WO2012132406A1 - 活性線硬化型インクジェット用インクおよびそれを用いた画像記録方法 - Google Patents
活性線硬化型インクジェット用インクおよびそれを用いた画像記録方法 Download PDFInfo
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- WO2012132406A1 WO2012132406A1 PCT/JP2012/002110 JP2012002110W WO2012132406A1 WO 2012132406 A1 WO2012132406 A1 WO 2012132406A1 JP 2012002110 W JP2012002110 W JP 2012002110W WO 2012132406 A1 WO2012132406 A1 WO 2012132406A1
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- ink
- actinic radiation
- radiation curable
- curable inkjet
- inkjet ink
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- 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
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- 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
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- 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
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- 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
- C09D11/12—Printing inks based on waxes or bitumen
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- 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
Definitions
- the present invention relates to an actinic radiation curable ink jet ink and an image recording method using the same.
- the ink jet recording method is used in various printing fields because it can form an image easily and inexpensively.
- As one of the ink jet recording methods there is an ultraviolet curable ink jet method in which droplets of ultraviolet curable ink are landed on a recording medium and then cured by irradiation with ultraviolet rays to form an image.
- the ultraviolet curable ink jet method has been attracting attention in recent years because it can form an image having high scratch resistance and adhesion even on a recording medium having no ink absorbability.
- high-speed recording is being performed for the ultraviolet curable ink jet method; for example, high-speed recording is being studied by a single-pass recording method or a high-speed serial method with a few passes.
- high-speed recording is performed, there is a problem in that since the interval between adjacent ink droplets (dots) is small, adjacent dots are likely to be united and image quality is likely to be degraded. In order to suppress such unification of adjacent dots, it has been studied to improve the pinning property of the ultraviolet curable ink-jet ink.
- the gelling agents of Patent Documents 1 and 2 have low solubility in the curable compound contained in the ink, there is a problem that the injection property is low even in a high temperature state. Specifically, the ink may be clogged with the nozzle, or the deposit of the gelling agent may adhere to the tip of the nozzle, which may reduce the straightness of the ink droplet.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide an actinic radiation curable ink jet ink that achieves both high pinning performance and high ejection performance.
- the present inventors have found that in order to improve the pinning property of the ink, it is preferable to increase the sol-gel phase transition rate, and the “specific ketone compound” is preferable as the gelling agent for realizing it.
- the gelling agent is a “specific ketone compound”, and an ink containing it alone has a problem that the ejection property is low as described above.
- the present inventors have found that an ink containing “specific ketone compound” and “specific ester compound” as a gelling agent is as high as pinning equivalent to an ink containing “specific ketone compound” alone. It has been found that the ink ejection properties can be improved while maintaining the properties.
- an ink containing a “specific ketone compound” and a “specific ester compound” exhibits higher pinning properties with less addition of a gelling agent than an ink containing a “specific ketone compound” alone.
- the present invention has been made based on such findings.
- the first of the present invention relates to the following actinic ray curable inkjet ink.
- An actinic radiation curable inkjet ink comprising an actinic radiation curable compound, a ketone wax, and an ester wax, and reversibly undergoes a sol-gel phase transition depending on temperature.
- the ketone wax is a compound A represented by the following general formula (1):
- R1 and R2 are each independently an aliphatic hydrocarbon group containing a straight chain portion having 9 to 25 carbon atoms
- the ester wax is a compound B represented by the general formula (2).
- R3 and R4 are each independently an aliphatic hydrocarbon group containing a straight chain portion having 9 to 26 carbon atoms
- [1] to [5] Actinic radiation curable inkjet ink [7]
- the total amount of the ketone wax and the ester wax is any one of [1] to [6], which is 0.5% by mass or more and less than 10% by mass with respect to the actinic radiation curable inkjet ink.
- Active ray curable ink jet ink [8] The actinic radiation curable type according to [1] to [6], wherein the total amount of the ketone wax and the ester wax is 1% by mass or more and less than 7% by mass with respect to the actinic radiation curable inkjet ink. Ink for inkjet. [9] The actinic radiation curable inkjet ink according to any one of [1] to [8], wherein the actinic radiation curable compound is a (meth) acrylate compound. [10] The actinic radiation curable inkjet ink according to [9], wherein the (meth) acrylate compound is an ethylene oxide-modified (meth) acrylate compound.
- R1 and R2 are aliphatic hydrocarbon groups including a straight chain portion having 11 to 23 carbon atoms. Actinic radiation curable inkjet ink.
- R1 and R2 are linear alkylene groups having 11 or more and less than 23 carbon atoms, and for actinic radiation curable inkjet according to any one of [6] to [10] ink.
- R3 is an aliphatic hydrocarbon group including a straight chain portion having 11 to 23 carbon atoms
- R4 is a straight chain portion having 12 to 24 carbon atoms.
- R3 is a linear alkylene group having 11 to 23 carbon atoms
- R4 is a linear alkylene group having 12 to 24 carbon atoms
- [6] The actinic radiation curable inkjet ink according to any one of [12] to [12].
- [15] The actinic radiation curable inkjet ink according to any one of [1] to [14], wherein the ketone wax contains 18-pentatriacontanone.
- the second of the present invention relates to the following image recording method.
- the temperature of the ink inside the recording head is higher by 10 ° C. or higher and 30 ° C. or lower than the gel temperature of the ink.
- the gel temperature of the ink is 75 mm in diameter and 1.0 in cone angle. When the temperature is decreased from 100 ° C. to 20 ° C.
- an actinic radiation curable ink jet ink that has both high pinning properties and high ejection properties.
- Actinic radiation curable inkjet ink includes at least an actinic radiation curable compound, a specific ketone compound A, and a specific ester compound B, and if necessary, a photopolymerization initiator or the like. Further, it may be included.
- actinic radiation curable compound is a photopolymerizable compound that crosslinks or polymerizes upon irradiation with actinic radiation.
- the actinic rays are, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, and preferably ultraviolet rays and electron beams.
- the actinic radiation curable compound is a radical polymerizable compound or a cationic polymerizable compound, and is preferably a radical polymerizable compound.
- the radical polymerizable compound is a compound (monomer, oligomer, polymer or mixture thereof) having an ethylenically unsaturated bond capable of radical polymerization.
- a radically polymerizable compound may be used independently and may be used in combination of 2 or more type.
- Examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include an unsaturated carboxylic acid and a salt thereof, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid urethane compound, an unsaturated carboxylic acid amide compound and an anhydride thereof, Examples include acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.
- Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.
- the radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth) acrylate compound.
- the (meth) acrylate compound may be not only a monomer described later, but also an oligomer, a mixture of a monomer and an oligomer, a modified product, an oligomer having a polymerizable functional group, and the like.
- Examples of (meth) acrylate compounds include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) ) Acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate , Methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (Meth)
- stearyl (meth) acrylate lauryl (meth) acrylate, isostearyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, tetraethylene glycol di (meth) acrylate , Glycerin propoxytri (meth) acrylate and the like are preferable.
- the (meth) acrylate compound may be a modified product.
- examples thereof include ethylene oxide-modified (meth) acrylate compounds such as ethylene oxide-modified trimethylolpropane tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetraacrylate; Caprolactone-modified (meth) acrylate compounds such as caprolactone-modified trimethylolpropane tri (meth) acrylate; and caprolactam-modified (meth) acrylate compounds such as caprolactam-modified dipentaerythritol hexa (meth) acrylate and the like are included.
- an ethylene oxide-modified (meth) acrylate compound is preferable from the viewpoint of high photosensitivity and easy formation of a card house structure described later when gelling at a low temperature.
- the ethylene oxide-modified (meth) acrylate compound is easily dissolved in other ink components at high temperatures and has little curing shrinkage, so that curling of the printed matter hardly occurs.
- Examples of ethylene oxide-modified (meth) acrylate compounds include 4EO-modified hexanediol diacrylate CD561 (molecular weight 358), 3EO-modified trimethylolpropane triacrylate SR454 (molecular weight 429), 6EO-modified trimethylolpropane triacrylate SR499 manufactured by Sartomer. (Molecular weight 560), 4EO-modified pentaerythritol tetraacrylate SR494 (molecular weight 528); Shin-Nakamura Chemical Co., Ltd.
- polyethylene glycol diacrylate NK ester A-400 (molecular weight 508), polyethylene glycol diacrylate NK ester A-600 (molecular weight 742) , Polyethylene glycol dimethacrylate NK ester 9G (molecular weight 536), polyethylene glycol dimethacrylate NK Este 14G (molecular weight 770); Tetraethylene glycol diacrylate V # 335HP (molecular weight 302) manufactured by Osaka Organic Chemical Co .; 3PO-modified trimethylolpropane triacrylate Photomer 4072 (molecular weight 471, ClogP 4.90) manufactured by Cognis; Shin-Nakamura Chemical 1,10-decanediol dimethacrylate NK ester DOD-N (molecular weight 310, Clog P 5.75), tricyclodecane dimethanol diacrylate NK ester A-DCP (molecular weight 304, Clog P 4.69) and tricyclodecane Methanol dimethacrylate NK este
- the (meth) acrylate compound may be a polymerizable oligomer.
- polymerizable oligomers include epoxy (meth) acrylate oligomers, aliphatic urethane (meth) acrylate oligomers, aromatic urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and linear (meth) acrylic. Oligomers and the like are included.
- the cationically polymerizable compound can be an epoxy compound, a vinyl ether compound, an oxetane compound, or the like.
- the cationically polymerizable compound may be contained alone in the actinic radiation curable ink jet ink, or two or more of them may be contained.
- the epoxy compound is an aromatic epoxide, an alicyclic epoxide, an aliphatic epoxide, or the like, and an aromatic epoxide or an alicyclic epoxide is preferable in order to increase curability.
- the aromatic epoxide may be a di- or polyglycidyl ether obtained by reacting a polyhydric phenol or an alkylene oxide adduct thereof with epichlorohydrin.
