WO2023068142A1 - インク組成物、インクセット、記録方法、記録物の製造方法、及び記録物 - Google Patents
インク組成物、インクセット、記録方法、記録物の製造方法、及び記録物 Download PDFInfo
- Publication number
- WO2023068142A1 WO2023068142A1 PCT/JP2022/038071 JP2022038071W WO2023068142A1 WO 2023068142 A1 WO2023068142 A1 WO 2023068142A1 JP 2022038071 W JP2022038071 W JP 2022038071W WO 2023068142 A1 WO2023068142 A1 WO 2023068142A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ink composition
- resin
- mass
- formula
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
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
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
-
- 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
-
- 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
- C09D11/54—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
Definitions
- the present invention relates to an ink composition, an ink set, a recording method, a method for producing a recorded matter, and a recorded matter.
- non-aqueous ink compositions in which various coloring materials and resins are dissolved or dispersed in a mixed liquid with an organic solvent are widely used. Characters and images can be obtained by ejecting the ink composition from a nozzle of an inkjet method or the like onto a substrate such as paper directly or via another layer, and drying the non-aqueous ink composition.
- Patent Document 1 an ink jet ink containing an acrylic resin obtained by solution polymerization using a radical polymerization initiator in a glycol ether dialkyl ether solvent in an oil-based ink composition containing a glycol ether dialkyl ether as a main solvent A recording oil-based ink composition is disclosed.
- Patent Document 1 discloses that this composition obtains good print drying properties, scratch resistance, and re-solubility by solubilizing acrylic resins, which were conventionally difficult to dissolve. is described as possible.
- such an inkjet ink composition may be stored for a long period of time, for example, in an ink cartridge, and even when stored for a long period of time in a low-temperature or high-temperature environment, there is no change in ejection properties. is required.
- the ink composition is ejected by the inkjet method
- the ink composition is ejected through the inkjet head, so the member suitability for the members constituting the inkjet head is also required.
- An object of the present invention is to provide an inkjet ink composition that has excellent ejection stability and excellent suitability for members even when stored for a long period of time.
- An ink composition that contains a resin and an organic solvent and is ejected by an inkjet method, wherein the content of residual monomers derived from the resin is 2000 ppm or less in the total amount of the ink composition.
- the resin contains at least one or more polymers or copolymers selected from the group consisting of acrylic resins, vinyl chloride resins, vinyl acetate resins, polyester resins, and polyurethane resins ( 1) The ink composition described in 1).
- the resin further contains at least one polymer or copolymer selected from the group consisting of vinyl chloride-based resins, vinyl acetate-based resins, polyester-based resins, and polyurethane-based resins (4)
- the ink composition according to .
- a recording method comprising ejecting the ink composition according to any one of (1) to (16) onto a substrate.
- a method for producing a recorded matter comprising the step of ejecting the ink composition according to any one of (1) to (16) onto a substrate.
- a substrate and a layer of an ink composition formed on the substrate, the layer of the ink composition containing a resin, and the content of residual monomers derived from the resin Recorded matter of 4.0 parts by mass or less per 100 parts by mass.
- the ink composition of the present invention even if it is an ink composition containing a resin, has excellent ejection stability and excellent suitability for members.
- the ink composition of the present invention is an ink composition that contains an organic solvent and a resin and is ejected by an inkjet method.
- the ink composition of the present invention is characterized in that the content of residual monomers derived from the resin is 2000 ppm or less in the total amount of the ink composition.
- Residual monomers derived from resins are unreacted monomers that are raw materials for resin polymerization. If a predetermined amount or more of such residual monomers are present in the resin, the residual monomers derived from the resin will be dissolved or dispersed in the ink composition.
- the ink composition is stored for a long period of time, the ejection stability is lowered and the member suitability for the member constituting the inkjet head is also deteriorated.
- the resin is a homopolymer composed of one polymerizable monomer
- the amount of residual monomer tends to be greater than that of a copolymer, and the ink composition containing a homopolymer as the resin.
- the discharge stability is lowered and the suitability for members is deteriorated.
- ppm in this specification means a mass ratio.
- Methods for reducing the content of residual monomers derived from the resin to 2,000 ppm or less in the total amount of the ink composition include, for example, a method of additionally adding a polymerization initiator in the synthesis process, a method of extending the synthesis time, and a method obtained in the synthesis process.
- the object is a novel ink composition.
- the content of residual monomers derived from the resin is preferably 2000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less in the total amount of the ink composition. Also, the content of residual monomers derived from the resin is preferably 1 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more. By setting the concentration to 1 ppm or more, it is possible to suppress a significant increase in production cost due to purification such as reprecipitation of the resin. Therefore, it is possible to produce an ink composition having good physical properties that do not cause problems in practical use at a low cost.
- the content of residual monomers derived from the resin can be measured by the absolute calibration curve method using gas chromatography.
- a measurement device for gas chromatography for example, NEXIS GC-2030 (manufactured by Shimadzu Corporation) is used, and as a detector for gas chromatography, a flame ionization detector (FID) is used.
- FID flame ionization detector
- a polyethylene glycol-based adsorbent can be used as the sorbent and nitrogen as the carrier gas.
- the ink composition of the present invention may be a colored ink composition containing a coloring material (including a colored coloring material and a black-white coloring material) to give a recorded matter (substrate) a metallic tone. It may be an ink composition containing a luster pigment (scale-like metal particles) for coloring, or a clear ink composition containing no coloring material. In the case of a clear ink that does not contain a coloring material, inks for forming a layer having a desired function can be used. Such inks include, for example, an overcoat ink composition for forming an overcoat layer that protects a recorded article (substrate), a matting ink composition for matting a recorded article (substrate), and a weather resistant layer. An ink composition containing an ultraviolet absorber, a light stabilizer, or the like for forming the ink composition, or an ink composition having adhesiveness, for example, for bonding a substrate and a foil or the like.
- a coloring material including a colored
- the ink composition according to the present embodiment is a non-aqueous ink composition that does not intentionally contain water.
- a non-aqueous ink composition is an ink composition that does not intentionally contain water and contains an organic solvent (oily ink composition), and is different from an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixture of water and an organic solvent. Being a non-aqueous ink composition, it dries quickly and facilitates printing (recording) on non-absorbent substrates such as resin substrates and metal substrates.
- the ink composition of the present invention may be an aqueous ink composition or a non-aqueous ink composition.
- residual monomers derived from resins are organic substances such as monomers constituting acrylic resins and vinyl chloride-vinyl acetate copolymer resins. Therefore, residual monomers derived from resins (in particular, monomers constituting acrylic resins and vinyl chloride-vinyl acetate copolymer resins) are easily dissolved in a non-aqueous ink composition containing an organic solvent as a main component. .
- the resin contained in the non-aqueous ink composition exists dissolved in the non-aqueous ink composition, unlike the resin constituting the resin emulsion contained in the aqueous ink composition, for example. For this reason, in a non-aqueous ink composition containing a resin, residual monomers derived from the resin tend to flow out into the non-aqueous ink composition, and the residual monomer content is higher than in an aqueous ink composition.
