US20100007708A1 - Actinic ray curable composition, actinic ray curable ink, image formation method employing it, and ink-jet recording apparatus - Google Patents

Actinic ray curable composition, actinic ray curable ink, image formation method employing it, and ink-jet recording apparatus Download PDF

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US20100007708A1
US20100007708A1 US12/562,595 US56259509A US2010007708A1 US 20100007708 A1 US20100007708 A1 US 20100007708A1 US 56259509 A US56259509 A US 56259509A US 2010007708 A1 US2010007708 A1 US 2010007708A1
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group
ink
actinic ray
ray curable
compound
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Wataru Ishikawa
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Konica Minolta Medical and Graphic Inc
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Konica Minolta Medical and Graphic Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • 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
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2103—Features not dealing with the colouring process per se, e.g. construction of printers or heads, driving circuit adaptations
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to an actinic ray curable composition, and particularly to an actinic ray curable ink with a low viscosity, which is capable of being cured with high speed, and forms an ink layer which is high in hardness and in adhesion to a recording sheet, an image formation method employing it, and an ink-jet recording apparatus.
  • a curable composition capable of being cured by actinic rays such as ultraviolet rays or electron beams or heat has been applied to various fields, for example, coating materials for plastics, paper, or wood work; adhesives; printing inks, printed circuit boards, or electrical insulations.
  • UV-curable ink jet inks are disclosed, for example, in Japanese Patent O.P.I. Publication No. 6-20204 and Japanese Patent Publication No 2000-504778.
  • UV-curable inks are required which have a low viscosity, and provide an ink layer with high fastness, high flexibility, and high adhesion to a recording sheets. Curing speed of these UV-curable ink jet inks is likely to change due to kinds of recording sheets, or operating conditions.
  • ink composition containing a radically polymerizable compound is susceptible to oxygen. Therefore, when such ink composition is used in a small amount as ink droplets, curing is likely to be inhibited.
  • inks employing a cationically polymerizable compound disclosed in Japanese Patent O.P.I. Publication Nos. 2001-220526, 2002-188025, 2002-317139, and 2003-55449), are not affected by oxygen, however, they have problem in that the polymerization reaction is susceptible to moisture in the molecular level (or humidity)
  • An object of the invention is to provide an actinic ray curable composition with a low viscosity, which is capable of being cured with high speed, and forms a coating layer with high hardness under various operating conditions, an actinic ray curable ink employing it, an image formation method employing it, and an ink-jet recording apparatus employing it.
  • FIG. 1 shows a schematic view of one embodiment of the structure of the main section of the ink-jet recording apparatus of the invention.
  • FIG. 2 shows a schematic view of another embodiment of the structure of the main section of the ink-jet recording apparatus of the invention.
  • An actinic ray curable composition comprising, as a photopolymerizable compound, both an oxetane compound with an oxetane ring and an epoxy compound, and a non-reactive compound having a viscosity at 25° C. of from 0.1 to 20 mPa ⁇ s and a boiling point of not less than 150° C.
  • R 100 represents a substituent
  • m0 represents an integer of from 0 to 2
  • r0 represents an integer of from 1 to 3
  • L 0 represents a single bond or a (r0+1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain.
  • R 101 represents a substituent
  • m1 represents an integer of from 0 to 2
  • r1 represents an integer of from 1 to 3
  • L 1 represents a single bond or a (r1+1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain
  • R 102 represents a substituent
  • m2 represents an integer of from 0 to 2
  • r2 represents an integer of from 1 to 3
  • L 2 represents a single bond or a (r2+1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain.
  • R 200 represents an aliphatic group
  • m3 represents an integer of from 0 to 2
  • X 1 represents —(CH 2 ) n0 — or —(O) n0 —, in which n0 represents an integer of 0 or 1
  • p1 and q1 independently represent 0 or 1, provided that p1 and q1 are not simultaneously 0
  • r3 represents an integer of from 1 to 3
  • L 3 represents a single bond or a (r3+1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain,
  • R 201 represents an aliphatic group
  • m4 represents an integer of from 0 to 2
  • X 2 represents —(CH 2 ) n1 — or —(O) n1 —, in which n1 represents an integer of 0 or 1
  • p2 and q2 independently represent 0 or 1, provided that p2 and q2 are not simultaneously 0
  • r4 represents an integer of from 1 to 3
  • L 4 represents a single bond or a (r4+1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain.
  • An actinic ray curable composition comprising a radically polymerizable compound as a photopolymerizable compound, and a non-reactive compound having a viscosity at 25° C. of from 0.1 to 20 mPa ⁇ s and a boiling point of not less than 150° C.
  • An actinic ray curable ink comprising pigment and the actinic ray curable composition of any one of items 1 through 14 above.
  • a process of forming an image on a recording sheet employing an ink-jet recording head comprising the steps of ejecting the actinic ray curable ink of item 15 above from the ink-jet recording head onto the recording sheet to form an image on the recording sheet, and exposing the image to actinic rays between 0.001 seconds and 2.0 seconds after the ink has been ejected onto the recording sheet.
  • a process of forming an image on a recording sheet employing an ink-jet recording head comprising the steps of ejecting the actinic ray curable ink of item 15 above from the ink-jet recording head onto the recording sheet to form an image on the recording sheet, the ink being ejected as ink droplets from each of nozzles of the ink-jet recording head, wherein the ink droplets have a volume of from 2 to 15 pl.
  • An ink-jet recording apparatus used in the process of items 16 and 17 above, wherein the actinic ray curable ink and the ink-jet recording head was heated to a temperature of from 35 to 100° C., and then the heated ink was ejected.
  • An ink-jet recording apparatus used in the process of items 16 and 17 above, wherein the actinic ray curable ink was ejected to a recording sheet heated to a temperature of from 35 to 60° C.
  • An actinic ray curable composition comprising a radically polymerizable compound as a photopolymerizable compound, and a non-reactive compound having a viscosity at 25° C. of from 0.1 to 20 mPa ⁇ s and a boiling point of not less than 150° C.
  • An actinic ray curable composition comprising, as a photopolymerizable compound, both an oxetane compound with an oxetane ring and an epoxy compound, and a non-reactive compound having a viscosity at 25° C. of from 0.1 to 20 mPa ⁇ s and a boiling point of not less than 150° C.
  • actinic ray curable composition of any one of items 1-1 through 1-10 above, wherein the actinic ray curable composition has a viscosity at 25° C. of from 7 to 40 mPa ⁇ s.
  • An actinic ray curable ink comprising pigment and the actinic ray curable composition of any one of items 1-1 through 1-11 above.
