WO2022219816A1 - インクセット及びインクジェット記録方法 - Google Patents
インクセット及びインクジェット記録方法 Download PDFInfo
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- WO2022219816A1 WO2022219816A1 PCT/JP2021/015750 JP2021015750W WO2022219816A1 WO 2022219816 A1 WO2022219816 A1 WO 2022219816A1 JP 2021015750 W JP2021015750 W JP 2021015750W WO 2022219816 A1 WO2022219816 A1 WO 2022219816A1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229940099800 pigment red 48 Drugs 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
- B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
-
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
Definitions
- the present invention relates to an ink set and an inkjet recording method, and more particularly to an ink set that suppresses image defects, produces high image quality, and has excellent adhesion to a substrate.
- the inkjet recording method can easily and inexpensively create images, it has been applied to various printing fields including special printing such as photography, various printing, marking, and color filters.
- the inkjet recording method enables digital printing without using a plate, and is particularly suitable for applications such as forming various images in small quantities.
- a substrate is coated in advance with a treatment liquid (also referred to as a "pretreatment liquid” or “primer”) containing a flocculant such as an organic acid or a polyvalent metal salt.
- a treatment liquid also referred to as a "pretreatment liquid” or “primer”
- a flocculant such as an organic acid or a polyvalent metal salt.
- the present invention has been made in view of the above problems and circumstances, and the problem to be solved is to provide an ink set and an inkjet recording set that suppress image defects, produce high image quality, and have excellent adhesion to substrates. is.
- the present inventors in the process of studying the causes of the above problems, have found that high image quality can be achieved by controlling the static surface tension and dynamic surface tension of the treatment liquid and ink within specific ranges.
- the inventors have found that it is possible to provide an ink set and an ink jet recording method that can achieve the above, and have arrived at the present invention. That is, the above problems related to the present invention are solved by the following means.
- An ink set containing ink and a treatment liquid contains a pigment, resin fine particles, a water-soluble solvent having a boiling point of 150 to 250° C., and a surfactant,
- the treatment liquid contains a polyvalent metal salt, a water-soluble solvent with a boiling point of 150 to 250 ° C.
- the static surface tension of the ink is 5 mN/m or more higher than the static surface tension of the treatment liquid
- the dynamic surface tension of the ink at a surface life of 15 ms is 5 mN/m or more higher than the dynamic surface tension of the treatment liquid at a surface life of 15 ms
- the ink has a dynamic surface tension within a range of 35 to 45 mN/m at a surface life of 15 ms
- An ink set, wherein the dynamic surface tension of the treatment liquid at a surface life of 15 ms is in the range of 25 to 35 mN/m.
- An inkjet recording method for recording an image using the ink set according to any one of items 1 to 6 An inkjet recording method comprising applying the treatment liquid to a base material, and then applying the ink to the area to which the treatment liquid has been applied in a state in which the treatment liquid is wet without going through a heating and drying step.
- Item 9 The inkjet recording method according to Item 7 or 8, wherein the ink is applied to the area to which the treatment liquid has been applied within 10 seconds after applying the treatment liquid to the substrate.
- the above means of the present invention it is possible to provide an ink set and an inkjet recording set that suppress image defects and have excellent adhesion to substrates.
- the expression mechanism or action mechanism of the effects of the present invention has not been clarified, it is speculated as follows.
- the wet-on-wet recording method in which ink is applied while the treatment liquid is wet, it is necessary to thin out the treatment liquid, but the treatment liquid must instantly spread and spread evenly while reducing the printing rate. For this reason, the dynamic surface tension of the treatment liquid is preferably as low as possible.
- the ink contains pigments, resin fine particles, a water-soluble solvent having a boiling point within the range of 150 to 250° C., and a surfactant.
- the treatment liquid contains a polyvalent metal salt, a water-soluble solvent with a boiling point of 150 to 250 ° C., and a surfactant in order to thicken and aggregate the ink and achieve high image quality. and Furthermore, the relationship between the static surface tension and the dynamic surface tension of the treatment liquid and ink is specified within the above range.
- the ink aggregates and thickens while appropriately diffusing in the treatment liquid. Therefore, it is possible to suppress image defects such as beading and mottling while preventing characters and fine lines from bleeding, and as a result, it is possible to achieve high image quality. Further, by setting the dynamic surface tension of the treatment liquid and the ink within the above ranges, it is possible to obtain high injection stability and storage stability while ensuring high wettability to the substrate.
- FIG. 1 is a cross-sectional view showing a schematic configuration of an image recorded matter according to the present invention
- Cross-sectional view of packaging material for canned food Schematic diagram showing an inkjet head used in Examples
- FIG. 4 shows the dynamic surface tension of the ink set 44 in the example.
- the ink set of the present invention is an ink set containing an ink and a treatment liquid, wherein the ink contains a pigment, resin fine particles, a water-soluble solvent having a boiling point of 150 to 250° C., and a surfactant, and
- the treatment liquid contains a polyvalent metal salt, a water-soluble solvent with a boiling point in the range of 150 to 250° C., and a surfactant, and at 25° C., the static surface tension of the ink is equal to the static surface tension of the treatment liquid.
- the dynamic surface tension of the ink at a surface life of 15 ms is 5 mN/m or more higher than the dynamic surface tension of the treatment liquid at a surface life of 15 ms, and the surface life of the ink is
- the dynamic surface tension at 15 ms is in the range of 35-45 mN/m
- the dynamic surface tension at the surface life of 15 ms of the treatment liquid is in the range of 25-35 mN/m.
- the pigment is dispersed with an anionic polymer dispersant in terms of excellent dispersibility and moderate reaction with the treatment liquid for pinning.
- the ink contains 3 to 15% by mass of the resin fine particles having an aggregability of 0.2 or less with a 0.15% by mass aqueous calcium acetate monohydrate solution.
- the fine resin particles prefferably contain a water-dispersible polyester resin having a sulfonic acid group from the viewpoint of obtaining high adhesion to the substrate.
- the dynamic surface tension at the surface life of 15 ms of the undried treatment liquid is A, and the treatment liquid is dried, and the drying rate of the treatment liquid is 30%.
- the dynamic surface tension is B, it is preferable to satisfy the following formula (I).
- the treatment liquid preferably contains a surfactant that is not contained in the ink.
- the inkjet recording method of the present invention is an inkjet recording method for recording an image using the ink set, wherein after applying the treatment liquid to a substrate, the treatment liquid is wetted without a heat drying step. In this state, the ink is applied to the area to which the treatment liquid has been applied.
- the ink when the ink is applied to the area to which the treatment liquid has been applied in a state where the drying rate of the treatment liquid is 30% or less, the ink and the treatment liquid are appropriately mixed, and the effects of the present invention can be obtained. It is preferable in that it can be exhibited more remarkably.
- Applying the ink to the area to which the treatment liquid has been applied within 10 seconds after applying the treatment liquid to the base material prevents the treatment liquid from permeating into the absorbent base material and the non-absorbent base material. This is preferable in that repelling of the treatment liquid on the material can be suppressed and higher image quality can be achieved.
- the amount of the ink applied per unit area is in the range of 2 to 25 times the amount of the treatment liquid applied, in that higher image quality can be achieved.
- the ink set of the present invention is an ink set containing an ink and a treatment liquid, wherein the ink contains a pigment, resin fine particles, a water-soluble solvent having a boiling point of 150 to 250° C., and a surfactant, and
- the treatment liquid contains a polyvalent metal salt, a water-soluble solvent with a boiling point of 150-250° C., and a surfactant.
- the static surface tension of the ink is higher than the static surface tension of the treatment liquid by 5 mN/m or more
- the dynamic surface tension at a surface life of 15 ms of the ink is higher than that of the treatment liquid.
- the dynamic surface tension at a surface life of 15 ms of the ink is 35 mN/m or more and 45 mN/m or less
- the surface life of the treatment liquid is Dynamic surface tension at 15 ms is 25 mN/m or more and 35 mN/m or less.
- treatment liquid and "ink” used in the present invention refer to “treatment liquid (also referred to as “pretreatment liquid” or “primer”) and “ink ("aqueous ink” or “ Also referred to as “water-based ink.)”. In all cases, 60% by mass or more of the solvent used is “water”.
- static surface tension refers to the diffusion of each component in the ink or treatment liquid on the surface of the liquid as the surface life elapses and approaches an equilibrium state. That's what I mean.
- the static surface tension of the ink or treatment liquid can be measured using an automatic surface tension meter (manufactured by Kyowa Interface Science Co., Ltd., model "CBVP-Z") using a platinum plate.
- static surface tension in this specification is static surface tension measured at 25°C.
- the static surface tension of the ink is 5 mN/m or more higher than the static surface tension of the treatment liquid at 25°C. It is preferably high within the range of 6-12 mN/m.
- the static surface tension of the ink is preferably in the range of 25 to 35 mN/m, and the static surface tension of the treatment liquid is in the range of 20 to 30 mN/m. is preferred.
- the difference between the ink having the lowest static surface tension and the static surface tension of the treatment liquid should be within the above range.
- dynamic surface tension means the surface tension immediately after the liquid surface (air-liquid interface) is formed and when the liquid surface is in a non-equilibrium state. It is a value measured in °C.
- surface life is the elapsed time from the formation of the liquid surface, that is, the life of the bubbles generated in the maximum bubble pressure method. It refers to the time from when a new interface is generated to when the maximum bubble pressure is reached.
- the dynamic surface tension of the treatment liquid or ink can be measured by using a dynamic surface tensiometer.
- the dynamic surface tensiometer examples include a bubble pressure dynamic surface tensiometer (manufactured by KRUSS, model "BP100"). Unless otherwise specified, the dynamic surface tension in this specification is the dynamic surface tension measured at 25° C. for 15 ms using the maximum bubble pressure method.
- the dynamic surface tension (also referred to as “dynamic surface tension A”) at a surface life of 15 ms of the ink is 5 mN/m higher than the dynamic surface tension at a surface life of 15 ms of the treatment liquid. higher than m. Preferably, it is high within the range of 7-15 mN/m. In the case of using a plurality of types of ink, the difference between the ink having the lowest dynamic surface tension and the dynamic surface tension of the treatment liquid should be within the above range.
- the dynamic surface tension of the treatment liquid at a surface life of 15 ms is in the range of 25 to 35 mN/m, preferably in the range of 27 to 33 mN/m. Furthermore, the dynamic surface tension of the ink at a surface life of 15 ms is in the range of 35-45 mN/m, preferably in the range of 37-43 mN/m.
- the type and content of the surfactant, the type and content of the water-soluble solvent, and the type and content of the flocculant are control.
- various polyether-modified silicones and/or acetylene glycol-based surfactants are used as surfactants contained in the treatment liquid, and the content thereof is within the range of 0.1 to 2.0% by mass.
- the water-soluble solvent a water-soluble solvent having an SP value of 24 (J/cm 3 ) 1/2 or more and a boiling point in the range of 150° C. to 250° C. is used, and the content thereof is in the range of 5 to 40% by mass. preferably within.
- the type and content of the surfactant, the type and content of the water-soluble solvent, and the type and content of the pigment dispersant controlling the type and content of fine resin particles, and controlling the type and content of additives.
- various polyether-modified silicones and/or acetylene glycol-based surfactants are used as surfactants contained in the ink, and the content thereof is in the range of 0.1 to 2.0% by mass. is preferred.
- the water-soluble solvent a water-soluble solvent having an SP value of 24 (J/cm 3 ) 1/2 or more and a boiling point in the range of 150° C. to 250° C.
- the content thereof is in the range of 5 to 40% by mass. preferably.
- the pigment dispersant it is preferable to use various low-molecular-weight dispersants, nonionic polymer dispersants, anionic polymer dispersants, or appropriately use a resin-coated pigment dispersant.
- resin fine particles such as polyester resin, acrylic resin, styrene-acrylic resin, and urethane resin are used, and the content thereof is preferably within the range of 3 to 15% by mass.
- the dynamic surface tension at 25° C. at a surface life of 15 ms of the undried treatment liquid is defined as A, and the dynamic surface tension at a surface life of 15 ms when the drying rate of the treatment liquid is 30%. It is preferable that the following formula (I) is satisfied, where B is the target surface tension.
- the "dynamic surface tension A” is the dynamic surface tension of the processing liquid before drying the processing liquid as described below, that is, in the undried (state) and with a surface life of 15 ms at 25 ° C. This is the value measured at 25° C. by the maximum bubble pressure method described above.
- “Dynamic surface tension B” is the dynamic surface tension of the treatment liquid at a surface life of 15 ms when the treatment liquid is dried and the drying rate is 30%. Specifically, 100 g of the treatment liquid was weighed into a shallow container and dried in a reduced pressure environment at 25° C. until the weight of the liquid reached 70 g. This is defined as the dynamic surface tension B after 30% drying. From the dynamic surface tension B after 30% drying and the dynamic surface tension A thus measured, the difference "(BA)" is calculated.
- the treatment liquid according to the present invention accelerates the image formation of the ink by aggregating or increasing the viscosity of the ink when recording an image on a substrate by an inkjet printing method, and improves the physical properties of the treatment liquid layer and the ink layer. can have a function to improve the image quality.
- the treatment liquid according to the present invention contains at least a polyvalent metal salt, a water-soluble solvent with a boiling point within the range of 150 to 250°C, and a surfactant. Moreover, the treatment liquid may contain water.
- the treatment liquid according to the present invention contains a material that forms aggregates when in contact with ink, that is, an aggregating agent that is a polyvalent metal salt. can be more immobilized.
- the polyvalent metal salt can aggregate the anionic components (usually coloring materials, pigments, etc.) in the ink described later by salting out.
- the polyvalent metal salt a salt of a metal having a valence of 2 or more can be used.
- the type of metal ( cation ) that constitutes the polyvalent metal salt is not particularly limited. , Al 3+ , Fe 3+ , Cr 3+ , Y 3+ and other trivalent metal ions, and Zr 4+ and other tetravalent metal ions.
