, an amino group and salts thereof, an amide group, an amide linkage group, an ester linkage group, and a sulfone linkage group.
• the molecular weight of the water-soluble monomer according to the present invention is favorably within a range of 200 or more and 2,000 or less.
• the water-soluble monomer according to the present invention is dissolved in water in an amount of 5% by mass or more, and is more favorably dissolved in an amount of 20% by mass or more.
• the water-soluble monomer used in the present invention it is satisfactory for the water-soluble monomer used in the present invention to have 2 or more ethylenically unsaturated bonds. Since a faster film can be formed as the number of the ethylenically unsaturated bonds increases, no particular limitation is imposed on the upper limit of the number thereof. However, since there is a tendency for the viscosity of the liquid composition to increase as the number of the ethylenically unsaturated bonds in the water-soluble monomer increases, the number of the ethylenically unsaturated bonds is favorably 2 to 6. The number of the ethylenically unsaturated bonds in the water-soluble monomer is more favorably 3 or 4.
• a synthesis process for the water-soluble monomer used in the present invention is not limited at all, and any conventionally known process may be used.
• the synthesis process of an amide compound as described above is described in, for example, Japanese Patent Application Laid-Open No. 2007-119449.
• the synthetic process of an N-vinylamide compound as described above is described in, for example, Japanese Patent Application Laid-Open Nos. H08-81428 and 2002-167369.
• commercially available compounds may also be used.
• the content of the water-soluble monomer in the liquid composition is favorably 1.0% by mass or more and 40.0% by mass or less based on the total mass of the liquid composition.
• the mass ratio between the polymer emulsion and the water-soluble monomer, which are used in combination in the liquid composition in the present invention is favorably within a range of from 5:1 to 1:10. When the mass ratio is controlled within this range, both of the glossiness of the film and the fastness of the film can be achieved extremely suitably.
• the photopolymerization initiator used in the present invention is favorably a hydrophilic photopolymerization initiator and is also favorably a compound which generates a radical by active energy rays.
• the photopolymerization initiator is further favorably an initiator generating a radical upon using ultraviolet rays as the active energy rays.
• Specific examples of the hydrophilic photopolymerization initiator satisfying these favorable conditions include compounds represented by the following general formulae (1) to (5).
• R 15 is an alkyl group having 1 to 5 carbon atoms or a phenyl group, with the proviso that the phenyl group may be unsubstituted or mono- to tetra-substituted by any substituent selected from halogen atoms, alkyl groups having 1 to 5 carbon atoms, alkyloxy groups having 1 to 5 carbon atoms, a sulfonic group, a carboxyl group, a hydroxyl group and salts thereof; —SO 3 ⁇ M + , —CO 2 ⁇ M + , —O ⁇ M + , and the following atomic group (E), R 16 is an alkyloxy group having 1 to 5 carbon atoms or a phenyl group, with the proviso that the phenyl group may be unsubstituted or mono- to tetra-substituted by any substituent selected from halogen atoms, alkyl groups having 1 to 5 carbon atoms
• R 18 is —[CH 2 ] x2 — (x 2 being 0 or 1) or an unsubstituted or substituted phenylene group
• R 19 is a hydrogen atom, or a sulfonic group, a carboxyl group, a hydroxyl group or a salt thereof; or —SO s ⁇ M + , —CO 2 ⁇ M + or —O ⁇ M +
• k is an integer of 0 to 10, and 1 is 0 or 1.
• M + ions are, independently of one another, a hydrogen ion, alkali metal ion or alkaline earth metal ion, or an ammonium ion represented by HNR 20 R 21 R 22 (R 20 , R 21 and R 22 being, independently of one another, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms or a monohydroxyl-substituted phenyl group).
• m3 is an integer of 1 or more
• n3 is an integer of 0 or more
• m3+n3 is an integer of 1 to 8.
• R 23 and R 24 are, independently of each other, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m4 is an integer of 5 to 10.
• R 26 and R 27 are, independently of each other, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R 25 is —(CH 2 ) x — (x being 0 or 1), —O— (CH 2 ) y — (y being 1 or 2) or a phenylene group
• M is a hydrogen atom or an alkali metal.
