WO2013161270A1 - 活性光線硬化型インクジェットインク、及びこれを用いた画像形成方法 - Google Patents
活性光線硬化型インクジェットインク、及びこれを用いた画像形成方法 Download PDFInfo
- Publication number
- WO2013161270A1 WO2013161270A1 PCT/JP2013/002719 JP2013002719W WO2013161270A1 WO 2013161270 A1 WO2013161270 A1 WO 2013161270A1 JP 2013002719 W JP2013002719 W JP 2013002719W WO 2013161270 A1 WO2013161270 A1 WO 2013161270A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink
- recording medium
- compound
- curable inkjet
- image
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J11/00—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
- B41J11/0015—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
- B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
- B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
- B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
-
- 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
Definitions
- the present invention relates to an actinic ray curable inkjet ink and an image forming 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 inkjet recording methods there is an ultraviolet curable inkjet method in which droplets of inkjet ink are landed on a recording medium and then irradiated with ultraviolet rays to cure the ink and form an image.
- the ultraviolet curable ink jet method has been attracting attention in recent years because an image having high scratch resistance and adhesion can be formed on a recording medium having no ink absorbability.
- Ink-jet inks containing a gelling agent described in Patent Document 1 and Patent Document 2 gel quickly after landing on a recording medium, so that coalescence of adjacent droplets can be suppressed.
- gelled inkjet ink has high viscosity and is difficult to level. Therefore, fine irregularities are likely to occur on the surface of the printed image, and the glossiness of the printed image tends to be insufficient.
- the density of the printed image is adjusted by the amount of ink droplets, the thick part of the coating film tends to be thick, and the thin part of the coating film tends to be thin. That is, a step is likely to occur at the boundary between regions having different densities and at the boundary between the image forming unit and the non-image forming unit.
- the present invention has been made in view of the above circumstances, and has an actinic ray curable inkjet ink that is excellent in gloss and can form a printed image with a small thickness difference (so-called relief feeling) of the coating film.
- An object of the present invention is to provide an image forming method using the.
- the first of the present invention relates to the actinic ray curable inkjet ink shown below.
- Actinic ray curable inkjet ink Actinic ray curable inkjet ink.
- the second of the present invention relates to an image forming method described below.
- [4] A step of ejecting ink droplets of the actinic ray curable inkjet ink described in [1] above from an inkjet recording head and adhering the ink droplets onto a recording medium, and a droplet landed on the recording medium. Irradiating actinic rays and curing each droplet, and heating the recording medium before and / or after irradiating the actinic rays.
- the recording medium is heated before and after the step of irradiating with actinic rays, and the temperature of the recording medium after the step of irradiating with actinic rays is made higher than the temperature of the recording medium before the step of irradiating with actinic rays.
- the actinic ray curable ink jet ink of the present invention coalescence of ink droplets after landing is suppressed, so that a high quality image can be obtained.
- the surface gloss of the printed image is increased and the relief feeling is further suppressed.
- FIG. 2 is a diagram (top view) illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus. It is a figure which shows an example of a structure of the principal part of the inkjet recording device of a serial recording system.
- the present invention is an actinic ray curable inkjet ink and a method of forming an image by applying this ink.
- Actinic ray curable inkjet ink contains a photopolymerizable compound, a liquid compound, a gelling agent, and a photopolymerization initiator.
- the actinic ray curable inkjet ink contains a coloring material and other additives as necessary.
- the photopolymerizable compound is a compound that crosslinks or polymerizes when irradiated with actinic rays.
- the actinic rays are, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X-rays, and are preferably ultraviolet rays.
- the photopolymerizable compound can be a radical polymerizable compound or a cationic polymerizable compound. A radical polymerizable compound is preferred.
- the radical polymerizable compound is a compound (monomer, oligomer, polymer or mixture thereof) having an ethylenically unsaturated bond capable of radical polymerization.
- the actinic ray curable inkjet ink only one kind of radical polymerizable compound may be contained, or two or more kinds thereof may be contained.
- Examples of compounds having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids and salts thereof, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid urethane compounds, unsaturated carboxylic acid amide compounds and anhydrides 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 but also an oligomer, a mixture of a monomer and an oligomer, a modified product, an oligomer having a polymerizable functional group, or the like.
- “(meth) acrylate” refers to both and / or “acrylate” and “methacrylate”
- (meth) acryl” refers to both and / or “acryl” and “methacryl”.
- a (meth) acrylate compound (hereinafter referred to as “(meth) acrylate compound A”) having a CLogP value in the range of 4.0 to 7.0. It is preferable that the (meth) acrylate compound A having a CLogP value in the range of 4.0 to 7.0 is included, the solubility of the gelling agent is improved in the sol-like ink, and the ink is ejected from the inkjet recording head. Stability is improved.
- the ClogP value of the (meth) acrylate compound A is less than 4.0, the actinic ray curable inkjet ink becomes hydrophilic and the gelling agent is hardly dissolved. Therefore, even when heated, the gelling agent is not completely dissolved, and the ink may not sufficiently undergo sol-gel phase transition. In addition, defective ejection of ink from the ink jet recording head is likely to occur.
- the ClogP value of the (meth) acrylate compound A exceeds 7.0, the solubility of the photopolymerization initiator in the ink decreases, the curability of the ink decreases, and the ink from the ink jet recording head decreases. Dischargeability tends to decrease.
- the ClogP value of the (meth) acrylate compound A is more preferably in the range of 4.5 to 6.0.
- the “Log P value” is a coefficient indicating the affinity of an organic compound for water and 1-octanol.
- the 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent.
- Their logarithm LogP for the base 10 is shown. That is, the “Log P value” is a logarithmic value of the 1-octanol / water partition coefficient, and is known as an important parameter representing the hydrophilicity / hydrophobicity of a molecule.
- ClogP value is a LogP value calculated by calculation.
- the CLogP value can be calculated by a fragment method, an atomic approach method, or the like. More specifically, ClogP values can be calculated in the literature (C. Hansch and A. Leo, “Substituent Constants for Correlation Analysis in Chemistry and Biology” (John Wiley & Sons 69, described in John Wiley & Sons 69). Or the following commercially available software package 1 or 2 may be used.
- the numerical value of the ClogP value described in the present specification and the like is a “CLogP value” calculated using the software package 2.
- the molecular weight of the (meth) acrylate compound A is preferably in the range of 300 to 1500, and more preferably in the range of 300 to 800.
- the ink viscosity at the ejection temperature needs to be between 7 and 14 mPa ⁇ s.
- An ink composition containing a (meth) acrylate compound A having a molecular weight of less than 300 and a gelling agent has a large change in ink viscosity before and after the ejection temperature. Therefore, it is difficult to adjust the ink viscosity within the above range.
- the (meth) acrylate compound A having a molecular weight of 300 or more has little odor, it can reduce the odor of the actinic ray curable inkjet ink and its cured product.
- the molecular weight of the (meth) acrylate compound A exceeds 1500, the sol viscosity of the ink becomes excessively high.
- the amount of (meth) acrylate compound A contained in the actinic ray curable inkjet ink is preferably in the range of 5 to 30% by mass.
- the amount of the (meth) acrylate compound A having a CLogP value in the range of 4.0 to 7.0 is less than 5% by mass, the ink becomes hydrophilic and the solubility of the gelling agent decreases. The ejection stability from the ink jet recording head tends to decrease.
- the amount of the (meth) acrylate compound A exceeds 30% by mass, the solubility of the photopolymerization initiator in the ink tends to be insufficient. Therefore, the curability tends to be insufficient.
- (meth) acrylate compound A having a CLogP value in the range of 4.0 to 7.0 include (1) (—C (CH 3 ) H—CH 2 —O—) in the molecule.
- a trifunctional or higher functional methacrylate or acrylate compound having 3 to 14 structures represented, and (2) a bifunctional or higher functional methacrylate or acrylate compound having a cyclic structure in the molecule are included.
- These (meth) acrylate compounds A have high photocurability and little shrinkage when cured. Furthermore, the reproducibility of the sol-gel phase transition is high.
- a trifunctional or higher functional methacrylate or acrylate compound having 3 to 14 structures represented by (—C (CH 3 ) H—CH 2 —O—) in the molecule includes, for example, 3 or more A hydroxyl group of a compound having a hydroxyl group is modified with propylene oxide, and the resulting modified product is esterified with (meth) acrylic acid.
- this compound include 3PO-modified trimethylolpropane triacrylate Photor 4072 (molecular weight 471, Clog P4.90, manufactured by Cognis), 3PO-modified trimethylolpropane triacrylate Miramer M360 (molecular weight 471, Clog P4.90, manufactured by Miwon) and the like are included.
- the bifunctional or higher functional methacrylate or acrylate compound having a cyclic structure in the molecule is obtained by esterifying the hydroxyl group of a compound having two or more hydroxyl groups and tricycloalkane with (meth) acrylic acid. is there.
- this compound include Tricyclodecane dimethanol diacrylate NK ester A-DCP (molecular weight 304, CLog P4.69), Tricyclodecane dimethanol dimethacrylate NK ester DCP (molecular weight 332, CLog P5.12) and the like are included.
- (meth) acrylate compound A examples include 1,10-decanediol dimethacrylate NK ester DOD-N (molecular weight 310, Clog P 5.75, manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the photopolymerizable compound has a molecular weight in the range of 300 to 1500 and a structure represented by (—CH 2 —CH 2 —O—) in the molecule of 3 or more and less than 14, preferably 4 As described above, it is also preferable to include a (meth) acrylate compound containing less than 10 (hereinafter also referred to as “(meth) acrylate compound B”).