- the type of salt that constitutes the polyvalent metal salt is not particularly limited, but known salts such as carbonates, sulfates, nitrates, hydrochlorides, organic acid salts, borates, and phosphates can be used.
- particularly preferred polyvalent metal salts include, for example, calcium chloride, magnesium chloride, calcium nitrate, magnesium nitrate, magnesium acetate, calcium acetate, magnesium lactate, and calcium or magnesium salts of carboxylic acids such as calcium pantothenate. is mentioned.
- the treatment liquid according to the present invention may further contain an organic acid as a coagulant.
- Organic acids can aggregate the anionic components in the ink by pH fluctuations.
- a monovalent carboxylic acid is preferable from the viewpoint of not weakening the cohesive force of the polyvalent metal salt.
- the organic acid is capable of aggregating pigments that may be contained in the ink described later.
- examples of the organic acid include formic acid, acetic acid, propionic acid, isobutyric acid, and benzoic acid.
- an organic acid that has not been completely neutralized with a base.
- Neutralization with a base means that the acidic groups of these acids are ionically bonded with other positively charged elements or compounds (eg, inorganic compounds such as metals).
- not completely neutralized means that among the acidic groups of the organic acid, there are acidic groups that do not form the above ionic bond.
- Preferred organic acids from the above point of view include formic acid, acetic acid, propionic acid, benzoic acid, and the like.
- the treatment liquid according to the present invention may further contain an inorganic acid as a coagulant.
- Inorganic acids can aggregate the anionic components in the ink by pH fluctuations.
- the inorganic acid is capable of aggregating pigments that may be contained in the ink described later.
- examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid and the like.
- the content of the polyvalent metal salt is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 1 to 10% by mass, relative to 100% by mass of the total mass of the treatment liquid. This makes it possible to effectively aggregate the anionic component in the ink, which is preferable from the viewpoint of balancing image quality and hot water resistance.
- the content of the organic acid is preferably in the range of 0.1 to 10% by mass, and in the range of 1 to 3% by mass, with respect to 100% by mass of the total mass of the treatment liquid. is more preferred.
- the content of the inorganic acid is preferably in the range of 0.1 to 10% by mass, and in the range of 1 to 3% by mass, with respect to 100% by mass of the total mass of the treatment liquid. is more preferred.
- the content of the polyvalent metal salt or organic acid in the aqueous solution can be measured by a known method.
- the content can be measured by ICP emission spectrometry in the case of polyvalent metal salts, and by high performance liquid chromatography (HPLC) in the case of organic acids.
- the amount of organic acid to be added is preferably an amount that adjusts the pH of the treatment liquid to be equal to or less than the neutralization equivalent of the anionic component contained in the ink.
- the anion component is a compound having a carboxyl group
- the first dissociation constant of the organic acid is preferably 3.5 or less from the viewpoint of preventing image blurring.
- the water-soluble solvent contained in the treatment liquid according to the present invention is a water-soluble solvent having a boiling point within the range of 150 to 250°C.
- water-soluble solvents include alcohols, polyhydric alcohols, amines, amides, glycol ethers, and 1,2-alkanediols having 4 or more carbon atoms.
- the cloud point of the treatment liquid is lowered.
- the treatment liquid can be heated to a temperature higher than the clouding point, and an image having particularly good adhesion to a non-absorbing substrate can be obtained.
- the SP value is called a solubility parameter.
- the SP value in the present invention is a value calculated by the Fedors method. It is determined from the molar heat of vaporization of the water-soluble solvent and the molar volume of the water-soluble solvent at 25°C. In general , cal is used as the unit of SP value. ) Just use the 1/2 relationship. In the following description, the unit of the SP value may be omitted, but the SP value is a value expressed in units of (J/cm 3 ) 1/2 .
- water-soluble solvents having an SP value of 24 (J/cm 3 ) 1/2 or more and a boiling point of 150° C. to 250° C. include polyhydric alcohols and polyalkylene glycols having 2 to 8 carbon atoms. etc.
- polyhydric alcohols having 2 to 8 carbon atoms examples include 1,2-ethanediol (SP value: 30.3, boiling point: 197°C), 1,2-propanediol (SP value: 28.0, boiling point: 188°C ), 1,3-propanediol (SP value: 32.9, boiling point 213° C.), 1,2-butanediol (SP value: 26.1, boiling point 192° C.), 1,3-butanediol (SP value: 30.3, boiling point: 207°C), 1,4-butanediol (SP value: 30.7, boiling point: 230°C), 2,3-butanediol (SP value: 29.9, boiling point: 177°C), 2 -methyl-1,3-propanediol (SP value: 30.3, boiling point: 214°C), 1,2-pentanediol (SP value: 25.0, boiling point: 210°C), 1,5-pentanediol
- polyalkylene glycols examples include diethylene glycol (SP value: 30.6, boiling point: 244°C), dipropylene glycol (SP value: 27.2, boiling point: 230°C), and the like.
- the treatment liquid can contain one or a combination of two or more selected from these water-soluble solvents.
- At least one water-soluble solvent having a boiling point of 150° C. to 250° C. may be contained in the ink.
- the above 1,2-alkanediols may be included.
- solvents other than water-soluble solvents having a boiling point of 150°C to 250°C include glycerin (SP value: 33.5, boiling point: 290°C), trimethylolpropane (SP value: 32.5, boiling point: 295°C), and triethylene.
- Glycol SP value: 27.8, boiling point: 287°C
- tetraethylene glycol SP value: 26.1, boiling point: 275°C
- the total content of the water-soluble solvent is preferably in the range of 5 to 40% by mass, more preferably in the range of 10 to 40% by mass, relative to 100% by mass of the treatment liquid.
- the surfactant contained in the treatment liquid according to the present invention can improve the ejection stability of the treatment liquid from the nozzle and control the spread of droplets (enlarging the dot diameter) that land on the recording medium.
- the surfactant that can be used in the treatment liquid of the present invention can be used without any particular limitation.
- Nonionic or betaine types are preferred.
- fluorine-based or silicone-based surfactants with high static surface tension reducing ability preferably fluorine-based or silicone-based surfactants with high static surface tension reducing ability, anionic surfactants such as dioctyl sulfosuccinate with high dynamic surface tension reducing ability, relatively Nonionic surfactants such as low-molecular-weight polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, acetylene glycols, pluronic surfactants (Pluronic is a registered trademark), sorbitan derivatives and the like are preferably used. It is also preferable to use a fluorine-based or silicone-based surfactant in combination with a surfactant having a high dynamic surface tension-reducing ability.
- a silicone-based or fluorine-based surfactant as a surfactant, it can be used for recording media made of various hydrophobic resins such as vinyl chloride sheets, and recording media with low ink absorbency such as printed paper. , is preferable in that ink contamination (beading) can be further suppressed and a high-quality printed image can be obtained.
- the above-mentioned silicone-based surfactants are preferably polyether-modified silicones, and examples thereof include siloxanes having alkylene oxide groups on the side chains and/or both ends of a polydimethylsiloxane chain.
- examples thereof include siloxanes having alkylene oxide groups on the side chains and/or both ends of a polydimethylsiloxane chain.
- trisiloxane having alkylene oxide groups at the side chains and/or at both ends of the polydimethylsiloxane chain is particularly preferred.
- the dynamic surface tension of the treatment liquid can be effectively lowered, and an image with good adhesion to the substrate can be obtained.
- trisiloxane it is preferable to have a structure represented by the following general formula (1).
- EO represents a repeating unit structure of polyethylene oxide, that is, a ring-opened structure of ethylene oxide, which is a three-membered cyclic ether.
- PO represents a repeating unit structure of polypropylene oxide, that is, a ring-opened structure of propylene oxide, which is a three-membered cyclic ether.
- [EO]m and [PO]n may be in either order” means that in the compound molecule represented by the general formula (1), the order of the bonding positions with respect to the base siloxane skeleton is changed as appropriate. Say good things.
- X is preferably an alkylene group having 3 carbon atoms (that is, a propylene group). Moreover, in the said general formula (1), it is preferable that m is an integer of 5-20, and n is an integer of 0-6.
- S-1 to S-8 are shown below as specific examples of the silicone-based surfactant having the structure represented by the general formula (1), but are not limited thereto.
- the trisiloxane examples include BYK-3450 and BYK-3451 manufactured by BYK-Chemie Japan, and TEGOWET-KL245, TEGOWET-250 and TEGOWET-260 manufactured by Evonik.
- the content of the polyether-modified silicone is preferably in the range of 0.5 to 2% by mass, more preferably in the range of 0.5 to 1.5% by mass, relative to 100% by mass of the total mass of the treatment liquid. It is more preferable to contain within.
- the above-mentioned fluorine-based surfactant means one in which some or all of the hydrogen atoms in the hydrophobic groups of ordinary surfactants are replaced with fluorine.
- those having a perfluoroalkyl group in the molecule are preferred.
- fluorine-based surfactants certain types are available from Dainippon Ink and Chemicals under the trade name of Megafac F, from Asahi Glass Co. under the trade name of Surflon, and from Minnesota Mining & Co., Ltd. Manufacturing Company under the trade name Fluorad FC; Imperial Chemical Industries under the trade name Monflor; and from mistakewerke Hoechst under the trade name Licowet VPF, respectively.
- the treatment liquid according to the present invention preferably contains a surfactant that is not contained in the ink, which will be described later.
- Examples of the two patterns are as follows.
- the surfactant contained in the ink is surfactant S1
- the surfactant contained in the treatment liquid is preferably a surfactant S2 different from the surfactant S1 contained in the ink.
- the surfactant contained in the treatment liquid preferably contains the surfactant S2 in addition to the surfactant S1.
- the surfactant contained in the treatment liquid is preferably a polyether-modified silicone or the like, and the surfactant contained in the ink is an acetylene glycol-based surfactant and the like.
- Polyether-modified silicone and the like are preferred. As described above, by adding a surfactant that is not contained in the ink (that is, a surfactant that destabilizes the dispersion stability of the ink) to the treatment liquid, it is possible to further increase the cohesiveness. .
- the content of the surfactant in the treatment liquid is not particularly limited, but is preferably within the range of 0.1 to 5.0% by mass of the total weight of the treatment liquid.
- the treatment liquid according to the present invention may contain water, and usable water is not particularly limited, and may be ion-exchanged water, distilled water, or pure water.
- the treatment liquid can appropriately contain other components such as a cross-linking agent, an antifungal agent, and a bactericide within a range that does not impair the effects of the present invention.
- UV absorber described in JP-A-57-74193, JP-A-57-87988 and JP-A-62-261476, JP-A-57-74192, JP-A-57-87989, JP-A-60 -72785, JP-A-61-146591, JP-A-1-95091 and JP-A-3-13376 anti-fading agents, various anionic, cationic or nonionic surfactants, JP-A-59 No. -42993, No. 59-52689, No. 62-280069, No.
- the treatment liquid layer by directly applying the treatment liquid according to the present invention as a coating liquid on the substrate and drying it. It is preferable that the additive preferably used in the treatment liquid is used as the coating liquid after being sufficiently dissolved.
- an inkjet method As the coating method of the treatment liquid, an inkjet method, a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294 is preferably used. , especially the inkjet method is preferred.
- the ink according to the present invention contains at least a pigment, fine resin particles, a water-soluble solvent having a boiling point of 150 to 250° C., and a surfactant. Moreover, you may contain water.
- an anionic dispersing pigment for example, a self-dispersing pigment having an anionic group on the surface, or an anionic polymeric dispersant. It is preferable to use a dispersed pigment or a dispersed pigment whose surface is coated with an anionic resin. In particular, it is preferable to use a pigment dispersed with an anionic polymer dispersant in terms of excellent dispersibility and appropriate reaction with the treatment liquid for pinning.
- pigments conventionally known pigments can be used without particular limitation.
- organic pigments such as insoluble pigments and lake pigments, and inorganic pigments such as titanium oxide can be preferably used.
- the present invention makes it possible to prevent bleeding and improve adhesion, particularly preferably.
- Titanium oxide has three crystal forms: anatase, rutile, and brookite.
- General-purpose forms can be roughly divided into anatase and rutile.
- the rutile type having a high refractive index and high hiding power is preferable. Specific examples include the TR series of Fuji Titanium Industry Co., Ltd., the JR series of Tayca Co., Ltd., and the Typaque of Ishihara Sangyo Co., Ltd.
- insoluble pigments include, but are not limited to, azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, Dioxazines, thiazoles, phthalocyanines, diketopyrrolopyrroles and the like are preferred.
- Specific organic pigments that can be preferably used include the following pigments.
- pigments for magenta or red for example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I.
- Pigment Red 166 C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 202, C.I. I. Pigment Red 222, C.I. I. Pigment Violet 19 and the like.
- pigments for orange or yellow for example, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 15:3, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 155 and the like. Especially in the balance between color tone and light resistance, C.I. I. Pigment Yellow 155 is preferred.
- pigments for green or cyan for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.
- black pigments for example, C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7 and the like.
- the ink according to the present invention preferably contains a pigment dispersant for dispersing the pigment.
- a pigment dispersant for dispersing the pigment.
- the pigment dispersant is not particularly limited, a polymer dispersant having an anionic group is preferable, and one having a molecular weight within the range of 5,000 to 200,000 can be suitably used.
- polymer dispersants examples include 2 selected from styrene, styrene derivatives, vinylnaphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, and fumaric acid derivatives.
- Block copolymers, random copolymers and salts thereof, polyoxyalkylenes, polyoxyalkylene alkyl ethers, etc. having structures derived from more than one kind of monomers can be mentioned.
- the polymer dispersant preferably has an acryloyl group and is preferably added after being neutralized with a neutralizing base.
- a neutralizing base is not particularly limited here, it is preferably an organic base such as ammonia, monoethanolamine, diethanolamine, triethanolamine or morpholine.
- the pigment is titanium oxide
- the titanium oxide is preferably dispersed with a polymer dispersant having an acryloyl group.
- the amount of polymer dispersant added is preferably in the range of 10 to 100% by mass, more preferably in the range of 10 to 40% by mass, based on the pigment.