• R 28 and R 29 are, independently of each other, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M is a hydrogen atom or an alkali metal.
• the alkyl group or phenyl group of R 15 and the phenylene group of R 18 may have a substituent.
• substituents include halogen atoms, alkyl group having 1 to 5 carbon atoms, alkyloxy groups having 1 to 5 carbon atoms, groups represented by the atomic group (E), a sulfonic group, a carboxyl group, a hydroxyl group, and salts of the sulfonic, carboxyl and hydroxyl groups (—SO 3 M, —CO 2 M and —OM).
• R 15 is particularly favorably a phenyl group having an alkyl group having 1 to 5 carbon atoms as a substituent.
• Ms are, independently of one another, a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium represented by HNR 30 R 31 R 32 (R 30 , R 31 and R 32 being, independently of one another, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms or a monohydroxyl-substituted phenyl group).
• Examples of the salt of R 15 in the general formula (1) include —SO 3 M, —CO 2 M and —OM.
• the Ms are, independently of one another, a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium represented by HNR 33 R 34 R 35 (R 33 , R 34 and R 35 being, independently of one another, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms or a monohydroxyl-substituted phenyl group).
• the alkyloxy group or phenyl group of R 16 in the general formula (1) may have a substituent, and examples of the substituent include halogen atoms, alkyl groups having to 5 carbon atoms and alkyloxy groups having 1 to 5 carbon atoms.
• R 16 is particularly favorably an alkyloxy group, and —OC 2 H 5 or —OC(CH 3 ) 3 is favorable.
• the alkyl groups of R 23 , R 24 , and R 26 to R 29 in the general formulae (3) to (5) may have a substituent.
• a substituent include halogen atoms, a sulfonic group, a carboxyl group, a hydroxyl group and salts of the sulfonic, carboxyl and hydroxyl groups (—SO 3 M, —CO 2 M and —OM).
• the Ms are, independently of one another, a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium represented by HNR 36 R 37 R 38 (R 36 , R 37 and R 38 being, independently of one another, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a monohydroxyl-substituted alkyl group having 1 to 5 carbon atoms or a monohydroxyl-substituted phenyl group).
• a water-soluble acylphosphine oxide represented by the general formula (1) is favorable. More specifically, the following Exemplified
• Compound A is favorably used as the photopolymerization initiator.
• a synthetic process for the following Exemplified Compound A may be suitably used the process described in Japanese Patent Application Laid-Open No. 2005-307199.
• a hydrogen donor is favorably added.
• Example of the hydrogen donor usable in the present invention include triethanolamine and monoethanolamine.
• 2 or more photopolymerization initiators may be used in combination.
• the use of 2 or more photopolymerization initiators can expect that light having a wavelength which cannot be effectively utilized with one photopolymerization initiator is used to more accelerate the generation of the radical so as to improve the curing characteristics.
• the liquid composition according to the present invention contains an aqueous medium.
• water is favorably used as the aqueous medium.
• a mixed solvent of water and a water-soluble organic solvent is more favorably used as the aqueous medium.
• the water-soluble organic solvent is particularly favorably one that is water-soluble and can satisfy ink jet characteristics such as ejection stability, and all conventionally known organic solvent may be applied.
• the mixed solvent contains water in an amount of favorably 50% by mass or more, more favorably 90% by mass or more, based on the total mass of the mixed solvent from the viewpoints of influence on the environment and odor upon work.
• water-soluble organic solvents usable in the present invention include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; polyhydric alcohols such as glycerol, and water-soluble amide compounds such as 2-pyrrolidone.
• glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene
• the water-soluble organic solvent in particular, a highboiling-point water-soluble organic solvent, may be incorporated in a film formed in some cases to deteriorate the fastness of the resulting image as described above, the content of the water-soluble organic solvent is favorably less than 10.0% by mass based on the total mass of the liquid composition.
• the active energy ray curable liquid composition according to the present invention may be used as being colorless without containing such a coloring material as described below.