  • a process of forming an image on a recording sheet employing an ink-jet recording head comprising the steps of ejecting the actinic ray curable ink of item 1-12 above from the ink-jet recording head onto the recording sheet to form an image on the recording sheet, and exposing the image to actinic rays between 0.001 seconds and 2.0 seconds after the ink has been ejected onto the recording sheet.
  • a process of forming an image on a recording sheet employing an ink-jet recording head comprising the steps of ejecting the actinic ray curable ink of item 1-12 above from the ink-jet recording head onto the recording sheet to form an image on the recording sheet, the ink being ejected as ink droplets from each of nozzles of the ink-jet recording head, wherein the ink droplets have a volume of from 2 to 15 pl.
  • An ink-jet recording apparatus used in the process of item 1-13 or 1-14 above, wherein the actinic ray curable ink and the ink-jet recording head was heated to a temperature of from 35 to 100° C., and then the heated ink was ejected.
  • An ink-jet recording apparatus used in the process of item 1-13 or 1-14 above, wherein the actinic ray curable ink was ejected to a recording sheet heated to a temperature of from 35 to 60° C.
  • ink-jet ink is ejected onto a recording medium (or material), and the ejected ink is cured by actinic ray exposure.
  • actinic ray types of the actinic ray are not specifically limited.
  • actinic ray visible or ultraviolet light or electron beam can be used, and ultraviolet light is preferably used.
  • exposure amount is preferably from 100 to 10,000 mJ/cm 2 , and preferably from 500 to 5,000 mJ/cm 2 . This range of exposure amount is advantageous in providing sufficient curing of ink and preventing a colorant from fading.
  • Examples of an ultraviolet ray include a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low pressure mercury lamp, and a high pressure mercury lamp.
  • An H lamp, D lamp and V lamp are also used.
  • the metal halide lamp Unlike the high pressure mercury lamp (having an emission wavelength of 365 nm as a main wavelength), the metal halide lamp has a continuous emission spectra, a high emission efficiency at the wavelength regions of from 200 to 450 nm, and rich longer wavelength light. Accordingly, as the ultraviolet ray lamp, the metal halide lamp is preferred in the invention.
  • the non-reactive compound in the invention (hereinafter also referred to simply as the non-reactive compound) is a compound having a viscosity at 25° C. of from 0.1 to 20 mPa ⁇ s and a boiling point of not less than 150° C., which does not react with the photopolymerizable compound in the invention.
  • the non-reactive compound in the invention has a viscosity at 25° C. of preferably from 0.1 to 10 mPa ⁇ s and a boiling point of preferably from 150 to 200° C.
  • non-reactive compound in the invention there are aromatic hydrocarbon compounds, halogenated hydrocarbons, esters, ketones, and ethers.
  • the content of the non-reactive compound in the invention in the actinic ray curable composition is preferably from 1 to 50% by weight, and more preferably from 2 to 20% by weight.
  • non-reactive compound examples include methyl acetoacetate (bp. 172° C., viscosity: 1.6 mPa ⁇ s), 3-methyl-3-methoxybutyl acetate (bp. 188° C., viscosity: 1.7 mPa ⁇ s), cyclohexanone (bp. 156° C., viscosity: 2.0 mPa ⁇ s), ethyl lactate (bp. 155° C., viscosity: 2.4 mPa ⁇ s), methyl 2-methyllactate (bp. 137° C., viscosity: 2.6 mPa ⁇ s), propylene glycol mono-n-butyl ether (bp.
  • the radically polymerizable compound in the invention is a compound having an ethylenically unsaturated bond capable of being radically polymerized, and may be any as long as it has in the molecule at least one ethylenically unsaturated bond which enables radical polymerization.
  • the radically polymerizable compound may be in the form of monomer, oligomer or polymer.
  • the radically polymerizable compound may be used alone or as a mixture of two or more kinds thereof, according to the object.
  • unsaturated carboxylic acids such as acrylic acid, meth acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid; and salts, esters, urethanes, amides, and anhydrides each derived therefrom; acrylonitrile; styrene; various unsaturated polyesters; various unsaturated polyethers; various unsaturated polyamides; and various unsaturated polyurethanes.
  • Typical examples of the radically polymerizable compound include an acrylic acid derivative such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis(4-acryloxypolyethoxyphenyl)propane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethyl
  • the content of the radical polymerizable compound in the actinic ray curable composition is preferably from 1 to 97% by weight, and more preferably from 30 to 95% by weight.
  • radical polymerization initiators there are a triazine derivative disclosed in Japanese Patent Publication Nos. 591281 and 61-9621 and Japanese Patent O.P.I. Publication No. 60-60104; an organic peroxide compound disclosed in Japanese Patent O.P.I. Publication Nos. 59-1504 and 61-243807; a diazonium compound in Japanese Patent Publication Nos. 43-23684, 44-6413, 47-1604 and U.S. Pat. No. 3,567,453; an organic azide compound disclosed in U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853; orthoquinondiazide compounds disclosed in Japanese Patent Publication Nos.
  • titanocenes disclosed in Japanese Patent O.P.I. Publication Nos. 59-152396 and 61-151197; transition metal complexes containing a transition metal such as ruthenium disclosed in “Coordination Chemistry Review”, Volume 84, p. 85-277 (1988) and Japanese Patent O.P.I. Publication No. 2-182701; 2,4,5-triarylimidazol dimmer disclosed in Japanese Patent O.P.I. Publication No. 3-209477; carbon tetrabromide; and organic halide compounds disclosed in Japanese Patent O.P.I. Publication No. 59-107344.
  • the actinic ray curable composition of the invention preferably contains, as a photopolymerizable compound, an oxetane compound with an oxetane ring.
  • the compound with an oxetane ring is preferably an oxetane compound with an oxetane ring having a substituent at the 2-position.
  • an oxetane compound with an oxetane ring represented by formula 1 having a substituent at the 2-position is preferably used.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 independently represent a hydrogen atom or a substituent. At least one of R 3 through R 6 is preferably a substituent.
  • examples of the substituent represented by R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 include a fluorine atom, an alkyl group having from 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), a fluoroalkyl group having from 1 to 6 carbon atoms, an allyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a furyl group and a thienyl group. These substituents may have further have the substituent.
  • an oxetane compound with an oxetane ring represented by the following formula 2, 3, 4, or 5 is preferred.
  • R 1 through R 6 independently represent a hydrogen atom or a substituent
  • R 7 and R 8 independently represent a substituent
  • Z represents an oxygen atom, a sulfur atom, a divalent hydrocarbon group or a divalent hydrocarbon group in which an oxygen atom or a sulfur atom is intervened.