- the pigment is particularly preferably in the form of a so-called capsule pigment, in which the pigment is coated with the polymer dispersant.
- a method for coating the pigment with the polymer dispersant various known methods can be used.
- the phase inversion emulsification method, the acid precipitation method, or the A preferred example is a method of supplying a monomer to the film and coating the film while polymerizing the film.
- a water-insoluble resin is dissolved in an organic solvent such as methyl ethyl ketone, and after partially or completely neutralizing the acidic groups in the resin with a base, a pigment and ion-exchanged water are added and dispersed. After that, the organic solvent is removed, and if necessary, water is added for preparation.
- an organic solvent such as methyl ethyl ketone
- the average particle diameter of the dispersed pigment in the ink is preferably 50 nm or more and less than 200 nm. Thereby, the dispersion stability of the pigment can be improved, and the storage stability of the ink can be improved.
- the particle size of the pigment can be determined by a commercially available particle size measuring instrument using a dynamic light scattering method, an electrophoresis method, or the like. Accurate measurement is possible.
- the pigment can be used by dispersing it with a dispersing machine together with a dispersant and other additives necessary for various desired purposes.
- a disperser conventionally known ball mills, sand mills, line mills, high pressure homogenizers, etc. can be used. Among them, it is preferable to disperse the pigment by a sand mill because the particle size distribution becomes sharp.
- the material of the beads used for sand mill dispersion is not particularly limited, but zirconia or zircon is preferable from the viewpoint of preventing the generation of bead fragments and contamination with ionic components.
- the bead diameter is preferably within the range of 0.3 to 3 mm.
- the content of the pigment in the ink is not particularly limited, it is preferably in the range of 7 to 18% by mass for titanium oxide, and 0.5 to 7% by mass for the organic pigment.
- the fine resin particles contained in the ink according to the present invention are preferably water-insoluble fine resin particles.
- the glass transition temperature (glass transition point (Tg)) of the fine resin particles is preferably in the range of 40 to 90°C.
- the glass transition temperature is obtained by using a DSC (differential scanning calorimeter) from the endothermic peak when the temperature is raised at a temperature increase rate of 10 ° C./min in the temperature range of -30 to 200 ° C., the glass transition temperature Tg can be identified by reading
- the water-insoluble resin used in the present invention is a water-insoluble resin that can accept ink and exhibits solubility or affinity for the ink.
- Water-insoluble resin fine particles are originally water-insoluble, but have a form in which the resin is dispersed in an aqueous medium as microscopic particles. It is a resin or a water-insoluble resin capable of self-emulsification that forms a stable aqueous dispersion by itself without using an emulsifier or a dispersion stabilizer by introducing a hydrophilic functional group into the molecule. These resins are usually used in a state of being emulsified and dispersed in water or a water/alcohol mixed solvent.
- the term "water-insoluble” means that when the resin is dried at 105°C for 2 hours and then dissolved in 100 g of water at 25°C, the dissolved amount is 10 g or less, preferably 5 g or less. Preferably, it refers to a resin weighing 1 g or less. However, when the resin has a salt-forming group, the dissolved amount is the dissolved amount when the salt-forming group of the resin is 100% neutralized with acetic acid or sodium hydroxide, depending on the type.
- the resin having a glass transition temperature in the range of 40 to 90° C. is preferably an acrylic resin, a urethane resin, a polyester resin, or a composite resin of a urethane resin and an acrylic resin, particularly an acrylic resin, a urethane resin, It is a composite resin of a polyester resin or a urethane resin and an acrylic resin, and the average particle size of the resin particles of these resins is preferably 200 nm or less. In particular, the average particle size is preferably within the range of 100-150 nm.
- polyester resin, urethane resin, acrylic resin, or composite resin particles of urethane resin and acrylic resin are preferably anionic or nonionic.
- the fine resin particles used in the ink preferably contain an acid structure, and even if the amount of surfactant added is small, they can be dispersed in water and the water resistance of the ink layer is improved.
- This is called a self-emulsifying type, which means that the resin can be dispersed and stabilized in water only with molecular ionic properties without using a surfactant.
- acid structures include acid groups such as a carboxy group (--COOH) and a sulfonic acid group (--SO 3 H).
- the acid structure may be present in the side chain of the resin, or may be present at the end.
- the ink according to the present invention preferably contains a water-dispersible polyester resin having a sulfonic acid group. As a result, high adhesion to the substrate can be obtained.
- a part or all of the acid structure is preferably neutralized.
- neutralizing agents that neutralize the acid structure are preferably organic amines, and organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine and triethanolamine are preferably used.
- the ink according to the present invention preferably contains 3 to 15% by mass of resin fine particles having an aggregating property of 0.2 or less with a 0.15% by mass calcium acetate aqueous solution.
- resin fine particles with low cohesion in this manner, high injection stability can be obtained while ensuring high wettability to the substrate, resulting in higher image quality and excellent adhesion to the substrate.
- "cohesiveness” is a value calculated by the following formula after measuring the remaining amount according to the following procedure. (i) 5 g of resin fine particle aqueous solution (solid content: 10 mass %) containing resin fine particles and 5 g of 0.3 mass % calcium acetate monohydrate aqueous solution are mixed.
- Examples of the fine resin particles having a cohesiveness of 0.2 or less include Vylonal MD2000 manufactured by Toyobo Co., Ltd., Movinyl 6969D manufactured by Japan Coating Resin, and Evaphanol HA-560 manufactured by Nicca Chemical.
- polyester resin A polyester resin having a polyester skeleton as water-insoluble resin particles can be obtained by using a polyhydric alcohol component and a polycarboxylic acid component such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic acid ester. can.
- a dihydric alcohol specifically an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butylene glycol, 1,6-hexanediol, etc.), alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), Alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxides having 2 to 4 carbon atoms (ethylene oxide (hereinafter referred to as , abbreviated as EO.), propylene oxide (hereinafter abbreviated as PO.), butylene oxide (hereinafter abbreviated as BO.)) adduct (addition mole), EO.), propylene oxide (hereinafter
- polyvalent carboxylic acid component examples include divalent carboxylic acids (dicarboxylic acids), specifically alkanedicarboxylic acids having 4 to 36 carbon atoms (succinic acid, apidic acid, sebacic acid, etc.), alkenylsuccinic acids.
- polyester resin a polyester resin having an anionic group in the molecule is preferable, and a polyester resin containing a sulfonic acid group is particularly preferable.
- a known synthesis method for obtaining a polyester containing a sulfonic acid group for example, it can be obtained by a method such as a polycondensation reaction of a dicarboxylic acid having a sulfonic acid group and a diol, or a dicarboxylic acid and a diol having a sulfonate can be used. It can also be obtained by a method such as a polycondensation reaction of.
- Dicarboxylic acid components having a sulfonic acid group include, for example, 2-sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthaleneisophthalic acid-2,7-dicarboxylic acid and 5-(4-sulfophenoxy)isophthalic acid, Or those alkali metal salts etc. are mentioned.
- Diols having a sulfonic acid group include, for example, 2-sulfo-1,4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol, and alkali metal salts thereof.
- the number average molecular weight of the polyester resin is preferably in the range of 1,000 to 50,000, more preferably in the range of 2,000 to 20,000.
- polyester resin Commercially available products may be used as the polyester resin, and commercial products of the water-dispersible polyester resin having a sulfonic acid group include, for example, Vylonal MD-1100, MD-1200, MD-1245 and MD manufactured by Toyobo Co., Ltd. -1480, MD-1500, MD-2000, Plascoat Z-221, Z-446, Z-561, Z-880, Z-3310 manufactured by Goo Chemical Co., Ltd. Pesresin A-520, A-613D manufactured by Takamatsu Oil Co., Ltd. A-615GE, A-640, A-645GH, A-647GEX, A-110F, A-160P and the like.
- resins having a glass transition temperature of 40 to 90° C. are particularly preferable.
- urethane resin A urethane resin having a hydrophilic group can be used as the water-insoluble resin particles.
- the above urethane resin is an aqueous dispersion in which a self-emulsifying urethane having a water-soluble functional group in its molecule is dispersed, or a forced emulsifying urethane emulsified under strong mechanical shearing force in combination with a surfactant.
- An aqueous dispersion is preferred.
- the urethane resin in the aqueous dispersion can be obtained by reacting a polyol with an organic polyisocyanate and a hydrophilic group-containing compound.
- polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 3-methylpentanediol, Low-molecular-weight polyols such as hexamethylene glycol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, cyclohexanedimethanol; succinic acid, glutaric acid, adipine Acids, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuranic acid, endomethinetetrahydrofuranic acid, and condensates with polycarboxylic acids such as hexahydrophthalic acid.
- polyether polyols examples include polyethylene glycol, polypropylene glycol, polyethylene polytetramethylene glycol, polypropylene polytetramethylene glycol, and polytetramethylene glycol.
- polycarbonate polyols can be obtained by reacting carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene with diols.
- diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propylene glycol, neopentyl glycol, 1,3- and 1,4-butanediol, 3-methylpentanediol, hexamethylene glycol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, cyclohexanedimethanol, and the like.
- organic polyisocyanates examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate. (TMXDI); aliphatic isocyanates such as hexamethylene diisocyanate (HMDI); isophorone diisocyanate (IP DI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI, H12MDI). These may be used individually by 1 type, and may use 2 or more types together.
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- XDI xylylene diisocyanate
- TMXDI tetramethylxylylene diisocyanate
- HMDI hexamethylene diisocyanate
- IP DI isophorone di
- a urethane resin can be obtained by a known method.
- a urethane prepolymer can be obtained by mixing the above-described polyol, organic polyisocyanate, and hydrophilic group-containing compound and reacting them at 30 to 130° C. for 30 minutes to 50 hours.
- the above urethane prepolymer becomes a urethane resin having a hydrophilic group by extending it with a chain extender and polymerizing it.
- the chain extender is preferably water and/or an amine compound.
- amine compounds as chain extenders include aliphatic polyamines such as ethylenediamine and triethylenediamine; aromatic polyamines such as metaxylenediamine and toluylenediamine; and polyhydrazino compounds such as hydrazine and adipic acid dihydrazide.
- the amine compound may contain, together with the polyamine, a monovalent amine such as dibutylamine, methyl ethyl ketoxime, or the like as a reaction terminator, to the extent that polymerization is not greatly hindered.
- a solvent that is inert with isocyanate and capable of dissolving the urethane prepolymer may be used.
- these solvents include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, propylene glycol monomethyl ether acetate, and the like.
- These hydrophilic organic solvents used in the reaction step are preferably finally removed.
- amine catalysts e.g., triethylamine, N-ethylmorpholine, triethyldiamine, etc.
- tin-based catalysts e.g., dibutyltin dilaurate, dioctyltin dilaurate, octyl acid
- titanium-based catalysts eg, tetrabutyl titanate, etc.
- the number average molecular weight of the urethane resin is preferably increased as much as possible by introducing a branched structure or an internal crosslinked structure, and is preferably from 50,000 to 1,000,000. By setting the molecular weight within the above range, the urethane resin becomes difficult to dissolve in a solvent, so that a coating film having excellent weather resistance and water resistance can be obtained.
- the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC). Solvent: tetrahydrofuran (THF), column temperature: 40° C.) can be determined from a calibration curve prepared from polystyrene standard samples.
- urethane resin examples include Neorez R-967, R-600 and R-9671 manufactured by Kusumoto Kasei Co., Ltd., Evaphanol HA-560 manufactured by Nicca Chemical Co., Ltd., SF870 manufactured by Ichi Kogyo Seiyaku Co., Ltd. is included.
- the acrylic resin as the water-insoluble resin particles can be obtained by using an acrylic acid ester component, a methacrylic acid ester component, or a copolymer with a styrene component or the like.
- acrylic acid ester components and methacrylic acid ester components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, blue (meth) acrylate, (meth) acrylic acid-2- Hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate ) benzyl acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, (
- styrene components include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-acetylstyrene and styrenesulfonic acid. These components may be used alone or in combination of two or more.
- the number average molecular weight (Mn) of the acrylic resin is preferably 1,000 to 50,000, more preferably 2,000 to 20,000.
- Mn number average molecular weight
- the number average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC). Solvent: tetrahydrofuran (THF), column temperature: 40° C.) can be determined from a calibration curve prepared from polystyrene standard samples.
- acrylic resin a commercially available product may be used as the acrylic resin.
- acrylic resins having a glass transition temperature of 40 to 90°C include Movinyl 6899D, 6969D, 6800 manufactured by Japan Coating Resin Co., Ltd. TOCRYL W-7146, W-7147, W-7148, W- 7149, W-7150 and other acrylic emulsions.
- the fine composite resin particles that can be contained in the ink are preferably fine composite resin particles obtained by emulsifying an acrylic resin with a urethane resin. That is, it is preferable that the fine composite resin particles have an inner layer made of an acrylic resin and a surface layer made of a urethane resin.
- the urethane resin exists at the interface between the acrylic resin as the water-insoluble resin particles and water as the continuous phase, and functions as a water-insoluble resin particle layer different from the resin that protects the water-insoluble resin particles.
- the composite resin fine particles obtained by emulsifying the acrylic resin with the urethane resin in this way, the physical properties of the image (coating film) can be improved compared to emulsifying and mixing the acrylic resin and the urethane resin respectively. In addition, the storage stability of the composite resin fine particles can be improved.
- the mass ratio (U/A) of the urethane resin (U) and the acrylic resin (A) is 40/60 to 95/5. is preferred.
- the content of the urethane resin (U) is within the above range, the compatibility with the dispersant is improved, and the solvent resistance is also improved.
- the abundance of the acrylic resin (A) is within the above range, the adhesiveness to the acrylic film is excellent.
- the mass ratio (U/A) between the urethane resin (U) and the acrylic resin (A) is preferably 40/60 to 80/20.