- the gelling agent can exist uniformly and stably in the sol-like ink. Therefore, it is possible to stably discharge the actinic ray curable inkjet ink from the inkjet recording head. Further, when the (meth) acrylate compound B is contained, the sol-gel phase transition of the ink is easily performed, and the coalescence of the ink can be prevented.
- the flexibility of the cured product of the actinic ray curable inkjet ink is increased.
- the structure represented by (—CH 2 —CH 2 —O—) contained in the (meth) acrylate compound B is 14 or more, the hydrophilicity of the (meth) acrylate compound B becomes excessively high and active. There is a possibility that the gelling agent is not sufficiently dissolved in the light-curable inkjet ink.
- the ClogP value of the (meth) acrylate compound B containing a structure represented by (—CH 2 —CH 2 —O—) in the molecule is preferably less than 4.0, more preferably 0.1 or more and 4 Less than 0.0.
- the ClogP value of the (meth) acrylate compound B is too low, the hydrophilicity of the ink becomes high, the compatibility between the (meth) acrylate compound B and the gelling agent becomes low, and the ink becomes unstable.
- the molecular weight of the (meth) acrylate compound B is in the range of 300 to 1500, and preferably in the range of 300 to 800.
- the molecular weight is 300 or more, the (meth) acrylate compound B hardly volatilizes in the ink jet recording apparatus, and the ink ejection stability is improved.
- the molecular weight exceeds 1500, the viscosity of the sol-like ink tends to be excessively high.
- the (meth) acrylate compound B is a (meth) acrylic acid ester having an ethylene glycol repeating unit (—CH 2 —CH 2 —O—) at the ester site.
- the (meth) acrylate compound A preferably has two or more (meth) acryl groups; preferably 2, 3, or 4 (meth) acryl groups.
- the (meth) acrylate compound B examples include 4EO-modified hexanediol diacrylate (CD561, manufactured by Sartomer, molecular weight 358), 3EO-modified trimethylolpropane triacrylate (SR454, manufactured by Sartomer, molecular weight 429), and 4EO-modified penta.
- CD561 manufactured by Sartomer, molecular weight 358
- SR454 3EO-modified trimethylolpropane triacrylate
- penta examples include 4EO-modified penta.
- Erythritol tetraacrylate (SR494, manufactured by Sartomer, molecular weight 528), 6EO-modified trimethylolpropane triacrylate (SR499, manufactured by Sartomer, molecular weight 560), polyethylene glycol diacrylate (NK ester A-400, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight) 508), (NK ester A-600, manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 708), polyethylene glycol dimethacrylate (NK ester 9G, manufactured by Shin-Nakamura Chemical Co., Ltd., molecule) 536), tetraethylene glycol diacrylate (V # 335HP, Osaka Organic Chemical Industry Co., Ltd., molecular weight 302), and the like.
- V # 335HP Osaka Organic Chemical Industry Co., Ltd., molecular weight 302
- the content of the (meth) acrylate compound B is preferably 12 to 50% by mass, more preferably 15 to 40% by mass with respect to the total mass of the actinic ray curable inkjet ink.
- the amount of the (meth) acrylate compound B exceeds 50% by mass, the hydrophilicity of the ink increases, the solubility of the gelling agent decreases, and the gelation stability decreases.
- the amount of the (meth) acrylate compound B is less than 12% by mass, the flexibility of the cured product of the ink is lowered, and the image film may break when the image is bent.
- the photopolymerizable compound may further contain a photopolymerizable compound other than (meth) acrylate compound A and (meth) acrylate compound B.
- the other photopolymerizable compound may be a (meth) acrylate monomer and / or oligomer, or other polymerizable oligomer.
- Examples of (meth) acrylate monomers and / or oligomers include, for example, isoamyl acrylate, stearyl acrylate, lauryl acrylate, octyl acrylate, decyl acrylate, isomyristyl acrylate, isostearyl acrylate, 2-ethylhexyl-diglycol acrylate, 2- Hydroxybutyl acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate , 2-hydroxy Ethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropy
- Examples of other polymerizable oligomers include epoxy acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyester acrylate, linear acrylic oligomer, and the like.
- the actinic ray curable inkjet ink of the present invention contains a liquid compound.
- the liquid compound is a liquid that is liquid at 25 ° C. and is non-polymerizable.
- the “non-polymerizable” compound is a compound that does not have an active group with respect to actinic rays.
- the actinic ray curable inkjet ink of the present invention contains a liquid compound, a printed image having excellent gloss and high smoothness can be obtained.
- Liquid compounds are inert to actinic rays. Therefore, the liquid compound exists as a liquid in the ink coating film after irradiation with actinic rays.
- the liquid compound volatilizes from the surface of the ink coating or penetrates into the recording medium, whereby the thickness of the coating gradually decreases. As the thickness decreases, the unevenness and steps on the coating film surface become smaller. That is, the smoothness of the printed image finally obtained is increased and the surface gloss is also increased.
- the ink component easily enters the recording medium together with the liquid compound, and the adhesion between the recording medium and the printed image is increased.
- the liquid compound preferably has an SP value which is a solubility parameter of 8.5 or more and less than 10.0.
- SP value of the liquid compound is less than 8.5, there is little difference from the SP value of the gelling agent described later, and the compatibility between the gelling agent and the liquid compound is likely to increase.
- compatibility between the gelling agent and the liquid compound is high, the gelling agent is difficult to deposit after landing on the recording medium, and pinning of ink droplets tends to be insufficient.
- the SP value of the liquid compound is 10 or more, the difference from the SP value of a general recording medium tends to increase.
- the SP value of the liquid composition specified in the present invention is a numerical value obtained by the Fedor calculation method.
- the SP value calculation method by Fedor is described in R.D. F. Fedor; Polymer Engineering Science, 14 (2) 147-154 (1974).
- the boiling point of the liquid compound is preferably 120 ° C. or higher and lower than 200 ° C. If the boiling point of the liquid compound is less than 120 ° C., the liquid compound tends to volatilize in the ink jet recording apparatus, and the ejection stability of the ink tends to decrease. On the other hand, when the boiling point of the liquid compound exceeds 200 ° C., it is difficult for the liquid compound to volatilize from the ink cured film. That is, it is difficult to reduce the thickness of the ink coating film, and unevenness and steps on the surface of the printed image are difficult to be reduced. Therefore, the glossy feeling is not sufficient, and the relief feeling is hardly reduced. Furthermore, the liquid component tends to remain in the printed image, and the film curability of the printed image tends to be insufficient.
- liquid compound is not particularly limited.
- liquid compounds include Hydrocarbon compounds; Aromatic compounds such as anisole (boiling point 153 ° C., SP value 9.4); Ketone compounds such as isophorone (boiling point 218 ° C., SP value 9.8); lower alcohols such as n-propyl alcohol (boiling point 97 ° C., SP value 11.84); Higher alcohols; Glycols such as 1,3-butylene glycol (boiling point 208 ° C., SP value 13.78); Propylene glycol monomethyl ether (boiling point 121 ° C., SP value 10.19), diethylene glycol monomethyl ether (boiling point 202 ° C., SP value 10.94), propylene glycol n-propyl ether (boiling point 150 ° C., SP value 9.82), propylene Glycol butyl ether (boiling point 170 ° C., SP value 9.69), dipropylene glycol
- the content of the liquid compound is 15 to 50% by mass, preferably 25 to 40% by mass with respect to the total mass of the actinic ray curable ink.
- the content of the liquid compound is less than 15% by mass, the amount of the liquid compound that volatilizes from the ink coating after landing on the recording medium or penetrates into the recording medium is small, and the thickness of the coating does not easily decrease. For this reason, it is difficult to smooth the surface of the print image. Furthermore, it is difficult to obtain an effect of improving adhesion.
- the amount of the liquid compound exceeds 50% by mass, the amount of the photopolymerizable compound is relatively decreased, so that the curability of the coating film tends to be lowered, and the sharpness of characters and images may be lowered. Further, since the amount of the photopolymerizable compound is small, the strength of the ink cured film is likely to be lowered.
- the actinic ray curable inkjet ink contains a gelling agent.
- the gelling agent has a function of reversibly sol-gel phase transition of the ink jet ink depending on the temperature.
- Such a gelling agent is at least 1) soluble in a photopolymerizable compound or non-polymerizable resin at a temperature higher than the gelation temperature, and 2) crystallizes in the ink at a temperature below the gelation temperature. It is necessary.
- the gelling agent When the gelling agent is crystallized in the ink, it is preferable that a plate crystal which is a crystallized product of the gelling agent forms a space three-dimensionally enclosed, and the photopolymerizable compound is included in the space.
- the structure in which the photopolymerizable compound is encapsulated in the space three-dimensionally surrounded by the plate crystal is sometimes referred to as “card house structure”.
- the card house structure is formed, the liquid photopolymerizable compound can be held and ink droplets can be pinned. Thereby, coalescence of droplets can be suppressed.
- the photopolymerizable compound dissolved in the ink and the gelling agent are compatible.
- the photopolymerizable compound dissolved in the ink and the gelling agent are phase-separated, it may be difficult to form a card house structure.