  • R 7 and R 8 independently represent an alkyl group having from 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), an alkenyl group having from 1 to 6 carbon atoms (a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, etc.), an aryl group (for example, a phenyl group, a naphthyl group, etc.), an aralkyl group (for example, a benzyl group, a fluorobenzyl group, a methoxybenzyl group), an acyl group having from 1 to 6 carbon atoms (a propylcarbonyl group, a butylcarbonyl group, a pent
  • the divalent hydrocarbon group represented by Z is an alkylene group (for example, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, etc.), an alkenylene group (for example, a vinylene group, a propenylene group, etc.), an alkinylene group (an ethynylene group, or 3-pentynylene group, etc.).
  • alkylene group for example, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group,
  • the divalent hydrocarbon group represented by Z in which an oxygen atom or a sulfur atom is intervened is the alkylene group, alkenylene group, or alkynylene group described above each having an oxygen atom or a sulfur atom intervened therein.
  • R 1 is a lower alkyl group, and particularly an ethyl group
  • R 7 and R 8 are independently a propyl group, a phenyl group or a benzyl group
  • Z is the divalent hydrocarbon group, particularly, an alkylene group, an alkenylene group, or an alkynylene group.
  • an oxetane compound with two or more of an oxetane ring represented by the following formula 6 or 7 in the molecule can be used.
  • R 1 through R 6 independently represent a hydrogen atom, a fluorine atom, an alkyl group having a carbon atom number of from 1 to 6 such as a methyl group, an ethyl group, a propyl group or a butyl group, a fluoroalkyl group having a carbon atom number of from 1 to 6, an allyl group, an aryl group, or a furyl group.
  • R 3 through R 6 is a substituent.
  • R 9 represents a straight chain or branched chain alkylene group having from 1 to 12 carbon atoms, a straight chain or branched chain poly(alkylene oxy) group, or a divalent group selected from the group consisting of the following formula 9, 10 and 11.
  • the straight chain or branched chain alkylene group having from 1 to 12 carbon atoms is preferably a group represented by the following formula 8.
  • R 10 represents a lower alkyl group such as a methyl group, an ethyl group, or propyl group.
  • R 12 represents an alkyl group having from 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, etc.), and R 11 represents an alkyl group having from 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, etc.), or a group represented by the following formula 12.
  • R 13 represents an alkyl group having from 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, etc.).
  • R 14 represents an alkyl group having from 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, etc.), an alkoxy group having from 1 to 10 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc.), a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, etc.), a nitro group, a cyano group, a mercapto group, an alkoxycarbonyl group (for example, a methyloxycarbonyl group, an ethyloxycarbonyl group, a but
  • R 15 represents an oxygen atom, a sulfur atom, —NH—, —SO—, —SO 2 , —(CH 2 )—, —C(CH 3 ) 2 — or —(CF 3 ) 2 —.
  • R 1 is preferably a lower alkyl group such as a methyl group, an ethyl group, or a propyl group, and more preferably an ethyl group.
  • R 9 is preferably a hexamethylene group or one in which R 14 in formula 10 above is a hydrogen atom.
  • R 10 is preferably an ethyl group, and in formulae 9 and 12 above, R 12 and R 13 each are preferably hydrogen atoms. In formula 6 above, it is preferred that at least one of R 3 through R 6 is a substituent.
  • r is an integer of from 25 to 200
  • R 16 represents an alkyl group having from 1 to 4 carbon atoms or a trialkylsilyl group.
  • R 1 and R 4 through R 6 are the same as those denoted in formula 1. it is preferred that at least one of R 3 through R 6 is a substituent.
  • Exemplified compounds 1 through 15 will be listed below as examples of the oxetane compound with an oxetane ring with a substituent at the 2-position, but the invention is not limited thereto.
  • the oxetane compound with an oxetane ring with a substituent at the 2-position can be synthesized according to the procedures disclosed in the following literatures.
  • the actinic ray curable ink contains the oxetane compound with an oxetane ring with a substituent at the 2-position in an amount of preferably from 1 to 97% by weight, and more preferably from 30 to 95% by weight.
  • the oxetane compound with an oxetane ring with a substituent at the 2-position can be used alone or as a mixture of two or more kinds thereof. Further, the oxetane compound with an oxetane ring with a substituent at the 2-position can be used in combination with another polymerizable compound. In combined use thereof it is preferred that in a mixture the content ratio of the oxetane compound with an oxetane ring with a substituent at the 2-position to the polymerizable compound is from 10 to 98% by weight, and that of the polymerizable compound is from 2 to 90% by weight.
  • oxetane compound with an oxetane ring having a substrate at the 2-position in addition to the above-described oxetane compound with an oxetane ring having a substrate at the 2-position, a known oxetane compound can be used in combination, and an oxetane compound with an oxetane ring having a substituent only at the 3-position is preferably used in combination.
  • oxetane compound with an oxetane ring having a substituent only at the 3-position known ones disclosed in Japanese Patent O.P.I. Publication Nos. 2001-220526 and 2001-310397 can be used.
  • R 1 represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.; a fluoroalkyl group having from 1 to 6 carbon atoms; an allyl group; an aryl group; a furyl group; or a thienyl group; and R 2 represents an alkyl group having from 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.; an alkenyl group having from 2 to 6 carbon atoms such as a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, etc.), an aromatic ring-containing group
  • an oxetane compound represented by the following formula 15 is cited.
  • R 1 represents the same group as those denoted in R 1 in formula 14; and R 3 represents a straight chained or branched alkylene group such as an ethylene group, a propylene group, a butylene group, etc.; a straight chained or branched polyalkyleneoxy group such as a poly(ethyleneoxy) group, a poly(propyleneoxy group, etc.; a straight chained or branched unsaturated hydrocarbon group such a propenylene group, a methylpropenylene group, a butenylene group, etc.; an alkylene group containing a carbonyl group; an alkylene group containing a carbonyloxy group; or an alkylene group containing a carbamoyl group.
  • R 3 represents a straight chained or branched alkylene group such as an ethylene group, a propylene group, a butylene group, etc.
  • a straight chained or branched polyalkyleneoxy group such as
  • R 3 also represents a polyvalent group selected from groups represented by the following formulae 16, 17 and 18.
  • R 4 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.; an alkoxy group having from 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.; a halogen atom such as a chlorine atom, a bromine atom, etc.; a nitro group; a cyano group; a mercapto group; a lower alkylcarboxy group; a carboxyl group; or a carbamoyl group.
  • R 5 represents an oxygen atom, a sulfur atom, a methylene group, —NH—, —SO—, —SO 2 —, —(CF 3 ) 2 —, or —C(CH 3 ) 2 —.
  • R 6 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., or an aryl group
  • “n” represents an integer of from 0 to 2000
  • R 7 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc, or an aryl group, or a group represented by the following formula 19.
  • R 8 represents an alkyl group having from 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., or an aryl group; and m represents an integer of from 0 to 100.
  • Examples of a compound having two oxetane rings include the following compounds.