- the total resin concentration of the acrylic resin and the urethane resin in the composite resin fine particles is not particularly limited, but is preferably 5.0% by mass or more, and is preferably 10.0 to 70.0% by mass. more preferred. When the resin concentration is within the above range, the fixability between the substrate and the ink is improved.
- a surfactant that acts as an emulsifier can be used together with the urethane resin.
- the storage stability of the fine composite resin particles can be improved.
- An anionic surfactant and a nonionic surfactant can be used as the emulsifier.
- the total amount of the anionic surfactant and the nonionic surfactant is preferably 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the total resin mass.
- the total amount of the anionic surfactant and the nonionic surfactant can be 20.0 parts by mass or less, the water resistance and solvent resistance can be improved.
- the blending mass ratio (X/Y) of the anionic surfactant (X) and the nonionic surfactant (Y) is preferably 100/0 to 50/50.
- anionic surfactants examples include alkyl sulfates, polyoxyethylene alkyl ether sulfates, sulfosuccinates, alpha olefin sulfonates, N-acylamino acid salts, carboxylates, and phosphate esters.
- sulfosuccinates and alpha-olefin sulfonates are preferred.
- types of salts include, but are not particularly limited to, metal salts such as sodium salts, potassium salts, and magnesium salts, triethanolamine salts, and the like.
- nonionic surfactants examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamine ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, Sugar fatty acid esters and the like are included. Among these, polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers are preferred.
- the average particle size of the composite resin fine particles described above is not particularly limited, but is preferably 10 to 500 nm, more preferably 10 to 300 nm, and even more preferably 10 to 200 nm. Measurement of the average particle size can be obtained by a commercially available particle size measuring instrument using dynamic light scattering method, electrophoresis method, etc., but measurement by dynamic light scattering method is simple and the particle size range can be determined. Accurate measurement is possible.
- composite resin fine particles obtained by emulsifying an acrylic resin in a urethane resin it is possible to improve the fixability of an image (coating film) on an absorbent base material or a non-absorbent base material.
- the water-soluble solvent contained in the ink according to the present invention is a water-soluble solvent having a boiling point within the range of 150 to 250°C.
- water-soluble solvents include alcohols, polyhydric alcohols, amines, amides, glycol ethers, 1,2-alkanediols having 4 or more carbon atoms, and the like. Those exemplified for the liquid can be mentioned.
- the ink can contain one or a combination of two or more selected from the water-soluble solvents described above.
- the content of the water-soluble solvent in the ink is not particularly limited, but is preferably within the range of 10-60% by mass.
- ⁇ Surfactant> By including a surfactant in the ink according to the present invention, it is possible to improve the ink jetting stability and control the spread (dot diameter) of droplets landed on the recording medium.
- the surfactant that can be used in the ink according to the present invention can be used without any particular limitation, and includes those exemplified for the treatment liquid.
- the activator is preferably not contained in the treatment liquid.
- the content of the surfactant in the ink is not particularly limited, but is preferably within the range of 0.1 to 5.0% by mass.
- Water contained in the ink according to the present invention is not particularly limited, and may be ion-exchanged water, distilled water, or pure water.
- ink used in the present invention in addition to those described above, depending on the purpose of improving ejection stability, compatibility with print heads and ink cartridges, storage stability, image storage stability, and other various performances, Various known additives such as polysaccharides, viscosity modifiers, resistivity modifiers, film-forming agents, UV absorbers, antioxidants, anti-fading agents, anti-mold agents, anti-rust agents, etc. are appropriately selected and used.
- additives such as polysaccharides, viscosity modifiers, resistivity modifiers, film-forming agents, UV absorbers, antioxidants, anti-fading agents, anti-mold agents, anti-rust agents, etc.
- liquid paraffin, dioctyl phthalate, tricresyl phosphate, oil droplet fine particles such as silicone oil, described in JP-A-57-74193, JP-A-57-87988, JP-A-62-261476, etc.
- UV absorber JP-A-57-74192, JP-A-57-87989, JP-A-60-72785, JP-A-61-146591, JP-A-1-95091, JP-A-3-13376, etc.
- a whitening agent etc. can be mentioned.
- the ink used in the present invention having the above structure preferably has a viscosity of 1 to 40 mPa ⁇ s at 25° C., more preferably 2 to 10 mPa ⁇ s.
- the inkjet recording method of the present invention is an inkjet recording method for recording an image using the ink set containing the treatment liquid and the ink described above.
- one ink jet printer is used to continuously apply the treatment liquid constituting the ink set of the present invention to the surface of the substrate and print with the ink. can be done efficiently.
- the inkjet recording method of the present invention is an inkjet recording method in which an image is recorded using the ink set of the present invention described above, and after applying the treatment liquid to a substrate, without a heat drying step. and applying the ink to the region to which the treatment liquid has been applied while the treatment liquid is wet. That is, a step of applying the treatment liquid to the recording area of the substrate (treatment liquid application step), and a process of applying the ink to the area to which the treatment liquid has been applied by an inkjet recording method while the treatment liquid is wet. (Ink application step).
- the inkjet recording method of the present invention also includes an ink heating drying step of heating and drying the treatment liquid and ink applied to the substrate after the ink application step to form a treatment liquid layer and an ink layer. is preferably provided.
- the ink is preferably applied to the area to which the treatment liquid has been applied in a state where the drying rate of the treatment liquid is 30% or less, and the ink is applied within 10 seconds after the treatment liquid application step. It is preferred to carry out the steps. In particular, it is preferable to perform the ink application step within 0.1 to 5 seconds after the treatment liquid application step when the drying rate of the treatment liquid is within the range of 1 to 10%.
- the substrate (recording medium) applicable to the inkjet recording method of the present invention is not particularly limited. Although it may be a non-absorbent base material, it is preferably a non-absorbent base material from the viewpoint of exhibiting the effects of the present invention.
- “absorbent” means absorbability to water
- “non-absorbent” means non-absorbent to water.
- a known plastic film can be used as the non-absorbent substrate.
- plastic films include polyester films such as polyethylene terephthalate, polyethylene films, polypropylene films, polyamide films such as nylon, polystyrene films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, and polylactic acid films.
- biodegradable films such as
- a film coated with polyvinylidene chloride on one or both sides thereof, or a film deposited with a metal oxide can also be preferably used.
- the non-absorbent film can be preferably used whether it is an unstretched film or a stretched film.
- the thickness of the substrate is preferably in the range of 10-120 ⁇ m, more preferably 12-60 ⁇ m in the case of a plastic film.
- metal substrates such as tin plates for three-piece cans and tin-free steel plates (TFS plates, thickness 0.1 to 0.6 ⁇ m) are also preferably used. It can be suitably used as a packaging material for canned foods, which is provided with a resin as a coating layer.
- the packaging material for canned food for example, blocks air, moisture, and light, and seals the food inside. Polyester-based and acrylic-based thermosetting paints are generally used for the outside.
- Treatment liquid application step the above-described treatment liquid is applied onto the recording medium, which is the substrate.
- the method of applying the treatment liquid onto the recording medium is not particularly limited, but preferred examples include a roller coating method, a curtain coating method, a spray coating method, an inkjet method, and the like.
- the roller coating method is preferable from the viewpoint that a roller coating machine or the like can be connected to an inkjet device and used, and even if the viscosity is relatively high, the coating can be efficiently applied.
- the process of applying the treatment liquid is a process using an inkjet method, it is not necessary to apply the coagulant to the non-ink-coated area, so the coagulant that has not reacted with the ink is liberated and becomes cloudy. This is preferable in that such a situation does not occur.
- the substrate to be used is a metal substrate, etc.
- the metal substrate is placed on the conveying belt, and the processing liquid layer is applied and formed while the belt is conveyed, or the substrate is fixed. It is also preferable to use a flatbed type printer for forming the treatment liquid layer.
- the ink applying step is a step of applying the ink of the above-described ink set by an inkjet method at the same time as or immediately after forming the treatment liquid layer on the recording medium which is the substrate.
- the drying rate of the treatment liquid is defined by the following formula.
- (Drying rate of treatment liquid) 1 - ((mass of treatment liquid after drying (g))/(mass of treatment liquid before drying (g))
- the ink and the treatment liquid are appropriately mixed, and the effects of the present invention can be exhibited more remarkably.
- the ink within 10 seconds after applying the treatment liquid to the substrate, the penetration of the treatment liquid into the absorbent substrate and the repelling of the treatment liquid on the non-absorbent substrate can be suppressed. Higher image quality can be achieved.
- the time from application of the treatment liquid to application of the ink may be adjusted, the temperature of the recording medium may be appropriately adjusted, etc.
- the amount of ink droplets is adjusted so that the amount of ink applied per unit area (also referred to as "applied amount") is within the range of 2 to 25 times the amount of treatment liquid applied.
- a more preferable range of the amount to be applied is 2.5 to 3.5 times.
- the inkjet method is not particularly limited, and a printer equipped with an inkjet head loaded with ink can be used. Specifically, ink can be ejected as droplets from nozzles of an inkjet head based on a digital signal, and the droplets can be made to land on the treatment liquid layer of the substrate for printing.
- the inkjet head may be either an on-demand type or a continuous type.
- on-demand ink jet heads include electro-mechanical conversion, including single-cavity, double-cavity, bender, piston, shear mode and shared wall types, as well as thermal ink jet and bubble jet ( "Bubble jet” includes electric-heat conversion methods, including those of Canon Inc.'s registered trademark) type.
- an inkjet head (also called a piezo inkjet head) using a piezoelectric element as an electro-mechanical conversion element used in an electro-mechanical conversion system is preferable.
- a single-pass type inkjet printer which may be either a scan type or a single-pass type inkjet head
- a line head type inkjet head is an inkjet head that has a length greater than the width of the printing range.
- a single head having a width equal to or larger than the printing range may be used, or a plurality of heads may be combined to form an ink jet head having a width equal to or larger than the printing range.
- a plurality of heads may be arranged side by side so that their nozzles are arranged in a zigzag arrangement to increase the resolution of the heads as a whole.
- the transport speed of the recording medium which is the base material
- the transport speed of the recording medium can be set, for example, within the range of 1 to 120 m/min.
- the faster the conveying speed the faster the image forming speed.
- a high-definition image with high ink fixability can be obtained even at a very high linear velocity of 50 to 120 m/min, which is applicable to a single-pass ink jet image forming method.
- the ink heating and drying step the ink applied onto the recording medium, which is the base material, that is, the area to which the ink is applied is heated. Thereby, the ink and the treatment liquid can be dried.
- the heating temperature of the area to which the ink is applied is preferably within the range of 60 to 200°C.
- the heating time of the ink is appropriately adjusted according to the type of recording medium and the amount of applied ink.
- heat drying may be performed using, for example, a non-contact heating drying device such as a drying furnace or a hot air blower, or a contact heating drying device such as a hot plate or a heat roller. you can go
- the drying temperature is (a) when a non-contact heating drying device such as a drying furnace or hot air blower is used, the temperature in the furnace or the ambient temperature such as the hot air temperature, (b) a hot plate or a heat roller
- a non-contact heating drying device such as a drying furnace or hot air blower
- the temperature in the furnace or the ambient temperature such as the hot air temperature
- a hot plate or a heat roller In the case of using a contact heating type drying apparatus such as, the temperature of the contact heating part or (c) the surface temperature of the surface to be dried is measured during the entire drying period of the treatment liquid. It is more preferable to measure (c) the surface temperature of the surface to be dried.
- the thickness of the ink layer obtained as described above is preferably within the range of 0.3 to 3.0 ⁇ m, more preferably within the range of 0.3 to 2.0 ⁇ m.
- the thickness of the ink layer is 0.3 ⁇ m or more, the adhesion of the image and the abrasion resistance can be easily improved.
- the thickness of the ink layer is 3.0 ⁇ m or less, the deformation stress applied to the ink layer can be reduced, so that the adhesion of the image is less likely to be impaired.
- FIG. 1 is a schematic diagram of a preferred recording apparatus for the present invention.
- the present invention is not limited to this.
- the recording apparatus 1 mainly includes a treatment liquid applying section 10 and an ink applying section 20 .
- a treatment liquid layer C is formed on the substrate F in the treatment liquid applying section 10
- an ink layer R is formed by the ink applying section 20 .
- the treatment liquid application unit 10 is not particularly limited as long as it is configured to apply the treatment liquid to the base material, but in the present invention, it is preferably an inkjet head 21 .
- Other than the inkjet head 21, for example, a roll coater or the like may be used.
- the ink applying unit 20 is an inkjet head 21 capable of ejecting ink.
- the treatment liquid droplets 12 are ejected from the inkjet head 11 onto the base material F fed out from the delivery roller 30 to form the treatment liquid layer C.
- ink droplets 22 are ejected from the inkjet head 21 onto the treatment liquid layer C to form an ink layer R, and the second drying section 23 heats and dries the area to which the ink has been applied.
- the substrate F on which the treatment liquid layer C and the ink layer R are formed is wound up by the winding roller 40 to obtain an image recorded matter.
- FIG. 1 shows the case where the substrate F is a film substrate, in the case of a metal substrate, etc., the metal substrate is placed on a conveying belt, and the treatment liquid layer C and the The ink layer R can be formed by coating in one pass.
- the apparatus is configured to apply ink after applying the treatment liquid onto the base material, but the apparatus may be configured to apply the treatment liquid and the ink simultaneously. is preferably 30% or less, the ink is ejected from the inkjet head.
- a flat bed type printer for applying the treatment liquid and the ink as an apparatus other than the recording apparatus shown in FIG.
- the substrate is fixed, and the inkjet head can be moved in the main scanning direction and the sub-scanning direction that intersects the main scanning direction, making it possible to print without transporting the substrate.
- Metal substrates such as tin plate cannot be conveyed from roll to roll unlike resin film substrates. Therefore, it is preferable to use a flatbed printer that does not need to convey the substrate. Examples of such flatbed printers include the printers described in FIG. 1 of Japanese Patent Application Laid-Open No. 2015-74161 and FIG. 1 of Japanese Patent Application Laid-Open No. 2017-177578.