• the liquid composition When the liquid composition is prepared so as to have ink jet recording characteristics, it can be provided as a transparent ink jet liquid composition of the active energy ray curing type. When such a liquid composition is used, a clear film can be obtained because the liquid composition contains no coloring material.
• uses of the liquid composition containing no coloring material include the following: an undercoat for imparting various suitabilities for image recording to a recording medium and an overcoat for the purpose of protecting the surface of an image formed with an ordinary ink and imparting decoration and gloss.
• a colorless pigment or fine particles which do not intend to provide coloring, may also be dispersed and contained according to uses such as prevention of oxidation and prevention of fading.
• the addition of them can improve various characteristics such as image quality, fastness and handling property of the resulting recorded article in either the undercoat or the overcoat.
• the total amount of the polymer emulsion and water-soluble monomer is favorably 10.0% by mass or more and 70.0% by mass or less based on the total mass of the liquid composition.
• the photopolymerization initiator is favorably contained in an amount of 1.0 part by mass or more and 10.0 parts by mass or less per 100.0 parts by mass in total of the polymer emulsion and water-soluble monomer and in an amount of at least 0.5 parts by mass per 100.0 parts by mass of the liquid composition.
• a polymerizable low-viscosity monomer is favorably contained as a solvent therein.
• the advantage of the use of such a material, which is not an ordinary solvent, resides in that influence on solid physical properties is reduced because such a material does not remain as a plasticizer in the solid after the curing reaction by the active energy rays.
• Specific examples of the polymerizable low-viscosity monomer include acryloylmorpholine, acrylamide, methylenebisacrylamide, monoacrylates of monosaccharides, monoacrylates of oligoethylene oxides and monoacrylates of dibasic acids.
• liquid composition according to the present invention When the liquid composition according to the present invention is used in a form of containing no coloring material, it is favorable not to use an additive imparting moisturization as described below.
• the reason for it is that viscosity increase is small because a solid component such as a pigment is not contained, and some viscosity increase can be easily recovered if any.
• an additive having higher moisturization properties as described below may be added in a necessary and minimum amount.
• Various kinds of additives such as a surfactant may also be added. These may be selected from many compounds commonly used in aqueous ink jet liquids.
• liquid composition according to the present invention is used in a state (as an ink) that a coloring material is contained will now be described.
• a liquid composition is hereinafter referred to as an ink.
• the liquid composition according to the present invention may contain a coloring material such as a pigment in addition to the components described above.
• a pigment dispersion obtained by uniformly dispersing a pigment in an aqueous medium is favorably used as the coloring material.
• a pigment dispersion obtained by stably dispersing a pigment in water by the action of an anionic group is favorably used as the coloring material.
• the average particle size of pigment particles is within a range of favorably 25 nm or more and 350 nm or less, more favorably 70 nm or more and 200 nm or less.
• the average particle size of the pigment particles can be made sufficiently smaller than the wavelength of visible rays to obtain a clear recorded image with less light scattering.
• the average particle size of the pigment particles can be determined by measuring its d50 particle diameter that is a median diameter by means of a laser light scattering type particle size measuring apparatus.
• the concentration of the pigment in the liquid composition is favorably 0.3% by mass or more and 10.0% by mass or less based on the total mass of the ink.
• the concentration of the pigment is of the order of 0.3% by mass or more and 1.0% by mass or less, the concentration is within such a range that it is usable as a light-color ink though it varies according to the coloring power of the pigment and the dispersed state of the pigment particles.
• the concentration is higher than the above range, a concentration used for a general color ink is given.
• a conventionally known dye may be used as the coloring material without limiting it to a pigment as described above, and the ink can be provided as an ink containing a water-soluble dye in a dissolved state within such a range that no practical problem in fading caused by irradiation of active energy rays occurs.
• a coloring material dispersion containing a disperse dye or oil-soluble dye in a dispersed state may also be applied like the pigment dispersion. These dispersions may be suitably selected as necessary for the end application intended.