- non-aqueous ink compositions containing a resin have more pronounced problems such as a decrease in ejection stability due to the dissolution or dispersion of residual monomers derived from the resin and a deterioration in suitability for members constituting an inkjet head. tend to occur in A non-aqueous ink composition in which the content of residual monomers derived from a resin is controlled to 2000 ppm or less more effectively solves the above-mentioned problems that are more likely to occur in a non-aqueous ink composition containing a resin. can be done.
- the water content in the ink composition according to the present embodiment is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, based on the total amount of the ink composition. It is more preferably 0% by mass or less, and even more preferably 0.5% by mass or less. If water originating from raw materials or water in the air during the production process is mixed, the storage stability of the ink composition may be deteriorated, or solid matter may be generated due to the components contained in the ink composition. Storage stability and the like can be more effectively improved by reducing the water content in the ink composition so that it contains as little water as possible (intentionally avoiding water). It becomes possible.
- the ink composition according to the present embodiment is an ink composition that can obtain a recorded matter by drying (volatilizing) the organic solvent. Specifically, volatile components such as an organic solvent contained in the ink composition dry (volatilize), and the residue deposits on the surface of the substrate to form a recorded matter.
- the ink composition according to the present embodiment is different from an active energy ray-curable ink composition that is polymerized and cured on a substrate by an active energy ray such as ultraviolet rays.
- an active energy ray-curable ink composition contains a polymerizable compound
- the ink composition according to the present embodiment contains an organic solvent, but the inclusion of a polymerizable compound is an essential configuration. It may or may not contain a polymerizable compound.
- the ink composition according to this embodiment contains a resin.
- the resin imparts abrasion resistance to the recording layer (recorded matter). Since the ink composition does not intentionally contain water and contains an organic solvent, the resin is mainly contained in the ink composition in a form dissolved in the organic solvent. It is different from a resin emulsion that is contained in a dispersed form.
- the term "resin” mainly means a binder resin that imparts abrasion resistance to the recording layer (recorded matter), and a dispersant (polymeric dispersant) containing a coloring material (pigment) described later. ) and polymeric surfactants such as surfactants having a siloxane skeleton.
- the type of resin is not particularly limited, and examples include acrylic resins (including copolymers such as styrene-acrylic resins), polystyrene resins, polyester resins, vinyl chloride resins, and vinyl acetate.
- resin vinyl chloride vinyl acetate copolymer resin, polyethylene resin, polyurethane resin, rosin modified resin, phenol resin, terpene resin, polyamide resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate copolymers, cellulose acetate butyrate, cellulose acetate propionate, silicone (silicon) resins, acrylamide resins, epoxy resins, polyether resins, polycarbonate resins, or copolymer resins thereof. can.
- the resin preferably contains an acrylic resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, a polyester resin, or a polyurethane resin. It is more preferable to contain at least one selected from the group consisting of vinyl chloride-vinyl acetate copolymer resins, and it is particularly preferable to contain an acrylic resin.
- the content of the acrylic resin is preferably in the range of 30% by mass or more and 100% by mass or less based on the total amount of the resin contained in the ink composition.
- the acrylic resin is not particularly limited as long as it is contained as a main component of the monomers that make up the (meth)acrylic acid ester monomer.
- the acrylic resin may be a homopolymer of one kind of radically polymerizable monomer, or may be a copolymer of two or more kinds of selected radically polymerizable monomers.
- a preferred acrylic resin for the ink composition according to the embodiment is a homopolymer of methyl methacrylate, or at least one selected from the group consisting of methyl methacrylate, butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. It is a copolymer with one or more compounds.
- the acrylic resin may be synthesized or commercially available.
- Commercially available (meth)acrylic resins include, for example, trade names such as Rohm and Haas Paraloid B99N, Paraloid B60, Paraloid B66, and Paraloid B82, which have a low residual monomer content (e.g., resin 4.0% by mass or less in the total amount) can be used.
- a resin having a high residual monomer content for example, more than 4.0% by mass of the total amount of the resin
- the vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer using two or more selected polymerizable monomers.
- copolymers of vinyl chloride resins include vinyl chloride-vinyl acetate copolymer resins.
- a vinyl chloride-vinyl acetate copolymer resin is a polymer of vinyl chloride monomer and vinyl acetate monomer.
- Vinyl chloride-vinyl acetate copolymer resins include, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic acid copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate / hydroxyalkyl acrylate copolymers, etc., and mixtures thereof.
- the vinyl chloride resin may be synthesized or commercially available. Commercially available vinyl chloride-vinyl acetate copolymer resins from Nissin Chemical Co., Ltd.
- a vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer.
- a conventionally known polymerization method may be used as the polymerization method.
- the polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.
- a polyester resin contains at least a structural unit obtained by polycondensation of an alcohol component and a carboxylic acid component.
- the polyester-based resin may include a modified polyester-based resin.
- the polyester resin may be a synthetic product or a commercially available product.
- Commercially available polyester resins include "VYLON226", “VYLON270", “VYLON560”, “VYLON600”, “VYLON630” and “VYLON660” manufactured by Toyobo Co., Ltd. , "VYLON885", "VYLONGK250", “VYLONGK810", “VYLON GK890”, etc.
- a polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component.
- Polyurethane-based resins may include polyurethane-based resins modified with polyester, polyether, or caprolactone. Polyurethane resins may be synthesized or commercially available. Commercially available polyurethane resins include "Uriano KL-424", “Uriano KL-564" and “Uriano KL-593" manufactured by Arakawa Chemical Industries. ”, “Yuriano 3262”, etc.
- acrylic resins vinyl chloride resins, polyester resins, and polyurethane resins may be used alone, or two or more of them may be used in combination.
- the weight average molecular weight (relative molecular mass) of the resin is not particularly limited, it is preferably 10,000 or more, more preferably 15,000 or more.
- the weight average molecular weight (relative molecular mass) is preferably 60,000 or less, more preferably 50,000 or less.
- Relative molecular weights of resins can be measured by conventional GPC (gel permeation chromatography).
- the content of the residual monomer derived from the resin depends on the content of the resin contained in the ink composition, but is preferably 4.0 parts by mass or less, more preferably 2.0 parts by mass or less per 100 parts by mass of the resin. is more preferably 1.0 parts by mass or less, and even more preferably 0.5 parts by mass or less.
- the content of the resin contained in the ink composition is not particularly limited. % or more, more preferably 3.0 mass % or more, and even more preferably 4.0 mass % or more. Thereby, the abrasion resistance of the recording layer (recorded matter) can be improved.
- the resin content is 1.0% by mass or more and the content of residual monomers derived from the resin is 2000 ppm or less. ) can be improved in abrasion resistance.
- the upper limit of the content of the resin contained in the ink composition is not particularly limited, but it is preferably contained in the range of 20.0% by mass or less, and contained in the range of 15.0% by mass or less based on the total amount of the ink composition. More preferably, it is contained in the range of 12.0% by mass or less. This improves the ejection property of the ink composition. In addition, the content of residual monomers derived from the resin contained in the ink composition can be reduced, and the ink composition effectively exhibits the effects of the present invention.