- the compatibility between the photopolymerizable compound and the gelling agent is good in the sol-like ink (at high temperature). is required. Furthermore, in order to stably suppress coalescence of droplets even during high-speed printing, after the ink droplets have landed on the recording medium, the gelling agent quickly crystallizes to form a strong card house structure. is necessary.
- gelling agents include An aliphatic ketone compound; Aliphatic ester compounds; Petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; Plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester; Animal waxes such as beeswax, lanolin and whale wax; Mineral waxes such as montan wax and hydrogenated wax; Hydrogenated castor oil or hydrogenated castor oil derivative; Modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives or polyethylene wax derivatives; Higher fatty acids such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid; Higher alcohols such as stearyl alcohol and behenyl alcohol; Hydroxystearic acid such as 12-hydroxystearic acid; 12-hydroxystearic acid derivative
- Nomucoat series, etc. 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 Chemical); And low molecular oil gelling agents described in JP-A-2005-126507, JP-A-2005-255821 and JP-A-2010-11117.
- 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
- the actinic ray curable inkjet ink for the image forming method of the present invention preferably contains a compound containing a linear alkyl group having 12 or more carbon atoms as a gelling agent.
- the gelling agent contains a linear alkyl group having 12 or more carbon atoms, the aforementioned “card house structure” is easily formed.
- the gelling agent may have a branched chain.
- gelling agent containing a linear alkyl group having 12 or more carbon atoms include aliphatic ketone compounds, aliphatic ester compounds, higher fatty acids, higher alcohols having a linear alkyl group having 12 or more carbon atoms, Fatty acid amides and the like are included.
- the gelling agent is preferably an aliphatic ketone compound or an aliphatic ester compound. That is, a compound represented by the following general formulas (G1) and (G2) is preferable.
- R1-CO-R2 General formula (G2): R3-COO-R4
- R1 to R4 each independently represents an alkyl group having a straight chain portion having 12 or more carbon atoms.
- R1 to R4 may have a branched portion.
- the alkyl groups represented by R1 and R2 preferably each independently include a linear alkyl group having 12 to 25 carbon atoms.
- the number of carbon atoms in the straight chain portion contained in the group represented by R1 and R2 is less than 12, not only does not function as a gelling agent because it does not have sufficient crystallinity, There is a possibility that a sufficient space for encapsulating the photopolymerizable compound cannot be formed.
- the number of carbon atoms in the linear portion contained in the group represented by R1 or R2 exceeds 25, the melting point becomes too high, so that the ink may not be dissolved in the ink unless the ink discharge temperature is increased. There is.
- Examples of the aliphatic ketone compound represented by the general formula (G1) include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22, melting point 88 ° C.), distearyl ketone (C18-C18, 84 ° C.), dieicosyl ketone (C20-C20), dipalmityl ketone (C16-C16, melting point 80 ° C.), dimyristyl ketone (C14-C14), dilauryl ketone (C12-C12, melting point 68 ° C.) , Lauryl myristyl ketone (C12-C14), lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14-C18), myristyl behenyl ketone (C14-C22), palmityl Stearyl
- Examples of commercially available compounds represented by the general formula (G1) include 18-Pentriacontanon (Alfa Aeser), Hentriacontan-16-on (Alfa Aeser), Kao Wax T1 (Kao Corporation), etc. Is included.
- the aliphatic ketone compound contained in the actinic ray curable inkjet ink may be only one kind or a mixture of two or more kinds.
- the alkyl group represented by R3 and R4 is not particularly limited, but is preferably an alkyl group including a linear portion having 12 to 26 carbon atoms.
- the crystallinity necessary for the gelling agent is the same as in the compound represented by the general formula (G1).
- the above-mentioned card house structure can be formed while having a melting point, and the melting point is not too high.
- Examples of the aliphatic ester compound represented by the general formula (G2) include behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), stearyl stearate (C17-C18, melting point 60).
- Examples of commercially available aliphatic ester compounds represented by the general formula (G2) include Unistar M-2222SL (manufactured by NOF Corporation), EXCEPARL SS (manufactured by Kao Corporation, melting point 60 ° C.), EMALEX® CC-18 (Manufactured by Nippon Emulsion Co., Ltd.), Amreps PC (manufactured by Higher Alcohol Industry Co., Ltd.), EXCEPARL MY-M (manufactured by Kao Corporation), SPARM ACETI (manufactured by NOF Corporation), EMALEX ALCC-10 (manufactured by Nippon Emulsion Co., Ltd.) Etc. are included. Since these commercial products are often a mixture of two or more types, they may be separated and purified as necessary.
- the aliphatic ester compound contained in the actinic ray curable inkjet ink may be only one kind or a mixture of two or more kinds.
- the gelling agent is precipitated by using a hydrophilic liquid compound having an SP value in the range of 8.5 to 10.0. This improves the pinning performance of the ink.
- the amount of the gelling agent contained in the actinic ray curable inkjet ink is preferably 0.5 to 10.0% by mass, more preferably 1 to 7% by mass with respect to the total amount of the ink. If it is less than 0.5% by mass, the ink droplets may not be gelled (sol-gel phase transition due to temperature). On the other hand, if it exceeds 10% by mass, the gelling agent cannot be sufficiently dissolved in the ink, and there is a possibility that the discharge property of the ink droplets is lowered.
- Photopolymerization initiator The actinic ray curable inkjet ink contains a photopolymerization initiator.
- 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.
- intramolecular hydrogen abstraction type photopolymerization initiators examples include benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl.
- Benzophenones such as sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 -Thioxanthone series such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Michler ketone, 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethyl Anthraquinone, 9,10-phenanthrene Quinone, include camphor quinone and the like.
- the content of the photopolymerization initiator in the actinic ray curable ink-jet ink is preferably 0.01% by mass to 10% by mass, although it depends on the type of actinic ray or photopolymerizable compound.
- a photoacid generator may be contained in the photopolymerization initiator in the actinic ray curable inkjet ink.
- 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 ray curable ink-jet ink may further contain a photopolymerization initiator auxiliary agent or a polymerization inhibitor, 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. Only one kind of these compounds may be contained in the actinic ray curable inkjet ink, or two or more kinds thereof may be contained.
- 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-t-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 oxime
- the actinic ray curable inkjet ink usually further includes a color material.
- the colorant can be a dye or a pigment.
- a pigment is more preferable because it has good dispersibility with respect to the components of the ink and is excellent in weather resistance.
- 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 pigment is not particularly limited, but 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, Chromofine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY
- the average particle diameter of the pigment is preferably 0.08 to 0.5 ⁇ m, and the maximum particle diameter of the pigment is preferably 0.3 to 10 ⁇ m, more preferably 0.3 to 3 ⁇ m.
- 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 total mass of the actinic ray curable inkjet ink. This is because when the content of the pigment or dye is too small, the resulting image is not sufficiently colored, and when it is too large, the viscosity of the ink is increased and the dischargeability is lowered.
- 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 average particle size of the pigment particles is preferably 0.08 to 0.5 ⁇ m, the maximum particle size is more preferably 0.3 to 10 ⁇ m, and further preferably 0.3 to 3 ⁇ m.
- 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 actinic ray 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 Solspers
- the actinic ray 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 ray curable inkjet ink may further include a dispersion medium for dispersing the pigment as necessary.
- a dispersion medium for dispersing the pigment as necessary.
- the above-described photopolymerizable compound is preferably the dispersion medium.
- the actinic ray curable inkjet 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.
- actinic-light curable inkjet ink contains a gelatinizer as mentioned above, it changes a sol-gel phase reversibly with temperature.
- Actinic ray curable ink that undergoes a sol-gel phase transition is a liquid (sol) at a high temperature (for example, about 80 ° C.), and therefore can be ejected in a sol state from an inkjet recording head.
- a high temperature for example, about 80 ° C.
- the viscosity of the ink at a high temperature is below a certain level.
- the viscosity of the actinic ray curable inkjet ink at 80 ° C. 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 ray 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 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 (1 / 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 a temperature at which the viscosity changes greatly in the temperature change curve of the viscosity, for example, a temperature at which the viscosity becomes 500 mPa ⁇ s.
- 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 ray curable inkjet ink of the present invention contains a liquid compound that is inert to actinic rays.
- the liquid compound exists as a liquid in the ink coating film after irradiation with actinic rays.
- the liquid compound volatilizes from the surface of the ink coating or penetrates into the recording medium, whereby the thickness of the coating gradually decreases. As the thickness decreases, the irregularities and steps on the coating film surface also become smaller. That is, the printed image made of the actinic ray curable inkjet ink of the present invention has high smoothness and high surface gloss.
- the actinic ray curable inkjet ink of the present invention has an ink component that easily enters the recording medium together with the liquid compound, and has high adhesion between the recording medium and the printed image.
- the actinic ray curable inkjet ink is obtained by mixing the above-mentioned photopolymerizable compound, liquid compound, gelling agent, photopolymerization initiator, colorant and the like under heating.
- a pigment dispersant in which a color material (particularly a pigment) is dispersed in a part of the photopolymerizable compound is prepared and mixed with the pigment dispersant and other ink components.
- the obtained ink is preferably filtered through a predetermined filter.
- the image forming method of the present invention includes at least the following three steps. (1) A step of causing an actinic ray curable inkjet ink to be ejected from an inkjet recording head and adhering it onto a recording medium. (2) The ink liquid is obtained by irradiating the droplets landed on the recording medium with light from an LED light source. Step of curing droplet (3) Step of heating recording medium before and / or after step (2)
- the step (3) that is, the step of heating the recording medium before and / or after the actinic ray irradiation is performed.