• the favorable content of the dye in the ink is within a range of 0.1% by mass or more and 10.0% by mass or less based on the total mass of the ink.
• such an ink may be suitably applied to the so-called light-color ink.
• liquid composition according to the present invention When the liquid composition according to the present invention is used as an ink containing a coloring material, various additives such as water-soluble organic solvents and surfactants may be added into the ink.
• the additives are used for the purpose of inhibiting the volatility of the ink, lowering the viscosity of the ink and controlling wetting tendency with respect to a recording medium.
• the additives When the additives are added in an amount of 10.0% by mass or more into the ink, the additive themselves may be incorporated in the film in some cases. Therefore, it is favorable to use a recording medium having high liquid absorbability and conduct natural or forced drying after the ink is cured with the active energy rays for inhibiting the lowering of the film strength by the additives.
• the monomer in the ink according to the present invention is water-soluble, and thus has high affinity for water and certain moisturizability in itself. Therefore, the ink according to the present invention may not contain any additive according to the composition thereof.
• the recording medium cannot be expected to have the ability to absorb the additives. It is thus favorable to limit the amount of the additives to a minimum. Specifically, the content of the additives is favorably less than 10% by mass based on the total mass of the ink. The content is more favorably less than 5% by mass. When the above-described recording medium is used, no additive is favorably added to the ink if possible.
• liquid composition according to the present invention when used as the ink containing the coloring material, examples of the additives suitably used include such various glycol ethers and polyhydric alcohols such as glycerol as mentioned above as the water-soluble organic solvents usable in the present invention.
• the content of the aqueous medium, the content of the photopolymerization initiator and the total amount of the polymer emulsion and water-soluble monomer are favorably adjusted according to the absorption property of the coloring material.
• the content of the aqueous medium is favorably 40.0% by mass or more and 90.0% by mass or less, more favorably 60.0% by mass or more and 75.0% by mass or less, based on the total mass of the liquid composition.
• the total amount of the polymer emulsion and water-soluble monomer in the liquid composition is favorably 1.0% by mass or more and 35.0% by mass or less, more favorably 10.0% by mass or more and 25.0% by mass or less, based on the total mass of the liquid composition.
• the content of the photopolymerization initiator is favorably 0.1% by mass or more and 7.0% by mass or less, more favorably 0.3% by mass or more and 5.0% by mass or less, based on the total mass of the liquid composition though it varies according to the total amount of the polymer emulsion and the water-soluble monomer.
• an ink jet recording apparatus equipped with a unit for applying the liquid composition to a recording medium and a unit for irradiating the liquid composition applied to the recording medium with active energy rays may be favorably used.
• an apparatus in which an UV lamp is arranged on a front side of a paper discharge section, paper feeding and discharging are conducted by winding a paper sheet on a roll, or a drying section is separately provided may be suitably selected as the ink jet recording apparatus.
• an ultraviolet irradiation apparatus is favorably used as an active energy ray irradiation unit.
• the ultraviolet irradiation apparatus is favorably a mercury lamp with a vapor pressure of 1 Pa or more and 10 Pa or less during lighting. Since the emission spectrum in an ultraviolet region of the mercury lamp is within a range of 450 nm or less, in particular, 184 nm or more and 450 nm or less, the mercury lamp is suitable for efficiently reacting the polymer emulsion and water-soluble monomer contained in the liquid composition.
• the mercury lamp may be suitably used a metal halide lamp, high pressure mercury lamp, extra-high pressure mercury lamp, xenon flash lamp, deep UV lamp, electrodeless UV lamp using microwaves or UV laser.
• An ultraviolet irradiation apparatus using UV-LED of a light emitting diode system or an UV excimer lamp may also be suitably used.
• the ultraviolet irradiation intensity of the ultraviolet irradiation apparatus such as the ultraviolet irradiation apparatus using UV-LED of the light emitting diode system or the UV excimer lamp is favorably 500 mW/cm 2 or more and 5,000 mW/m 2 or less from the viewpoint of polymerization rate. If the ultraviolet irradiation intensity is insufficient, the strength of the resulting film may not be sufficiently achieved in some cases. If the irradiation intensity is too strong, a recording medium may be damaged, or the fading of a coloring material may occur in some cases.