- the ink composition according to this embodiment contains an organic solvent.
- the organic solvent is a liquid medium for the ink composition, and has the function of dissolving (or dispersing) each component such as the resin.
- the organic solvent preferably contains a glycol ether solvent represented by the following formula (1).
- R a (—OR b ) n —OR c (1)
- R a and R c are each independently hydrogen or an optionally branched alkyl group having 1 to 8 carbon atoms
- R b is a branched group having 1 to 4 carbon atoms.
- n represents an integer of 1 or more and 6 or less).
- Glycol ether solvents include glycol ether monoalkyl represented by the following formula (2) and glycol ether dialkyl represented by the following formula (3).
- R d (—OR e ) n —OH (2)
- R d is an alkyl group having 1 to 8 carbon atoms and may be branched
- R e represents an alkylene group having 1 to 4 carbon atoms and may be branched
- n represents an integer of 1 or more and 6 or less.
- R f (—OR g ) n —OR h (3)
- R f and R h are each independently an optionally branched alkyl group having 1 to 8 carbon atoms
- R g is an optionally branched alkyl group having 1 to 4 carbon atoms. represents a good alkylene group
- n represents an integer of 1 or more and 6 or less.
- acrylic resins are easily dissolved in glycol ether solvents, and by containing a predetermined amount of glycol ether solvents, it is possible to effectively improve the ejection stability from the ink head nozzles.
- glycol ether monoalkyl examples include ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, propyl, isopropyl , n-butyl, isobutyl, t-butyl, 2-ethylhexyl ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl ether, Propylene glycol mono-n-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhe
- diethylene glycol monomethyl ether diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol Monomethyl Ether, Tetraethylene Glycol Monoethyl Ether, Tetraethylene Glycol Monopropyl Ether, Tetraethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether , dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl Ether ,
- Glycol ether dialkyl includes ethylene glycol dibutyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl.
- diethylene glycol dimethyl ether diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol Dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether , dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether
- the preferred content of the glycol ether-based solvent represented by formula (1) is preferably 20% by mass or more, more preferably 50% by mass or more, and 70% by mass or more in the total amount of the ink composition. is more preferred.
- the preferred content of the glycol ether-based solvent represented by formula (1) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less in the total amount of the ink composition. is more preferred.
- the content of the glycol ether monoalkyl represented by formula (2) is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass or more in the total amount of the ink composition. is more preferred.
- a preferable content of the glycol ether monoalkyl represented by formula (2) is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass or less in the total amount of the ink composition. is more preferred.
- the content of the glycol ether dialkyl represented by formula (3) is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more in the total amount of the ink composition. is more preferred.
- the preferred content of the glycol ether dialkyl represented by formula (3) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less in the total amount of the ink composition. is more preferred.
- the solvent represented by the general formula (4), the solvent represented by the general formula (5), and the general formula (6) It is preferable to contain at least one or more selected from the group consisting of the represented solvents.
- R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 2 and R 3 in formula (4) are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.
- R 4 is an alkylene group having 3 to 5 carbon atoms
- R 5 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an unsaturated hydrocarbon group.
- Unsaturated hydrocarbon group means a hydrocarbon group containing at least one or more multiple bonds such as a vinyl group.
- R 5 in formula (5) is preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, or an unsaturated hydrocarbon group, and is preferably hydrogen, an alkyl group having 1 to 2 carbon atoms, or an unsaturated hydrocarbon group.
- a hydrogen group is preferred.
- R6 is an alkylene group having 3 to 5 carbon atoms
- R7 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 6 is preferably an alkylene group of 3 or more and 4 or less, more preferably 3.
- R 7 is preferably hydrogen or an alkyl group having 1 carbon atom, more preferably hydrogen.
- the solvent represented by formula (4) include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N- Examples include alkylamide solvents such as diethylpropanamide, N,N-dipropylpropanamide, N-ethylformamide and N-ethylacetamide.
- alkylamide solvents such as diethylpropanamide, N,N-dipropylpropanamide, N-ethylformamide and N-ethylacetamide.
- solvents represented by formula (5) include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2 -pyrrolidone, ⁇ -caprolactam, N-methyl- ⁇ -caprolactam, N-vinylcaprolactam, N-ethyl- ⁇ -caprolactam, N-propyl- ⁇ -caprolactam, N-butyl- ⁇ -caprolactam, N-acetylcaprolactam, etc.
- a cyclic amide-based solvent can be mentioned. Among these, it is preferable to contain at least one selected from the group consisting of ⁇ -caprolactam, N-methylcaprolactam, and N-vinylcaprolactam.
- solvents represented by formula (6) include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonalactone, ⁇ - decalactone, ⁇ -undecalactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonalactone, ⁇ -decalactone, ⁇ -undecalactone, ⁇ -caprolactone, etc.
- a lactone solvent can be mentioned.
- the content of the solvent represented by formula (4) is not particularly limited, but the lower limit of the content of the solvent represented by formula (4) is 1.0% by mass or more in the total amount of the ink composition. It is preferably 5.0% by mass or more, more preferably 8.0% by mass or more.
- the upper limit of the content of the solvent represented by formula (4) is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and 75.0% by mass in the total amount of the ink composition. % or less.
- the content of the solvent represented by formula (5) is not particularly limited, but the lower limit of the content of the solvent represented by formula (5) is 1.0% by mass or more in the total amount of the ink composition. It is preferably 5.0% by mass or more, more preferably 8.0% by mass or more.
- the upper limit of the content of the solvent represented by formula (5) is preferably 90.0% by mass or less, more preferably 80.0% by mass or less, and 75.0% by mass in the total amount of the ink composition. % or less.
- the content of the solvent represented by formula (6) is not particularly limited, but the lower limit of the content of the solvent represented by formula (6) is 1.0% by mass or more in the total amount of the ink composition. It is preferably 3.0% by mass or more, more preferably 5.0% by mass or more.
- the upper limit of the content of the solvent represented by formula (6) is preferably 70.0% by mass or less, more preferably 50.0% by mass or less, and 30% by mass or less in the total amount of the ink composition. is more preferably 20.0% by mass or less.
- the general formula (7) A solvent represented by the general formula (8), a solvent represented by the general formula (9), a solvent represented by the general formula (10), or a solvent represented by the general formula (11) It is preferable to contain at least one or more selected from the group consisting of solvents. As a result, the ink composition effectively exhibits the above effects.
- R 8 is hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 9 represents an alkylene group having 1 to 3 carbon atoms.
- R 10 , R 11 and R 12 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 13 represents an alkylene group having 1 to 4 carbon atoms. .
- R 14 represents an optionally branched alkyl group or unsaturated hydrocarbon group having 1 to 4 carbon atoms
- R 15 represents an alkylene group having 1 to 4 carbon atoms.
- R 16 and R 17 are each independently an alkyl group having 1 to 4 carbon atoms and may be branched, and R 18 represents an alkylene group having 2 to 4 carbon atoms.