- a step of heating the recording medium before irradiation with actinic rays hereinafter also referred to as “(3-1) step”
- the ink before curing is easily leveled.
- a step of heating the recording medium after irradiation with actinic rays hereinafter also referred to as “(3-2) step
- the liquid compound is volatilized from the cured coating film, resulting in unevenness and steps generated on the coating film surface. Is easily relaxed.
- the step (3) may be performed only between the steps (1) and (2) or after the step (2), but the steps (1) and (2). It is preferable from the viewpoint of smoothing the printed image that it is performed both during and after the step (2).
- Actinic-light curable inkjet ink is discharged on a recording medium from an inkjet recording device.
- the actinic radiation curable inkjet ink is the inkjet ink described above.
- Ink droplets are ejected from the inkjet recording head of the inkjet recording apparatus.
- the ink is heated by an ink jet recording head of the ink jet recording apparatus, an ink flow path connected to the ink jet recording head, an ink tank connected to the ink flow path, or the like.
- the amount of droplets ejected from each nozzle of the inkjet recording head is preferably 0.5 to 10 pl depending on the resolution of the image. In order to form a high-definition image, 0 More preferably, it is 5 to 2.5 pl. In order to form a high-definition image with such a droplet amount, the ink after landing does not coalesce; that is, the ink needs to undergo a sol-gel phase transition sufficiently. In the above-mentioned actinic ray curable inkjet ink, the sol-gel transition is rapidly performed. Therefore, a high-definition image can be stably formed even with such a droplet amount.
- the ink droplets landed on the recording medium are cooled and gelled quickly by the sol-gel phase transition. As a result, the ink droplets can be pinned without diffusing. Furthermore, since it is difficult for oxygen to enter the ink droplets, the curing of the photopolymerizable compound is not easily inhibited by oxygen.
- the recording medium may be paper or a resin film.
- paper include coated paper for printing, coated paper B for printing, and the like.
- the resin film include a polyethylene terephthalate film, a polypropylene film, and a vinyl chloride film.
- the material has high affinity with the liquid compound and allows the liquid compound to easily penetrate.
- the temperature of the recording medium when the ink droplet lands is preferably set to a temperature that is 10 to 20 ° C. lower than the gelation temperature of the ink. If the temperature of the recording medium is too low, the ink droplets gel excessively and pinning, so that the ink droplets are not sufficiently leveled and the image gloss may be lowered. On the other hand, if the temperature of the recording medium is too high, the ink droplets are difficult to gel, and adjacent dots of the ink droplets may be mixed together. By appropriately adjusting the temperature of the recording medium, it is possible to achieve appropriate leveling and appropriate pinning so that adjacent dots of ink droplets do not mix with each other.
- the conveyance speed of the recording medium is preferably 30 to 120 m / s.
- the higher the conveyance speed the higher the image forming speed, which is preferable.
- the conveyance speed is too high, the image quality is deteriorated or the photocuring (described later) of the ink becomes insufficient.
- step (3) As described above, during the period from step (1) to step (2); that is, between the time when the ink droplets land on the recording medium and before the irradiation with actinic rays, You may perform the process to heat. By heating the recording medium before irradiation with actinic rays, the ink droplets are leveled, and the unevenness and steps formed on the coating film surface are reduced.
- the temperature of the recording medium is preferably 10 to 20 ° C. lower than the gelation temperature of the ink. If the temperature of the recording medium is too high, the viscosity of the ink is lowered, and adjacent dots of the ink droplets may be mixed.
- the heating time (the time from the ink droplet landing on the recording medium to the irradiation with active light) is preferably within 10 seconds, more preferably within 0.001 seconds to 5 seconds, and 0.01 seconds. More preferably, it is within ⁇ 2 seconds. If the heating time is long, adjacent ink droplets may be united.
- Step (2) By irradiating the ink droplets landed on the recording medium with an actinic ray from an LED light source, the photopolymerizable compound contained in the ink droplets is crosslinked or polymerized to cure the ink droplets.
- the actinic ray applied to the ink droplets attached to the recording medium is preferably ultraviolet light from an LED light source.
- LED light source Specific examples include 395 nm, water-cooled LED, etc., manufactured by Phoseon Technology.
- a metal halide lamp is an example of a general ultraviolet light source.
- the LED light source is installed such that ultraviolet light of 370 to 410 nm is set so that the peak illuminance on the image surface is 0.5 to 10 W / cm 2 and is set to 1 to 5 W / cm 2 .
- the amount of light applied to the image is set to be less than 350 mJ / cm 2 . This is to prevent the radiant heat from being applied to the ink droplets.
- the irradiation with actinic rays is preferably performed after ejecting ink droplets from all the ink jet recording heads accommodated in the head carriage.
- the temperature of the recording medium is preferably higher than the temperature of the recording medium before irradiation with actinic rays. This is to sufficiently volatilize the liquid compound. Specifically, the temperature is preferably 30 to 80 ° C, more preferably 40 to 55 ° C. If the heating temperature is too low, the liquid compound may not volatilize sufficiently. On the other hand, when the heating temperature is too high, the coating film and the recording medium are easily affected by heat.
- the heating time of the recording medium is preferably about 1 to 100 seconds, more preferably 2 to 20 seconds. If the heating time is too short, the liquid compound may not volatilize sufficiently. On the other hand, if the heating time is too long, the recording medium may be deformed by heat.
- Actinic ray curable ink jet 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. 1A is a side view illustrating an example of a configuration of a main part of an ink jet recording apparatus of a line recording type
- FIG. 1B is a top view thereof.
- the inkjet recording apparatus 10 supplies a head carriage 16 that houses a plurality of inkjet recording heads 14, an ink flow path 30 connected to the head carriage 16, and an ink flow path 30.
- An ink tank 31 that stores ink, a light irradiation unit 18 that covers the entire width of the recording medium 12 and is arranged downstream of the head carriage 16 (in the conveyance direction of the recording medium), and a lower surface of the recording medium 12
- the head carriage 16 is fixedly arranged so as to cover the entire width of the recording medium 12, and accommodates a plurality of inkjet recording heads 14 provided for each color.
- Ink is supplied to the ink jet 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 inkjet recording heads 14 are arranged in the transport direction of the recording medium 12 for each color.
- the number of inkjet recording heads 14 arranged in the conveyance direction of the recording medium 12 is set according to the nozzle density of the inkjet 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 inkjet recording head 14 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four inkjet recording heads 14 may be arranged so as to be shifted with respect to the conveyance direction of the recording medium 12. That's fine.
- the two ink jet recording heads 14 may be arranged in a shifted manner.
- dpi represents the number of ink droplets (dots) per 2.54 cm.
- the ink tank 31 is connected to the head carriage 16 via the ink flow path 30.
- the ink flow path 30 is a path for supplying the ink in the ink tank 31 to the head carriage 16.
- the ink in the ink tank 31, the ink flow path 30, the head carriage 16, and the ink jet recording head 14 is heated to a predetermined temperature to maintain the gel state.
- the light irradiation unit 18 covers the entire width of the recording medium 12 and is disposed on the downstream side of the head carriage 16 in the conveyance direction of the recording medium.
- the light irradiating unit 18 irradiates the droplets ejected by the inkjet recording head 14 and landed on the recording medium with light, thereby curing the droplets.
- the temperature controller 19 (19a, 19b, and 19c) 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 temperature control unit 19a controls the temperature of the recording medium when ink droplets land on the recording medium.
- the temperature controller 19b controls the temperature of the recording medium from the ink droplet landing to the light irradiation.
- the temperature control unit 19c controls the temperature of the recording medium after light irradiation.
- 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 19a.
- high temperature ink droplets are ejected from the ink jet recording head 14 of the head carriage 16 and adhered (landed) on the recording medium 12.
- the recording medium 12 is controlled to a predetermined temperature by the temperature control unit 19b, and the light irradiating unit 18 irradiates the ink droplets attached on the recording medium 12 with light to be cured.
- the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19c.
- the total ink droplet thickness after curing is preferably 2 to 25 ⁇ m.
- the “total ink droplet thickness” is the maximum value of the ink droplet 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 includes a plurality of inkjet recording heads that are narrower than the entire width of the recording medium, instead of the head carriage 16 that is fixedly arranged so as to cover the entire width of the recording medium. 1A and 1B except that it includes a head carriage 26 that accommodates 24 and a guide portion 27 for moving the head carriage 26 in the width direction of the recording medium 12.
- an ink droplet is ejected from the inkjet recording head 24 accommodated in the head carriage 26 while the head carriage 26 moves 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. Thereafter, the coating film is cured by the light irradiation unit 28. Except for these operations, an image is recorded in substantially the same manner as the line recording type inkjet recording apparatus 10 described above.
- the actinic ray curable ink-jet ink of each example and comparative example was prepared with the following components.
- NK ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.): polyethylene glycol diacrylate (Clog P value: 0.47)
- CD561 (Sartomer): alkoxylated hexanediol diacrylate (Clog P value: 2.52)
- SR499 (manufactured by Sartomer): 6EO-modified trimethylolpropane triacrylate (Clog P value: 3.57)
- SR494 (manufactured by Sartomer): 4EO-modified pentaerythritol tetraacrylate (Clog P value: 2.28)
- Miramer M360 (manufactured by Miwon): trimethylolpropane PO-modified triacrylate (ClogP value: 4.90) -Laromer PE9074 (BASF): polyester acrylate oligomer-CN2270 (Sartomer): polyester acrylate oligomer
- Example 1 to 3 and Comparative Examples 1 to 3 Each compound was mixed with the composition ratio described in Table 1, and heated to 100 ° C. and stirred. Thereafter, the obtained liquid was filtered through a # 3000 metal mesh filter under heating. This was cooled to prepare a cyan ink. About the obtained cyan ink, the discharge property of the ink from the ink jet recording apparatus and the printed image were evaluated as follows. The results are shown in Table 1.