- examples of the polyhydric phenol to be reacted or its alkylene oxide adduct include bisphenol A or its alkylene oxide adduct.
- the alkylene oxide in the alkylene oxide adduct can be ethylene oxide, propylene oxide, and the like.
- the alicyclic epoxide can be a cycloalkane oxide-containing compound obtained by epoxidizing a cycloalkane-containing compound with an oxidizing agent such as hydrogen peroxide or peracid.
- the cycloalkane in the cycloalkane oxide-containing compound can be cyclohexene or cyclopentene.
- the aliphatic epoxide can be a di- or polyglycidyl ether obtained by reacting an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof with epichlorohydrin.
- the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, alkylene glycol such as 1,6-hexanediol, and the like.
- the alkylene oxide in the alkylene oxide adduct can be ethylene oxide, propylene oxide, and the like.
- vinyl ether compounds include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether.
- -Monovinyl ether compounds such as o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether; Diethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane trivinyl ether, etc. Or a trivinyl ether compound etc. are contained. Of these vinyl ether compounds, di- or trivinyl ether compounds are preferred in view of curability and adhesion.
- the oxetane compound is a compound having an oxetane ring, and examples thereof include oxetane compounds described in JP-A Nos. 2001-220526, 2001-310937, and JP-A-2005-255821.
- the compound represented by the general formula (1) described in paragraph No. 0089 of JP-A No. 2005-255821 the compound represented by the general formula (2) described in paragraph No. 0092 of the same publication
- the paragraph Examples include a compound represented by general formula (7) of number 0107, a compound represented by general formula (8) of paragraph number 0109, a compound represented by general formula (9) of paragraph number 0116, and the like.
- the general formulas (1), (2), (7) to (9) described in JP-A-2005-255821 are shown below.
- the content of the actinic radiation curable compound is preferably 1 to 97% by mass, more preferably 30 to 95% by mass with respect to the actinic radiation curable inkjet ink.
- Ketone waxes and ester waxes can act as gelling agents.
- the “wax” is an organic substance that is solid at normal temperature and melts when heated; specifically, an organic substance having a melting point of 30 ° C. or higher and lower than 150 ° C.
- Gelling agent gives a function of reversibly sol-gel phase transition of ink depending on temperature.
- a gelling agent must be at least 1) soluble in the actinic radiation curable compound at a temperature higher than the gelling temperature, and 2) crystallized in the ink at a temperature below the gelling temperature. It is.
- a plate crystal which is a crystallized product of the gelling agent forms a space three-dimensionally and encloses the active ray curable compound in the space. It is preferable.
- a structure in which the active ray curable compound is included in a space three-dimensionally surrounded by the plate-like crystal is sometimes referred to as a “card house structure”.
- the liquid actinic radiation curable compound can be retained and ink droplets can be pinned. Thereby, coalescence of droplets can be suppressed.
- the actinic radiation curable compound dissolved in the ink and the gelling agent are compatible.
- the active ray curable compound dissolved in the ink and the gelling agent are phase-separated, it may be difficult to form a card house structure.
- the present inventors combine gelling agents having similar chemical structures and different crystallinities; Found that it is effective to combine a gelling agent having high crystallinity with a gelling agent having low crystallinity.
- the ink when the ink falls below a certain temperature, first, crystal nuclei of the gelling agent having high crystallinity are precipitated. Next, a crystal of a gelling agent having low crystallinity grows and precipitates around the precipitated crystal nucleus.
- the sol-gel phase transition rate of the ink containing the gelling agent having different crystallinity is as high as that of the ink containing the gelling agent having high crystallinity alone.
- the ink containing the gelling agent having different crystallinity includes a gelling agent having low crystallinity, the ink has high solubility at high temperatures and high ejection properties. Furthermore, since these gelling agents having different crystallinities have chemical structures similar to each other, the crystal structure after crystallization becomes uniform, so that the film strength of the image after curing can be increased.
- the actinic radiation curable inkjet ink of the present invention contains at least two kinds of gelling agents having a similar chemical structure and different crystallinity.
- the gelling agent having high crystallinity is preferably a ketone wax.
- a ketone wax refers to a wax having a ketone group.
- the number of carbon atoms in the molecule constituting the ketone wax is preferably 19 or more and less than 100. If the number of carbon atoms in the molecule is 100 or more, the melting point of the ketone wax may be too high. On the other hand, when the number of carbon atoms in the molecule is less than 19, the ketone wax may not be sufficiently crystallized.
- the number of ketone groups contained in the molecules constituting the ketone wax is not particularly limited, but is preferably one. That is, the ketone wax is preferably Compound A represented by the following general formula (1).
- R1 and R2 in the formula (1) each independently represent a saturated or unsaturated hydrocarbon group.
- the hydrocarbon group represented by R1 and R2 may be linear or branched.
- the total number of carbons contained in the hydrocarbon group represented by R1 and R2 is preferably 20 or more and less than 100.
- the hydrocarbon groups represented by R1 and R2 in the formula (1) are preferably each independently an aliphatic hydrocarbon group containing a straight chain portion having 9 to 25 carbon atoms.
- the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group represented by R1 and R2 is less than 9, it does not function as a gelling agent because it does not have sufficient crystallinity, and the card described above In the house structure, a sufficient space for encapsulating the actinic radiation curable compound cannot be formed.
- the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group exceeds 25, the melting point becomes too high, so that the ink does not dissolve in the ink unless the ink ejection temperature is increased.
- the above-mentioned card house structure can be formed while having the crystallinity necessary as a gelling agent, and the melting point Is not too high.
- the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group of R1 and R2 is preferably 11 or more and less than 23.
- Examples of the aliphatic hydrocarbon group containing a straight chain portion having 9 to 25 carbon atoms include docosanyl group (C22), icosanyl group (C20), octadecanyl group (C18), heptadecanyl group (C17), hexadecanyl group ( C16), pentadecanyl group (C15), tetradecanyl group (C14), tridecanyl group (C13), dodecanyl group (C12), undecanyl group (C11), decanyl group (C10) and the like.
- the aliphatic hydrocarbon group represented by R1 and R2 in the formula (1) may be a saturated or unsaturated aliphatic hydrocarbon group, but is preferably a saturated aliphatic carbon group from the viewpoint of increasing the gelation temperature. It is a hydrogen group (alkylene group). If the R1 and R2 aliphatic hydrocarbon groups in the formula (1) have the same number of carbon atoms, the melting point of the compound in which R1 and R2 in the formula (1) are saturated aliphatic hydrocarbon groups is It is often higher than the melting point of the compound (1) in which R1 and R2 are unsaturated aliphatic hydrocarbon groups, and the gelation temperature tends to be high.
- the saturated aliphatic hydrocarbon group may be a branched or straight chain aliphatic hydrocarbon group, but in order to obtain high crystallinity, a straight chain saturated aliphatic hydrocarbon group (straight chain alkylene) is preferable.
- Group a straight chain saturated aliphatic hydrocarbon group (straight chain alkylene) is preferable.
- R1 and R2 in the general formula are particularly preferably a linear saturated aliphatic hydrocarbon group (straight chain alkylene group) having 11 to 23 carbon atoms.
- Examples of the compound represented by the formula (1) include 25-nonatetracontanone (C24-C24), 22-tritetracontanone (C21-C21, melting point 88 ° C.), 19-heptatricontanone (C18- C18), 18-pentatriacontanone (C17-C17, melting point 84 ° C.), 21-hentetracontanone (C20-C20), 16-hentriacontanone (C15-C15, melting point 80 ° C.), 14-heptacosanone (C13-C13), 12-tricosanone (C11-C11, melting point 68 ° C.), 11-hencosanone (C10-C10), 13-heptacosanone (C12-C14), 13-nonacosanone (C12-C16), 13-hentria Contanon (C12-C18), 13-Pentatria Contanone (C12-C22), 15-Hentry Cont
- Examples of commercially available compounds represented by formula (1) include 18-Pentriacontanon (AlfaAlAeser), Hentriacontan-16-on (Alfa Aeser), Kao Wax T1 (Kao Corporation), and the like. included. Since these commercially available products are often a mixture of two or more kinds, they may be used after being separated and purified as necessary.
- the ketone wax contained in the actinic radiation curable ink-jet ink may be composed of one kind of compound represented by the formula (1), and two or more kinds of compounds represented by the formula (1) are contained. It may be a mixture.
- the gelling agent having low crystallinity is preferably an ester wax.
- An ester wax refers to a wax containing an ester group.
- the number of ester groups in the molecule constituting the ester wax is not particularly limited, but is preferably one. That is, the compound B represented by the following general formula (2) is preferable.
- R3 and R4 in the formula (2) each independently represent a saturated or unsaturated hydrocarbon group.
- the hydrocarbon group may be linear or branched.
- the total number of carbon atoms of the hydrocarbon group represented by R3 and R4 in the general formula (2) is preferably 20 or more and less than 100.
- the hydrocarbon group represented by R3 and R4 is not particularly limited, but is preferably an aliphatic hydrocarbon group including a straight chain portion having 9 to 26 carbon atoms.
- the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group represented by R3 and R4 is 9 or more and 26 or less, it is necessary as a gelling agent as in the compound represented by the formula (1). While having crystallinity, the above-mentioned card house structure can be formed, and the melting point is not too high.
- the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group of R3 is 11 or more and less than 23, and the fatty acid of R4 It is preferable that the straight chain portion contained in the group hydrocarbon group has 12 or more and less than 24 carbon atoms.
- Examples of the aliphatic hydrocarbon group containing a straight chain part having 9 to 26 carbon atoms are the same as the aliphatic hydrocarbon group containing a straight chain part having 9 to 25 carbon atoms in the above formula (1). Is included.
- the aliphatic hydrocarbon group represented by R3 and R4 may be a saturated or unsaturated aliphatic hydrocarbon group, but is preferably a saturated aliphatic hydrocarbon group (alkylene group).