  • Exemplified compound 1 is a compound in which in formula 15, R 1 is an ethyl group, and R 3 is a carbonyl group.
  • Exemplified compound 2 is a compound in which in formula 15, R 1 is an ethyl group, and R 3 is a group in which in formula 18, R 6 is a methyl group, R 7 is a methyl group, and n is 1.
  • an oxetane compound represented by the following formula 20 is cited.
  • R 1 is the same as those denoted in R 1 of formula 14 above.
  • an oxetane compound represented by the following formula 21 is cited.
  • R 1 is the same as those denoted in R 1 of formula 14;
  • R 9 represents a branched alkylene group having 1 to 12 carbon atoms such as a group represented by formula A, B or C below, a branched polyalkyleneoxy group such as a group represented by formula D below, or a branched alkylene group containing a silylether group such as a group represented by E below; and
  • j represents an integer of 3 or 4.
  • R 10 represents a lower alkyl group such as a methyl group, an ethyl group, or a propyl group.
  • p represents an integer of from 1 to 10.
  • R 8 is the same as those denoted in R 8 of formula 19;
  • R 11 represents an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a trialkylsilyl group;
  • r represents an integer of from 1 to 4, and
  • R 1 is the same as those denoted in R 1 of formula 14.
  • the preferred oxetane compounds used in the invention are Exemplified compounds 4, 5, and 5 as shown below.
  • Synthetic method of the above-described oxetane compounds is not specifically limited, and known methods can be used. There is, for example, a method disclosed in D. B. Pattison, J. Am. Chem. Soc., 3455, 79 (1957) in which an oxetane ring is synthesized from diols.
  • polymeric oxetane compounds having 1 to 4 oxetane rings with a molecular weight of 1000 to 5000 can be used.
  • examples thereof include the following exemplified compounds 7, 8 and 9.
  • the content of the oxetane compound in the actinic ray curable composition of the invention is preferably from 1 to 97% by weight, and more preferably from 30 to 95% by weight.
  • the epoxy compound herein referred to is a compound with an oxirane ring (hereinafter referred to simply as the epoxy compound).
  • the epoxy compound there are known epoxy compounds, for example, an aromatic epoxy compound (aromatic epoxide), an alicyclic epoxy compound (alicyclic epoxide), and an aliphatic epoxy compound (aliphatic epoxide).
  • the epoxy compound has preferably a low molecular weight, and more preferably a molecular weight less than 1000.
  • the content of the alicyclic epoxy compound in the actinic ray curable composition of the invention is preferably from 10 to 80% by weight.
  • the aromatic epoxide is preferably a di- or poly-glycidyl ether manufactured by a reaction of polyhydric phenol having at least one aromatic ring or of an alkylene oxide adduct thereof with epichlorohydrin, and includes, for example, such as di- or poly-glycidyl ether of bisphenol A or of an alkylene oxide adduct thereof, di- or poly-glycidyl ether of hydrogenated bisphenol A or of an alkylene oxide adduct thereof and novolac type epoxy resin.
  • alkylene oxide includes such as ethylene oxide and propylene oxide.
  • the alicyclic epoxide is preferably a compound containing cyclohexene oxide or cyclopentene oxide obtained by epoxydizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene by use of a suitable oxidizing agent such as hydrogen peroxide or a peracid. Examples thereof include compounds described later.
  • the aliphatic epoxide is preferably a di- or polyglycidyl ether of aliphatic polyhydric alcohol or of an alkylene oxide adduct thereof; the typical examples include diglycidyl ether of alkylene glycol, such as diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol and diglycidyl ether of 1,6-hexane dial; polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or of an alkylene oxide adduct thereof; and diglycidyl ether of polyalkylene glycol such as diglycidyl ether of polyethylene glycol or of an alkylene oxide adduct thereof and diglycidyl ether of polypropylene glycol or of an alkylene oxide adduct thereof.
  • alkylene oxide includes such as ethylene oxide and propylene oxide.
  • a monoglycidyl ether of higher alcohols, phenol or cresol which is a monomer having one oxirane ring in the molecule
  • phenol or cresol which is a monomer having one oxirane ring in the molecule
  • the aromatic epoxide and alicyclic epoxide are preferable, and the alicyclic epoxide is specifically preferable, taking a quick curing property in consideration.
  • the epoxides described above may be utilized alone or as a mixture of two or more kinds thereof.
  • an alicyclic epoxide represented by formula A, I, or II above is preferred, which will be explained below.
  • R 100 , R 101 , and R 102 independently represent a substituent.
  • the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, etc.), an alkyl group having a carbon atom number of from 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group); an alkoxy group having from 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group), an acyl group (for example, an acetyl group, a propionyl group or a trifluoroacetyl group), an acyloxy group (for example, an acetoxy group, a halogen atom (for
  • n 0 , m 1 , and m 2 independently represent an integer of from 0 to 2, and are preferably 0 or 1.
  • L 0 represents a single bond or a (r 0 +1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain.
  • L 1 represents a single bond or a (r 1 +1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain.
  • L 2 represents a single bond or a (r 2 +1)-valent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain.
  • Examples of a divalent linkage group having a carbon atom number of from 1 to 15, which may contain an oxygen atom or a sulfur atom in the main chain include groups described below and a combination of these groups and —O—, —S—, —CO—, or —CS—.
  • Examples of the 3 or more valent linkage group include groups, which is obtained by eliminating a hydrogen atom from the divalent linkage groups exemplified above, and a combination of these groups and —O—, —S—, —CO—, or —CS—.
  • L o , L 1 and L 2 may have a substituent.
  • substituents include a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom), an alkyl group having a carbon atom number of from 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group), an alkoxy group having a carbon atom number of from 1 to 6 (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a n-butoxy group or a tert-butoxy group), an acyl group (for example, an acetyl group, a propionyl group, or a trifluoroacetyl group), an acyloxy group (for example, an acetoxy group, a propionyloxy group, or a trifluoro
  • L o , L 1 and L 2 represent preferably a divalent linkage group having a carbon atom number of from 1 to 8, which may contain an oxygen atom or a sulfur atom in the main chain, and more preferably a divalent linkage group having a carbon atom number of from 1 to 5, the main chain of which consists of a carbon atom
  • an alicyclic epoxide compound represented by formula (III) or (IV) above is also preferred.
  • R 200 and R 201 independently represent an aliphatic group.
  • the aliphatic group include an alkyl group having a carbon atom number of from 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group); a cycloalkyl group having a carbon number of from 3 to 6 (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group); an alkenyl group having a carbon atom number of from 1 to 6 (for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, or a 2-butenyl group); and an alkinyl group having a carbon atom number of from 1 to 6 (for example, an acetylenyl group, a 1-propinyl group,
  • m 3 and “m 4 ” independently represent an integer of from 0 to 2, and preferably not less than 1.