- Cyan ink was loaded into a line head type ink jet recording apparatus equipped with a piezo type ink head recording head. Ink was ejected from a piezo head having a nozzle diameter of 24 ⁇ m and a resolution of 512 dpi.
- the ink supply system of the ink jet recording apparatus includes an ink tank, a supply pipe, a front chamber ink tank immediately before the recording head, a pipe with a filter, and a piezo head. Heat was insulated from the front chamber ink tank to the recording head and heated to 80 ° C. A 3.5 pl droplet was ejected from the piezo head at a frequency of 42 kHz for 1 minute and rested for 30 seconds.
- a monochromatic image was formed by a line head type ink jet recording apparatus provided with the piezo type ink jet recording head shown in FIGS. 1A and 1B. Cyan ink was loaded on the cyan head carriage, and heat was insulated from the front chamber ink tank to the recording head and heated to 80 ° C. Piezo heads with a nozzle diameter of 24 ⁇ m and a resolution of 600 dpi were arranged in a staggered manner to form a 1200 dpi nozzle row. The amount of cyan ink droplets ejected from the head was 3.5 pl per droplet.
- the recording medium was adjusted to the temperature shown in Table 1 while being transported by adsorbing the recording medium to the transport table.
- the temperatures shown in Table 1 are the temperature of the recording medium at the time of ink ejection, the temperature of the recording medium for about 1 second after ink ejection and before UV irradiation, and the temperature of the recording medium for 15 seconds after UV irradiation. Heating was performed by placing an IR heater on the ink landing surface side of the recording medium.
- UV exposure an LED lamp (emission center wavelength: 395 nm, distance between recording medium and lamp: 2 mm, maximum output: 7000 mW / cm 2 ) was used. Image formation was performed in an environment of 23 ° C. and 55% RH.
- dpi represents the number of dots per 2.54 cm.
- the formed images were evaluated for character quality, white spots, gloss, relief, bending resistance, scratching, and adhesion as follows.
- a streak was put on a solid image formed on a PP film with a cutter at 10 mm vertically and horizontally with a width of 5 mm. After that, 3M cellophane tape was attached so as to adhere, and the cellophane tape was peeled off.
- the image after peeling the cellophane tape was evaluated by visual observation according to the following criteria. ⁇ : No peeling of image film ⁇ : Edge with streaks slightly lifted up, but never peeled off. X: The image peeled off at one or more places. XX: The image was peeled off at 10 or more locations.
- Example 1 in which the amount of the liquid compound was 18% by mass with respect to the total mass of the ink, a glossiness with no practical problem was obtained, and the relief feeling was also small. Furthermore, in Example 2 in which the amount of the liquid compound was 30% by mass with respect to the total mass of the ink, a good glossiness was obtained although a slight relief was observed. Further, in Example 3 in which the amount of the liquid compound was 45% by mass with respect to the total mass of the ink, the glossiness was good, and no step was observed between the image forming part and the image non-forming part.
- the liquid compound in the ink soaks or volatilizes into the recording medium, thereby reducing the thickness of the printed image, the unevenness of the image surface, and the gap between the image forming portion and the non-forming portion. It is inferred that the level difference has been relaxed.
- Example 4 to 6 Each compound was mixed in the composition ratio described in Table 2, and heated to 100 ° C. and stirred. Thereafter, the obtained liquid was filtered through a # 3000 metal mesh filter under heating. This was cooled to prepare a cyan ink. With respect to the obtained cyan ink, the ink dischargeability from the ink jet recording apparatus was evaluated. In these examples, cyan ink having the same composition is used, and the temperature of the recording medium at the time of ink jet recording, the temperature of the recording medium after ink jet recording and before UV irradiation, and the temperature of the recording medium after UV irradiation are changed. Formed. The formed image was evaluated in the same manner as in Example 1 and the like. The results are shown in Table 2. Table 2 also shows the results of Example 2 above.
- Example 4 when the temperature of the recording medium after ink landing until UV irradiation was low (Example 4), the evaluation of gloss and relief was slightly low. Since the temperature until the UV irradiation after the ink droplet landing was low, it is presumed that the pinning property of the ink droplet was very high, and relatively large irregularities and steps were formed on the coating film surface.
- Example 7 to 15 Each compound was mixed with the composition ratio described in Table 3, and heated to 100 ° C. and stirred. Thereafter, the obtained liquid was filtered through a # 3000 metal mesh filter under heating. This was cooled to prepare cyan inks containing various liquid compounds. With respect to the obtained cyan ink, the ink dischargeability from the ink jet recording apparatus was evaluated. In addition, evaluation of images formed using these cyan inks was performed in the same manner as in Example 1 and the like. The results are shown in Table 3. Table 3 also shows the results of Example 5 above.
- Example 7 when the isophorone having a boiling point exceeding 200 ° C. or dipropylene glycol methylpropyl ether was used as the liquid compound (Example 7 and Example 11), the evaluation of glossiness and relief feeling was slightly low. It was. Since a liquid compound having a high boiling point was added, it is presumed that the liquid compound was hardly volatilized from the printed image, and the film thickness reduction amount was small.