- the saturated aliphatic hydrocarbon group may be a branched or straight-chain saturated aliphatic hydrocarbon group, but in order to obtain a certain level of crystallinity, preferably a straight-chain saturated aliphatic hydrocarbon group Group (straight chain alkylene group). That is, it is particularly preferable that R3 is a linear alkylene group having 11 to 23 carbon atoms, and R4 is a linear alkylene group having 12 to 24 carbon atoms.
- Examples of the compound represented by the formula (2) include behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), stearyl stearate (C17-C18, melting point 60 ° C.), stearin Palmitate (C17-C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16, melting point 54 ° C.), stearyl palmitate (C15-C18), myristyl myristate (C13-C14, melting point 43 ° C.) ), Cetyl myristate (C13-C16, melting point 50 ° C.), octyldodecyl myristate (C13-C20), lauryl laurate (C11-C12, melting point 30 ° C.), cetyl caprate (C9-C16, melting point 30 ° C.) , Stearyl oleate (
- Examples of commercially available compounds represented by formula (2) include UNISTA-M-2222SL (manufactured by NOF Corporation), EXCEPARL SS (manufactured by Kao Corporation, melting point 60 ° C.), EMALEX® CC-18 (Japan Emulsion) Included), Amreps PC (manufactured by Higher Alcohol Industry Co., Ltd.), Exepar® MY-M (manufactured by Kao Corporation), Spalm Acechi (manufactured by NOF Corporation), EMALEX CC-10 (manufactured by Nippon Emulsion Co., Ltd.), etc. It is. Since these commercially available products are often a mixture of two or more kinds, they may be used after being separated and purified as necessary.
- the ester wax contained in the actinic radiation curable inkjet ink may be composed of one type of compound represented by the formula (2), and two or more types of compounds represented by the formula (1) are included. It may be a mixture.
- the crystallinity of ketone wax (for example, compound A represented by formula (1)) is higher than that of ester wax (for example, compound B represented by formula (2)).
- ester wax for example, compound B represented by formula (2).
- the crystallinity of the ketone wax and the ester wax varies depending on the number of linear carbon atoms contained in each wax.
- One of the indicators of the crystallinity of a compound is its melting point.
- the aliphatic hydrocarbon group of R1 of the formula (1) that is a ketone wax is similar to the aliphatic hydrocarbon group of R3 of the formula (2) that is an ester wax (for example, the number of carbon atoms of both is similar).
- the aliphatic hydrocarbon group represented by R2 in the formula (1) and the aliphatic hydrocarbon group represented by R4 in the formula (2) are similar (for example, the number of carbon atoms of both is approximate)
- the melting point of the compound A represented by the formula (1) which is a ketone wax is higher than the melting point of the compound B represented by the formula (2) which is an ester wax.
- a ketone wax and ester wax have a similar chemical structure.
- the aliphatic hydrocarbon group of R1 of the formula (1) which is a ketone wax is similar to the aliphatic hydrocarbon group of R3 of the formula (2) which is an ester wax, and the fat of the R2 of the formula (1)
- the aliphatic hydrocarbon group and the aliphatic hydrocarbon group of R4 in the formula (2) are similar. Therefore, the melting point of the ketone wax is preferably higher than the melting point of the ester wax, and the melting point of the compound A represented by the formula (1) is preferably higher than the melting point of the compound B represented by the formula (2).
- the melting point of the compound with the highest content (the main component compound) in the ketone wax group has the highest content in the ester wax group. It is preferably higher than the melting point of a compound having a large amount (compound as a main component).
- the ketone wax group includes compound A-1 and compound A-2 (content: compound A-1> compound A-2), and the ester wax group includes compound B-1 and compound B-2 (content)
- the melting point of the compound A-1 which is the main component of the ketone wax group is higher than the melting point of the compound B-1 which is the main component of the ester wax group. preferable.
- the melting points of all the compounds of the ketone wax group contained in the ink are preferably 30 ° C. or more and less than 150 ° C. from the viewpoint of the handleability of the ink.
- the temperature is more preferably 60 ° C. or higher and 100 ° C. or lower.
- the melting points of all the compounds of the ester wax group contained in the ink are preferably 30 ° C. or higher and lower than 150 ° C. from the viewpoint of ink handling properties.
- the upper limit is more preferably 100 ° C., and preferably 30 ° C. or higher and 75 ° C. or lower in order to improve the ink ejection properties.
- the difference between the melting point of the compound that is the main component of the ketone wax group and the melting point of the compound that is the main component of the ester wax group is preferably 5 ° C. or more, more preferably 10 ° C. or more. preferable.
- the content ratio of ketone wax to ester wax is 1/9 to 9 in terms of mass ratio, although it depends on the gelling temperature setting temperature and the required pinning properties and ink ejection properties. / 1 is preferable. In order to increase the gelation temperature of the ink, the content ratio of the ketone wax may be increased.
- the total amount of ketone wax and ester wax is preferably 0.5% by mass or more and less than 10% by mass, more preferably 1% by mass or more and less than 7% by mass with respect to the actinic radiation curable inkjet ink. preferable. If the total amount of the ketone wax and the ester wax is less than 0.5% by mass, the ink cannot be gelled (sol-gel phase transition due to temperature), and if it exceeds 10% by mass, it is sufficiently dissolved in the ink. This is because the ink ejection property is lowered.
- the actinic radiation curable ink-jet ink may further contain other gelling agent as required, as long as the effects of the present invention are not impaired.
- other gelling agents include a high molecular compound and a low molecular weight compound, and a low molecular weight compound is preferable in order to improve the ejection properties of the ink.
- gelling agents for polymer compounds include fatty acid inulins such as inulin stearate; fatty acid dextrins such as dextrin palmitate and dextrin myristate (such as the Leopard series manufactured by Chiba Flour Mills); glyceryl behenate, glyceryl behenate, behenic acid Eikosan polyglyceryl and the like (Nisshin Oilio Co., Ltd. Nomucoat series etc.) are included.
- gelling agents for low molecular compounds include An aliphatic diketone compound other than the compound represented by the formula (1); An aliphatic ester compound other than the compound represented by the formula (2); Low molecular oil gelling agents described in JP-A-2005-126507, JP-A-2005-255821 and JP-A-2010-111170; Amide compounds such as N-lauroyl-L-glutamic acid dibutylamide and N- (2-ethylhexanoyl) -L-glutamic acid dibutylamide (available from Ajinomoto Fine Techno); Dibenzylidene sorbitols such as 1,3: 2,4-bis-O-benzylidene-D-glucitol (available from Gelol D Shin Nippon Rika); Petroleum waxes such as paraffin wax, microcrystalline wax and petrolactam; plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba
- N-substituted fatty acid amides such as N-stearyl stearic acid amide, N-oleyl palmitic acid amide; Special fatty acid amides such as N, N'-ethylenebisstearylamide, N, N'-ethylenebis12-hydroxystearylamide, and N, N'-xylylenebisstearylamide; Higher amines such as dodecylamine, tetradecylamine or octadecylamine; Stearyl stearic acid, oleyl palmitic acid, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, polyoxyethylene fatty acid ester, etc.
- Sucrose fatty acid esters such as sucrose stearic acid and sucrose palmitic acid (for example, Ryoto Sugar Ester series manufactured by Mitsubishi Chemical Foods); Synthetic waxes such as polyethylene wax and ⁇ -olefin maleic anhydride copolymer wax (UNILIN series manufactured by Baker-Petrolite); Dimer acid; dimer diol (such as PRIDA series produced by CRODA) and the like are included.
- These gelling agents may be used alone or in combination of two or more.
- the actinic radiation curable inkjet ink may further contain a photopolymerization initiator as necessary.
- a photopolymerization initiator may ordinarily not be included.
- a photopolymerization initiator is preferably included.
- Photopolymerization initiators include an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.
- Examples of intramolecular bond cleavage type photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4 Acetophenones such as -thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether; Acylphosphine oxide
- intramolecular hydrogen abstraction type photopolymerization initiators examples include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl Benzophenone series such as sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; Thioxanthone systems such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Mihira-ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-
- the content of the photopolymerization initiator is preferably 0.01% by mass to 10% by mass with respect to the actinic radiation curable inkjet ink, although it depends on the type of actinic radiation and the actinic radiation curable compound.
- the actinic radiation curable inkjet ink may contain a photoacid generator as a photopolymerization initiator.
- photoacid generators include chemically amplified photoresists and compounds used for photocationic polymerization (Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. See page 192).
- the actinic radiation curable inkjet ink may further contain a photopolymerization initiator auxiliary agent, a polymerization inhibitor, and the like, if necessary.
- the photopolymerization initiator assistant may be a tertiary amine compound, preferably an aromatic tertiary amine compound.
- aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included.
- N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. These compounds may be used alone or in combination of two or more.
- polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-Dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxi
- the actinic radiation curable inkjet ink may further contain a color material as necessary.
- the coloring material can be a dye or a pigment, but is preferably a pigment because it has good dispersibility with respect to the components of the ink and is excellent in weather resistance.
- the pigment is not particularly limited, and may be, for example, an organic pigment or an inorganic pigment having the following numbers described in the color index.
- red or magenta pigments examples include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, etc. are included.
- Examples of blue or cyan pigments include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60 and the like.
- Examples of green pigments include Pigment Green 7, 26, 36, and 50.
- Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137. 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193 and the like.
- Examples of the black pigment include Pigment Black 7, 28, 26 and the like.
- Examples of commercially available pigments include chromofine yellow 2080, 5900, 5930, AF-1300, 2700L, chromofine orange 3700L, 6730, chromofine scarlet 6750, chromofine magenta 6880, 6886, 6891N, 6790, 6887, chromo Fine Violet RE, Chromo Fine Red 6820, 6830, Chromo Fine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromofine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromopha Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY
- the pigment can be dispersed by, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like.