- solvent represented by formula (7) examples include carbonate esters such as propylene carbonate and ethylene carbonate.
- solvent represented by formula (8) examples include 3-methoxypropanamide, 3-butoxypropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dibutyl Propanamide, 3-butoxy-N,N-dibutylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethyl-3-methoxypropanamide, N,N-dibutyl-3-methoxypropanamide , N,N-dibutyl-3-butoxypropanamide and N,N-dimethyl-3-butoxypropanamide.
- solvent represented by formula (9) examples include oxazolidinone-based solvents such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, and N-vinylmethyloxazolidinone.
- Solvents represented by formula (10) include 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and the like. and imidazolidinone-based solvents.
- the content of the solvent represented by formula (7) is not particularly limited, but the lower limit of the content of the solvent represented by formula (7) is preferably 1% by mass or more based on the total amount of the ink composition. It is more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit of the content of the solvent represented by formula (7) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the ink composition. More preferably, it is still more preferably 20% by mass or less.
- the content of the solvent represented by formula (8) is not particularly limited, but the lower limit of the content of the solvent represented by formula (8) is preferably 1% by mass or more in the total amount of the ink composition, It is more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit of the content of the solvent represented by formula (8) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the ink composition. More preferably, it is still more preferably 20% by mass or less.
- the content of the solvent represented by formula (9) is not particularly limited, but the lower limit of the content of the solvent represented by formula (9) is preferably 1% by mass or more in the total amount of the ink composition, It is more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit of the content of the solvent represented by formula (9) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the ink composition. More preferably, it is still more preferably 20% by mass or less.
- the content of the solvent represented by formula (10) is not particularly limited, but the lower limit of the content of the solvent represented by formula (10) is preferably 1% by mass or more in the total amount of the ink composition, It is more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit of the content of the solvent represented by formula (10) is preferably 70% by mass or less, more preferably 50% by mass or less, and 30% by mass or less in the total amount of the ink composition. More preferably, it is still more preferably 20% by mass or less.
- a solvent represented by formula (4), a solvent represented by formula (5), a solvent represented by formula (6), a solvent represented by formula (7), a solvent represented by formula (8) Among the solvent represented by the formula (9), or the solvent represented by the formula (10), the solvent represented by the formula (4), the solvent represented by the formula (5), the solvent represented by the formula (6) a solvent represented by the formula (7), or a solvent represented by the formula (8)” is preferable, and “a solvent represented by the formula (4), a solvent represented by the formula (5) , or a solvent represented by formula (6)” is more preferable.
- the ink composition exhibits the above effects more effectively. Two or more of these organic solvents may be mixed.
- the ink composition according to the present embodiment includes the above-described glycol ether solvent, the solvent represented by formula (4), the solvent represented by formula (5), the solvent represented by formula (6), and the solvent represented by formula ( Organic solvents other than the solvent represented by 7), the solvent represented by formula (8), the solvent represented by formula (9), and the solvent represented by formula (10) may be contained.
- diols diols
- glycerin trimethylolethane, trimethylolpropane, triols such as 1,2,6-hexanetriol: tetrahydric alcohols such as mesoerythritol and pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, N -Alkanolamines such as methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine; methyl acetate, ethyl acetate, -n-propyl acetate, acetic acid Acetate esters such as isopropyl, n-butyl acetate, isobutyl acetate, hexyl acetate, and octyl acetate; Saturated hydrocarbons such as hexane, isohexane, n
- the content of the other organic solvent is not particularly limited, but the lower limit of the content of the other organic solvent is preferably in the range of 10% by mass or more in the total amount of the ink composition, and in the range of 20% by mass or more. It is more preferable that the content is in the range of 30% by mass or more.
- the upper limit of the content of other organic solvents is preferably 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less in the total amount of the ink composition. is more preferred.
- the volatilization suppression and solidification prevention of the ink composition in devices such as nozzles and tubes, and resolubility when solidified are used.
- a surfactant may be incorporated for the purpose of reducing the .DELTA.
- surfactants include polyoxyalkylene alkyl ethers such as nonionic P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S -207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by NOF Corporation), Emulgen 106, 108, 707, 709, A-90, A-60 (Kao ( Co., Ltd.), Floren G-70, D-90, TG-740W (manufactured by Kyoeisha Chemical Co., Ltd.), Poem J-0081HV (manufactured by Riken Vitamin Co., Ltd.), and as aliphatic phosphates, Adekatol NP -620, NP-650, NP-660, NP-675, NP-683, NP-686, Adekacol CS-141E, TS-230E (manufactured by Adeka Co., Ltd.
- polyester-modified silicone or polyether-modified silicone as the silicone-based surfactant having a siloxane skeleton.
- acetylene glycol-based surfactants include Surfynol (registered trademark) 82, 104, 465, 485, TG (both manufactured by Air Products Japan), Olfin (registered trademark) STG, E1010 (both manufactured by Nisshin Kagaku Co., Ltd.), and the like.
- Surfactants are not limited to those described above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used.
- the surfactant preferably contains a surfactant having a siloxane skeleton.
- a surfactant having a siloxane skeleton in the ink composition according to the present embodiment, it is possible to improve the glossiness of the obtained recorded matter. In addition, bleeding during printing is reduced, and a recorded matter with improved abrasion resistance can be obtained.
- polyester-modified silicone or polyether-modified silicone As the surfactant having a siloxane skeleton, it is preferable to use polyester-modified silicone or polyether-modified silicone. Specific examples include BYK-313, 315N, 322, 326, 331, 347, 348, 3753 and BYK-UV3500. , 3510, 3530, 3570 (all manufactured by BYK-Chemie Japan) and the like can be used.
- the ink composition according to the present embodiment may contain a surfactant different from the surfactant having a siloxane skeleton together with the surfactant having a siloxane skeleton.
- the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is 0 in the total amount of the ink composition. It is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and even more preferably at least 0.1% by mass.
- the upper limit of the surfactant content is preferably 1.0% by mass or less, more preferably 0.9% by mass or less, and 0.8% by mass or less in the total amount of the ink composition. is more preferred.
- the ink composition according to the present embodiment may be a colored ink containing a coloring material (including a colored coloring material and a black-white coloring material), and gives a metallic tone to a recorded matter (substrate). It may be an ink containing a luster pigment (scale-like metal particles) for the purpose, or a clear ink containing no coloring material. In the case of a clear ink that does not contain a coloring material, inks for forming a layer having a desired function can be used.
- Such inks include, for example, an overcoat ink composition for forming an overcoat layer that protects a recorded article (substrate), a matting ink composition for matting a recorded article (substrate), and a weather resistant layer.
- These ink compositions may or may not contain a coloring material.
- the coloring material is not particularly limited, and may be a dye-based or a pigment-based coloring material. pigment-based coloring materials) are preferably used.
- the pigment that can be used in the ink composition according to the present embodiment is not particularly limited, and examples thereof include organic pigments and inorganic pigments that are used in conventional ink compositions. These may be used individually by 1 type, or may be used in combination of 2 or more type.