- Examples 16 to 20 and Comparative Example 4 Each compound was mixed with the composition ratio described in Table 4, heated to 100 ° C. and stirred. Thereafter, the obtained liquid was filtered through a # 3000 metal mesh filter under heating. This was cooled to prepare a cyan ink. With respect to the obtained cyan ink, the ink dischargeability from the ink jet recording apparatus was evaluated. In addition, evaluation of images formed from these cyan inks was performed in the same manner as in Example 1. The results are shown in Table 4.
- the gelling agent was stearamide or behenic acid (Examples 19 and 20)
- the glossiness was improved and the relief feeling was small by adding the liquid compound.
- the image quality was also good.
- the image formed from the actinic ray curable inkjet ink of the present invention is excellent in gloss and does not easily cause a step between the recording portion and the non-recording portion. Therefore, the present invention is suitable for producing various printed materials that require glossiness and smoothness.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
[1]光重合性化合物、光重合開始剤、ゲル化剤、及び25℃で液体かつ非重合性の液体化合物を含み、前記液体化合物を、インク質量に対して15質量%~50質量%含む、活性光線硬化型インクジェットインク。
[2]前記液体化合物は、SP値が8.5以上、10.0未満であり、かつ沸点が120℃以上200℃未満である、[1]に記載の活性光線硬化型インクジェットインク。
[3]前記光重合性化合物は、ClogP値が4.0~7.0の範囲内にある(メタ)アクリレート化合物を含む、[1]に記載の活性光線硬化型インクジェットインク。
[4]前述の[1]に記載の活性光線硬化型インクジェットインクのインク液滴を、インクジェット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、前記記録媒体上に着弾した液滴に、活性光線を照射し、各液滴を硬化させる工程と、を含み、前記活性光線照射する工程前、及び/または前記活性光線を照射する工程後に、記録媒体を加熱する、画像形成方法。
[5]前記活性光線照射する工程前及び工程後に記録媒体を加熱し、前記活性光線を照射する工程前の記録媒体の温度より、前記活性光線を照射する工程後の記録媒体の温度を高くする、[4]に記載の画像形成方法。
本発明の活性光線硬化型インクジェットインクには、光重合性化合物と、液体化合物と、ゲル化剤と、光重合開始剤とが含まれる。活性光線硬化型インクジェットインクには、必要に応じて、色材や、その他の添加剤が含まれる。
光重合性化合物は、活性光線を照射されることにより架橋又は重合する化合物である。活性光線は、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、好ましくは紫外線である。光重合性化合物は、ラジカル重合性化合物又はカチオン重合性化合物であり得る。好ましくはラジカル重合性化合物である。
ソフトウェアパッケージ2:Chem Draw Ultra ver.8.0.(2003年4月、CambridgeSoft Corporation,USA)
3PO変性トリメチロールプロパントリアクリレートPhotomer 4072(分子量471、ClogP4.90、Cognis社製)、
3PO変性トリメチロールプロパントリアクリレートMiramer M360(分子量471、ClogP4.90、Miwon社製)等が含まれる。
トリシクロデカンジメタノールジアクリレート NKエステルA-DCP(分子量304、CLogP4.69)、
トリシクロデカンジメタノールジメタクリレート NKエステルDCP(分子量332、CLogP5.12)等が含まれる。
本発明の活性光線硬化型インクジェットインクには、液体化合物が含まれる。液体化合物は、25℃で液体であり、かつ非重合性の化合物である。本発明において「非重合性」の化合物とは、「活性光線に対して活性な基を有さない」化合物とする。
液体化合物は、活性光線に対して不活性である。そのため、液体化合物は、活性光線照射後のインク塗膜内で、液体のまま存在する。この液体化合物がインク塗膜表面から揮発、もしくは記録媒体に浸透することで、徐々に塗膜の厚みが減少する。厚み減少に伴い、塗膜表面の凹凸や段差が小さくなる。つまり、最終的に得られる印刷画像の平滑性が高まり、表面光沢性も高まる。
本発明で特定する液体組成物のSP値はFedorの計算方法により求められる数値である。FedorによるSP値の計算方法はR.F.Fedor;Polymer Engineering Science、14(2)147-154(1974)に記載されている。
炭化水素化合物;
アニソール(沸点153℃、SP値9.4)等の芳香族化合物;
イソフォロン(沸点218℃、SP値9.8)等のケトン化合物;
n-プロピルアルコール(沸点97℃、SP値11.84)等の低級アルコール;
高級アルコール;
1,3-ブチレングリコール(沸点208℃、SP値13.78)等のグリコール類;
プロピレングリコールモノメチルエーテル(沸点121℃、SP値10.19)、ジエチレングリコールモノメチルエーテル(沸点202℃、SP値10.94)、プロピレングリコールn-プロピルエーテル(沸点150℃、SP値9.82)、プロピレングリコールブチルエーテル(沸点170℃、SP値9.69)、ジプロピレングリコールモノメチルエーテル(沸点190℃、SP値9.69)、ジプロピレングリコールn-プロピルエーテル(沸点212℃、SP値9.5)、ジプロピレングリコールブチルエーテル(沸点229、SP値9.43)、ジプロピレングリコールジメチルエーテル(沸点175℃、SP値7.88)、ジプロピレングリコールメチルプロピルエーテル(沸点203℃、SP値7.99)、トリプロピレングリコールモノメチルエーテル(沸点242℃、SP値9.43)、トリプロピレングリコールブチルエーテル(沸点274℃、SP値9.27)等のグリコールエーテル類;
メチルアセテート(沸点56℃、SP値8.78)、エチルアセテート(沸点77℃、SP値8.74)、イソプロピルエーテルアセテート(沸点85℃、SP値8.5)、ブチルアセテート(沸点126℃、SP値8.7)、n-プロピルアセテート(沸点102℃、SP値8.72)、3-メトキシブチルアセテート(沸点171℃、SP値8.71)、1,3-ブチレングリコールジアセテート(沸点232℃、SP値9.51)、1,4-ブタンジオールジアセテート(沸点220℃、SP値9.64)、1,6-ヘキサンジオールジアセテート(沸点260℃、SP値9.48)、シクロヘキサノールアセテート(沸点173℃、SP値9.18)等のエステル類;
エチレングリコールモノメチルエーテルアセテート(沸点145℃、SP値8.96)、エチレングリコールモノブチルエーテルアセテート(沸点188℃、SP値8.85)、ジエチレングリコールモノメチルエーテルアセテート(沸点217℃、SP値9.01)、ジエチレングリコールモノブチルエーテルアセテート(沸点247℃、SP値8.94)、プロピレングリコールモノメチルエーテルアセテート(沸点146℃、SP値8.73)、プロピレングリコールジアセテート(沸点190℃、SP値9.6)、ジプロピレングリコールメチルエーテルアセテート(沸点213℃、SP値8.71)等のグリコールエーテルアセテート類;等が含まれる。
活性光線硬化型インクジェットインクには、ゲル化剤が含まれる。ゲル化剤は、カインクジェットインクを温度により可逆的にゾルゲル相転移させる機能を有する。そのようなゲル化剤は、少なくとも1)ゲル化温度よりも高い温度で、光重合性化合物や非重合性樹脂に溶解すること、2)ゲル化温度以下の温度で、インク中で結晶化すること、が必要である。
脂肪族ケトン化合物;
脂肪族エステル化合物;
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のエステル(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);
ステアリン酸イヌリン等の脂肪酸イヌリン;
パルミチン酸デキストリン、ミリスチン酸デキストリン等の脂肪酸デキストリン(千葉製粉社製 レオパールシリーズ等);
ベヘン酸エイコサン二酸グリセリル;
ベヘン酸エイコサンポリグリセリル(日清オイリオ社製 ノムコートシリーズ等);
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;
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;等が含まれる。
一般式(G1):R1-CO-R2
一般式(G2):R3-COO-R4
一般式(G1)及び(G2)中、R1~R4は、それぞれ独立に、炭素数12以上の直鎖部分を有するアルキル基を表す。R1~R4は、分岐部分を有していてもよい。
活性光線硬化型インクジェットインクには、光重合開始剤が含まれる。
光重合開始剤は、分子内結合開裂型と分子内水素引き抜き型とがある。分子内結合開裂型の光重合開始剤の例には、ジエトキシアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、ベンジルジメチルケタール、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、4-(2-ヒドロキシエトキシ)フェニル-(2-ヒドロキシ-2-プロピル)ケトン、1-ヒドロキシシクロヘキシル-フェニルケトン、2-メチル-2-モルホリノ(4-チオメチルフェニル)プロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン等のアセトフェノン系;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。
活性光線硬化型インクジェットインクには、通常、色材がさらに含まれる。色材は、染料または顔料でありうる。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、顔料がより好ましい。
KET Yellow 401、402、403、404、405、406、416、424、KET Orange 501、KET Red 301、302、303、304、305、306、307、308、309、310、336、337、338、346、KET Blue 101、102、103、104、105、106、111、118、124、KET Green 201(大日本インキ化学製);
Colortex Yellow 301、314、315、316、P-624、314、U10GN、U3GN、UNN、UA-414、U263、Finecol Yellow T-13、T-05、Pigment Yellow1705、Colortex Orange 202、Colortex Red101、103、115、116、D3B、P-625、102、H-1024、105C、UFN、UCN、UBN、U3BN、URN、UGN、UG276、U456、U457、105C、USN、Colortex Maroon601、Colortex BrownB610N、Colortex Violet600、Pigment Red 122、Colortex Blue516、517、518、519、A818、P-908、510、Colortex Green402、403、Colortex Black 702、U905(山陽色素製);
Lionol Yellow1405G、Lionol Blue FG7330、FG7350、FG7400G、FG7405G、ES、ESP-S(東洋インキ製)、
Toner Magenta E02、Permanent RubinF6B、Toner Yellow HG、Permanent Yellow GG-02、Hostapeam BlueB2G(ヘキストインダストリ製);
Novoperm P-HG、Hostaperm Pink E、Hostaperm Blue B2G(クラリアント製);
カーボンブラック#2600、#2400、#2350、#2200、#1000、#990、#980、#970、#960、#950、#850、MCF88、#750、#650、MA600、MA7、MA8、MA11、MA100、MA100R、MA77、#52、#50、#47、#45、#45L、#40、#33、#32、#30、#25、#20、#10、#5、#44、CF9(三菱化学製)などが挙げられる。