- the actinic radiation curable inkjet ink may further contain a dispersant in order to enhance the dispersibility of the pigment.
- the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester , Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate and the like are included.
- Examples of commercially available dispersants include Avecia's Solsperse
- the actinic radiation curable inkjet ink may further contain a dispersion aid as necessary.
- the dispersion aid may be selected according to the pigment.
- the total amount of the dispersing agent and the dispersing aid is preferably 1 to 50% by mass with respect to the pigment.
- the actinic radiation curable inkjet ink may further include a dispersion medium for dispersing the pigment as necessary.
- a solvent may be included in the ink as a dispersion medium.
- the actinic radiation curable compound particularly a monomer having a low viscosity as described above is used as the dispersion medium. It is preferable.
- the pigment is dispersed so that the average particle diameter of the pigment particles is preferably 0.08 to 0.5 ⁇ m, and the maximum particle diameter is preferably 0.3 to 10 ⁇ m, more preferably 0.3 to 3 ⁇ m. Is preferred.
- the dispersion of the pigment is adjusted by the selection of the pigment, the dispersant, and the dispersion medium, the dispersion conditions, the filtration conditions, and the like.
- the dye can be an oil-soluble dye or the like.
- oil-soluble dyes include the following various dyes.
- magenta dyes include MS Magenta VP, MS Magenta HM-1450, MS Magenta HSo-147 (above, manufactured by Mitsui Toatsu), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOTRed-3, AIZEN SOT Pink-1, SPIRON Red GEH SPECIAL (above, manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MACROLEX Red Violet R, MACROLEX ROT5B (above, manufactured by Bayer Japan Co., Ltd.), KAYASET Red B, KAYA 802 (above, Nippon Kayaku Co., Ltd.), PHLOXIN, ROSE Bengal, ACID Red (above, Manufactured by Iva Kasei), HSR-31, DIARESIN Red K (manufactured by Mitsubishi Kasei Corp
- cyan dyes examples include MS Cyan HM-1238, MS Cyan HSo-16, Cyan HSo-144, MS Cyan VPG (manufactured by Mitsui Toatsu), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN BR. Blue BGLN 200%, MACROLEX Blue RR, CERES Blue GN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUTRA TURQ. Blue FB-LL 330% (from Bayer Japan), KAYASET Blue FR, KAYASET Blue N, KAYASET Blue 814, Turq.
- Blue GL-5 200 Light Blue BGL-5 200 (Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Olesol Fast Blue GL (Daiwa Kasei Co., Ltd.), DIARESIN Blue P (Mitsubishi Chemical Co., Ltd.) Blue 670, NEOPEN Blue 808, ZAPON Blue 806 (above, manufactured by BASF Japan Ltd.) and the like are included.
- yellow dyes examples include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (Mitsui Toatsu), AIZEN SOT Yellow-1, AIZEN SOT Yellow W-3, AIZEN SOT Yellow-6 (above, Hodogaya (Manufactured by Kagakusha), MACROLEX Yellow 6G, MACROLEX FLUOR.
- black dyes examples include MS Black VPC (Mitsui Toatsu Co., Ltd.), AIZEN SOT Black-1, AIZEN SOT Black-5 (above, manufactured by Hodogaya Chemical Co., Ltd.), RESORIN Black GSN 200%, RESOLIN BlackBS (above, Bayer Japan), KAYASET Black AN (Nippon Kayaku), DAIWA Black MSC (Daiwa Kasei), HSB-202 (Mitsubishi Kasei), NEPTUNE Black X60, NEOPEN Black X58 (above, BASF) Japan product).
- the content of the pigment or dye is preferably from 0.1 to 20% by mass, more preferably from 0.4 to 10% by mass, based on the actinic radiation curable inkjet ink. This is because if the content of the pigment or dye is too small, the color of the resulting image is not sufficient, and if it is too large, the viscosity of the ink increases and the jetting property decreases.
- the actinic radiation curable ink-jet ink may further contain other components as necessary.
- Other components may be various additives, other resins, and the like.
- the additive include a surfactant, a leveling additive, a matting agent, an ultraviolet absorber, an infrared absorber, an antibacterial agent, and a basic compound for enhancing the storage stability of the ink.
- basic compounds include basic alkali metal compounds, basic alkaline earth metal compounds, basic organic compounds such as amines, and the like.
- other resins include resins for adjusting the physical properties of the cured film, such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes. It is.
- the actinic radiation curable inkjet ink contains a gelling agent as described above, it undergoes a sol-gel phase transition reversibly depending on the temperature.
- Actinic radiation curable ink that undergoes a sol-gel phase transition is liquid at a high temperature (for example, about 80 ° C.), and thus can be ejected from an inkjet recording head.
- the actinic radiation curable inkjet ink is ejected at a high temperature, the ink droplets (dots) land on the recording medium and then naturally cool to gel. Thereby, coalescence of adjacent dots can be suppressed and image quality can be improved.
- the viscosity of the ink at a high temperature is not more than a certain level.
- the viscosity at 80 ° C. of the actinic ray curable inkjet ink is preferably 3 to 20 mPa ⁇ s.
- the viscosity of the ink at normal temperature after landing is a certain level or more.
- the viscosity at 25 ° C. of the actinic radiation curable inkjet ink is preferably 1000 mPa ⁇ s or more.
- the gelation temperature of the ink is preferably 40 ° C. or higher and 70 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
- the gelation temperature of the ink exceeds 70 ° C. when the ejection temperature is around 80 ° C., gelation tends to occur at the time of ejection, resulting in low ejection properties.
- the gelation temperature is less than 40 ° C., the recording medium This is because it does not gel immediately after landing.
- the gelation temperature is a temperature at which the fluidity decreases due to gelation in the process of cooling the ink in the sol state.
- the viscosity of the ink at 80 ° C., the viscosity at 25 ° C., and the gelation temperature can be determined by measuring the temperature change of the dynamic viscoelasticity of the ink with a rheometer. Specifically, a temperature change curve of viscosity is obtained when the ink is heated to 100 ° C. and cooled to 20 ° C. under conditions of a shear rate of 11.7 (/ s) and a temperature decrease rate of 0.1 ° C./s. And the viscosity in 80 degreeC and the viscosity in 25 degreeC can be calculated
- the gelation temperature can be determined as the temperature at which the viscosity becomes 200 mPa ⁇ s in the temperature change curve of the viscosity.
- the rheometer can be a stress control type rheometer Physica MCR series manufactured by Anton Paar.
- the cone plate can have a diameter of 75 mm and a cone angle of 1.0 °.
- the actinic radiation curable ink-jet ink can be obtained by mixing each component containing the actinic radiation curable compound and the gelling agent under heating.
- the actinic radiation curable ink-jet ink of the present invention contains two or more kinds of compounds (ketone wax and ester wax) having different crystallinity. For this reason, the actinic radiation curable ink jet ink has high ejection properties at high temperatures and a high sol-gel phase transition rate, and thus gels quickly after landing (high pinning property). Thereby, the unification of adjacent dots can be suppressed and the image quality can be improved.
- the temperature of the ink when filled in the ejection recording head is set to (gelation temperature + 10) of the ink in order to improve the ejection property of the ink from the ejection recording head. ) ° C. to (gelling temperature + 30) ° C. is preferable.
- the temperature of the ink in the ejection recording head is less than (gelation temperature + 10) ° C., the ink is gelled in the ejection recording head or on the nozzle surface, and the ink ejection property is likely to deteriorate.
- the temperature of the ink in the ejection recording head exceeds (gelation temperature + 30) ° C., the ink becomes too high, and the ink component may deteriorate.
- Actinic radiation curable inkjet recording apparatuses include a line recording method (single pass recording method) and a serial recording method.
- the line recording method is preferable from the viewpoint of high-speed recording, although it may be selected according to the required image resolution and recording speed.
- FIG. 1 is a diagram illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus.
- Fig.1 (a) is a side view
- FIG.1 (b) is a top view.
- the inkjet recording apparatus 10 covers a head carriage 16 that accommodates a plurality of ejection recording heads 14 and the entire width of the recording medium 12, and is downstream of the head carriage 16 (the conveyance direction of the recording medium).
- An active ray irradiation unit 18 disposed on the side and a temperature control unit 19 disposed on the lower surface of the recording medium 12 are provided.
- the head carriage 16 is fixedly arranged so as to cover the entire width of the recording medium 12, and accommodates a plurality of ejection recording heads 14 provided for each color.
- Ink is supplied to the ejection recording head 14.
- the ink may be supplied directly or by an ink supply unit (not shown) from an ink cartridge (not shown) that is detachably attached to the inkjet recording apparatus 10.
- a plurality of ejection recording heads 14 are arranged in the transport direction of the recording medium 12 for each color.
- the number of ejection recording heads 14 arranged in the conveyance direction of the recording medium 12 is set according to the nozzle density of the ejection recording head 14 and the resolution of the print image. For example, when an image having a resolution of 1440 dpi is formed using the ejection recording head 14 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four ejection recording heads 14 are shifted with respect to the conveyance direction of the recording medium 12. What is necessary is just to arrange.
- dpi represents the number of ink droplets (dots) per 2.54 cm.
- the active ray irradiating unit 18 covers the entire width of the recording medium 12 and is arranged on the downstream side of the head carriage 16 in the conveyance direction of the recording medium.
- the actinic radiation irradiation unit 18 irradiates the droplets ejected by the ejection recording head 14 and landed on the recording medium with the actinic radiation to cure the droplets.
- examples of the active ray irradiation unit 18 include a fluorescent tube (low pressure mercury lamp, germicidal lamp), a cold cathode tube, an ultraviolet laser, and an operating pressure of several hundred Pa to 1 MPa. These include low pressure, medium pressure, high pressure mercury lamps, metal halide lamps and LEDs. From the viewpoint of curability, ultraviolet irradiation means for irradiating ultraviolet rays having an illuminance of 100 mW / cm 2 or more; specifically, high-pressure mercury lamps, metal halide lamps, and LEDs are preferable, and LEDs are more preferable from the viewpoint of low power consumption. Specifically, a 395 nm, water-cooled LED manufactured by Phoseon Technology can be used.