  • X 1 represents —(CH 2 ) n0 — or —(O) n0 —
  • X 2 represents —(CH 2 ) n1 — or —(O) n1 —, in which n0 and n1 independently represent an integer of 0 or 1, provided that when n0 and n1 are 0, respectively, neither X 1 nor X 2 exists.
  • P1 and q1 independently represent 0 or 1, provided that they are not simultaneously 0.
  • P2 and q2 independently represent 0 or 1, provided that they are not simultaneously 0.
  • (m 3 +n 0 ) is not less than 1, or (m 4 +n 1 ) is not less than 1.
  • L 3 represents a single bond, or a (r3+1)-valent linkage group having a branched structure, provided that the linkage group may contain an oxygen atom or a sulfur atom in the main chain; and L 4 represents a single bond, or a (r4+1)-valent linkage group having a branched structure, provided that the linkage group may contain an oxygen atom or a sulfur atom in the main chain.
  • divalent linkage group with a carbon number of from 1 to 15 which may contain an oxygen atom or a sulfur atom in the main chain
  • divalent linkage group with a carbon number of from 1 to 15 which may contain an oxygen atom or a sulfur atom in the main chain
  • groups and their combination with —O—, —S—, —CO— and/or —CS— are cited the following groups and their combination with —O—, —S—, —CO— and/or —CS—.
  • a tri- or more-valent linkage group a group in which an arbitrary hydrogen atom is withdrawn from the divalent linkage group described above and its combination with —O—, —S—, —CO— and/or —CS—.
  • L 3 and L 4 preferably have a substituent.
  • substituents include a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom), an alkyl group having a carbon atom number of from 1 to 6 (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group), an alkoxy group having a carbon atom number of from 1 to 6 (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a n-butoxy group or a tert-butoxy group), an acyl group (for example, an acetyl group, a propionyl group, or a trifluoroacetyl group), an acyloxy group (for example, an acetoxy group, a propionyloxy group, or a trifluoroacetoxy group
  • Mw is molecular weight
  • the content of the alicyclic epoxy compound in the invention is preferably from 10 to 80% by weight.
  • the alicyclic epoxy compound may be used alone or as a mixture of two or more kinds thereof.
  • a synthetic method of the epoxy compound in the invention is not specifically limited.
  • the epoxy compound can be synthesized according to the methods described in for example, “Jiken Kagaku Koza 20, Yukigosei II”, 213-(1992), Fourth Edition, published by Maruzen K K Shuppan; Ed. by Alfred Hasfner, “The chemistry of heterocyclic compounds-Small Ring Heterocycles part 3 Oxiranes”, John and Wiley and Sons, An Interscience Publication, New York (1985); Yoshimura, “Secchaku”, Vol. 29, 12, pp. 32 (1985); Yoshimura, “Secchaku”, Vol. 30, 5, pp. 42 (1986); Yoshimura, “Secchaku”, Vol. 30, 7, pp. 42 (1986); and Japanese Patent O.P.I. Publication No. 11-100378.
  • epoxidated fatty acid ester or epoxidated glyceride is contained in an amount of preferably up to 20% by weight, based on the actinic ray curable composition.
  • incorporación of the epoxidated fatty acid ester or epoxidated glyceride is preferred in safety such as AMES, sensitization, less skin irritation or odor, and can solve problems such as occurrence of creases due to shrinkage or deterioration of curability or ejection stability which is caused depending on environmental conditions (such as temperature and humidity).
  • At least one of epoxidated fatty acid ester or epoxidated glyceride is preferably used as the oxirane ring-containing compound, in view of AMES or sensitization.
  • the epoxidated fatty acid ester or epoxidated glyceride usable in the invention is obtained by incorporating an epoxy group into fatty acid ester or glyceride, and can be used without any limitations.
  • epoxidated fatty acid ester there is one manufactured by epoxidation of fatty acid ester, and examples thereof include epoxy methyl stearate, epoxy butyl stearate, and epoxy octyl stearate.
  • epoxidated glyceride there is one manufactured by epoxidation of soybean oil, linseed oil or castor oil, and examples thereof include epoxy soybean oil, epoxy linseed oil and epoxy castor oil.
  • the actinic ray curable composition the invention can contain a photopolymerization initiator, for example, a known photolytically acid generating agent.
  • photolytically acid generating agent for example, compounds used in a chemical amplification type photo resist or in a light cation polymerizable composition are used (Organic electronics material seminar “Organic material for imaging” from Bunshin publishing house (1993), refer to page 187-192). Examples suitable for the present invention will be listed below.
  • an onium compound for example, a B(C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CF 3 SO 3 ⁇ salt of an aromatic onium ion such as an aromatic diazonium, ammonium, iodonium, sulfonium, or phosphonium, can be listed.
  • an aromatic onium ion such as an aromatic diazonium, ammonium, iodonium, sulfonium, or phosphonium
  • sulfone compounds which generate sulfonic acid, can be listed. Examples thereof will be shown below.
  • halide compounds which generate hydrogen halide, can also be used. Examples thereof will be shown below.
  • iron arene complexes as described below can be listed.
  • a photolytically radical generating agent can be used in combination.
  • photolytically radical generating agents such as aryl alkyl ketone, oxime ketone, S-phenyl thiobenzoate, titanocene, aromatic ketones, thioxanthone, benzil, quinone derivatives and coumarin derivatives.
  • Those agents are described in detail in “Application and Market of UV ⁇ EB Hardening Technology”, edited by Radotech Kenkyuu Kai/supervised by Y. Tabata, published by CMC Syuppan.
  • acylphosphine oxide and acylphosphonate are particularly effective for internal hardening of an ink image layer having a thickness of from 5 to 12 ⁇ m per one color ink according to an ink-jet process, since they are high in the sensitivity and reduce the light absorption on account of their photodecomposition.
  • bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide are preferable.
  • 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1[4-methylthio]phenyl]-2-morpholinopropane-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphin oxide, and 2-hydroxy-2-methyl-1-phenylpropane-1-one are preferably used.
  • the addition amount of the photolytically radical generating agent is preferably from 1 to 6% by weight, and more preferably from 2 to 5% by weight, based on the ink composition.
  • the actinic ray curable ink of the invention contains any known dye or pigment, and preferably pigment, in addition to the actinic ray curable composition as described above.
  • Pigments preferably utilized in the invention will be listed below, but the invention is not limited thereto.
  • white ink is preferably utilized to increase a covering power of colors with transparent base materials such as a plastic film. It is preferable to utilize white ink, specifically in light package printing and label printing, however, due to increase of ejection amount, the using amount is naturally limited in respect to the above-mentioned ejection stability, and generation of curl and wrinkles of a recording material.