- the dispersion stability of the pigment can be improved by using a dispersant or dispersion aid (pigment derivative), which will be described later.
- organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, and anthraquinone-based pigments.
- Organic pigments (anthrone-based organic pigments), xanthene-based organic pigments, diketopyrrolopyrrole-based organic pigments, dioxazine-based organic pigments, nickel azo-based pigments, isoindolinone-based organic pigments, pyranthrone-based organic pigments, thioindigo-based organic pigments, condensed azo organic solid solution pigments such as organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindoline organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, and other pigments such as lake pigments and carbon black. be done.
- C.I. color index
- azo dyes benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, Merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dye
- inorganic pigments that can be used in the ink composition according to the present embodiment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, alumina, and zinc.
- flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron (III)), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic iron black, Inorganic solid solution pigments and the like can be mentioned.
- the average dispersed particle size of the pigment that can be contained is not particularly limited as long as the desired color development is possible.
- the volume average particle diameter is preferably 5 nm or more, preferably 20 nm or more, from the viewpoint of good dispersibility and dispersion stability of the pigment and obtaining sufficient coloring power. is more preferable, and 30 nm or more is even more preferable.
- the volume average particle size is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less.
- the ejection stability of the inkjet can be improved by setting the volume average particle diameter to be equal to or less than the above upper limit.
- the volume-average particle size of the pigment is measured at 25° C. using a particle size distribution measuring device (particle size analyzer NANOTRACWAVE manufactured by Microtrack Bell Co., Ltd.). diameter (D50).
- volume-based cumulative 50% particle diameter (D50) means a particle diameter at which the cumulative volume calculated from the smaller diameter side becomes 50%.
- “Volume-based cumulative 50% particle size (D50)” may also be referred to as “volume average particle size D50" or "median (median) size”.
- the content of the pigment contained in the ink composition according to the present embodiment is not particularly limited as long as the desired image can be formed, and can be adjusted as appropriate. Specifically, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total amount of the ink composition, although it varies depending on the type of pigment. It is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the ink composition. When the content of the pigment is in the range of 0.05% by mass or more and 20% by mass or less, the balance between the dispersion stability and the coloring power of the pigment can be excellent.
- the ink composition according to the present embodiment is not particularly limited in the color to be recorded (printed), and coloring materials may be selected and used in combination according to the intended color. Colors can also be used for each color ink such as yellow, magenta, cyan, black, light magenta, light cyan, light black, orange, green, red, white, and the like. At this time, coloring materials of the same color may be selected.
- a dispersant When the ink composition according to the present embodiment contains a coloring material (pigment), a dispersant may be used as necessary. Any dispersant used in ink compositions can be used as the dispersant. As the dispersant, a polymer dispersant is preferably used. Such a dispersant has a main chain of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group as a side chain. is.
- polyacrylic dispersants for example, Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131 , 9132, 9133, 9151 (manufactured by Vic Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), TREPLUS D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), Floren DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are used.
- Polycaprolactone-based dispersants include, for example, Ajisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J10 TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.
- Preferred dispersants include BYKJET-9130, 9131, 9132, 9133, 9151, Efka PX4310, PX4320, PX4330, PX4700, PX4701, Solsperse 20000, 24000, 32000, 33000, 33500, 34000, 6500, 71000, 71000, 71000, 710000, 39 6000, 88000, J180, J200, TEGO Dispers 655, 685, 688, 690, etc. are used. These individual or mixtures thereof can be used.
- the content of the dispersant is not particularly limited, but the lower limit of the content of the dispersant is preferably 5 parts by mass or more, and 15 parts by mass or more with respect to 100 parts by mass of the pigment in the ink composition. is more preferable, and 20 parts by mass or more is even more preferable.
- the upper limit of the content of the dispersant is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and preferably 100 parts by mass or less with respect to 100 parts by mass of the pigment in the ink composition. More preferred.
- a dispersing aid may be used as necessary in the ink composition according to the present embodiment.
- the dispersing aid is adsorbed on the surface of the coloring material (pigment), and the functional group increases the affinity with the organic solvent and dispersant in the ink composition to improve the dispersion stability.
- a known pigment derivative having a functional group such as an acidic group, a basic group, or a neutral group in the organic pigment residue can be used.
- the ink composition according to the present embodiment includes stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, slip agents, leveling agents (acrylic, silicone, etc.), Known additives such as antifoaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents and wetting agents may be included as optional components.
- stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface conditioners, slip agents, leveling agents (acrylic, silicone, etc.)
- Known additives such as antifoaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents and wetting agents may be included as optional components.
- Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like.
- Specific examples include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol).
- a benzophenone-based compound or a benzotriazole-based compound can be used as the ultraviolet absorber.
- Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples include ADEKA CIZER O-130P and ADEKA CIZER O-180A (manufactured by ADEKA). exemplified.
- Specific examples of polycarboxylic acids include citric acid and maleic acid.
- the viscosity of the ink composition according to this embodiment is not particularly limited.
- the viscosity at 25° C. is preferably 15.0 mPa ⁇ s or less, more preferably 13.0 mPa ⁇ s, and more preferably 10.0 mPa ⁇ s or less from the viewpoint of inkjet dischargeability and discharge stability. It is even more preferable to have Further, the viscosity of the ink composition according to the present embodiment is preferably 1.0 mPa ⁇ s or more, more preferably 2.0 mPa ⁇ s or more, and more preferably 3.0 mPa ⁇ s or more. More preferred.
- the surface tension of the ink composition according to the present embodiment is not particularly limited and is not limited.
- the surface tension at 25° C. is preferably 20 mN/m or more, more preferably 22 mN/m or more, more preferably 24 mN, in terms of inkjet dischargeability, discharge stability, and leveling property to the substrate. /m or more is more preferable.
- the surface tension of the ink composition according to the present embodiment is preferably 40 mN/m or less, more preferably 37 mN/m or less, and even more preferably 35 mN/m or less.
- the ink composition according to the present embodiment can be produced by mixing an organic solvent, a resin, and various components (for example, a resin, a coloring material, etc.) using a paint shaker. At this time, each component may be dissolved or dispersed with zirconia beads. If necessary, after preparing a dispersion in which a coloring material is dispersed in a specific solvent, other components may be added to prepare the ink composition. In addition, the ink composition according to the present embodiment may be adjusted to a desired dissolved oxygen amount and dissolved nitrogen amount by performing a deaeration treatment or the like as necessary.
- a non-aqueous ink composition it is preferable to dry the organic solvent in advance.
- the organic solvent By drying the organic solvent in advance, the amount of water contained in the non-aqueous ink composition can be reduced.
- a method for drying the organic solvent for example, a method of spraying an inert gas (e.g., nitrogen gas) dried in an inert gas atmosphere such as nitrogen for a predetermined time, a method of distilling and refining the organic solvent, and water are selected.
- an inert gas e.g., nitrogen gas
- Examples include a method of allowing the organic solvent to permeate through a semi-permeable membrane that selectively permeates the organic solvent, and a method of selectively adsorbing water mixed in the organic solvent with a water adsorbent that adsorbs water.