- examples of the active beam irradiation unit 18 include electron beam irradiation units such as a scanning method, a curtain beam method, and a broad beam method. Therefore, a curtain beam type electron beam irradiation means is preferable.
- Examples of electron beam irradiation means include “Curetron EBC-200-20-30” manufactured by Nissin High Voltage Co., Ltd., “Min-EB” manufactured by AIT Co., Ltd., and the like.
- the temperature control unit 19 is disposed on the lower surface of the recording medium 12 and maintains the recording medium 12 at a predetermined temperature.
- the temperature control unit 19 can be, for example, various heaters.
- the recording medium 12 is conveyed between the head carriage 16 and the temperature control unit 19 of the inkjet recording apparatus 10.
- the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19.
- high-temperature ink is ejected from the ink ejection recording head 14 of the head carriage 16 and adhered (landed) on the recording medium 12.
- the actinic radiation irradiating unit 18 irradiates the ink droplets attached on the recording medium 12 with the actinic radiation and cures the ink droplets.
- the temperature of the ink in the ejection recording head 14 is 10 to 30 ° C. higher than the gelation temperature of the ink in order to improve the ink ejection property. It is preferable to set to.
- the ink temperature in the ejection recording head 14 is less than (gelation temperature + 10) ° C., the ink gels in the ejection recording head 14 or on the nozzle surface, and the ink ejection property is likely to deteriorate.
- the temperature of the ink in the ejection recording head 14 exceeds (gelation temperature + 30) ° C., the ink becomes too high, and the ink component may deteriorate.
- the amount of droplets ejected from each nozzle of the ink ejection recording head 14 is preferably 1 pl to 10 pl in order to form a high resolution image, although it depends on the resolution of the image. More preferably, it is 0.5 to 4.0 pl.
- Irradiation with actinic rays is performed within 10 seconds, preferably within 0.001 seconds to 5 seconds, more preferably after ink droplets are deposited on the recording medium, in order to prevent the adjacent ink droplets from coalescing. It is preferable to carry out within 0.01 second to 2 seconds.
- the irradiation of the active ray is preferably performed after ink is ejected from all the ink ejection recording heads 14 accommodated in the head carriage 16.
- the acceleration voltage of electron beam irradiation is preferably 30 to 250 kV, more preferably 30 to 100 kV, in order to perform sufficient curing.
- the electron beam irradiation amount is preferably 30 to 100 kGy, and more preferably 30 to 60 kGy.
- the total ink film thickness after curing is preferably 2 to 25 ⁇ m.
- the “total ink film thickness” is the maximum value of the ink film thickness drawn on the recording medium.
- FIG. 2 is a diagram illustrating an example of a configuration of a main part of the serial recording type inkjet recording apparatus 20.
- the inkjet recording apparatus 20 has a width narrower than the entire width of the recording medium, instead of the head carriage 16 fixedly arranged so as to cover the entire width of the recording medium, and a plurality of ink ejection devices. Except for having a head carriage 26 that accommodates the recording head 24 and a guide portion 27 for moving the head carriage 26 in the width direction of the recording medium 12, the configuration can be the same as in FIG.
- the head carriage 26 is ejected from the ejection recording head 24 accommodated in the head carriage 26 while moving in the width direction of the recording medium 12 along the guide portion 27. After the head carriage 26 has completely moved in the width direction of the recording medium 12 (for each pass), the recording medium 12 is fed in the transport direction. Except for these operations, an image is recorded in substantially the same manner as the line recording type inkjet recording apparatus 10 described above.
- Example 1 Preparation of Pigment Dispersion Liquid 1 (M: Magenta) The following dispersant, actinic ray curable compound and polymerization inhibitor were placed in a stainless beaker and heated and stirred for 1 hour while heating on a hot plate at 65 ° C. Dissolved. After cooling the resulting solution to room temperature, 21 parts by mass of the following magenta pigment 1 was added, sealed in a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm, and dispersed for 8 hours with a paint shaker. Thereafter, the zirconia beads were removed to prepare a pigment dispersion 1 having the following composition.
- M Magenta
- Dispersant Azisper PB824 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 9 parts by mass
- Actinic ray curable compound APG-200 (tripropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 70 parts by mass
- Polymerization inhibitor Irgastab UV10 (Ciba Japan) 0.02 part by mass
- Magenta pigment 1 Pigment Red 122 (manufactured by Dainichi Seika, Chromo Fine Red 6112JC)
- Actinic radiation curable compound A-400 (polyethylene glycol # 400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 32.0 parts by mass: SR494 (4EO-modified pentaerythritol tetraacrylate, manufactured by SARTOMER) 17.0 parts by mass: SR499 ( 6EO-modified trimethylolpropane triacrylate (manufactured by SARTOMER) 17.9 parts by mass Ketone wax (compound A represented by formula (1)) : 18-pentatriacontanone 1.5 parts by mass 16-hentriacontanone 0.5 parts by mass Ester wax (compound B represented by formula (2)) : Behenyl behenylate 1.0 part by mass Polymerization inhibitor: Irgastab UV10 (manufactured by Ciba Japan) 0.1 parts by mass Photopolymerization initiator: TPO (phosphine oxide, DAROCURE TPO, manufactured by Ciba Japan) 6.0
- Example 2 An ink was prepared in the same manner as in Example 1 except that the composition of the ink was changed as shown in Table 1.
- Example 9 An ink was prepared in the same manner as in Example 1 except that the composition of the ink was changed as shown in Table 2.
- Example 17 to 19 An ink was prepared in the same manner as in Example 1 except that the composition of the ink was changed as shown in Table 4.
- the physical properties (viscosity at 25 ° C. and 80 ° C., gelation temperature) of the inks obtained in the respective examples and comparative examples were measured by the following methods.
- the obtained ink was set in a stress control type rheometer (Physica MCR300, manufactured by Anton Paar) capable of controlling temperature. Next, after the ink was heated to 100 ° C., it was cooled to 20 ° C. under conditions of a temperature drop rate of 0.1 ° C./s and a shear rate of 11.7 (/ s), and the dynamic viscoelasticity at the time of temperature drop was measured. The dynamic viscoelasticity was measured using a cone plate (CP75-1, manufactured by Anton Paar) having a diameter of 75.033 mm and a cone angle of 1.017 °. Moreover, temperature control was performed by the Peltier device type
- TEK150P / MC1 mold temperature control apparatus attached to PhysicaMCR300.
- the viscosities at 25 ° C. and 80 ° C. were read, respectively, as “viscosity at 25 ° C.” and “viscosity at 80 ° C.”.
- the temperature at which the viscosity reached 200 cP or higher was read from the obtained dynamic viscoelastic temperature change curve and was defined as “gelation temperature (° C.)”.
- an image was formed by the following method using a line-type ink jet recording apparatus, using the ink obtained in each of the examples and comparative examples.
- Image forming method (single color image forming method) A monochrome (magenta) image was formed using a line recording type inkjet recording apparatus. Specifically, coated paper A for printing (OK top coat, US basis weight 128 g / m 2 manufactured by Oji Paper Co., Ltd.) was prepared, and the temperature was adjusted to 25 ° C. by a temperature control unit. On the other hand, the obtained ink was filled in an ejection recording head of an ink jet recording apparatus and heated so that the ink temperature was 80 ° C. Then, ink droplets were ejected onto the coated paper A for printing, and a blank character and a solid image of 5 cm ⁇ 5 cm were formed. Thereafter, the ink was cured by irradiating ultraviolet rays with an LED lamp (395 nm manufactured by Phoseon Technology, water-cooled LED) disposed in the downstream portion of the ink jet recording apparatus to form an image.
- LED lamp 395 nm manufactured by Phoseon Technology, water-cooled LED
- a piezo head having a nozzle diameter of 20 ⁇ m and a nozzle number of 512 nozzles (256 nozzles ⁇ 2 rows, staggered arrangement, 1 row nozzle pitch 360 dpi) was used.
- the ejection conditions were such that the droplet volume was 2.5 pl, and the droplet was ejected at a droplet velocity of about 6 m / s and recorded at a resolution of 1440 dpi ⁇ 1440 dpi.
- the recording speed was 500 mm / s.
- Image formation was performed in an environment of 23 ° C. and 55% RH.
- dpi represents the number of dots per 2.54 cm.
- Density unevenness A solid image of 5 cm ⁇ 5 cm was formed on the coated paper A for printing by the above-described image forming method and visually observed. The density unevenness of the solid image was evaluated based on the following criteria. ⁇ : Density unevenness is not recognized even when observed from a position 15 cm away. ⁇ : Density unevenness is observed in a part of the image when observed from a position 15 cm away, but density unevenness is observed when observed from a position 30 cm away. X: Density unevenness is observed even when observed from a position 30 cm away
- Table 1 shows the evaluation results of Examples 1 to 8; Table 2 shows the evaluation results of Examples 9 to 16; Table 3 shows the evaluation results of Comparative Examples 1 to 5; Table 4 shows the results of Examples 17 to 19 Each is shown.
- ketone wax for example, compound A represented by formula (1)
- a specific ester wax for example, compound B represented by formula (2)
- the inks of Examples 1 to 19 including the ink can achieve both high character quality and high ejection stability.
- the ink of Comparative Example 1 cannot improve the character quality because the ketone compound content is too small.
- the inks of Comparative Examples 2 to 3 containing only the ketone compound as the gelling agent have relatively high character quality, but have low ejection stability.
- the ink of the comparative example 4 which contains only an ester compound as a gelatinizer has comparatively high injection stability, it turns out that character quality is low.
- the ink of Comparative Example 5 contains a ketone compound and an ester compound as gelling agents, it can be seen that the pinning property is low since the character quality is low. This is presumably because the number of carbon atoms of the alkylene group of the ester compound contained in the ink of Comparative Example 5 is less than 9, and the crystallinity is too low.