- An image recorded matter according to the present invention includes a substrate, a treatment liquid layer formed on the substrate using the treatment liquid, and an ink layer formed on the treatment liquid layer using the ink. It is preferable to have
- the image recorded material P forms a treatment liquid layer C by applying the treatment liquid according to the present invention on the base material F with a roll coater or the like or by ejecting it from an inkjet head.
- An image recording layer R is formed by ejecting and fixing ink from an inkjet head on the position where the treatment liquid layer C is fixed.
- the above configuration shows the minimum configuration, and another functional layer may be formed between the base material and the treatment liquid layer, and a non-absorbent layer may be formed on the ink layer via, for example, a laminate adhesive layer.
- a flexible film substrate or the like may be laminated. At least, a structure in which the treatment liquid layer and the ink layer are in contact with each other is essential.
- An example of an image recorded matter of the present invention is an image recorded matter using at least the treatment liquid and ink of the present invention, wherein a first layer containing a thermosetting resin and the treatment liquid are formed on a metal substrate. It is a preferred embodiment that a second layer containing, a third layer containing the ink, and a fourth layer containing a thermosetting resin are laminated in this order.
- packaging materials for packaging canned food, retort food, beverages, etc. can be preferably mentioned.
- FIG. 3 shows a cross-sectional view of a packaging material for canned food, which is an example of the image recorded matter of the present invention.
- a thermosetting resin for example, TW-1407 series manufactured by T&K TOKA
- a thermosetting resin layer (base coat) 52 is roller-coated on a tinplate substrate 51 to form a thermosetting resin layer (base coat) 52, and a treatment liquid layer 53 and an ink layer are formed thereon. 54 forms an image.
- a thermosetting resin for example, AX-10 series manufactured by T&K TOKA
- top coat thermosetting resin layer
- treatment liquid T1 Calcium acetate hydrate 3% by mass as polyvalent metal salt, dipropylene glycol 14% by mass, propylene glycol 14% by mass, glycerin 10%, polyether-modified silicone BYK3450 1% by mass, antifungal agent (Proxel GXL (S )) 0.1% by mass and ion-exchanged water (remaining amount; total amount is 100% by mass) were added with stirring, and the resulting mixed solution was filtered through a 1 ⁇ m filter to obtain treatment solution T1.
- each treatment liquid T2 was prepared in the same manner except that the types and amounts of the polyvalent metal salt, the solvent, the surfactant, and the amount of water added were changed as shown in Table I below.
- ⁇ T6 was prepared.
- TEGOWET250 polyether-modified silicone TEGOWET-250 (manufactured by Evonik)
- BYK3450 polyether-modified silicone BYK-3450 (manufactured by BYK-Chemie)
- BYK348 polyether-modified silicone BYK-348 (manufactured by BYK-Chemie)
- ⁇ Treatment solution storage stability> The treatment solutions T1 to T6 prepared above were stored in a thermostat at 60° C. for 2 weeks, and then visually evaluated according to the following criteria. (standard) ⁇ : No change such as cloudiness or separation is visually observed in the treated solution after storage at 60° C. for 2 weeks. x: The treatment solution after storage at 60°C for 2 weeks is slightly cloudy or separated. x: Clearly cloudy or separated after storage at 60°C for 2 weeks.
- the treatment liquid of the present invention which has a dynamic surface tension within the range of 25 to 35 mN/m at a surface life of 15 ms, is found to be excellent in injection stability and storage stability.
- Cohesiveness was measured by the following method. First, in order to prepare a mixed solution containing 5% by mass of fine resin particles and 0.15% by mass of calcium acetate monohydrate, calcium acetate/monohydrate was added to 0.30% by mass. Calcium acetate aqueous solution dissolved in ion-exchanged water and each resin fine particle dispersion P1 to P5 shown in Table II are used to dilute the resin fine particle dispersion prepared with ion-exchanged water so that the solid content is 10% by mass. Each liquid was prepared.
- the glass transition temperature (Tg) of the resin particles is determined from the endothermic peak when the temperature is raised in the temperature range of ⁇ 30 to 200° C. at a temperature elevation rate of 10° C./min using a DSC (differential scanning calorimeter). , was identified by reading the glass transition temperature Tg.
- the mixture was dispersed using a bead mill filled with 0.3 mm zirconia beads at a volume ratio of 50% to prepare a pigment dispersion D1 having a pigment content of 20% by mass.
- the average particle diameter of the pigment particles contained in this pigment dispersion was 140 nm.
- the average particle size was measured using "Zetasizer Nano S-90" manufactured by Maruballoon.
- magenta pigment dispersion was prepared in the same manner as in the preparation of magenta pigment dispersion D1, except that the pigment dispersant was changed from the acrylic dispersant "Joncryl 819" to a nonionic polymer dispersant ("BYK190" manufactured by BYK). D2 was adjusted. The average particle size of the pigment particles contained in this pigment dispersion was 130 nm.
- M1 to M15 were prepared in the same manner as in the preparation of magenta ink M1, except that the types and blending amounts of the fine resin particle dispersion, water-soluble solvent, and surfactant were changed as shown in Table III below.
- Cyan pigment (Pigment Blue 15:3) 20% by mass, a pigment dispersant (dimethylaminoethanol-neutralized acrylic dispersant having a carboxyl group ("Joncryl 819" manufactured by BASF, acid value 75 mgKOH/g, 6% by mass of solid content 20% by mass), 20% by mass of propylene glycol, 0.1% by mass of antifungal agent Proxel GXL (S), and ion-exchanged water (the balance; the amount that makes the total amount 100% by mass) The added mixture was premixed.
- the mixture was dispersed using a bead mill filled with 0.3 mm zirconia beads at a volume ratio of 50% to prepare a cyan pigment dispersion D1 having a pigment content of 20% by mass.
- the average particle diameter of the pigment particles contained in this pigment dispersion was 120 nm.
- Cyan inks C2 and C3 were prepared in the same manner as in the preparation of ink C1 except that the type and amount of water-soluble solvent and surfactant, the amount of antifungal agent, etc. were changed as shown in Table III below. did.
- the dynamic surface tension of each obtained ink was measured by the following method. ⁇ Dynamic surface tension> For the inks M1 to M15 and C1 to C3 prepared above, the dynamic surface tension was measured with a surface life of 10 ms to 1000 ms using a dynamic surface tensiometer (BP-100: manufactured by KRUSS) using the maximum bubble pressure method. . The measurement temperature was adjusted to 25°C. Table IV shows the dynamic surface tension (unit: mN/m) at surface lifetimes of 15 ms, 100 ms and 1000 ms.
- the inks M1 to M15 and C1 to C3 prepared above were stored in a thermostat at 60° C. for 2 weeks, and then measured for average particle size using a particle size analyzer (Zetasizer Nano S-90). After that, the ink storability was evaluated according to the following criteria.
- ⁇ The difference between the average particle size after storage at 60° C. for 2 weeks and the average particle size before storage at 60° C. for 2 weeks is 10 nm or more and less than 30 nm.
- x The difference between the average particle size after storage at 60°C for 2 weeks and the average particle size before storage at 60°C for 2 weeks is 30 nm or more.
- the treatment liquid of the present invention which has a dynamic surface tension within the range of 35 to 45 mN/m at a surface life of 15 ms, is found to be excellent in injection stability and storage stability.
- Print test 1 A printing test was carried out by the following method using an ink set in which the treatment liquid and ink prepared above were combined as shown in Tables V to X below.
- the recording medium M a PET film (FE2001, thickness 50 ⁇ m, manufactured by Futamura Chemical Co., Ltd.) was prepared.
- a scan type printer (see FIG. 4) equipped with two Konica Minolta independently driven inkjet heads (360 npi, ejection volume of 6 pL or 14 pL, 1024 nozzles) was prepared, and each treatment liquid was applied to head H1, which was recorded first. , and the head H2 to be recorded later was filled with each ink.
- an image with a resolution of 720 x 720 dpi is divided into four images (180 x 180 dpi) each in the scanning direction X and the transport direction Y, and in a 4-pass mode in which one printing area is printed four times, the treatment liquid always comes first.
- Printing was carried out unidirectionally in the direction recorded in the The transport speed of the carriage C was set to 300 mm/sec, and no drying process was provided between the recording of the treatment liquid and the ink. Printing was tested under an environment of 25°C and 50% RH.
- the treatment liquid was recorded at a liquid volume of 6 pL and a maximum print rate of 33%, and was applied imagewise according to the ink image area.
- Ink recording was set at a liquid volume of 14 pL and a maximum print rate of 100%.
- the amount of treatment liquid applied to the solid area is 1.7 g/m 2 and the amount of ink applied to the solid area is 11.9 g/m 2 .
- the ratio (ink application amount/treatment liquid application amount) is 7.0 times.
- FIG. 5 shows the results of measuring the dynamic surface tension of the treatment liquid and ink in ink set 1 at 25° C. with a surface life of 10 ms to 1000 ms.
- FIG. 6 shows the result of measuring the dynamic surface tension of the treatment liquid and ink in the ink set 44 at 25° C. with a surface life of 10 ms to 1000 ms.
- ⁇ Spotted solid area> A solid image of 5 cm ⁇ 5 cm was recorded by the method described above, and the mottling of the solid portion was visually evaluated according to the following criteria.
- x Density unevenness is observed in the image when observed from a position separated by 30 cm.
- ⁇ Adhesion> A solid image of 5 cm ⁇ 5 cm was recorded by the method described above, and the printed surface was rubbed with a fingernail to evaluate adhesion according to the following criteria.
- standard ⁇ : The printed surface does not change and cannot be removed even when rubbed with a fingernail.
- ⁇ When rubbed with a fingernail, the printed surface is scratched and the printed surface is partially peeled off.
- x The printed surface is peeled off when rubbed with a fingernail.
- the ink set of the present invention suppresses image defects and is superior in adhesion to the substrate compared to the ink set of the comparative example.
- a 720 dpi x 720 dpi head module was created by arranging two independently driven piezoelectric inkjet heads (360 dpi, discharge volume 6 pL) made by Konica Minolta Co., Ltd. so that the nozzles were alternately arranged, and a single-pass type shown in Fig. 1. The printer was installed so that the nozzle rows were perpendicular to the transport direction.
- the inkjet head of the head module installed in the treatment liquid applying section is filled with the treatment liquid T1 obtained above, and the inkjet head of the head module installed in the ink applying section is filled with the ink M1 obtained above. did.
- a single-pass ink jet recording apparatus capable of recording with the ink set 1 shown in Table V was constructed.
- the same image as in Printing Test 1 was recorded under the recording conditions shown in Table XI, and evaluated using the same indices as in Printing Test 1.
- the recording medium M a PET film (FE2001, thickness 50 ⁇ m, manufactured by Futamura Chemical Co., Ltd.) was prepared. The conveying speed during recording was set to 300 mm/sec. The time from application of the treatment liquid to application of the ink was adjusted by allowing the recording medium to wait for a predetermined time after passing through the treatment liquid application section, and then moving to the ink application section.
- the drying rate of the treatment liquid was calculated by measuring the mass change rate of the treatment liquid applied to the PET film and the amount of solvent volatilized during the time from the application of the treatment liquid to the application of the ink.
- the amount of treatment liquid applied and the amount of ink applied were each adjusted by changing the droplet size and printing rate. Evaluation results are shown in Table XI. In Table XI, " ⁇ 1" represents "1% or less”.
- the present invention can be used for ink sets and inkjet recording methods that suppress image defects and have excellent adhesion to substrates.