- the acrylic resin having a low residual monomer content is preliminarily added to the glycol ether solvent represented by the formula (1), the alkylamide solvent represented by the formula (4), And by dissolving or dispersing in at least one solvent selected from cyclic amide solvents represented by formula (5), and then dissolving or dispersing other ingredients, viscosity stability and ejection stability can be improved. A very good ink composition can be produced.
- the vinyl chloride-vinyl acetate copolymer resin is contained as the resin, the vinyl chloride-vinyl acetate copolymer resin is preliminarily added to the alkylamide solvent represented by the formula (4), or the alkylamide solvent represented by the formula (5).
- Cyclic amide solvent and by dissolving or dispersing in at least one solvent selected from lactone-based solvents represented by formula (6), and then dissolving or dispersing other ingredients, viscosity stability and ejection stability are extremely improved. Excellent ink compositions can be produced.
- the ink set according to the present embodiment is an ink set containing the ink composition described above. Since the above ink composition has a resin-derived residual monomer content of 2000 ppm or less, it suppresses a decrease in ejection stability and has good member suitability for members constituting an inkjet head. Also in the ink set according to the present embodiment, deterioration in ejection stability is suppressed and member suitability is improved.
- the recording method according to the present embodiment is a recording method in which the ink composition described above is applied to the surface of a substrate. Since the above ink composition has a resin-derived residual monomer content of 2000 ppm or less, it suppresses a decrease in ejection stability and has good member suitability for members constituting an inkjet head. Also in the recording method using the ink composition according to the present embodiment, deterioration in ejection stability is suppressed, member suitability is improved, and recorded matter with high image reproducibility can be obtained.
- the method of ejecting ink by the inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.
- a method for producing a recorded matter according to the present embodiment is a recording method in which the ink composition described above is applied to the surface of a substrate. Since the above ink composition has a resin-derived residual monomer content of 2000 ppm or less, it suppresses a decrease in ejection stability and has good member suitability for members constituting an inkjet head. Also in the method of manufacturing a recorded matter according to the present embodiment, deterioration in ejection stability is suppressed, member suitability is improved, and a recorded matter with high image reproducibility can be obtained.
- a recorded matter according to the present embodiment includes a substrate and an ink composition layer formed on the substrate.
- the ink composition layer contains a resin, and the content of residual monomers derived from the resin is 4.0 parts by mass or less per 100 parts by mass of the resin.
- This recorded matter is obtained by inkjet-ejecting the above-mentioned ink composition onto the surface of a substrate, and the above-mentioned ink composition suppresses a decrease in ejection stability and has good suitability for members. Therefore, the recorded matter according to the present embodiment also has high image reproducibility.
- the content of residual monomers derived from the resin is preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, and 0.5 parts by mass or less with respect to 100 parts by mass of the resin. is more preferable.
- the base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited. It may be an absorbent substrate such as , or a substrate having a surface coating such as a substrate having a receiving layer, and various substrates can be used.
- Non-absorbent base materials include polyester-based resin, polypropylene-based synthetic paper, polyolefin-based resin (polypropylene-based resin, polyethylene-based resin, etc.), acrylic-based resin, styrene-based resin, polycarbonate-based resin, ABS resin, and vinyl chloride-based resin. , resin substrates such as polyimide resin, metals, metal foil-coated paper, glass, synthetic rubber, natural rubber, and the like.
- absorbent substrates include dry paper, medium-quality paper, high-quality paper, synthetic paper, cotton, synthetic fiber fabric, silk, hemp, fabric, non-woven fabric, leather, and the like.
- Examples of surface-coated substrates include coated paper, art paper, cast paper, lightweight coated paper, and lightly coated paper.
- the surface is mainly made of a resin.
- resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP. Further, it may be used for a resin base material (so-called resin base material for lamination) on the premise that a film is attached to the recording surface of a recorded matter.
- a base material (recording medium) whose surface is made of a hard or soft polyvinyl chloride polymer is preferred.
- the substrate (recording medium) whose surface is made of a polyvinyl chloride polymer include polyvinyl chloride substrates (films or sheets).
- the recording layer is a layer formed by volatilization of the solvent contained in the ink composition, and is a layer that mainly forms a desired image. Since the above ink composition has a resin-derived residual monomer content of 2000 ppm or less, it suppresses a decrease in ejection stability and has good member suitability for members constituting an inkjet head. A recording layer formed by evaporating the solvent contained in the ink composition provides a recorded matter with high image reproducibility.
- the layer formed by evaporating the solvent contained in the ink composition may be formed from a plurality of layers.
- a layer of colored inks (eg, yellow, magenta, cyan, black) of the composition may be formed.
- the recorded matter according to the present embodiment may further include a layer having a desired function on the upper surface of the ink composition layer.
- a layer having a desired function on the upper surface of the ink composition layer For example, an overcoat layer containing at least one of resin and wax may be formed for the purpose of further imparting abrasion resistance and glossiness to the recorded matter.
- a layer having an uneven surface may be formed by adding a filler or changing the film thickness for each pixel.
- a weather resistant layer containing an ultraviolet absorber, a light stabilizer, etc., a glittering layer containing a glittering pigment, or the like may be formed.
- a recorded matter including a recording layer formed from the ink composition described above has been described.
- a layer having a desired function may be formed by ejecting the above ink composition.
- a layer having a desired function may be formed by ejecting the above ink composition on the recording layer formed with the above ink composition.
- the apparatus according to the present embodiment includes an ink ejection section containing the above ink composition, and ejects the above ink composition onto a substrate.
- This apparatus is an apparatus for producing recorded matter by ejecting the above ink composition onto the surface of a substrate, and the above ink composition suppresses deterioration in ejection stability and has good suitability for members. Therefore, the apparatus according to the present embodiment is also an apparatus capable of producing a printed matter with high image reproducibility.
- the apparatus is preferably an inkjet recording apparatus capable of inkjet-discharging the ink composition onto a substrate.
- a conventionally known inkjet recording apparatus that ejects the above ink composition by an inkjet method can be used.
- inkjet printers such as VersaArt RE-640 and VersaCAMM VS300i (both manufactured by Roland DG Co.) can be used.
- An example of the configuration of the inkjet recording apparatus may be an on-carriage type serial printer type inkjet recording apparatus or an off-carriage type inkjet recording apparatus in which an ink cartridge is fixed to the outside.
- a line printer type inkjet recording apparatus that ejects an ink composition onto a recording medium (substrate) without moving the head may be used.
- the inkjet recording apparatus preferably includes a heating mechanism and a fixing mechanism for fixing the substrate.
- the solvent contained in the ink composition can be volatilized by drying the ink composition that has landed on the substrate (recording medium) by controlling the substrate surface temperature with a heating mechanism provided in the inkjet recording apparatus. It becomes possible.