- Pigment Dispersion Liquid 3 (C: Cyan) Instead of magenta pigment 1, 21 parts by weight of Pigment Blue 15: 4 (Dainipei Seika Co., Ltd., Chromofine Blue 6332JC) was added, together with 200 g of zirconia beads having a diameter of 0.5 mm.
- a pigment dispersion 3 was prepared in the same manner as in the preparation of the pigment dispersion 1 of Example 1 except that it was sealed in a glass bottle and dispersed for 5 hours with a paint shaker.
- Pigment Dispersion 4 (Y: Yellow) Instead of magenta pigment 1, 21 parts by weight of Pigment Yellow 150 (E4GN-GT CH20015, manufactured by LANXESS) was added to a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm. A pigment dispersion 4 was prepared in the same manner as in the preparation of the pigment dispersion 1 of Example 1 except that it was sealed and dispersed for 8 hours using a paint shaker.
- Actinic radiation curable compound A-400 (polyethylene glycol # 400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30.0 parts by mass: SR494 (4EO-modified pentaerythritol tetraacrylate, manufactured by SARTOMER) 17.0 parts by mass: SR499 ( 6EO-modified trimethylolpropane triacrylate (manufactured by SARTOMER) 17.9 parts by mass Compound A represented by formula (1): 18-pentatriacontanone 1.5 parts by mass 16-hentriacontanone 0.5 parts by mass Compound B represented by the formula (2): stearyl stearate 2.0 parts by mass cetyl palmitate 1.0 part by mass Polymerization inhibitor: Irgastab UV10 (manufactured by Ciba Japan) 0.1 parts by mass Photopolymerization initiator: TPO (phosphine oxide, DAROCURE TPO manufactured by Ciba Japan) 6.0 parts by mass
- Image forming method (color image forming method) A color image was formed using a line recording type ink jet recording apparatus. Specifically, the obtained four color inks (Y, M, C, K) were filled in the respective ejection recording heads of the ink jet recording apparatus and heated to 80 ° C.
- coated paper A for printing (OK top coat, US basis weight 128 g / m 2 manufactured by Oji Paper Co., Ltd.), coated paper B for printing (New Age US basis weight 105 g / m 2 manufactured by Oji Paper Co., Ltd.), and polyethylene A terephthalate film (white pet, manufactured by Maru Adhesion Co., Ltd.) was prepared.
- Ink droplets were ejected on each recording medium under the same conditions as in the above-described image forming method to form an image of JIS / SCID N5 “bicycle” in A4 size. Thereafter, the ink was cured by irradiating ultraviolet rays with an LED lamp (Phoseon Technology 395 nm, water-cooled LED) disposed in the downstream portion of the ink jet recording apparatus to form an image.
- LED lamp Phoseon Technology 395 nm, water-cooled LED
- Example 18 In the color image forming method, a color image was formed in the same manner as in Example 17 except that the temperature of the ink in the ejection recording head was changed as shown in Table 5, and 1) character image quality and 2) density unevenness. 3) Scratch resistance, 4) Ink ejection stability was evaluated. The results are shown in Table 5.
- the injection temperature is as low as 72 ° C. (Example 18) or as high as 100 ° C. (Example 19). It can also be seen that it has a relatively good injection stability.
- an actinic radiation curable ink jet ink that has both high pinning properties and high ejection properties.
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Abstract
Description
[2]前記ケトンワックスの融点が、前記エステルワックスの融点より高い、[1]に記載の活性線硬化型インクジェット用インク。
[3]前記ケトンワックスの融点と前記エステルワックスの融点との差は10℃以上である、[1]又は[2]に記載の活性線硬化型インクジェット用インク。
[4]前記ケトンワックス及び前記エステルワックスを構成する分子中の炭素の数が、それぞれ19以上100未満である、[1]~[3]のいずれかに記載の活性線硬化型インクジェットインク。
[5]前記ケトンワックスおよび前記エステルワックスの融点が、それぞれ30℃以上150℃未満である[1]~[4]のいずれかに記載の活性線硬化型インクジェットインク。
[6]前記ケトンワックスが、下記一般式(1)で表される化合物Aであり、
前記エステルワックスが、一般式(2)で表される化合物Bである、
[7]前記ケトンワックス及び前記エステルワックスの合計量が、活性線硬化型インクジェット用インクに対して0.5質量%以上10質量%未満である、[1]~[6]のいずれかに記載の活性線硬化型インクジェット用インク。
[8]前記ケトンワックス及び前記エステルワックスの合計量が、活性線硬化型インクジェット用インクに対して1質量%以上7質量%未満である、[1]~[6]に記載の活性線硬化型インクジェット用インク。
[9]前記活性線硬化性化合物は、(メタ)アクリレート化合物である、[1]~[8]のいずれかに記載の活性線硬化型インクジェット用インク。
[10]前記(メタ)アクリレート化合物は、エチレンオキサイド変性(メタ)アクリレート化合物である、[9]に記載の活性線硬化型インクジェット用インク。
[11]前記一般式(1)において、R1およびR2は、炭素原子数11以上23未満の直鎖部分を含む脂肪族炭化水素基である、[6]~[10]のいずれかに記載の活性線硬化型インクジェット用インク。
[12]前記一般式(1)において、R1およびR2は、炭素原子数11以上23未満の直鎖アルキレン基である、[6]~[10]のいずれかに記載の活性線硬化型インクジェット用インク。
[13]前記一般式(2)において、R3は、炭素原子数11以上23未満の直鎖部分を含む脂肪族炭化水素基であり、かつR4は、炭素原子数12以上24未満の直鎖部分を含む脂肪族炭化水素基である、[6]~[12]のいずれかに記載の活性線硬化型インクジェット用インク。
[14]前記一般式(2)において、R3は、炭素原子数11以上23未満の直鎖アルキレン基であり、かつR4は、炭素原子数12以上24未満の直鎖アルキレン基である、[6]~[12]のいずれかに記載の活性線硬化型インクジェット用インク。
[15]前記ケトンワックスは、18-ペンタトリアコンタノンを含む、[1]~[14]のいずれかに記載の活性線硬化型インクジェット用インク。
[16]二種類以上のケトンワックスを含む、[1]~[15]のいずれかに記載の活性線硬化型インクジェット用インク。
[17]直径75mm、コーン角1.0°のコーンプレート型レオメータにより、80℃、剪断速度11.7/sにおいて測定される粘度が3~20mPa・sである、[1]~[16]のいずれかに記載の活性線硬化型インクジェット用インク。
[18]直径75mm、コーン角1.0°のコーンプレート型レオメータにより、25℃、剪断速度11.7/sにおいて測定される粘度が1000mPa・s以上である、[1]~[17]のいずれかに記載の活性線硬化型インクジェット用インク。
[19]直径75mm、コーン角1.0°のコーンプレート型レオメータにより、100℃から、降温速度0.1℃/s、剪断速度11.7/sで20℃に降温したときに、粘度が200mPa・sとなるゲル化温度が、40℃以上70℃以下である、[1]~[18]のいずれかに記載の活性線硬化型インクジェット用インク。
[20]前記[1]~[19]のいずれかに記載の活性線硬化型インクジェット用インクの液滴を、記録ヘッドから吐出させて記録媒体上に付着させる工程と、前記記録媒体上に付着した液滴に活性線を照射して硬化させる工程と、を含む、画像記録方法。