• the ink jet recording method according to the present invention has an ejection step of ejecting the liquid composition on a recording medium and a curing step of irradiating the recording medium on which the liquid composition has been applied with active energy rays to cure the water-soluble monomer.
• the above-described ink jet recording apparatus is favorably used for performing the ink jet recording method according to the present invention.
• the pigment dispersion was prepared in the following manner and used in such a manner that the solid content thereof is the value shown in Tables 1-1 to 1-5.
• C.I. Pigment Blue 15:3 was used as a pigment, and a styrene-acrylic acid/ethyl acrylate random copolymer (weight average molecular weight: 3,500, acid value: 150 mg KOH/g) was used as a dispersant.
• These materials were dispersed by a bead mill to finally obtain a cyan pigment dispersion having a pigment solid content of 10% by mass and a mass ratio of the pigment and the resin (P/B) of 3:1.
• the average particle size of the pigment used was 120 nm.
• the average particle size of the pigment was determined by measuring its d50 particle diameter that is a median diameter by means of Nanotrac 150 (manufactured by Microtrac Inc.) that is a laser light scattering type particle size measuring apparatus.
• Nanotrac 150 manufactured by Microtrac Inc.
• (*4) Available from SAN NOPCO LTD. (*5) Available from BASF Japan Ltd.
• Exemplified Compound 6 was synthesized according to the following process. Specifically, after ethylene oxide was added to diglycerol by an addition reaction, epichlorohydrin was further reacted to obtain a derivative of glycidyl ether. Thereafter, acrylic acid was added to the resultant derivative by an addition reaction to obtain Exemplified compound 6.
• Exemplified Compound A was obtained by conducting synthesis according to the process described in Synthesis Example 1 of Japanese Patent Application Laid-Open No. 2005-307199.
• each of the liquid compositions having the respective compositions shown in Tables 1-1 to 1-5 was used to evaluate its film properties in the following manner.
• each of the liquid compositions was ejected on a commercially available PET (polyethylene terephthalate) film from a recording head by means of BJF 9000 (manufactured by Canon Inc.) so as to give a coating amount of 10 g/m 2 .
• BJF 9000 manufactured by Canon Inc.
• the thus-coated PET film was immediately subjected to an ultraviolet (UV) irradiation apparatus.
• an UV curability evaluation apparatus, Model LH6B manufactured by FUSION UV Systems Inc. was used as an electrodeless UV lamp using microwaves.
• the irradiation intensity was 5,000 mW/cm 2 , and the conveying speed was 0.4 m/sec.
• the 20° glossiness was measured. In the present invention, the higher 20° glossiness indicates that a more uniform film is formed.
• the pencil hardness of the film was measured by means of a commercially available pencil hardness tester. These measured results are shown in Table 2. Incidentally, the pencil hardness test was conducted according to the JIS standard. The higher pencil hardness in Table 2 indicates that a stronger film is formed.
• A The conditions were not changed from the initial conditions even after the storage;
• B The viscosity and/or the average particle size was changed after the storage.
• Example 1 40 3H A Example 2 35 2H A Example 3 35 HB A Example 4 40 2H A Example 5 35 H A Example 6 35 HB A Example 7 35 4H A Example 8 30 3H A Example 9 20 3H A Example 10 40 H A Example 11 40 F A Example 12 45 HB A Example 13 43 HB A Example 14 45 H A Example 15 35 2H A Example 16 40 2H A Example 17 15 3H A Example 18 40 4H A Comparative 30 2B B Example 1 Comparative 30 2B B Example 2 Comparative (*6) 4B or less B Example 3 Comparative 40 4B or less A Example 4 Comparative 30 3B B Example 5 Comparative 30 2B B Example 6 Comparative (*6) 4B or less B Example 7 Comparative 40 4B or less A Example 8 Comparative 10 2B A Example 9 (*6) No film was formed under the preparation conditions described above.

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