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Abstract
Description
しかしながら、さらに、処理液やインクの静的表面張力及び動的表面張力を適切に制御しないと、処理液やインクの組み合わせによっては、抜き文字や細線の滲み、ビーディング、まだら等の画像欠陥が発生し、高画質の達成は困難であった。
すなわち、本発明に係る上記課題は、以下の手段により解決される。
前記インクが、顔料、樹脂微粒子、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有し、
前記処理液が、多価金属塩、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有し、
25℃において、前記インクの静的表面張力が、前記処理液の静的表面張力よりも5mN/m以上高く、
25℃において、前記インクの表面寿命15msにおける動的表面張力が、前記処理液の表面寿命15msにおける動的表面張力よりも5mN/m以上高く、
前記インクの表面寿命15msにおける動的表面張力が、35~45mN/mの範囲内であり、かつ、
前記処理液の表面寿命15msにおける動的表面張力が、25~35mN/mの範囲内であるインクセット。
前記処理液を乾燥させて、当該処理液の乾燥率が30%のときの表面寿命15msにおける動的表面張力をBとしたときに、下記式(I)を満たす第1項から第4項までのいずれか一項に記載のインクセット。
式(I):(B-A)≦5mN/m
前記処理液を基材に付与した後、加熱乾燥工程を経ずに、前記処理液が濡れた状態で前記インクを前記処理液が付与された領域に付与するインクジェット記録方法。
本発明の効果の発現機構又は作用機構については、明確にはなっていないが、以下のように推察している。
処理液が濡れた状態のままインクを付与するWet・on・wetの記録方法では、処理液を間引く必要があるが、印字率を下げながら処理液が瞬時に濡れ広がって均一になる必要があるため、処理液の動的表面張力は低い方が良い一方で、インクの動的表面張力が低すぎると抜き文字がつぶれてしまうため、あまり低すぎない方が良いという関係があった。
そこで、本発明では、まず、基材密着性を確保しつつ画像を記録することができる構成として、インクが、顔料、樹脂微粒子、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有し、さらに、インクを増粘・凝集させ高画質を達成するために、処理液が、多価金属塩、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有する構成とした。
さらに、処理液及びインクの静的表面張力と動的表面張力の関係を前記範囲に規定した。すなわち、処理液の静的表面張力及び動的表面張力が、インクの静的表面張力及び動的表面張力よりもそれぞれ低くすることで、インクが処理液に適度に拡散しつつ凝集・増粘するため、抜き文字や細線の滲みを防止しつつ、ビーディングやまだら等の画像欠陥を抑制することができ、その結果、高画質の達成を図ることができる。
また、処理液及びインクの動的表面張力をそれぞれ前記範囲内とすることで、基材への高い濡れ性を確保しつつ、高い射出安定性と保存安定性を得ることができる。
この特徴は、下記各実施形態に共通又は対応する技術的特徴である。
式(I):(B-A)≦5mN/m
Wet・on・wetの記録方法において、処理液がある程度乾燥しても動的表面張力が変化しないことにより、記録時の温湿度条件に対するロバスト性を向上させることができる。
本発明のインクセットは、インクと処理液とを含むインクセットであって、前記インクが、顔料、樹脂微粒子、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有し、前記処理液が、多価金属塩、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有する。また、25℃において、前記インクの静的表面張力が、前記処理液の静的表面張力よりも5mN/m以上高く、25℃において、前記インクの表面寿命15msにおける動的表面張力が、前記処理液の表面寿命15msにおける動的表面張力よりも5mN/m以上高く、前記インクの表面寿命15msにおける動的表面張力が、35mN/m以上45mN/m以下であり、かつ、前記処理液の表面寿命15msにおける動的表面張力が、25mN/m以上35mN/m以下である。
本発明において「静的表面張力」とは、表面寿命の経過に伴い、液表面はインク又は処理液中の各成分が拡散して平衡状態に近づくが、この平衡状態となったときの表面張力のことをいう。
インク又は処理液の静的表面張力の測定方法は、自動表面張力計(協和界面科学株式会社製、型式「CBVP-Z」)で白金プレートを用いて測定することができる。特に断りのない限り本明細書における静的表面張力は25℃で測定した静的的表面張力である。
本発明のインクセットは、25℃において、インクの静的表面張力が、処理液の静的表面張力よりも5mN/m以上高い。好ましくは6~12mN/mの範囲内で高い。
なお、インクが複数種の場合には、静的表面張力が最も低いインクと、前記処理液の静的表面張力との差が前記範囲となればよい。
本発明において「動的表面張力」とは、液表面(気液界面)が形成された直後であって、液表面が非平衡状態にあるときの表面張力のことをいい、最大泡圧法によって25℃において測定した値である。
また、「表面寿命」とは、液表面が形成されてからの経過時間、すなわち、最大泡圧法において発生させた気泡の寿命であり、バブルライフタイムともいい、動的表面張力計のプローブ先端内で新しい界面が生成した時点から最大泡圧となるまでの時間を指す。
処理液又はインクの動的表面張力の測定方法は、動的表面張力計を用いることにより測定することができる。動的表面張力計としては、例えばバブルプレッシャー動的表面張力計(KRUSS社製、型式「BP100」)等が挙げられる。
特に断りのない限り本明細書における動的表面張力は、最大泡圧法を用いて、25℃、15msで測定した動的表面張力である。
なお、インクが複数種の場合には、動的表面張力が最も低いインクと、前記処理液の動的表面張力との差が前記範囲となればよい。
さらに、インクの表面寿命15msにおける動的表面張力が、35~45mN/mの範囲内であり、好ましくは、37~43mN/mの範囲内である。
具体的には、処理液中に含有する界面活性剤として、各種ポリエーテル変性シリコーン及び、又はアセチレングリコール系界面活性剤を用い、その含有量を0.1~2.0質量%の範囲内とすることが好ましい。また、水溶性溶媒として、SP値が24(J/cm3)1/2以上でかつ沸点が150℃~250℃の範囲の水溶性溶媒を用い、その含有量を5~40質量%の範囲内とすることが好ましい。
具体的には、インク中に含有する界面活性剤として、各種ポリエーテル変性シリコーン及び、又はアセチレングリコール系界面活性剤を用い、その含有量を0.1~2.0質量%の範囲内とすることが好ましい。水溶性溶媒として、SP値が24(J/cm3)1/2以上でかつ沸点が150℃~250℃の範囲の水溶性溶を用い、その含有量を5~40質量%の範囲内とすることが好ましい。また、顔料分散剤としては、各種低分子分散剤、ノニオン性高分子分散剤、アニオン性高分子分散剤を用いたり、樹脂被覆型の顔料分散体を適宜用いることが好ましい。さらに、樹脂微粒子の種類としては、ポリエステル樹脂、アクリル樹脂、スチレンアクリル樹脂、ウレタン樹脂などの樹脂微粒子を用い、その含有量を3~15質量%の範囲内とすることが好ましい。
また、本発明のインクセットは、25℃において、未乾燥状態の前記処理液の表面寿命15msにおける動的表面張力をAとし、前記処理液の乾燥率が30%のときの表面寿命15msにおける動的表面張力をBとしたときに、下記式(I)を満たすことが好ましい。
式(I):(B-A)≦5mN/m
このように式(I)を満たすことにより、Wet・on・wetの記録方法において、処理液がある程度乾燥しても動的表面張力の変化を低減できるため、記録時の温湿度条件に対するロバスト性を向上させることができる。
ここで、「動的表面張力A」とは、下記のように処理液を乾燥させる前の、すなわち未乾燥(状態)の、かつ25℃での表面寿命15msにおける処理液の動的表面張力のことであり、前記した最大泡圧法によって25℃において測定した値である。
また、「動的表面張力B」とは、処理液を乾燥させて、乾燥率が30%のときの表面寿命15msにおける処理液の動的表面張力のことである。具体的には、処理液100gを浅い容器に秤量し、25℃の減圧環境下で液の質量が70gになるまで乾燥させ、このときの処理液の動的表面張力を前記の最大泡圧法で測定し、これを30%乾燥後の動的表面張力Bとする。
このようにして測定した30%乾燥後の動的表面張力Bと前記動的表面張力Aから、差分の「(B-A)」を算出する。
本発明に係る処理液は、基材にインクジェットプリント法によって画像を記録する際に、インクを凝集又は増粘させることにより、インクの画像形成を速めたり、処理液層及びインク層の物理的性質を改善したり、画質を向上させる機能を有することができる。
本発明に係る処理液には、インクと接触したときに、凝集物を生じさせる材料、すなわち多価金属塩である凝集剤を含有することで、インクとの相互作用が大きくなり、インクのドットをより固定化することができる。
多価金属塩を構成する塩の種類は特に限定されないが、例えば、炭酸塩、硫酸塩、硝酸塩、塩酸塩、有機酸塩、ホウ酸塩、リン酸塩などの公知の塩を使用できる。特に好ましい多価金属塩の具体例としては、例えば、塩化カルシウムや塩化マグネシウム、硝酸カルシウムや硝酸マグネシウム、酢酸マグネシウム、酢酸カルシウムや乳酸マグネシウム、パントテン酸カルシウムのようなカルボン酸のカルシウム塩又はマグネシウム塩などが挙げられる。
本発明に係る処理液は、前記多価金属塩に加えて、さらに凝集剤として有機酸を加えてもよい。有機酸は、pH変動によって上記インク中のアニオン性の成分を凝集させることができる。有機酸としては、多価金属塩の凝集力を弱めることがないという観点から、1価のカルボン酸が好ましい。
前記有機酸としては、例えば、ギ酸、酢酸、プロピオン酸、イソ酪酸、安息香酸等が挙げられる。
また、有機酸を用いることで処理液の保存安定性を維持しやすく、処理液を塗布、乾燥した後にブロッキングが起きにくい。上記観点から好ましい有機酸は、ギ酸、酢酸、プロピオン酸、安息香酸、などが含まれる。
本発明に係る処理液は、前記多価金属塩に加えて、さらに凝集剤として無機酸を加えても良い。無機酸は、pH変動によって上記インク中のアニオン性の成分を凝集させることができる。
また、有機酸を含有させる場合には、有機酸の含有量は、処理液の総質量100質量%に対し、0.1~10質量%の範囲内が好ましく、1~3質量%の範囲内がより好ましい。
また、無機酸を含有させる場合には、無機酸の含有量は、処理液の総質量100質量%に対し、0.1~10質量%の範囲内が好ましく、1~3質量%の範囲内がより好ましい。
本発明に係る処理液に含まれる水溶性溶媒としては、沸点150~250℃の範囲内の水溶性溶媒である。
このような水溶性溶媒としては、例えば、アルコール類、多価アルコール類、アミン類、アミド類、グリコールエーテル類、炭素数が4以上である1,2-アルカンジオール類などが挙げられる。
また、SP値24(J/cm3)1/2以上の水溶性溶媒を用いることが好ましい。
SP値が24(J/cm3)1/2以上である水溶性溶媒を使用することで、処理液の曇点が低下する。これにより、インク乾燥工程において、処理液の曇点以上に加熱することでき、特に非吸収性基材への密着性が良好な画像が得られる。
本発明に係る処理液に含まれる界面活性剤は、処理液のノズルからの出射安定性の向上や、記録媒体に着弾した液滴の広がり(ドット径の拡大)を制御することができる。
具体的には、ビックケミー社製のBYK-331、BYK-333、BYK-345、BYK-3450、BYK-3451、BYK-3455、BYK-346、BYK-347、BYK-348、BYK-349、エボニック社製のTEGOWetKL245、TEGOWet250、TEGOWet260、TEGOWet270、TEGOWet280、信越化学工業社製のKF-351A、KF-352A、KF-353、KF-354L、KF-355A、KF-615A、KF-640、KF-642、KF-643、KF-644、KF-945、KF-6011、KF-6012、KF-6015、KF-6017、KF-6020、KF-6204、X-22-4515等が挙げられる。
トリシロキサンとしては、下記一般式(1)で表される構造を有することが好ましい。
また、前記一般式(1)において、mが5から20の整数であり、nが0から6の整数であることが好ましい。
(S-1):前記一般式(1)において、R=メチル基、X=炭素数3のアルキレン基、m=9、n=0
(S-2):前記一般式(1)において、R=ブチル基、X=炭素数3のアルキレン基、m=25、n=6
(S-3):前記一般式(1)において、R=水素原子、X=炭素数3のアルキレン基、m=3、n=0
(S-4):前記一般式(1)において、R=水素原子、X=炭素数3のアルキレン基、m=33、n=0
(S-5):前記一般式(1)において、R=水素原子、X=炭素数3のアルキレン基、m=22、n=16
(S-6):前記一般式(1)において、R=水素原子、X=炭素数3のアルキレン基、m=9、n=0
(S-7):前記一般式(1)において、R=水素原子、X=炭素数3のアルキレン基、m=12、n=3
(S-8):前記一般式(1)において、R=水素原子、X=炭素数3のアルキレン基、m=1、n=0
また、ポリエーテル変性シリコーンの含有量は、処理液の総質量100質量%に対し、0.5~2質量%の範囲内で含有することが好ましく、0.5~1.5質量%の範囲内で含有することがより好ましい。
インクに含有する界面活性剤を界面活性剤S1としたとき、
(i)処理液に含有する界面活性剤は、インクに含有する界面活性剤S1とは異なる界面活性剤S2であることが好ましい。
(ii)処理液に含有する界面活性剤は、前記界面活性剤S1に加えて、前記界面活性剤S2を含有することが好ましい。
具体的に好ましい界面活性剤の組み合わせとしては、処理液中に含有する界面活性剤としては、ポリエーテル変性シリコーン等が好ましく、インクに含有する界面活性剤としては、アセチレングリコール系界面活性剤等及びポリエーテル変性シリコーン等が好ましい。
前記のようにインク中に含有しない界面活性剤(すなわち、インクの分散安定性を不安定化するような界面活性剤)を、処理液中に加えることで凝集性をより高めることが可能となる。
本発明に係る処理液には、水を含有してもよく、使用可能な水については、特に限定されるものではなく、イオン交換水、蒸留水、又は純水であり得る。
本発明に係るインクは、少なくとも、顔料、樹脂微粒子、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有する。また、水を含有してもよい。