  • a ball mill, a sand mill, an attritor mill, a roll mill, an agitator, a Henshel mixer, a colloidal mixer, a ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, etc. can be utilized.
  • a dispersant can be added at dispersion of a pigment.
  • a polymer dispersant is preferably utilized and Soisperse Series manufactured by Avecia Co. is included.
  • a synergist corresponding to each kind of a pigment can also be utilized.
  • the dispersant and dispersion aid are preferably added in a range of from 1 to 50 weight parts based on 100 parts of a pigment.
  • a dispersion medium a solvent or a polymerizable compound is utilized, however, the actinic ray curable ink used in the invention is preferably an ink containing no solvent, since curing was carried out immediately after the ink was deposited on recording material.
  • the actinic ray curable ink used in the invention is preferably an ink containing no solvent, since curing was carried out immediately after the ink was deposited on recording material.
  • a solvent is left in a cured image, there caused problems of deterioration of resistance against solvents and VOC of residual solvent. Therefore, as a dispersion medium, polymerizable compounds are used but a solvent not. Particularly monomers having the lowest viscosity among them are preferably used in view of dispersion suitability.
  • dispersion of a pigment selection of a pigment, a dispersant and a dispersion medium, dispersion conditions and filtering conditions are suitably set so as to make a mean particle diameter of a pigment of preferably from 0.08 to 0.5 ⁇ m and the maximum particle diameter of from 0.3 to 10 ⁇ m and preferably from 0.3 to 3 ⁇ m.
  • a mean particle diameter of a pigment preferably from 0.08 to 0.5 ⁇ m and the maximum particle diameter of from 0.3 to 10 ⁇ m and preferably from 0.3 to 3 ⁇ m.
  • colorant concentration is preferably from 1 to 10 weight % based on the total ink.
  • a surfactant for example, a surfactant, a leveling additive, a matting agent, polyester type resin, polyurethane type resin, vinyl type resin, acryl type resin, rubber type resin and wax series can be added to the ink when necessary.
  • various basic compounds can be used. Examples of the basic compounds include a basic alkali metal compound, a basic alkali earth metal compound and an organic basic compound such as amine.
  • the actinic ray curable ink of the invention may be a radical and cationic polymerization hybrid curable ink further containing a radical polymerization composition comprising a radical polymerization monomer and a radical initiator.
  • the ink of the invention has an ink viscosity at 25° C. of from 7 to 50 mPa ⁇ s, since it provides good ejection stability regardless of ambient atmosphere conditions (such as temperature and humidity) and good curability.
  • plastic films include for example, a polyethylene terephthalate (PET) film, an oriented polystyrene (OPS) film, an oriented polypropylene (OPP) film, an oriented nylon (Ony) film, a polyvinyl chloride (PVC) film, a polyethylene (PE) film and a triacetyl cellulose (TAC) film.
  • PET polyethylene terephthalate
  • OPS oriented polystyrene
  • OPP oriented polypropylene
  • Ony oriented nylon
  • PVC polyvinyl chloride
  • PE polyethylene
  • TAC triacetyl cellulose
  • plastic films other than these polycarbonate, acryl resin, ABS, polyacetal, PVA and a rubber series can be utilized. A metal series and a glass series are also applicable.
  • Plastic films greatly differ in surface energy depending on the kinds, and heretofore, there has been a problem in that the ink dot diameter after ink deposition on recording material varies depending on the kinds of the recording materials.
  • the constitution of the invention can form an image with high precision on recording materials having a surface energy of from 35 to 60 mN/m, the recording materials ranging from those having a low surface energy such as an OPP or OPS film to those having a relatively high surface energy such as a PET film.
  • a long length roll (web) of a recording material is advantageously utilized in respect to a cost of a recording material such as a packaging cost and a manufacturing cost, an efficiency of print preparation and applicability to variety of print sizes.
  • the ink described above be ejected onto a recording material according to an ink jet recording method, and then cured by irradiation of actinic ray such as UV ray.
  • the thickness of an ink layer is preferably from 2 to 20 ⁇ m.
  • the total thickness of the ink is at present over 20 ⁇ m. Ink ejecting to give an excessive layer thickness is not preferred in the field of flexible package printing where a thin plastic film is used as a recording material, because problems are caused in that stiffness and texture of printed matter vary, in addition to problems of the aforementioned curl and wrinkles of recording material.
  • the thickness of ink layer refers to a maximum thickness of the ink layer deposited on recording material. This applies to a single color ink layer, and an overlapped layer of two different color (secondary color) inks, three different color inks or four different color inks (including white ink as a base ink), which are formed on recording material according to an ink jet recording process.
  • ink ejection is preferably performed while a recording head and ink being heated at from 35 to 100° C. in respect to ejection stability. Since actinic ray curable ink shows a large viscosity variation width depending on temperature variation and which in turn significantly influences a liquid droplet size and a liquid drop let ejection speed resulting in deterioration of image quality, it is required to keep an ink temperature constant while raising the ink temperature.
  • a control width of ink temperature is a set temperature ⁇ 5° C., preferably a set temperature ⁇ 2° C. and furthermore preferably a set temperature ⁇ 1° C.
  • the droplet volume of the ink ejected from each ink nozzle is preferably 2 to 15 pl.
  • the droplet volume of the ink has to be in the range described above to form images with high resolution, however, this droplet volume tends to lower the aforementioned ejection stability. In the invention, even when a small droplet volume such as 2 to 15 pl is ejected, ejection stability is improved, and images with high resolution can be formed.
  • actinic ray is irradiated 0.001 to 2.0 seconds after ink has been ejected on recording material, and it is more preferred that actinic ray is irradiated 0.001 to 1.0 second after ink has been ejected on recording material. It is specifically important that the irradiation timing be as early as possible in order to form an image with high resolution.
  • JP-A No. 60-132767 a basic method is disclosed in JP-A No. 60-132767, in which light sources are provided at the both sides of a head unit where a head and a light are scanned in a shuttle mode. Irradiation is performed in a certain time interval after ink has been ejected onto recording material. Further, curing is completed by another light source which is not driven.
  • a light irradiation method a method utilizing optical fiber, and a method in which collimated light source is reflected by a mirror provided on the side surface of a head unit and UV light (ultraviolet light) is irradiated on a recording portion are disclosed in U.S. Pat. No. 6,145,979. In an image forming method of the invention, any of these irradiation methods can be utilized.
  • a method is also a preferable embodiment, in which actinic ray irradiation is divided into two steps; firstly, a first actinic ray irradiation is carried between the period from 0.001 to 2.0 seconds after ink was deposited on recording material by the above-described method and further a second actinic ray irradiation is carried after printing has been completed. Shrinkage of recording materials caused at the time of ink curing can be depressed by dividing actinic ray irradiation into two steps.