- the fixing mechanism for fixing the base material makes it possible to dry the ink composition while the base material (recording medium) is fixed. You can prevent it from becoming
- the heating mechanism provided in the inkjet recording apparatus may be a pre-heater, a platen heater, an after-heater, or the like, and even if it is a mechanism that blows hot air to the recorded matter, it is a mechanism that heats the recorded matter with infrared rays or the like. There may be. Also, a plurality of these heating mechanisms may be combined.
- the fixing mechanism for fixing the base material may be a fixing mechanism that fixes the base material with a predetermined jig, or a fixing mechanism that sucks and adsorbs the base material using negative pressure, and is not particularly limited.
- the ink jet head for ejecting the ink composition may be a piezo ink jet head using a piezoelectric element or a thermal ink jet head using a heating element, and is not particularly limited.
- Synthetic resin [15] was obtained by changing 150 g of methyl methacrylate and 50 g of butyl methacrylate in synthetic resin [2] to 200 g of methyl methacrylate.
- Synthetic resin [16] was obtained by changing 150 g of methyl methacrylate and 50 g of butyl methacrylate in synthetic resin [2] to 200 g of butyl methacrylate.
- Synthetic resin [17] was obtained by changing 150 g of methyl methacrylate and 50 g of butyl methacrylate in synthetic resin [2] to 100 g of methyl methacrylate and 100 g of cyclohexyl acrylate.
- a mixture of 0.6 parts by mass of glycidyl methacrylate and 10.65 parts of hydroxypropyl acrylate was continuously injected for 5.4 hours to carry out a copolymerization reaction.
- the internal pressure of the autoclave reached 0.3 MPa, the residual pressure was released, the autoclave was cooled, and the resin slurry was taken out, filtered and dried to obtain a vinyl chloride copolymer resin.
- the obtained resin was dissolved in a mixed solvent having the same ratio as the ink composition (solid content: 20%), and the mixture was stirred at 60° C. for the time shown in Table 2.
- Vinyl chloride resin in Table 2 means "vinyl chloride-vinyl acetate copolymer resin”.
- Polyester-based resin 104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were placed in a round-bottomed flask and allowed to cool for 4 hours. The temperature was gradually raised to 240° C., and the esterification reaction was carried out while removing the distillate out of the system. After completion of the esterification reaction, the pressure was reduced to 10 mmHg over 30 minutes, and the temperature was raised to 250° C. for initial polymerization.
- Polyurethane-based resin 192.5 parts by mass of polycarbonate diol (PLAXEL CD-220: manufactured by Daicel), 41.6 parts by mass of isophorone diisocyanate (IPDI: manufactured by Evonik), and 100 parts by mass of ⁇ -butyrolactone (GBL) were placed in a round bottom flask. After mixing uniformly, a mixture of 0.01 parts by mass of T100BHJ (catalyst) and 0.09 parts by mass of ⁇ -butyrolactone (GBL) is added and reacted at 75 ° C. for 3 hours to form a prepolymer having an isocyanate group at the end. Obtained.
- ⁇ -butyrolactone 250 parts by mass of ⁇ -butyrolactone (GBL) was added to this and after uniformly dissolving, 12 parts by mass of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPD: manufactured by Evonik) was added to 100 parts by mass of ⁇ -butyrolactone (GBL).
- a dissolved chain extender solution was added and stirred at 60° C. for an additional 40 minutes. After that, a reaction terminator of 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) dissolved in 50 parts by mass of ⁇ -butyrolactone (GBL) was added, and finally 250 parts by mass of ⁇ -butyrolactone (GBL) was added.
- MIPA monoisopropanolamine
- the content of residual monomers derived from the resin was measured for the obtained resin solution by gas chromatography.
- NEXIS GC-2030 manufactured by Shimadzu Corporation
- FID flame ionization detector
- a glycol-based adsorbent was used with nitrogen as the carrier gas.
- a measurement sample was prepared by diluting 0.5 g of the sample with MEK to 10 mL. Quantification of the monomers was performed by the absolute calibration curve method, and all the monomers used in synthesizing each synthetic resin were used as standard samples.
- the residual monomer content of the resin was calculated from the measured values and shown in Tables 1 to 4.
- Ink compositions of Examples and Comparative Examples were prepared so that each organic solvent, resin, surface control agent (surfactant), dispersant, and pigment had the proportions shown in the table below.
- a pigment dispersion was prepared by dispersing a pigment and a dispersant in an organic solvent with zirconia beads using a paint shaker, and an ink composition was prepared so that the ratio of each component was as shown in the table below. .
- the unit is % by mass.
- Viscosity stability was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, first, the initial viscosities (Va) of the ink compositions of Examples and Comparative Examples were measured. After that, about 25 ml of the sample was placed in a brown glass bottle with a capacity of 30 ml and sealed, and the sample was stored at 60° C. for a period of 42 days. (Vb) was measured. Then, from the initial viscosity (Va) and the viscosity after storage (Vb), (Vb ⁇ Va)/Va ⁇ 100 (unit: %) was calculated to obtain the viscosity change rate.
- Viscosity change rate is less than 3%.
- Evaluation 4 The viscosity change rate is 3% or more and less than 5%.
- Evaluation 3 Viscosity change rate is 5% or more and less than 8%.
- Evaluation 2 The viscosity change rate is 8% or more and less than 10%.
- Evaluation 1 Viscosity change rate is 10% or more.
- Viscosity stability (heat cycle) Viscosity stability (heated storage) was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, in the above “viscosity stability (heated storage)", the storage conditions were changed from room temperature to 5°C/min. The temperature was raised to 60°C at a temperature elevation rate of , and a storage test was performed at 60°C for 3 days, and then -5°C/min. The temperature was lowered to ⁇ 20° C. at a temperature decrease rate of 20° C. and stored at ⁇ 20° C. for 3 days.
- Discharge stability was evaluated for the ink compositions of Examples and Comparative Examples. Ejection stability was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, an inkjet printer (VersaCAMM VS300i, manufactured by Roland DG Co., Ltd.) was filled with the ink compositions of Examples and Comparative Examples after being heated and stored (60°C, stored for 42 days). Print mode (360 x 360 dpi), substrate surface temperature 40°C, fine lines printed on recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac), and visually check for missing dots, flight deflection, and ink splattering.
- Evaluation Criteria Evaluation 5 Fine lines are correctly reproduced when confirmed visually and with a magnifying glass. Evaluation 4: Fine lines can be correctly reproduced visually. Evaluation 3: A slight bend is observed in the thin wire. Evaluation 2: The landing position is displaced and bending is observed. Evaluation 1: The displacement of the landing position is severe, and fine lines cannot be expressed.
- Discharge stability Ejection stability was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, in the above “discharge stability (heated storage)", the storage condition is changed from room temperature to 5°C/min. The temperature was raised to 60°C at a temperature elevation rate of , and a storage test was performed at 60°C for 3 days, and then -5°C/min. The temperature was lowered to ⁇ 20° C. at a temperature decrease rate of 20° C. and stored at ⁇ 20° C. for 3 days. Ejection stability was evaluated under the same conditions and evaluation criteria except that one cycle was changed from one cycle to normal temperature at a rate of temperature increase of . (Indicated as “discharge stability (heat cycle)" in the table).