活性光線硬化型インクジェットインクには、必要に応じて他の成分がさらに含まれていてもよい。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。
活性光線硬化型インクジェットインクは、前述のようにゲル化剤を含むため、温度により可逆的にゾルゲル相転移する。ゾルゲル相転移する活性光線硬化型インクは、高温(例えば80℃程度)では液体(ゾル)であるため、インクジェット記録ヘッドからゾル状態で吐出することができる。高温下で活性光線硬化型インクジェットインクを吐出すると、インク液滴(ドット)が記録媒体に着弾した後、自然冷却されてゲル化する。これにより、隣り合うドット同士の合一を抑制し、画質を高めることができる。
活性光線硬化型インクジェットインクは、前述の光重合性化合物、液体化合物、ゲル化剤、光重合開始剤、及び色材等を、加熱下、混合して得られる。好ましくは、一部の光重合性化合物に色材(特に顔料)を分散させた顔料分散剤を用意し、顔料分散材と、他のインク成分と混合する。得られたインクは、所定のフィルターで濾過することが好ましい。
本発明の画像形成方法は、少なくとも以下の3工程を含む。
(1)活性光線硬化型インクジェットインクを、インクジェット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
(2)前記記録媒体上に着弾した液滴にLED光源からの光を照射して前記インク液滴を硬化させる工程
(3)前記(2)工程前、及び/または(2)工程後に、記録媒体を加熱する工程
活性光線硬化型インクジェットインクをインクジェット記録装置から、記録媒体上に吐出する。活性光線硬化型インクジェットインクは、上述したインクジェットインクである。
前述のように、(1)工程から(2)工程までの間;つまり、インク液滴が記録媒体に着弾してから、活性光線照射までの間、記録媒体を加熱する工程を行ってもよい。活性光線照射前に記録媒体を加熱することで、インク液滴がレベリングし、塗膜表面に形成される凹凸や段差が小さくなる。
記録媒体に着弾したインク液滴にLED光源から活性光線を照射することで、インク液滴に含有される光重合性化合物を架橋又は重合させてインク液滴を硬化させる。
活性光線照射後、塗膜が形成された記録媒体を、さらに加熱することが好ましい。記録媒体を加熱することで、塗膜中から液体化合物が揮発しやすくなり、塗膜の厚みが減少する。そのため、塗膜表面に生じている凹凸や段差が緩和され、平滑性の高い印刷画像が得られる。
本発明の画像形成方法は、活性光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を用いて行うことができる。活性光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。
・NKエステルA-400(新中村化学社製):ポリエチレングリコールジアクリレート(ClogP値:0.47)
・CD561(Sartomer社製):アルコキシ化ヘキサンジオールジアクリレート(ClogP値:2.52)
・SR499(Sartomer社製):6EO変性トリメチロールプロパントリアクリレート(ClogP値:3.57)
・SR494(Sartomer社製):4EO変性ペンタエリスリトールテトラアクリレート(ClogP値:2.28)
・Miramer M360(Miwon社製):トリメチロールプロパンPO変性トリアクリレート(ClogP値:4.90)
・Laromer PE9074(BASF社製):ポリエステルアクリレートオリゴマー
・CN2270(Sartomer社製):ポリエステルアクリレートオリゴマー
・カオーワックスT1(花王社製):ジステアリルケトン
・FATTY AMIDE T(花王社製):ステアリン酸アミド
・ルナックBA(花王社製):ベヘニン酸
・アニソール(融点:-37℃、沸点:153℃、SP値:9.4)
・イソフォロン(融点:-8.1℃、沸点:218℃、SP値:9.8)
・プロピレングリコールモノメチルエーテル(融点:-96℃、沸点:121℃、SP値:10.19)
・プロピレングリコール-n-プロピルエーテル(融点:-80℃、沸点:150℃、SP値:9.82)
・ジプロピレングリコールジメチルエーテル(融点:-80℃、沸点:175℃、SP値:7.88)
・ジプロピレングリコールメチルプロピルエーテル(融点:25度未満、沸点:203℃、SP値:7.99)
・エチルアセテート(融点:-83.6℃、沸点:77、SP値:8.74)
・ブチルアセテート(融点:-74℃、沸点126℃、SP値:8.7)
・シクロヘキサノールアセテート(融点:-77℃、沸点:173℃、SP値:9.18)
・プロピレングリコールモノメチルエーテルアセテート(融点:-65℃、沸点:146℃、SP値:8.73)
・DAROCURE TPO(BASF社製)
・ITX(DKSHジャパン社製)
・KF-352(信越化学社製)
・KayacureEPA(日本化薬社製)
以下に示す顔料分散剤、光重合性化合物、及び重合禁止剤をステンレスビーカーに入れ、65℃のホットプレートで加熱しながら、1時間加熱攪拌した。
・顔料分散剤:アジスパーPB824(味の素ファインテクノ社製) 9部
・光重合性化合物: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部
・重合禁止剤:Irgastab UV10(チバ・ジャパン社製) 0.02部
シアン顔料1:Pigment Blue15:4
表1に記載の組成比で各化合物を混合し、100℃に加熱して攪拌した。その後、得られた液体を加熱下、#3000の金属メッシュフィルターでろ過した。これを冷却して、シアンインクを調製した。
得られたシアンインクについて、インクジェット記録装置からのインクの吐出性、及び印刷画像を、以下のように評価した。結果を表1に示す。
ピエゾ型インクヘット記録ヘッドを備えたラインヘッド方式のインクジェット記録装置にシアンインクを装填した。インクの吐出は、ノズル径が24μm、解像度が512dpiであるピエゾヘッドから行った。
インクジェット記録装置のインク供給系は、インクタンク、供給パイプ、記録ヘッド直前の前室インクタンク、フィルター付き配管、ピエゾヘッドからなるものとした。前室インクタンクから記録ヘッド部分まで断熱して、80℃に加温した。
ピエゾヘッドから3.5plの液滴を42kHzの周波数で1分間吐出させ、30秒間休止した。その後、液滴を1分間吐出させた。吐出の状況を高速度ビデオで観察し下記のように評価した。
○:休止前後で欠、曲り無く良好に吐出した
△:休止後に曲りが発生した
×:休止後に欠が発生した
××:20ノズル以上で欠、曲りが発生した
図1A,図1Bに示すピエゾ型のインクジェット記録ヘッドを備えたラインヘッド方式のインクジェット記録装置で、単色画像を形成した。シアン用ヘッドキャリッジに、シアンインクを装填し、前室インクタンクから記録ヘッド部分まで断熱して、80℃に加温した。ノズル径24μm、解像度600dpiのピエゾヘッドを千鳥に配置し、1200dpiのノズル列を形成した。ヘッドからの吐出するシアンインクの液滴量は1滴当たり3.5plとした。
印刷用コート紙に形成された4pt明朝文字について、目視で確認した。評価は以下の基準で行った。
○:黒文字も白文字(ベタ画像中に白抜き文字)も綺麗に再現されている
△:細部でつぶれが見られるが、文字の判読は可能である
×:白文字のつぶれが酷く、文字の判読が困難である
××:黒文字でもつぶれが酷く、文字の判読が困難である
印刷用コート紙に形成されたベタ画像について、白ヌケ(ドットの合一による未印字部分)がないかを目視で確認した。評価は以下の基準で行った。
○:白抜けは見られない
△:完全な白抜けはないが、色が薄い場所が数か所見られる
×:白く抜けている場所が数か所見られる
××:全面で白抜けが見られる
印刷用コート紙及びPPフィルムに形成されたベタ画像について、光沢感を目視で確認した。評価は以下の基準で行った。
○:均質な光沢感である
△:やや光沢が低いが、均質な光沢感である
×:光沢感が低い
××:光沢が無い
印刷用コート紙及びPPフィルムに形成されたベタ画像について、レリーフ感を目視で確認した。評価は以下の基準で行った。
○:画像形成部と、画像非形成部との境界に段差が見られない
△:画像形成部と、画像非形成部との境界に僅かな段差が感じられる
×:画像形成部と、画像非形成部との境界に段差が見られる
××:画像形成部と、画像非形成部との境界に顕著な段差が見られる
PPフィルムに形成されたベタ画像を、25℃60%RHの環境下に24時間放置した後、二つ折りにした。評価は以下の基準で行った。
○:画像膜が割れない
△:折り部分の画像膜に僅かにヒビが入っている
×:折り部分の画像膜が割れている
××:折り部分の画像膜が大きく割れ、画像がずれた
PPフィルムに形成されたベタ画像について、「JIS規格 K5701-1 6.2.3 耐摩擦性試験」に記載の方法に則り擦過性を評価した。適切な大きさに切り取った記録用紙を画像上に設置し、上記JIS規格に則った荷重をかけて擦り合わせた。その後、画像濃度低下の程度を目視観察し、下記の基準に従って耐擦過性を評価した。
○:100回以上擦っても、画像の変化がまったく認められない
△:100回擦った段階で画像濃度の低下が認められるが、実用上許容範囲にある
×:100回未満の擦りで、明らかな画像濃度低下が認められ、実用に耐えない品質である
××:30回未満の擦りで、明らかな画像濃度低下が認められ、実用に耐えない品質である
PPフィルムに形成されたベタ画像に、5mm幅で縦横に10本ずつカッターでスジを入れた。その後3M製セロハンテープを密着するように貼り付け、セロハンテープを剥がした。セロハンテープを剥がした後の画像を下記の基準に従って目視観察して評価した。
○:画像膜の剥がれ無し
△:スジを入れた縁が少し持ち上がるが、剥がれることはなかった。
×:1箇所以上で画像が剥がれた。
××:10箇所以上で画像が剥がれた。
表2に記載の組成比で各化合物を混合し、100℃に加熱して攪拌した。その後、得られた液体を加熱下、#3000の金属メッシュフィルターでろ過した。これを冷却して、シアンインクを調製した。得られたシアンインクについて、インクジェット記録装置からのインクの吐出性の評価を行った。これらの例では、同一組成のシアンインクを用い、インクジェット記録時の記録媒体の温度、インクジェット記録後・UV照射前の記録媒体の温度、及びUV照射後の記録媒体の温度を変化させて、画像を形成した。形成された画像の評価を、実施例1等と同様に行った。結果を表2に示す。なお、表2には、上記実施例2の結果も併せて示す。
表3に記載の組成比で各化合物を混合し、100℃に加熱して攪拌した。その後、得られた液体を加熱下、#3000の金属メッシュフィルターでろ過した。これを冷却して、種々の液体化合物を含むシアンインクを調製した。得られたシアンインクについて、インクジェット記録装置からのインクの吐出性の評価を行った。また、これらのシアンインクを用いて形成した画像の評価を、実施例1等と同様に行った。結果を表3に示す。なお、表3には、上記実施例5の結果も併せて示す。
一方、SP値が10以上であるプロピレングリコールメチルエーテルを液体化合物とした場合(実施例8)には、記録媒体との密着性が低下した。SP値が高かったため、記録媒体(PPフィルム)との親和性が低く、液体化合物が記録媒体に浸透し難かった、と推察される。
表4に記載の組成比で各化合物を混合し、100℃に加熱して攪拌した。その後、得られた液体を加熱下、#3000の金属メッシュフィルターでろ過した。これを冷却して、シアンインクを調製した。得られたシアンインクについて、インクジェット記録装置からのインクの吐出性の評価を行った。また、これらのシアンインクから形成された画像の評価を、実施例1と同様に行った。結果を表4に示す。
本出願は、同出願人により先にされた日本国特許出願、すなわち、特願2012-098811号(出願日2012年4月24日)に基づく優先権主張を伴うものであって、これらの明細書の内容を参照して本発明の一部としてここに組み込むものとする。
12 記録媒体
14、24 インクジェット記録ヘッド
16、26 ヘッドキャリッジ
18、28 光照射部
19 温度制御部
27 ガイド部
Claims (5)
- 光重合性化合物、光重合開始剤、ゲル化剤、及び25℃で液体かつ非重合性の液体化合物を含み、
前記液体化合物を、インク質量に対して15質量%~50質量%含む、活性光線硬化型インクジェットインク。 - 前記液体化合物は、SP値が8.5以上、10.0未満であり、かつ沸点が120℃以上200℃未満である、請求項1に記載の活性光線硬化型インクジェットインク。
- 前記光重合性化合物は、CLogP値が4.0~7.0の範囲内にある(メタ)アクリレート化合物を含む、請求項1に記載の活性光線硬化型インクジェットインク。
- 請求項1に記載の活性光線硬化型インクジェットインクのインク液滴を、インクジェット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、
前記記録媒体上に着弾した液滴に、活性光線を照射し、各液滴を硬化させる工程と、を含み、
前記活性光線照射する工程前、及び/または前記活性光線を照射する工程後に、記録媒体を加熱する、画像形成方法。 - 前記活性光線照射する工程前及び工程後に記録媒体を加熱し、
前記活性光線を照射する工程前の記録媒体の温度より、前記活性光線を照射する工程後の記録媒体の温度を高くする、請求項4に記載の画像形成方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014512352A JP6176240B2 (ja) | 2012-04-24 | 2013-04-23 | 活性光線硬化型インクジェットインク、及びこれを用いた画像形成方法 |