[21]前記記録ヘッドの内部における前記インクの温度は、前記インクのゲル化温度よりも10℃以上30℃以下高く、前記インクのゲル化温度は、前記インクを直径75mm、コーン角1.0°のコーンプレート型レオメータにより、100℃から、降温速度0.1℃/s、剪断速度11.7/sで20℃に降温したときに、インクの粘度が200mPa・sとなる温度である、[20]に記載の画像記録方法。
[22]シングルパス記録モードにより画像を記録する、[20]または[21]に記載の画像記録方法。
活性線硬化型インクジェット用インクは、少なくとも活性線硬化性化合物と、特定のケトン化合物Aと、特定のエステル化合物Bとを含み、必要に応じて光重合開始剤等をさらに含んでもよい。
活性線硬化性化合物は、活性線の照射により架橋または重合する光重合性化合物である。活性線は、例えば電子線、紫外線、α線、γ線、およびエックス線等であり、好ましくは紫外線および電子線である。活性線硬化性化合物は、ラジカル重合性化合物またはカチオン重合性化合物であり、好ましくはラジカル重合性化合物である。
トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ジメチロール-トリシクロデカンジ(メタ)アクリレート、ビスフェノールAのPO付加物ジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレート、ポリテトラメチレングリコールジ(メタ)アクリレート等の二官能モノマー;
トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、グリセリンプロポキシトリ(メタ)アクリレート、ペンタエリスリトールエトキシテトラ(メタ)アクリレート等の三官能以上の多官能モノマー等が含まれる。
エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、トリメチロールプロパントリビニルエーテル等のジまたはトリビニルエーテル化合物等が含まれる。これらのビニルエーテル化合物のうち、硬化性や密着性などを考慮すると、ジまたはトリビニルエーテル化合物が好ましい。
ケトンワックスと、エステルワックスは、ゲル化剤として作用しうる。本発明において「ワックス」とは、常温で固体であり、加熱すると溶融する有機物;具体的には、融点が30℃以上150℃未満である有機物をいう。
前述の式(1)で表される化合物以外の脂肪族ジケトン化合物;
前述の式(2)で表される化合物以外の脂肪族エステル化合物;
特開2005-126507号公報、特開2005-255821号公報および特開2010-111790号公報に記載の低分子オイルゲル化剤;
N-ラウロイル-L-グルタミン酸ジブチルアミド、N-(2-エチルヘキサノイル)-L-グルタミン酸ジブチルアミド等のアミド化合物(味の素ファインテクノより入手可能);
1,3:2,4-ビス-O-ベンジリデン-D-グルシトール(ゲルオールD 新日本理化より入手可能)等のジベンジリデンソルビトール類;
パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタム等の石油系ワックス;キャンデリラワックス、カルナウバワックス、ライスワックス、木ロウ、ホホバ油、ホホバ固体ロウ、およびホホバエステル等の植物系ワックス;ミツロウ、ラノリンおよび鯨ロウ等の動物系ワックス;モンタンワックス、および水素化ワックス等の鉱物系ワックス;硬化ヒマシ油または硬化ヒマシ油誘導体;モンタンワックス誘導体、パラフィンワックス誘導体、マイクロクリスタリンワックス誘導体またはポリエチレンワックス誘導体等の変性ワックス;ベヘン酸、アラキジン酸、ステアリン酸、パルミチン酸、ミリスチン酸,ラウリン酸、オレイン酸、およびエルカ酸等の高級脂肪酸;
ステアリルアルコール、ベヘニルアルコール等の高級アルコール;
12-ヒドロキシステアリン酸等のヒドロキシステアリン酸;
12-ヒドロキシステアリン酸誘導体;
ラウリン酸アミド、ステアリン酸アミド、ベヘン酸アミド、オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、12-ヒドロキシステアリン酸アミド等の脂肪酸アミド(例えば日本化成社製 ニッカアマイドシリーズ、伊藤製油社製 ITOWAXシリーズ、花王社製 FATTYAMIDシリーズ等);
N-ステアリルステアリン酸アミド、N-オレイルパルミチン酸アミド等のN-置換脂肪酸アミド;
N,N′-エチレンビスステアリルアミド、N,N′-エチレンビス12-ヒドロキシステアリルアミド、およびN,N′-キシリレンビスステアリルアミド等の特殊脂肪酸アミド;
ドデシルアミン、テトラデシルアミンまたはオクタデシルアミンなどの高級アミン;
ステアリルステアリン酸、オレイルパルミチン酸、グリセリン脂肪酸エステル,ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、エチレングリコール脂肪酸エステル、ポリオキシエチレン脂肪酸エステル等の脂肪酸エステル化合物(例えば日本エマルジョン社製 EMALLEXシリーズ、理研ビタミン社製 リケマールシリーズ、理研ビタミン社製 ポエムシリーズ等);
ショ糖ステアリン酸、ショ糖パルミチン酸等のショ糖脂肪酸エステル(例えばリョートーシュガーエステルシリーズ 三菱化学フーズ社製);
ポリエチレンワックス、α-オレフィン無水マレイン酸共重合体ワックス等の合成ワックス(Baker-Petrolite社製 UNILINシリーズ等);
ダイマー酸;ダイマージオール(CRODA社製 PRIPORシリーズ等)等が含まれる。これらのゲル化剤は、単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
活性線硬化型インクジェット用インクは、必要に応じて光重合開始剤をさらに含んでもよい。具体的には、活性線が電子線である場合は、通常、光重合開始剤は含まれなくてもよいが、活性線が紫外線である場合は、光重合開始剤が含まれることが好ましい。
ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン類;
2,4,6-トリメチルベンゾインジフェニルホスフィンオキシド等のアシルホスフィンオキシド系;
ベンジルおよびメチルフェニルグリオキシエステル等が含まれる。
2-イソプロピルチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン等のチオキサントン系;
ミヒラ-ケトン、4,4′-ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系;
10-ブチル-2-クロロアクリドン、2-エチルアンスラキノン、9,10-フェナンスレンキノン、カンファーキノン等が含まれる。
活性線硬化型インクジェット用インクは、必要に応じて色材をさらに含んでもよい。色材は、染料または顔料でありうるが、インクの構成成分に対して良好な分散性を有し、かつ耐候性に優れることから、顔料が好ましい。顔料は、特に限定されないが、例えばカラーインデックスに記載される下記番号の有機顔料または無機顔料でありうる。
活性線硬化型インクジェット用インクは、必要に応じて他の成分をさらに含んでもよい。他の成分は、各種添加剤や他の樹脂等であってよい。添加剤の例には、界面活性剤、レベリング添加剤、マット剤、紫外線吸収剤、赤外線吸収剤、抗菌剤、インクの保存安定性を高めるための塩基性化合物等も含まれる。塩基性化合物の例には、塩基性アルカリ金属化合物、塩基性アルカリ土類金属化合物、アミンなどの塩基性有機化合物などが含まれる。他の樹脂の例には、硬化膜の物性を調整するための樹脂などが含まれ、例えばポリエステル系樹脂、ポリウレタン系樹脂、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、およびワックス類等が含まれる。
本発明に用いられる活性線硬化型インクジェット方式のインクジェット記録装置について説明する。活性線硬化型インクジェット方式のインクジェット記録装置には、ライン記録方式(シングルパス記録方式)のものと、シリアル記録方式のものと、がある。求められる画像の解像度や記録速度に応じて選択されればよいが、高速記録の観点では、ライン記録方式(シングルパス記録方式)が好ましい。
(実施例1)
1)顔料分散液1(M:マゼンタ)の調製
下記の分散剤、活性線硬化性化合物および重合禁止剤を、ステンレスビーカーに入れ、65℃のホットプレート上で加熱しながら1時間加熱攪拌して溶解させた。得られた溶液を室温まで冷却後、下記のマゼンタ顔料1を21質量部加えて、直径0.5mmのジルコニアビーズ200gとともにガラス瓶に入れて密栓し、ペイントシェーカーにて8時間分散処理した。その後、ジルコニアビーズを除去して、下記組成の顔料分散液1を調製した。
分散剤:アジスパーPB824(味の素ファインテクノ社製) 9質量部
活性線硬化性化合物:APG-200(トリプロピレングリコールジアクリレート、新中村化学社製) 70質量部
重合禁止剤:Irgastab UV10(チバ・ジャパン社製) 0.02質量部
マゼンタ顔料1:Pigment Red 122(大日精化製、クロモファインレッド6112JC)
得られた顔料分散液1と、下記の化合物とを混合して、80℃に加熱して攪拌した。得られた溶液を加熱下において#3000の金属メッシュフィルタで濾過した後、冷却してインクを調製した。
活性線硬化性化合物:A-400(ポリエチレングリコール#400ジアクリレート、新中村化学社製) 32.0質量部
:SR494(4EO変性ペンタエリスリトールテトラアクリレート、SARTOMER社製) 17.0質量部
:SR499(6EO変性トリメチロールプロパントリアクリレート、SARTOMER社製) 17.9質量部
ケトンワックス(式(1)で表される化合物A)
:18-ペンタトリアコンタノン 1.5質量部
16-ヘントリアコンタノン 0.5質量部
エステルワックス(式(2)で表される化合物B)
:ベヘニル酸ベヘニル 1.0質量部
重合禁止剤:Irgastab UV10(チバ・ジャパン社製)
0.1質量部
光重合開始剤:TPO(フォスフィンオキサイド、DAROCURE TPO チバ・ジャパン社製) 6.0質量部
光重合開始剤助剤:ITX(イソプロピルチオキサントン、Speedcure ITX Lambson社製) 2.0質量部
:EDB(アミン助剤、Speedcure EDB Lambson社製) 3.0質量部
顔料分散液1: 19.0質量部
インクの組成を表1に示されるように変更した以外は実施例1と同様にしてインクを調製した。
インクの組成を表2に示されるように変更した以外は実施例1と同様にしてインクを調製した。
インクの組成を表3に示されるように変更した以外は実施例1と同様にしてインクを調製した。
インクの組成を表4に示されるように変更した以外は実施例1と同様にしてインクを調製した。
得られたインクを、温度制御可能なストレス制御型レオメータ(PhysicaMCR300、Anton Paar社製)にセットした。次いで、インクを100℃に加熱した後、降温速度0.1℃/s、剪断速度11.7(/s)の条件で20℃に冷却し、降温時の動的粘弾性を測定した。動的粘弾性の測定は、直径75.033mm、コーン角1.017°のコーンプレート(CP75-1、Anton Paar社製)を用いた。また、温度制御は、PhysicaMCR300に付属のペルチェ素子型温度制御装置(TEK150P/MC1)により行った。
ライン記録方式のインクジェット記録装置を用いて、単色(マゼンタ)の画像を形成した。具体的には、印刷用コート紙A(OKトップコート 米坪量128g/m2 王子製紙社製)を準備し、温度制御部により25℃に調温した。一方、得られたインクを、インクジェット記録装置の吐出用記録ヘッドに充填し、インク温度が80℃となるように加温した。そして、印刷用コート紙A上にインク滴を吐出させて、抜き文字と、5cm×5cmのベタ画像を形成した。その後、インクジェット記録装置の下流部に配置したLEDランプ(Phoseon Technology社製395nm、水冷LED)により紫外線を照射して、インクを硬化させて、画像を形成した。