本発明に係るインクに含有される本発明に係るインクに用いられる顔料としては、アニオン性の分散顔料、例えば、表面にアニオン性基を有する自己分散性顔料や、アニオン性の高分子分散剤により分散された顔料、表面をアニオン性の樹脂で被覆されて分散された顔料を用いることが好ましい。特に、アニオン性高分子分散剤で分散された顔料を用いることが、分散性に優れ、処理液と適度に反応してピニングする点で好ましい。
本発明に係るインクは、前記顔料を分散させるための顔料分散剤を含有することが好ましい、
前記顔料分散剤は、格別限定されないがアニオン性基を有する高分子分散剤が好ましく、分子量が5000~200000の範囲内のものを好適に用いることができる。
本発明に係るインクに含有される樹脂微粒子(以下、単に「樹脂」ともいう。)は、水不溶性樹脂微粒子であることが好ましい。
また、樹脂微粒子のガラス転移温度(ガラス転移点(Tg))が40~90℃の範囲内であることが好ましい。前記ガラス転移温度は、DSC(示差走査熱量測定装置)を用いて-30~200℃の温度域で昇温速度10℃/分の条件で昇温させたときの吸熱ピークから、ガラス転移温度Tgを読み取ることによって特定することができる。
本発明で使用する水不溶性樹脂は、インクを受容でき、当該インクに対して溶解性又は親和性を示す水不溶性樹脂である。
本発明に係るインクは、特にスルホン酸基を有する水分散性ポリエステル樹脂を含有することが好ましい。これより、基材に対する高い密着性が得られる。
本発明において、「凝集性」とは、以下の手順で残量を計測した後、下記式により算出した値である。
(i)樹脂微粒子を含有する樹脂微粒子水溶液(固形分10質量%)5gと、0.3質量%の酢酸カルシウム・1水和物水溶液5gを混合する。
(ii)混合した混合液を遠心分離する。
(iii)遠心分離により分離した上澄み液2gを採取する。
(iV)採取した上澄み液2gを150℃で30分間乾燥した後の固形分の質量(残量(g))を計測する。
(V)下記式により凝集性の値を算出する。
式:凝集性=1-[固形分の質量(g)/(採取した上澄み液の質量(g)×5%)]
(ポリエステル樹脂)
水不溶性樹脂粒子としてのポリエステル骨格を有するポリエステル樹脂は、多価アルコール成分と多価カルボン酸、多価カルボン酸無水物、多価カルボン酸エステル等の多価カルボン酸成分とを用いて得ることができる。
スルホン酸基を有するジカルボン酸成分としては、例えば、2-スルホテレフタル酸、5-スルホイソフタル酸、4-スルホナフタレンイソフタル酸-2,7-ジカルボン酸および5-(4-スルホフェノキシ)イソフタル酸、またはそれらのアルカリ金属塩等を挙げられる。
スルホン酸基を有するジオールとしては、例えば、2-スルホ-1,4-ブタンジオール、2,5-ジメチル-3-スルホ-2,5-ヘキサンジオール、又はそれらのアルカリ金属塩等が挙げられる。
水不溶性樹脂粒子としてのウレタン樹脂としては、親水基を有するものを用いることができる。
DI)、4,4'-ジシクロヘキシルメタンジイソシアネート(水素添加MDI、H12MDI)などの脂環族イソシアネートが含まれる。これらは、1種類のみを単独で使用してもよく、2種類以上を併用してもよい。
水不溶性樹脂粒子としてのアクリル樹脂は、アクリル酸エステル成分、メタクリル酸エステル成分、またスチレン成分等との共重合体を用いて得ることができる。
アクリル酸エステル成分、メタクリル酸エステル成分の例には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ブル、(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸-4-ヒドロキブチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸テトラヒドロフルフリル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸-2-ヒドロキシブチル、(メタ)アクリル酸ベンジル、(メタ)アクリル酸グリシジル、(メタ)アクリル酸、ジ(メタ)アクリル酸(ジ)エチレングリコール、ジ(メタ)アクリル酸-1,4-ブタンジオ-ル、ジ(メタ)アクリル酸-1,6-ヘキサンジオ-ル、トリ(メタ)アクリル酸トリメチロ-ルプロパン、ジ(メタ)アクリル酸グリセリン、(メタ)アクリル酸-2-エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル、及びアクリルアミド等が含まれる。
インクに含有しうる複合樹脂微粒子は、アクリル樹脂が、ウレタン樹脂に乳化されてなる複合樹脂微粒子であることが好ましい。すなわち、アクリル樹脂から構成される内部層、及びウレタン樹脂から構成される表面層を有する複合樹脂微粒子であることが好ましい。
また、塩の種類の例には、特に限定されないが、ナトリウム塩、カリウム塩、マグネシウム塩などの金属塩、及びトリエタノールアミン塩などが含まれる。
い。
本発明に係るインクに含有される水溶性溶媒としては、沸点150~250℃の範囲内の水溶性溶媒である。
このような水溶性溶媒としては、例えば、アルコール類、多価アルコール類、アミン類、アミド類、グリコールエーテル類、炭素数が4以上である1,2-アルカンジオール類などが挙げられ、前記処理液で例示したものが挙げられる。
本発明に係るインクに界面活性剤を含有させることにより、インク出射安定性の向上や、記録媒体に着弾した液滴の広がり(ドット径)を制御することができる。
本発明に係るインクに含まれる水については、特に限定されるものではなく、イオン交換水、蒸留水、又は純水であり得る。
本発明のインクジェット記録方法は、前記した処理液とインクを含むインクセットを用い、画像を記録するインクジェット記録方法である。このインクセットを用いる方法であれば、例えば、1台のインクジェットプリンタを用いて、基材の表面に、前記本発明のインクセットを構成する処理液の塗布と、インクによる印刷とを連続して効率よく行うことができる。そして基材間のドット径のばらつきの少ない、画質の優れた文字や図柄等を印刷することが可能となる。
すなわち、前記処理液を基材の記録領域に付与する工程(処理液付与工程)と、前記処理液が付与された領域に、処理液が濡れた状態で前記インクをインクジェット記録方式で付与する工程(インク付与工程)と、を備える。
また、本発明のインクジェット記録方法は、前記工程のほか、インク付与工程後に基材上に付与された処理液及びインクを加熱して乾燥させて処理液層及びインク層を形成するインク加熱乾燥工程を備えることが好ましい。
本発明のインクジェット記録方法で適用可能な基材(記録媒体)としては、特に限定されるものではなく、吸収性の材料からなる吸収性基材であっても、非吸収の材料からなる非吸収性基材であってもよいが、本発明の効果発現の観点から非吸収性基材であることが好ましい。
本発明において「吸収性」とは水に対する吸収性で、「非吸収性」とは、水に対する非吸収性をいう。
前記非吸収性基材としては、公知のプラスチックのフィルムを使用することができる。
また、ガスバリアー性、防湿性、保香性などを付与するために、フィルムの片面又は両面にポリ塩化ビニリデンをコートしたものや、金属酸化物を蒸着したフィルムも好ましく用いることができる。非吸収性フィルムは、未延伸フィルムでも延伸フィルムでも好ましく用いることができる。
基材の厚さは、プラスチックのフィルムの場合は、好ましくは10~120μm、より好ましくは12~60μmの範囲内である。
外側は、ポリエステル系、アクリル系の熱硬化性塗料が使用されるのが一般的である。
<処理液付与工程>
処理液付与工程では、基材である記録媒体上に、前述の処理液を付与する。
また、処理液を塗布する工程として、インクジェット法を用いる工程であることが、インク非塗布領域に凝集剤を塗布しなくてもよくなるため、インクと未反応となる凝集剤が遊離して白濁するようなことが起こらない点で好ましい。
その場合、後述するように、用いる基材が金属基材などの場合は、搬送ベルト上に金属基材を配置し、ベルトを搬送しながら処理液層を塗布形成したり、基材を固定するフラットベッドタイプのプリンタを処理液層の形成に用いたりすることも好ましい。
インク付与工程では、基材である記録媒体上に処理液層を形成すると同時に又は直後に、前述のインクセットのインクを、インクジェット法により付与する工程である。特に、処理液付与工程後に処理液が付与された領域に、処理液の乾燥率が30%以下の状態で、インクを付与することが好ましく、また、処理液を基材に付与した後、10秒以内に処理液が付与された領域に、インクを付与することが好ましい。
なお、処理液の乾燥率とは、下記式で定義されるものである。
(処理液の乾燥率)=1 -((乾燥後の処理液の質量(g))/(乾燥前の処理液の質量(g))
処理液の乾燥率が30%以下の状態で、インクを付与することによって、インクと処理液が適度に混ざり合って、本発明の効果をより顕著に発揮することができる。
また、処理液を基材に付与した後、10秒以内にインクを付与することにより、吸収性基材への処理液の浸透や、非吸収性基材での処理液のハジキを抑制し、より高画質が達成できる。
前記処理液の乾燥率を30%以下の状態とするためには、前記したように、処理液付与後、インクを付与するまでの時間を調整したり、記録媒体の温度を適宜調整したり、等が挙げられる。
インク加熱乾燥工程では、基材である記録媒体上に付与したインク、すなわち、前記インクが付与された領域を加熱する。これにより、インク及び処理液を乾燥させることができる。
図1は、本発明に好ましい記録装置の模式図である。ただし、本発明はこれに限定されるものではない。
処理液付与部10は、処理液を基材に塗布できる構成であれば特に限定されるものではないが、本発明ではインクジェットヘッド21であることが好ましい。インクジェットヘッド21以外に、例えば、ロールコーター等であってもよい。
インク付与部20は、インクを吐出可能なインクジェットヘッド21である。
また、図1では、基材上に処理液を付与した後、インクを付与する構成の装置としたが、処理液とインクを同時に付与する構成の装置としてもよいが、処理液層の乾燥率が30%以下の状態で、インクジェットヘッドからインクを吐出することが好ましい。
このようなフラットベッドタイプのプリンタとしては、特開2015-74161号公報の図1や特開2017-177578号公報の図1に記載されているプリンタを一例として挙げることができる。
本発明に係る画像記録物は、基材と、基材上に前記処理液を用いて形成された処理液層と、当該処理液層上に前記インクを用いて形成されたインク層と、を有することが好ましい。
ブリキ基材51上に熱硬化性樹脂(例えば、TW-1407シリーズ T&K TOKA製)をローラー塗布して熱硬化性樹脂層(ベースコート)52を形成し、その上に、処理液層53とインク層54によって画像を形成する。次いで、熱硬化性樹脂(例えば、AX-10シリーズ T&K TOKA製)をローラー塗布して熱硬化性樹脂層(トップコート)55を形成し、加熱硬化、乾燥して、缶詰食品用包装材料50を得ることができる。
多価金属塩として酢酸カルシウム・水和物3質量%に、ジプロピレングリコール14質量%、プロピレングリコール14質量%、グリセリン10%、ポリエーテル変性シリコーンBYK3450 1質量%、防黴剤(プロキセルGXL(S))0.1質量%及びイオン交換水(残量;全量が100質量%なる量)を撹拌しながら添加し、得られた混合液を1μmのフィルターにより濾過して処理液T1を得た。
前記処理液T1の調製において、多価金属塩、溶媒、界面活性剤の種類及び添加量、水の添加量を、下記表Iに記載のとおりに変更した以外は同様にして、各処理液T2~T6を調製した。
<溶媒>
「DPG」:ジエチレングリコール
「PG」:プロピレングリコール
「1,2-HDO」:1,2-ヘキサンジオール
「Gly」:グリセリン
「TEGOWET250」:ポリエーテル変性シリコーン TEGOWET-250(エボニック社製)
「BYK3450」:ポリエーテル変性シリコーン BYK-3450(ビックケミー社製)
「BYK348」:ポリエーテル変性シリコーン BYK-348(ビックケミー社製)
「プロキセル GXL(S)」:1,2-ベンズイソチアゾリン-3-オン
得られた各処理液について、動的表面張力、静的表面張力及び30%乾燥後の動的表面張力を以下の方法で測定した。
前記で調製した処理液T1~T6について、最大泡圧法を用いた動的表面張力計(BP-100:KRUSS社製)を用いて表面寿命10ms~1000msの動的表面張力を測定した。測定温度は25℃に調整した。表面寿命15ms、100ms、1000msにおける動的表面張力(単位はmN/m)を下記表Iに示す。なお、ここでの表面寿命15msにおける動的表面張力を後述する「動的表面張力A」とした。
前記で調製したインク処理液T1~T6について、ウィルヘルミ法を用いた静的表面張力計(CBVP-Z:協和界面科学社製)を用いて、25℃における静的表面張力を測定した。測定値(単位はmN/m)を下記表Iに示す。
前記で調製したインク処理液T1~T6についてそれぞれ100gを浅い容器に秤量し、25℃の減圧環境下で液の質量が70gになるまで乾燥させた。その後、各処理液の動的表面張力を前記の方法で測定し、これを30%乾燥後の動的表面張力Bとした。また、30%乾燥後の動的表面張力Bと、前記で測定した処理液の表面寿命15msにおける動的表面張力Aとの差「(B-A)」を算出した。結果を下記表Iに示す。
<射出安定性>
前記で調製した処理液T1~T6をコニカミノルタ製の独立駆動型インクジェットヘッド(360npi、吐出量14pL、1024ノズル)に充填し、ストロボ同期型の液滴観測装置で30分間連続吐出試験を実施した。その後、以下の基準にしたがって射出安定性を評価した。
(基準)
○:評価した256ノズル中、256ノズル全てのノズルが正常に吐出されている。
△:評価した256ノズル中、異常吐出ノズルが1ノズル以上5ノズル未満観測される。
×:評価した256ノズル中、異常吐出ノズルが5ノズル以上観測される。
前記で調製した処理液T1~T6について、60℃サーモで2週間保存した後に、以下の基準にしたがって目視で評価した。
(基準)
○:60℃、2週間保存後の処理液に白濁、分離などの異変が目視で観察されない。
×:60℃、2週間保存後の処理液が僅かに白濁もしくは分離している。
×:60℃、2週間保存後の処理液が明らかに白濁もしくは分離している。
下記表IIに記載の市販品である樹脂微粒子分散液P1~P5における各樹脂微粒子について、凝集性及びガラス転移温度(Tg)を測定し、測定結果を下記表IIに示した。
凝集性は、以下の方法で測定した。
まず、樹脂微粒子が5質量%で、かつ、酢酸カルシウム・1水和物が0.15質量%の、混合液を調製するため、酢酸カルシウム・1水和物を0.30質量%となるようにイオン交換水で溶解した酢酸カルシウム水溶液と、表IIに示す各樹脂微粒子分散液P1~P5を用いて、固形分が10質量%となるようにイオン交換水で調製した樹脂微粒子分散液の希釈液をそれぞれ準備した。
次に、前記酢酸カルシウム水溶液5gを、前記樹脂微粒子分散液の希釈液5gに撹拌しながら添加し、固形分が5質量%で酢酸カルシウム・1水和物が0.15質量%の各混合液10gをそれぞれ調製した。
そして、各混合液10gを、日立工機社製の遠心分離機CF16RXを使用して遠心加速度200G、遠心時間10分で遠心分離し、分離後の溶液から上澄み液約2gをそれぞれ採取した。