US14/396,426 US9714354B2 (en) | 2012-04-24 | 2013-04-23 | Active ray-curable inkjet ink and image forming method using same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012098811 | 2012-04-24 | ||
JP2012-098811 | 2012-04-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013161270A1 true WO2013161270A1 (ja) | 2013-10-31 |
Family
ID=49482613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/002719 WO2013161270A1 (ja) | 2012-04-24 | 2013-04-23 | 活性光線硬化型インクジェットインク、及びこれを用いた画像形成方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9714354B2 (ja) |
JP (1) | JP6176240B2 (ja) |
WO (1) | WO2013161270A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017171789A (ja) * | 2016-03-24 | 2017-09-28 | コニカミノルタ株式会社 | バイオレットインク、インクセットおよび画像形成方法 |
JP2018065891A (ja) * | 2016-10-17 | 2018-04-26 | コニカミノルタ株式会社 | インクジェットインクおよび画像形成方法 |
JP2020105301A (ja) * | 2018-12-26 | 2020-07-09 | 花王株式会社 | インクジェット印刷用水系インク |
WO2021140977A1 (ja) * | 2020-01-12 | 2021-07-15 | 株式会社ミマキエンジニアリング | インクジェット印刷装置 |
WO2022185479A1 (ja) * | 2021-03-04 | 2022-09-09 | コニカミノルタ株式会社 | 乾燥装置、画像形成装置、および画像形成方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6251475B2 (ja) * | 2012-12-19 | 2017-12-20 | 株式会社ミマキエンジニアリング | インクジェットプリンタ及び印刷方法 |
US20190185696A1 (en) * | 2016-08-28 | 2019-06-20 | Scodix Ltd. | Selective Matte And Glossy Printing |
JP6717248B2 (ja) * | 2017-03-29 | 2020-07-01 | 京セラドキュメントソリューションズ株式会社 | 画像形成装置 |
EP3753734A4 (en) * | 2018-02-13 | 2021-11-24 | Think Laboratory Co., Ltd. | INKJET PRINTER AND INKJET PRINTING PROCESS |
WO2020130941A1 (en) * | 2018-12-17 | 2020-06-25 | Agency For Science, Technology And Research | A polymer composition and a method of preparing a polymer resin |
CN115703867A (zh) * | 2021-08-17 | 2023-02-17 | 财团法人工业技术研究院 | 光固化树脂组成物、含其的三维对象及该三维对象的制造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007297625A (ja) * | 2006-04-28 | 2007-11-15 | Xerox Corp | インキ組成物、インキ組成物の調製方法 |
JP2010208343A (ja) * | 2010-06-04 | 2010-09-24 | Konica Minolta Holdings Inc | インクジェット画像形成方法 |
JP2011057900A (ja) * | 2009-09-11 | 2011-03-24 | Ricoh Co Ltd | インクジェット用インク及びインクジェット記録方法 |
WO2011065095A1 (ja) * | 2009-11-30 | 2011-06-03 | コニカミノルタホールディングス株式会社 | インクジェット画像形成方法及びインクジェットインクセット |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3342335B2 (ja) * | 1996-03-06 | 2002-11-05 | キヤノン株式会社 | 画像形成方法及び記録物 |
JP2005126509A (ja) * | 2003-10-22 | 2005-05-19 | Konica Minolta Holdings Inc | インクジェット用インク及びそれを用いたインクジェット記録方法 |
US7459014B2 (en) * | 2005-01-14 | 2008-12-02 | Xerox Corporation | Radiation curable inks containing curable gelator additives |
AU2006203245A1 (en) | 2005-09-01 | 2007-03-15 | Oce-Technologies B.V. | A method for printing a substrate with radiation curable ink, and an ink suitable for application in the said method |
US8319916B2 (en) * | 2006-01-23 | 2012-11-27 | Fujifilm Corporation | Method of producing organic nanoparticles, organic nanoparticles thus obtained, inkjet ink for color filter, colored photosensitive resin composition and photosensitive resin transfer material, containing the same, and color filter, liquid crystal display device and CCD device, prepared using the same |
JP5416725B2 (ja) * | 2010-09-24 | 2014-02-12 | 積水化学工業株式会社 | インクジェット用硬化性組成物及びプリント配線板の製造方法 |
-
2013
- 2013-04-23 JP JP2014512352A patent/JP6176240B2/ja active Active
- 2013-04-23 US US14/396,426 patent/US9714354B2/en active Active
- 2013-04-23 WO PCT/JP2013/002719 patent/WO2013161270A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007297625A (ja) * | 2006-04-28 | 2007-11-15 | Xerox Corp | インキ組成物、インキ組成物の調製方法 |
JP2011057900A (ja) * | 2009-09-11 | 2011-03-24 | Ricoh Co Ltd | インクジェット用インク及びインクジェット記録方法 |
WO2011065095A1 (ja) * | 2009-11-30 | 2011-06-03 | コニカミノルタホールディングス株式会社 | インクジェット画像形成方法及びインクジェットインクセット |
JP2010208343A (ja) * | 2010-06-04 | 2010-09-24 | Konica Minolta Holdings Inc | インクジェット画像形成方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017171789A (ja) * | 2016-03-24 | 2017-09-28 | コニカミノルタ株式会社 | バイオレットインク、インクセットおよび画像形成方法 |
JP2018065891A (ja) * | 2016-10-17 | 2018-04-26 | コニカミノルタ株式会社 | インクジェットインクおよび画像形成方法 |
JP2020105301A (ja) * | 2018-12-26 | 2020-07-09 | 花王株式会社 | インクジェット印刷用水系インク |
JP7233917B2 (ja) | 2018-12-26 | 2023-03-07 | 花王株式会社 | インクジェット印刷用水系インク |
WO2021140977A1 (ja) * | 2020-01-12 | 2021-07-15 | 株式会社ミマキエンジニアリング | インクジェット印刷装置 |
JP2021109391A (ja) * | 2020-01-12 | 2021-08-02 | 株式会社ミマキエンジニアリング | インクジェット印刷装置 |
WO2022185479A1 (ja) * | 2021-03-04 | 2022-09-09 | コニカミノルタ株式会社 | 乾燥装置、画像形成装置、および画像形成方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6176240B2 (ja) | 2017-08-09 |
US9714354B2 (en) | 2017-07-25 |
US20150138289A1 (en) | 2015-05-21 |
JPWO2013161270A1 (ja) | 2015-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6176240B2 (ja) | 活性光線硬化型インクジェットインク、及びこれを用いた画像形成方法 | |
JP5780358B2 (ja) | 画像形成方法 | |
JP5991371B2 (ja) | インクジェットインクセット、及びこれを用いた画像形成方法 | |
JP5880228B2 (ja) | 活性光線硬化型インクジェットインク、及びこれを用いた画像形成方法 | |
JP5741870B2 (ja) | 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 | |
JP5880257B2 (ja) | 活性光線硬化型インクジェットインク及び画像形成方法 | |
JP6451733B2 (ja) | 画像形成方法 | |
JP6070698B2 (ja) | 活性光線硬化型インクジェットインク及びこれを用いた画像形成方法 | |
JP6269424B2 (ja) | 活性光線硬化型インクジェットインクおよび画像形成方法 | |
WO2016153035A1 (ja) | 活性光線硬化型インクジェットインク及びインクジェット記録方法 | |
JP6569674B2 (ja) | 活性光線硬化型インクジェットインク及び画像形成方法 | |
JP5857866B2 (ja) | 活性光線硬化型インクジェットインク、およびインクジェット記録方法 | |
JP6303330B2 (ja) | インクセット及びこれを用いた画像形成方法 | |
JP7043822B2 (ja) | 活性光線硬化型インクジェットインク | |
JP6451739B2 (ja) | インクジェット記録方法およびインクジェット記録装置 | |
WO2014196213A1 (ja) | 活性光線硬化型インクジェットインクおよびそれを用いた画像形成方法 | |
JP5807608B2 (ja) | 活性光線硬化型インクジェットインク | |
JP2017132861A (ja) | 活性光線硬化型インクジェットインク及びインクジェット画像形成方法 | |
WO2017010462A1 (ja) | 活性光線硬化型インクジェットインク、硬化膜の製造方法およびインクジェット画像形成方法 | |
JP2019104865A (ja) | 活性光線硬化型インクジェットインク及びインクジェット画像形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13780873 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014512352 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14396426 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13780873 Country of ref document: EP Kind code of ref document: A1 |