  • an actinic ray having a maximum illuminance in a wavelength range from 280 to 320 nm is preferably used, and even when a light source a power exceeding 1 kW ⁇ hr is used, images with high resolution can be formed, and shrinkage of a recording material is in the permissible range.
  • the power of light sources irradiating an actinic ray is preferably less than 1 kW ⁇ hr.
  • the light sources having a power of less than 1 kW ⁇ hr include a fluorescent lamp, a cold cathode tube and an LED, but are not limited thereto.
  • An ink jet recording apparatus (hereinafter also referred to as a recording apparatus) in the invention will be explained.
  • the recording apparatus in the invention will be explained suitably in reference to a drawing.
  • the recording apparatus of the drawing is only an embodiment of a recording apparatus of the invention, and a recording apparatus of the invention is not limited to the drawing.
  • FIG. 1 shows a schematic view of one embodiment of the structure of the main section of the ink-jet recording apparatus of the invention.
  • Recording apparatus 1 is equipped with head carriage 2 , recording head 3 , irradiation means 4 and platen portion 5 .
  • platen portion 5 is arranged under recording material P.
  • Platen portion 5 has a UV ray absorbing function, and absorbs extra UV ray having passed through recording sheet P. As a result, images with high resolution can be reproduced quite stably.
  • Recording sheet P is guided by guide member 6 to be moved to the back side from the front side in FIG. 1 by operation of a transport means (not illustrated). Scan of recording heads 3 held in the head carriage 2 is made by reciprocating head carriage 2 in the R direction in FIG. 1 according to a head scanning means (not illustrated).
  • Head carriage 2 is provided over recording sheet P, and stores recording heads 3 described below with the ink ejection outlets arranged downward, the number of recording heads 3 being the same as that of different color inks used in an ink image formed on the recording sheet.
  • Head carriage 2 is provided in the main body of recording apparatus 1 so as to reciprocate in the R direction shown in FIG. 1 by a drive of a head scanning means.
  • FIG. 1 illustrates that head carriage 2 is supposed to store recording heads 3 each containing a white ink composition W, a yellow ink composition Y, a magenta ink composition M, a cyan ink composition C, a black ink composition K, a light yellow ink composition Ly, a light magenta ink composition Lm, a light cyan ink composition Lc, a light black ink composition Lk and a white ink composition W, however, the number of recording heads 3 stored in head carriage 2 in practical operation is suitably determined.
  • Recording heads 3 eject an actinic ray curable ink (for example, UV curable ink) to be supplied by means of an ink supplying means (not illustrated) from the ink ejection outlets onto recording sheet P by action of plural ejecting means (not illustrated) equipped in the recording apparatus. Ink to have been ejected from recording heads 3 is cured by UV irradiation.
  • an actinic ray curable ink for example, UV curable ink
  • the recording heads 3 eject ink as ink droplets onto a pre-determined region (a region capable of receiving the ink) of recording sheet P while the scan of the head is made in which the head moves from one edge to another of the recording sheet in the R direction in FIG. 1 by drive of the head scanning means, whereby the ink is deposited on that region of the recording sheet.
  • a pre-determined region a region capable of receiving the ink
  • the above scan is suitably made several times to elect ink onto one region of recording sheet. After that, while the recording sheet P is transported from the front side to the back side of the page in FIG. 1 by a transport means and the scan of the recording heads 3 is again made by the head scan means, ink is ejected from the recording heads onto a region adjacent to the one region of the recording sheet transported to the back side of the page.
  • Irradiation means 4 is equipped with a UV lamp which emits ultraviolet ray with a specific wavelength region at a stable exposure energy and a filter which transmits ultraviolet ray with a specific wavelength.
  • the UV lamp include a mercury lamp, a metal halide lamp, an excimer laser, a UV laser, a cold cathode tube, a black light, and an LED, and a metal halide lamp tube, a cold cathode tube, a mercury lamp tube and a black light, having a band-shape, are preferable.
  • a cold cathode tube and a black light which emit a 365 nm ultraviolet ray are preferable, which can prevent bleeding-out, efficiently control a dot diameter, and reduce wrinkles on curing.
  • Utilizing a black light as a radiation source of irradiation means 4 reduces a manufacturing cost of irradiation means 4 for ink curing.
  • Irradiation means 4 has the possible largest size which can be installed in the recording apparatus 1 (an ink jet printer) or the irradiation region of the irradiation means 4 is larger than the largest region of recording sheet, onto which ink is ejected by one time scan of recording heads 3 driven by the head scanning means.
  • the irradiation means 4 is arranged nearly in parallel with recording sheet 4 at the both sides of head carriage 2 , and fixed.
  • the whole of recording heads 3 is light-shielded, however, in addition, it is preferable to make distance h 2 between the ink ejection outlet 31 of recording heads 3 and recording sheet P longer than distance h 1 between irradiation means 4 and recording sheet P (h 1 ⁇ h 2 ) or to make distance d between recording heads 3 and irradiation means 4 long (to make d large). Further, it is more preferable to provide bellows structure 7 between recording heads 3 and irradiation means 4 .
  • the wavelength of ultraviolet rays, which are irradiated through irradiation means 4 can be suitably changed by exchange of a UV lamp or a filter, which is installed in irradiation means 4 .
  • the ink-jet ink of the invention has excellent ejection stability, and is useful especially when used in a line head type ink-jet recording apparatus.
  • FIG. 2 shows a schematic view of another embodiment of the structure of the main section of the ink-jet recording apparatus.
  • the ink-jet recording apparatus in FIG. 2 is called a line head type ink-jet recording apparatus.
  • Recording heads 3 are provided in a head carriage 2 to cover the entire width of recording sheet P.
  • the recording heads 3 each stores a different color ink, a white ink composition W, a yellow ink composition Y, a magenta ink composition M, a cyan ink composition C, a black ink composition K, and a white ink composition W.
  • Irradiation means 4 is provided just downstream of head carriage 2 to cover the entire width of recording sheet P and the entire printed surface.
  • a metal halide lamp can be used as a light source in the irradiation means 4 .
  • head carriage 2 and irradiation means 4 are fixed, and recording sheet P only is transported in the direction as shown in FIG. 2 .
  • Ink is ejected onto the recording sheet to be transported and then exposed through the irradiation means to form a cured image on the recording sheet.
  • a photopolymerizable compound, a photopolymerization initiator, a non-reactive compound and other additives as shown in Table 1 were mixed to obtain an actinic ray curable composition.
  • the resulting actinic ray curable composition was coated on a synthetic paper sheet (synthetic paper YUPO FGS, produced by YUPO CORPORATION) to form a layer with a thickness of 3 ⁇ m, and exposed to a 800 mJ/cm2 UV rays employing a metal halide lamp to obtain a cured coating layer.