次に、各上澄み液を150℃で30分間加熱することで水を除去し、加熱後に残った固形物の質量を測定した。得られた固形分の質量を以下の計算式に代入し凝集性をそれぞれ算出した。
式:凝集性=1-(固形分の質量(g)/(採取した上澄み液の質量(g)×5%))
樹脂粒子のガラス転移温度(Tg)は、DSC(示差走査熱量測定装置)を用いて-30~200℃の温度域で昇温速度10℃/分の条件で昇温させたときの吸熱ピークから、ガラス転移温度Tgを読み取ることによって特定した。
<マゼンタ顔料分散液D1の調製>
マゼンタ顔料(ピグメント・レッド122とピグメント・バイオレット19の混晶)20質量%に、アニオン性高分子分散剤(ジメチルアミノエタノール中和されたカルボキシ基を有するアクリル系分散剤(BASF社製「ジョンクリル819」、酸価75mgKOH/g、固形分20質量%)を8質量%と、プロピレングリコール20質量%と、防黴剤プロキセルGXL(S)0.1質量%と、イオン交換水(残部;全量が100質量%となる量)を加えた混合液をプレミックスした。
その後、0.3mmのジルコニアビーズを体積率で50%充填したビーズミルを用いて分散し、顔料の含有量が20質量%の顔料分散液D1を調製した。
この顔料分散液に含まれる顔料粒子の平均粒径は140nmであった。なお、平均粒径の測定はマルバルーン社製「ゼータサイザーナノ S-90」により行った。
マゼンタ顔料分散液D1の調製において、顔料分散剤をアクリル系分散剤「ジョンクリル819」からノニオン性高分子分散剤(BYK社製「BYK190」)に変更した以外は同様にして、マゼンタ顔料分散液D2を調整した。この顔料分散液に含まれる顔料粒子の平均粒径は130nmであった。
マゼンタ顔料分散液D1 20質量%(固形分として4質量%)に、前記市販品の樹脂微粒子分散液P1(添加量は、インク中において樹脂微粒子(固形分)が5質量%となるように調整)、プロピレングリコール21質量%、グリセリン5質量%、界面活性剤KF351A(信越シリコーン社)0.2質量%、界面活性剤E1010(日信化学工業社)1質量%、防黴剤プロキセルGXL(S)0.1質量%及びイオン交換水(残部;全量が100質量%なる量)を撹拌しながら添加し、得られた混合液を1μmのフィルターにより濾過してマゼンタインクM1を得た。濾過前後で実質的な組成変化はなかった。
マゼンタインクM1の調製において、樹脂微粒子分散液、水溶性溶媒及び界面活性剤の種類及び配合量等を下記表IIIに記載のとおりに変更した以外は同様にして、M1~M15を調製した。
<シアン顔料分散液D3の調製>
シアン顔料(ピグメント・ブルー15:3)20質量%に、顔料分散剤(ジメチルアミノエタノール中和されたカルボキシ基を有するアクリル系分散剤(BASF社製「ジョンクリル819」、酸価75mgKOH/g、固形分20質量%)を6質量%と、プロピレングリコール20質量%と、防黴剤プロキセルGXL(S)0.1質量%と、イオン交換水(残部;全量が100質量%となる量)を加えた混合液をプレミックスした。
その後、0.3mmのジルコニアビーズを体積率で50%充填したビーズミルを用いて分散し、顔料の含有量が20質量%のシアン顔料分散液D1を調製した。この顔料分散液に含まれる顔料粒子の平均粒径は120nmであった。
シアン顔料分散液D3 20質量%(固形分として4質量%)に、前記市販品の樹脂微粒子分散液P1(添加量は、インク中において樹脂微粒子(固形分)が5質量%となるように調整)、プロピレングリコール21質量%、グリセリン5質量%、界面活性剤KF351A(信越シリコーン社)0.2質量%、界面活性剤E1010(日信化学工業社)1質量%、防黴剤0.1質量%及びイオン交換水(残部;全量が100質量%なる量)を撹拌しながら添加し、得られた混合液を1μmのフィルターにより濾過してシアンインクC1を得た。濾過前後で実質的な組成変化はなかった。
インクC1の調製において、水溶性溶媒及び界面活性剤の種類と配合量、防黴剤の配合量等を下記表IIIに記載のとおりに変更した以外は同様にして、シアンインクC2及びC3を調製した。
<溶媒>
「EG」:エチレングリコール
「PG」:プロピレングリコール
「1,2-PDO」:1,2-ペンタンジオール
「1,2-HDO」:1,2-ヘキサンジオール
「2Me-1,3-PDO」:2-メチル-1,3-プロパンジオール
Gly:グリセリン
「DEGBE」:ジエチレングリコールモノブチルエーテル
「E1010」:アセチレングリコール系界面活性剤 オルフィンE1010(日信化学工業製)
「KF-351A」:シリコーン変性界面活性剤 KF-351A(信越シリコーン社製)
「TEGOWET KL245」:ポリエーテル変性シリコーン TEGOWET-KL245(エボニック社製)
「TEGOWET 250」:ポリエーテル変性シリコーン TEGOWET-250(エボニック社製)
「TEGOWET 260」:ポリエーテル変性シリコーン TEGOWET-260(エボニック社製)
「BYK3450」:ポリエーテル変性シリコーン BYK-3450(ビックケミー社製)
「BYK3455」:ポリエーテル変性シリコーン BYK-3455(ビックケミー社製)
「BYK348」:ポリエーテル変性シリコーン BYK-348(ビックケミー社製)
「BYK349」:ポリエーテル変性シリコーン BYK-349(ビックケミー社製)
「プロキセル GXL(S)」:1,2-ベンズイソチアゾリン-3-オン
得られた各インクについて、動的表面張力を以下の方法で測定した。
<動的表面張力>
前記で調製したインクM1~M15及びC1~C3について、最大泡圧法を用いた動的表面張力計(BP-100:KRUSS社製)を用いて表面寿命10ms~1000msの動的表面張力を測定した。測定温度は25℃に調整した。表面寿命15ms、100ms、1000msにおける動的表面張力(単位はmN/m)を表IVに示す。
前記で調製したインクM1~M15及びC1~C3について、ウィルヘルミ法を用いた静的表面張力計(CBVP-Z:協和界面科学社製)を用いて、25℃における静的表面張力を測定した。測定値(単位はmN/m)を表IVに示す。
<射出安定性>
前記で調製したインクM1~M15及びC1~C3をコニカミノルタ製の独立駆動型インクジェットヘッド(360npi、吐出量6pL、1024ノズル)に充填し、ストロボ同期型の液滴観測装置で30分間連続吐出試験を実施した。その後、以下の基準にしたがって射出安定性を評価した。
(基準)
○:評価した256ノズル中、256ノズル全てのノズルが正常に吐出されている。
△:評価した256ノズル中、異常吐出ノズルが1ノズル以上5ノズル未満観測される。
×:評価した256ノズル中、異常吐出ノズルが5ノズル以上観測される。
前記で調製したインクM1~M15及びC1~C3について、60℃サーモで2週間保存した後に、粒子径測定器(ゼータサイザー Nano S-90)により平均粒子径を測定した。その後、以下の基準にしたがってインク保存性を評価した。
(基準)
○:60℃、2週間保存後の平均粒子径と60℃2週間保存前の平均粒子径の差が10nm未満である。
△:60℃、2週間保存後の平均粒子径と60℃2週間保存前の平均粒子径の差が10nm以上30nm未満である。
×:60℃、2週間保存後の平均粒子径と60℃2週間保存前の平均粒子径の差が30nm以上である。
前記で調製した処理液及びインクを、下記表V~表Xの組み合わせとしたインクセットを用いて、以下の方法で印字試験を実施した。
記録媒体Mとして、PETフィルム(FE2001、厚さ50μm、フタムラ化学社製)を用意した。
コニカミノルタ製の独立駆動型インクジェットヘッド(360npi、吐出量6pLもしくは14pL、1024ノズル)2個を搭載したスキャン型プリンタ(図4参照。)を準備し、先に記録されるヘッドH1に各処理液を充填し、後に記録されるヘッドH2に各インクを充填した。その後、解像度720×720dpiの画像を走査方向X及び搬送方向Yに各々2分割した4つの画像(180×180dpi)とし、一つの印刷領域を4回印刷する4パスモードで、必ず処理液が先に記録される向きに片方向で印刷を実施した。
キャリッジCの搬送速度は300mm/secに設定し、処理液とインクの記録間に乾燥工程を設けない構成とした。印字は25℃50%RHの環境下で試験した。
処理液の記録は、液量6pL、最大印字率33%に設定し、インクの画像領域に合わせて像様に付与した。またインクの記録は液量14pL、最大印字率100%に設定した。なお、上記の設定において、ベタ部の処理液の付量は1.7g/m2、ベタ部のインク付量は11.9g/m2となり、ベタ部のインク付与量と処理液付与量の比(インク付量/処理液の付量)は7.0倍となる。
上記印字試験1の中で、処理液が付与されてからインクが付与されるまでの時間を測定したところ、0.2秒と算出された。上記25℃50%RHの環境において、処理液が付与されてから0.2秒後の処理液の乾燥率を測定したところ、乾燥率は1%以下であった。なお、処理液の乾燥率は、処理液の質量変化量を測定することで算出した。
上記印字試験1において、インクを付与した後に、PETフィルムを90℃に設定した乾燥機に投入し、5分間加熱乾燥して画像記録物を得た。
<抜き文字の潰れ>
前記に記載の方法で、5ポイント及び7ポイントのMS明朝体で、漢字「口、四、日、回、因、困、固、国、目、図、國」の抜き文字を印字し、印字した文字画像を目視観察し、以下の基準にしたがって文字品質の評価を行った。
(基準)
○:5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。
△:5ポイントの抜き文字は一部しか判読できないが、7ポイントの抜き文字全てが判読可能である。
×:7ポイントの抜き文字の中にも判読できないものがある。
前記に記載の方法で、3画素幅の細線を記録し、以下の基準で細線のにじみを目視評価した。
(基準)
○:細線が細く直線状に印字されている。
△:細線の所々が膨らみ、少し歪んで印字されている。
×:線が大きく滲み、太く歪んでいる。
前記に記載の方法で、5cm×5cmのベタ画像を記録し、以下の基準でベタ部のまだらを目視評価した。
(基準)
○:15cm離れた位置から観測して、画像に濃度ムラが認められない。
△:15cm離れた位置から観測すると、画像の一部において濃度ムラが認められるが、30cm離した位置からは、濃度ムラが認められない。
×:30cm離した位置から観測して、画像に濃度ムラが認められる。
前記に記載の方法で、5cm×5cmのベタ画像を記録し、爪で印字面をこすり、以下の基準で密着性を評価した。
(基準)
○:爪でこすっても印字面は変化なく、とれない。
△:爪でこすると傷がつき、印字面が一部剥がれる。
×:爪でこすると印字面が剥がれ落ちる。
コニカミノルタ社製ピエゾ型インクジェットヘッド(360dpi、吐出量6pL)の独立駆動ヘッド2つをノズルが互い違いになるように配置し、720dpi×720dpiのヘッドモジュールを作成し、図1に例示するシングルパス型のプリンタに、搬送方向にノズル列が直交するように設置した。
なお、処理液付与後からインク付与までの時間は、記録媒体が処理液付与部を通過した後に所定の時間待機させた後、インク付与部へと移動することで調整した。
処理液の乾燥率は、処理液が付与されてからインクが付与されるまでの時間に揮発した溶媒量を、前記PETフィルムに付与された処理液の質量変化率を測定することで算出した。処理液の付量及びインクの付量は、液滴サイズと印字率を変えることでそれぞれ調整した。評価結果を表XIに示す。
なお、表XIにおいて「≦1」は、「1%以下」を表す。
10 処理液付与部
11 インクジェットヘッド
12 処理液液滴
20 インク付与部
21 インクジェットヘッド
22 インク液滴
23 第2乾燥部
30 送り出しローラー
40 巻取りローラー
C 処理液層
F 基材
P 画像記録物
R インク層
50 缶詰食品用包装材料
51 ブリキ基材
52 熱硬化性樹脂層(ベースコート)
53 処理液層
54 インク層
55 熱硬化性樹脂層(トップコート)
C キャリッジ
H1 ヘッド
H2 ヘッド
X 走査方向
Y 搬送方向
M 記録媒体(基材)
Claims (10)
- インクと処理液とを含むインクセットであって、
前記インクが、顔料、樹脂微粒子、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有し、
前記処理液が、多価金属塩、沸点150~250℃の範囲内の水溶性溶媒及び界面活性剤を含有し、
25℃において、前記インクの静的表面張力が、前記処理液の静的表面張力よりも5mN/m以上高く、
25℃において、前記インクの表面寿命15msにおける動的表面張力が、前記処理液の表面寿命15msにおける動的表面張力よりも5mN/m以上高く、
前記インクの表面寿命15msにおける動的表面張力が、35~45mN/mの範囲内であり、かつ、
前記処理液の表面寿命15msにおける動的表面張力が、25~35mN/mの範囲内であるインクセット。 - 前記顔料が、アニオン性高分子分散剤で分散されている請求項1に記載のインクセット。
- 前記インクが、0.15質量%の酢酸カルシウム・1水和物水溶液との凝集性が0.2以下である前記樹脂微粒子を、3~15質量%の範囲内で含有する請求項1又は請求項2に記載のインクセット。
- 前記樹脂微粒子が、スルホン酸基を有する水分散性ポリエステル樹脂を含有する請求項1から請求項3までのいずれか一項に記載のインクセット。
- 25℃において、未乾燥状態の前記処理液の表面寿命15msにおける動的表面張力をAとし、
前記処理液を乾燥させて、当該処理液の乾燥率が30%のときの表面寿命15msにおける動的表面張力をBとしたときに、下記式(I)を満たす請求項1から請求項4までのいずれか一項に記載のインクセット。
式(I):(B-A)≦5mN/m - 前記インク中に含有しない界面活性剤を、前記処理液中に含有する請求項1から請求項5までのいずれか一項に記載のインクセット。
- 請求項1から請求項6までのいずれか一項に記載のインクセットを用い、画像を記録するインクジェット記録方法であって、
前記処理液を基材に付与した後、加熱乾燥工程を経ずに、前記処理液が濡れた状態で前記インクを前記処理液が付与された領域に付与するインクジェット記録方法。 - 前記処理液が付与された領域に、前記処理液の乾燥率が30%以下の状態で、前記インクを付与する請求項7に記載のインクジェット記録方法。
- 前記処理液を前記基材に付与した後、10秒以内に前記処理液が付与された領域に、前記インクを付与する請求項7又は請求項8に記載のインクジェット記録方法。
- 単位面積当たりにおいて、前記インクの付量が、前記処理液の付量の2~25倍の範囲内である請求項7から請求項9までのいずれか一項に記載の記録方法。
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EP4296322A1 (en) | 2023-12-27 |
CN117120558A (zh) | 2023-11-24 |
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