前述の画像形成方法により、印刷用コート紙A上に、漢字「口、四、日、回、因、困、固、国、目、図、國」の抜き文字を印字した。抜き文字は、解像度1400dpi×1440dpi、3ポイントおよび5ポイントのMS明朝体とした。印字した文字画像を目視観察した。文字品質は、以下の基準に基づいて評価した。
○:3ポイントの抜き文字全てが、細部まで明瞭に記録されている
△:3ポイントの抜き文字は一部しか判読できないが、5ポイントの抜き文字全てが判読可能である
×:5ポイントの抜き文字の中にも判読できないものがある
前述の画像形成方法により、印刷用コート紙A上に、5cm×5cmのベタ画像を形成し、目視観察した。ベタ画像の濃度ムラは、以下の基準に基づいて評価した。
○:15cm離れた位置から観察しても、濃度ムラが認められない
△:15cm離れた位置から観察すると、画像の一部において濃度ムラが認められるが、30cm離れた位置から観察すると、濃度ムラが認められない
×:30cm離れた位置から観察しても、濃度ムラが認められる
前述の画像形成方法により、印刷用コート紙A上に、5cm×5cmのベタ画像を形成した。形成したベタ画像上に、「JIS規格 K5701-1 6.2.3 耐摩擦性試験」に記載の方法に準拠して、適切な大きさに切り取った印刷用コート紙Aを載置し、荷重をかけて擦り合わせた。その後、ベタ画像の濃度低下の程度を目視観察した。耐擦過性を、以下の基準に基いて評価した。
○:50回以上擦っても、画像濃度の変化はまったく認められない
△:50回擦った段階で、画像濃度の低下が認められるが、実用上許容されるレベルである
×:50回未満擦った段階で、明らかな画像濃度の低下が認められ、実用に耐えないレベルである
得られたインクを、インクジェット記録装置の吐出用記録ヘッドに充填し、吐出用記録ヘッドから出射させたときの、ノズル欠を目視観察した。出射安定性は、以下の基準に基づいて評価した。
○:ノズル欠の発生が全く認められなかった
△:512個の全ノズルのうち、1~4個のノズルでノズル欠が認められた
×:512個の全ノズルのうち、5個以上のノズルでノズル欠が認められた
(実施例17)
1)顔料分散液2~4の調製
実施例1で調製した顔料分散液1(M:マゼンタ)に加えて、さらに以下の顔料分散液2~4を調製した。
顔料分散液2(K:ブラック)の調製
マゼンタ顔料1の代わりに、Pigment Black7(三菱化学社製、#52)を21質量部加えて、直径0.5mmのジルコニアビーズ200gとともにガラス瓶に入れて密栓し、ペイントシェーカーにて5時間分散処理した以外は、実施例1の顔料分散液1の調製方法と同様にして顔料分散液2を調製した。
マゼンタ顔料1の代わりに、Pigment Blue15:4(大日精化社製、クロモファインブルー6332JC)を21質量部加えて、直径0.5mmのジルコニアビーズ200gとともにガラス瓶に入れて密栓し、ペイントシェーカーにて5時間分散処理した以外は、実施例1の顔料分散液1の調製方法と同様にして顔料分散液3を調製した。
マゼンタ顔料1の代わりに、Pigment Yellow150(LANXESS社製、E4GN-GT CH20015)を21質量部加えて、直径0.5mmのジルコニアビーズ200gとともにガラス瓶に入れて密栓し、ペイントシェーカーにて8時間分散処理した以外は、実施例1の顔料分散液1の調製方法と同様にして顔料分散液4を調製した。
顔料分散液1~4のいずれかと下記の化合物とを混合して、80℃に加熱して攪拌した。得られた溶液を加熱下において#3000の金属メッシュフィルタで濾過した後、冷却して4色のインク(M:マゼンタ、K:ブラック、C:シアン、Y:イエロー)をそれぞれ調製した。
活性線硬化性化合物:A-400(ポリエチレングリコール#400ジアクリレート、新中村化学社製) 30.0質量部
:SR494(4EO変性ペンタエリスリトールテトラアクリレート、SARTOMER社製) 17.0質量部
:SR499(6EO変性トリメチロールプロパントリアクリレート、SARTOMER社製) 17.9質量部
式(1)で表される化合物A:18-ペンタトリアコンタノン
1.5質量部
16-ヘントリアコンタノン
0.5質量部
式(2)で表される化合物B:ステアリン酸ステアリル 2.0質量部
パルミチン酸セチル 1.0質量部
重合禁止剤:Irgastab UV10(チバ・ジャパン社製)
0.1質量部
光重合開始剤:TPO(フォスフィンオキサイド、DAROCURE TPO チバ・ジャパン社製) 6.0質量部
光重合開始剤助剤:ITX(イソプロピルチオキサントン Speedcure ITX Lambson社製) 2.0質量部
:EDB(アミン助剤 Speedcure EDB Lambson社製) 3.0質量部
顔料分散液1~4のいずれか: 19.0質量部
4色のインク(M:マゼンタ、K:ブラック、C:シアン、Y:イエロー)を、それぞれ表5に示されるような組成とした以外は実施例17と同様にして4色のインク(M:マゼンタ、K:ブラック、C:シアン、Y:イエロー)を調製した。
ライン記録方式のインクジェット記録装置を用いて、カラー画像を形成した。具体的には、得られた4色のインク(Y、M、C、K)を、インクジェット記録装置のそれぞれの吐出用記録ヘッドに充填し、80℃に加温した。記録媒体としては、印刷用コート紙A(OKトップコート 米坪量128g/m2 王子製紙社製)、印刷用コート紙B(ニューエイジ 米坪量105g/m2 王子製紙社製)、およびポリエチレンテレフタレートフィルム(白ペット、マルウ接着社製)を準備した。
カラー画像の形成方法において、吐出用記録ヘッド内のインクの温度を表5に示されるように変更した以外は実施例17と同様にしてカラー画像を形成し、1)文字画質、2)濃度ムラ、3)耐擦過性、4)インクの射出安定性を評価した。その結果を表5に示す。
12 記録媒体
14、24 吐出用記録ヘッド
16、26 ヘッドキャリッジ
18、28 活性線照射部
19 温度制御部
27 ガイド部
Claims (22)
- 活性線硬化性化合物と、
ケトンワックスと、
エステルワックスとを含み、
温度により可逆的にゾルゲル相転移する、活性線硬化型インクジェット用インク。 - 前記ケトンワックスの融点が、前記エステルワックスの融点より高い、請求項1に記載の活性線硬化型インクジェット用インク。
- 前記ケトンワックスの融点と前記エステルワックスの融点との差は10℃以上である、請求項1又は2に記載の活性線硬化型インクジェット用インク。
- 前記ケトンワックス及び前記エステルワックスを構成する分子中の炭素の数が、それぞれ19以上100未満である、請求項1~3のいずれか一項に記載の活性線硬化型インクジェットインク。
- 前記ケトンワックスおよび前記エステルワックスの融点が、それぞれ30℃以上150℃未満である請求項1~4のいずれか一項に記載の活性線硬化型インクジェットインク。
- 前記ケトンワックス及び前記エステルワックスの合計量が、活性線硬化型インクジェット用インクに対して0.5質量%以上10質量%未満である、請求項1~6のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 前記ケトンワックス及び前記エステルワックスの合計量が、活性線硬化型インクジェット用インクに対して1質量%以上7質量%未満である、請求項1~6に記載の活性線硬化型インクジェット用インク。
- 前記活性線硬化性化合物は、(メタ)アクリレート化合物である、請求項1~8のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 前記(メタ)アクリレート化合物は、エチレンオキサイド変性(メタ)アクリレート化合物である、請求項9に記載の活性線硬化型インクジェット用インク。
- 前記一般式(1)において、
R1およびR2は、炭素原子数11以上23未満の直鎖部分を含む脂肪族炭化水素基である、請求項6~10のいずれか一項に記載の活性線硬化型インクジェット用インク。 - 前記一般式(1)において、
R1およびR2は、炭素原子数11以上23未満の直鎖アルキレン基である、請求項6~10のいずれか一項に記載の活性線硬化型インクジェット用インク。 - 前記一般式(2)において、
R3は、炭素原子数11以上23未満の直鎖部分を含む脂肪族炭化水素基であり、かつ
R4は、炭素原子数12以上24未満の直鎖部分を含む脂肪族炭化水素基である、請求項6~12のいずれか一項に記載の活性線硬化型インクジェット用インク。 - 前記一般式(2)において、
R3は、炭素原子数11以上23未満の直鎖アルキレン基であり、かつ
R4は、炭素原子数12以上24未満の直鎖アルキレン基である、請求項6~12のいずれか一項に記載の活性線硬化型インクジェット用インク。 - 前記ケトンワックスは、18-ペンタトリアコンタノンを含む、請求項1~14のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 二種類以上のケトンワックスを含む、請求項1~15のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 直径75mm、コーン角1.0°のコーンプレート型レオメータにより、80℃、剪断速度11.7/sにおいて測定される粘度が3~20mPa・sである、請求項1~16のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 直径75mm、コーン角1.0°のコーンプレート型レオメータにより、25℃、剪断速度11.7/sにおいて測定される粘度が1000mPa・s以上である、請求項1~17のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 直径75mm、コーン角1.0°のコーンプレート型レオメータにより、100℃から、降温速度0.1℃/s、剪断速度11.7/sで20℃に降温したときに、粘度が200mPa・sとなるゲル化温度が、40℃以上70℃以下である、請求項1~18のいずれか一項に記載の活性線硬化型インクジェット用インク。
- 請求項1~19のいずれか一項に記載の活性線硬化型インクジェット用インクの液滴を、記録ヘッドから吐出させて記録媒体上に付着させる工程と、
前記記録媒体上に付着した液滴に活性線を照射して硬化させる工程と、を含む、画像記録方法。 - 前記記録ヘッドの内部における前記インクの温度は、前記インクのゲル化温度よりも10℃以上30℃以下高く、
前記インクのゲル化温度は、前記インクを直径75mm、コーン角1.0°のコーンプレート型レオメータにより、100℃から、降温速度0.1℃/s、剪断速度11.7/sで20℃に降温したときに、インクの粘度が200mPa・sとなる温度である、請求項20に記載の画像記録方法。 - シングルパス記録モードにより画像を記録する、請求項20または21に記載の画像記録方法。
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Also Published As
Publication number | Publication date |
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US9340693B2 (en) | 2016-05-17 |
EP2692804A1 (en) | 2014-02-05 |
JP5741870B2 (ja) | 2015-07-01 |
JPWO2012132406A1 (ja) | 2014-07-24 |
US20140002534A1 (en) | 2014-01-02 |
CN103608414A (zh) | 2014-02-26 |
CN103608414B (zh) | 2016-08-31 |
EP2692804A4 (en) | 2015-11-18 |
EP2692804B1 (en) | 2016-11-16 |
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