  • synthetic paper YUPO FGS synthetic paper YUPO FGS, produced by YUPO CORPORATION
  • Viscosity was measured at a shear rate of 1000 (l/s) at 25° C., employing a viscoelasticity meter MCR 300 produced by Physica Co., Ltd.
  • Viscosity measured point Product (Trade name) (mPa ⁇ s) (° C.) (° C.) EXELPEARLHO (produced 14 25 228 by KAO CO., LTD.) EXCELPEARLIPM 6.6 25 304 (produced by KAO CO., LTD.) HISOLVE DB (produced 6.6 25 230 by TOHO CHEMICAL INDUSTRY CO., LTD.) HISOLVE BDB (produced 2.4 25 256 by TOHO CHEMICAL INDUSTRY CO., LTD.) HISOLVE BTM (produced 2.9 25 261 by TOHO CHEMICAL INDUSTRY CO., LTD.) HIMOL TM (produced by 8.3 25 249 TOHO CHEMICAL INDUSTRY CO., LTD.) Anisole 1.2 25 154 HISOL SAS296 (produced 8.3 25 300 by NIPPON PETROLEUM CHEMICAL CO., LTD.) Compounds used in the
  • the resulting cured layer was evaluated according to the following methods.
  • Hardness of the resulting layer was measured according to JIS K 5400.
  • Adhesive tape SCOTCH #250 (produced by SUMITOMO 3M CO., LTD.) was adhered onto the cured layer of a cured sample obtained according to the cross-cut adhesion test of JIS K 5400, and a 2 kg roller was reciprocated one time to press the adhered tape. After that, the tape was quickly peeled from the cured layer, and the percentage of the remaining layer was determined.
  • the resulting actinic ray curable composition was coated on a synthetic paper sheet YUPO FGS (produced by YUPO Corporation) to obtain a layer with a thickness of 30 ⁇ m, and exposed to 800 mJ/cm 2 UV rays within 1 second after coated, employing a metal halide lamp to form a cured layer.
  • the resulting cured layer was evaluated according to the flexibility test of JIS K 5600.
  • inventive samples provide a cured layer with improved adhesion and flexibility, and without lowering of hardness.
  • ink prepared from an actinic ray curable composition was evaluated.
  • the photopolymerizable compound shown in Table 5 and 5 parts by weight of dispersant PB822 (produced by AJINOMOTO CO., LTD.) were incorporated into a stainless steel beaker on a 65° C. hot plate and stirred for one hour to obtain a solution.
  • Each of the pigments as shown in Table 6 was added to the resulting solution, and incorporated in a plastic vessel together with 200 g of zirconia beads with a diameter of 1 mm.
  • the plastic vessel was tightly sealed and dispersed in a paint shaker for 2 hours to obtain a dispersion liquid.
  • the dispersion liquid was added with additives as shown in Table 5 such as the photopolymerization initiator, the basic compound and the surfactant, and filtered with a 0.8 ⁇ m membrane filter.
  • additives as shown in Table 5 such as the photopolymerization initiator, the basic compound and the surfactant, and filtered with a 0.8 ⁇ m membrane filter.
  • ink composition set sample was obtained, which included seven different color inks.
  • Viscosity of the ink prepared above was 20 to 30 mPa ⁇ S.
  • *-marked numerals represent the following: *1: Actinic Ray Curable Composition No., *2: Photopolymerizable Compound, *3: Oxetane compound, *4: Epoxy Compound, *5: Nonionic fluorine-containing surfactant, *6: Rosin-modified maleic acid resin, *7: 2-Methoxy-3,3-dimethyloxetane, *8: Celloxide 2021P, *9: Vf7010, Vikoflex 7010, produced by ATOFINA CO., LTD., *10: I-250, IRGACURE 250, *11: Tributylamine, *12: N-Ethyldiethanolamine, *13: MEGAFAC F1405, *14: MEGAFAC F178k, *15: MEGAFAC F179k, *16: HARITAC 145P, *17: HARITAC R100, *18: HARITAC R101,
  • Pigments used in the ink set samples are shown in Table 6.
  • Inks, Lk, Lc, Lm and Ly represent light color inks, and employed 1 ⁇ 5 of the amount used in inks K, C, M, and Y, respectively.
  • the ink set sample prepared above was mounted on an ink jet recording apparatus as shown in FIG. 1 equipped with a piezo-type ink jet nozzle, and image recording was performed continuously on each of 600 mm wide and 1000 m long recording sheets described later.
  • An ink supply system is comprised of an ink tank, a supply pipe, a pre-chamber ink tank directly before a head, a piping attached with a filter, and a piezo-head, and the portion from the pre-chamber tank to the head was heated at 50° C.
  • the piezo-head was appropriately heated to meet viscosity of each ink and driven so as to eject ink droplets of from 2 to 15 pl at a resolution of 720 dpi ⁇ 720 dpi. Thus, each ink was continuously ejected onto the recording sheet.
  • the recording sheet was heated to 50° C. by a heater. Within less than 0.5 seconds after ink was ejected and arrived at the recording sheet, exposure was carried out, employing the light sources on both sides of the carriage to form a cured ink image.
  • As the light source light source, light source A, a high pressure mercury lamp Vzero 085, produced by INTEGRATION TECHNOLOGY CO., or light source B, a metal halide lamp MAL400NL, produced by NIPPON DENCHI CO., LTD., 120 W/cm, output power: 3 kW ⁇ hr), was employed.
  • the total thickness of the resulting ink image layer was measured to be in a range of from 2.3 to 13 ⁇ m.
  • dpi represents a dot number per 2.54 cm.
  • the above ink image formation was carried out at 32° C. and 80% RH.
  • Luminance of each light source was measured through employing UVPF-A1 produced by IWASAKI DENKI CO., LTD., and integrated illuminance was determined.
  • Ink was continuously ejected for 30 minutes, and thereafter, failure of the ink was visually observed according to the following criteria.
  • 6-point MS Minchyc font characters were recorded at an aimed density, and the resulting characters were evaluated for roughness through a magnifying glass according to the following criteria.
  • inventive ink sets exhibit excellent ejection property, and improved image quality. Further, the inventive ink sets provide excellent results, regardless of ambient condition under which an ink image was recorded.
  • the present invention can provide an actinic ray curable composition with a low viscosity, which is capable of being cured with high speed, and forms a coating layer with high hardness under various operating conditions, an actinic ray curable ink employing it, an image formation method employing it, and an ink-jet recording apparatus employing it.
US12/562,595 2003-11-28 2009-09-18 Actinic ray curable composition, actinic ray curable ink, image formation method employing it, and ink-jet recording apparatus Abandoned US20100007708A1 (en)

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