- Printer member suitability test 1 The ink compositions of Examples and Comparative Examples were evaluated for member suitability (cured adhesive). Specifically, 0.2 g of an epoxy adhesive (two-liquid curing type epoxy adhesive "1500", manufactured by Cemedine Co., Ltd.) used for inkjet head members was dried at 60° C. for one day, It was immersed in the ink compositions of Examples and Comparative Examples, left at 60° C. for 1 week, and subjected to an immersion test to measure the weight change of the cured product (referred to as “Printer member suitability test 1” in the table). . Evaluation Criteria Evaluation 5: The weight change rate is less than 3%, and there is no deterioration of the material of the epoxy adhesive.
- Evaluation 4 The weight change rate is 3% or more and less than 5%, and there is no deterioration of the material of the epoxy adhesive.
- Evaluation 3 The weight change rate is 5% or more and less than 10%, and there is no deterioration of the material of the epoxy adhesive.
- Evaluation 2 The weight change rate is 10% or more and less than 15%, and there is no deterioration of the material of the epoxy adhesive.
- Evaluation 1 The weight change rate is 15% or more and/or the material of the epoxy adhesive is deteriorated.
- Printer member suitability test 2 The suitability for members (head cap member) was evaluated for the ink compositions of Examples and Comparative Examples. Specifically, 0.2 g of a cured product obtained by drying a silicon-based resin (one-liquid type liquid rubber “KE1831”, manufactured by Shin-Etsu Chemical Co., Ltd.) used for inkjet head members at 120° C. for 10 minutes was It was immersed in the ink composition of the comparative example and allowed to stand at 60° C. for 1 week to perform an immersion test to measure the weight change of the cured product (referred to as “printer member suitability test 2” in the table). Evaluation Criteria Evaluation 5: The rate of change in weight is less than 5%, and there is no deterioration of the silicone-based resin material.
- Evaluation 4 The weight change rate is 5% or more and less than 10%, and there is no deterioration of the silicone-based resin material.
- Evaluation 3 The weight change rate is 10% or more and less than 15%, and there is no deterioration of the silicone-based resin material.
- Evaluation 2 The weight change rate is 15% or more and less than 20%, and there is no deterioration of the silicone-based resin material.
- Evaluation 1 There is a weight change rate of 20% or more and/or deterioration of the silicon-based resin material.
- ink compositions in which the content of residual monomers derived from the resin is in the range of 2000 ppm or less in the total amount of the ink composition are excellent in ejection stability after heating storage and heat cycle storage conditions. , and is excellent in member suitability.
- the ink of Examples 1 to 7 in which the content of the residual monomer derived from the resin was in the range of 1000 ppm or less in the total amount of the ink composition was in the range of 1000 ppm or less in the total amount of the ink composition.
- the composition was even more excellent in ejection stability after heating storage and heat cycle storage conditions, and was even more excellent in member suitability.
- Example 1 containing ⁇ -butyrolactone examples 23 to 27 in which ⁇ -butyrolactone was replaced with an alkylamide solvent or a cyclic amide solvent, and Examples in which a lactone solvent different from ⁇ -butyrolactone was used.
- Nos. 28 and 29 were also excellent in ejection stability after storage under heating and storage under heat cycle conditions, and further excellent in suitability for members.
- Examples 1 to 7 and 47 to 51 which contain an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin and have different content ratios
- the content of the acrylic resin is Examples 1 to 7 and 46 to 49, which are in the range of 30% by mass or more and 100% by mass or less in the total amount of the resin, have further improved ejection stability after heating storage and heat cycle storage conditions compared to Example 50. It was excellent.
- the content of residual monomers derived from the resin is within the range of 2000 ppm or less in the total amount of the ink composition. By doing so, it was excellent in discharge stability after heating storage and heat cycle storage conditions, and excellent in member suitability.
- Comparative Examples 1 to 7 in which the content of the residual monomer derived from the resin was in the range of more than 2000 ppm in the total amount of the ink composition, had poor ejection stability after heating storage and heat cycle storage conditions, and member suitability. was not excellent.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Abstract
Description
Ra-(-O-Rb)n-O-Rc・・・(1)
(式(1)中、Ra、Rcは、それぞれ独立して、水素または炭素数1以上8以下の分岐しても良いアルキル基であり、Rbは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
Rd-(-O-Re)n-O-H・・・(2)
(式(2)中、Rd、は、炭素数1以上8以下の分岐しても良いアルキル基であり、Reは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
Rf-(-O-Rg)n-O-Rh・・・(3)
(式(3)中、Rf、Rhは、それぞれ独立して、炭素数1以上8以下の分岐しても良いアルキル基であり、Rgは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
本発明のインク組成物は、有機溶剤と、樹脂と、を含有するインクジェット法によって吐出されるインク組成物である。
以下では、本発明の具体的な実施形態(以下、「本実施の形態」という)を説明する。
本実施の形態に係るインク組成物は樹脂を含有する。樹脂は、記録層(記録物)に耐擦性を付与する。インク組成物は、水を意図的に含有させず、有機溶剤を含有するインク組成物であるので、この樹脂は、主に有機溶剤に溶解する形でインク組成物に含まれることになり、水中に分散する形で含まれる樹脂エマルジョンとは異なる。なお、本明細書において「樹脂」とは、主に記録層(記録物)に耐擦性を付与するバインダー樹脂を意味し、後述する色材(顔料)を含有させる分散剤(高分子分散剤)やシロキサン骨格を有する界面活性剤等の高分子の界面活性剤等とは異なるものである。
本実施の形態に係るインク組成物は、有機溶剤を含有する。有機溶剤は、インク組成物の液体の媒体であり、樹脂等の各成分を溶解(または分散)させる機能を有する。
(式(1)中、Ra、Rcは、それぞれ独立して、水素または炭素数1以上8以下の分岐しても良いアルキル基であり、Rbは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
(式(2)中、Rd、は、炭素数1以上8以下の分岐しても良いアルキル基であり、Reは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
(式(3)中、Rf、Rhは、それぞれ独立して、炭素数1以上8以下の分岐しても良いアルキル基であり、Rgは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。)
本実施の形態に係るインク組成物においては、ノズル部やチューブ内等の機器内でのインク組成物の揮発抑制、固化防止、又、固化した際の再溶解性を目的として、又、表面張力を低下させ記録媒体(基材)との濡れ性を向上させる目的で、また、塗膜の耐擦性向上を目的として、界面活性剤を含有させてもよい。
本実施の形態に係るインク組成物は、色材(有色の色材やブラックホワイトの色材を含む。)を含有する着色インクであってもよく、記録物(被体)をメタリック調にするための光輝性顔料(鱗片状金属粒子)を含むインクであってもよく、色材を含有しないクリアインクであってもよい。色材を含有しないクリアインクである場合には、所望の機能を有する層を形成するためのインクが挙げられる。このようなインクとしては、例えば、記録物(被体)を保護するオーバーコート層を形成するためのオーバーコートインク組成物や記録物(被体)の艶を消す艶消しインク組成物や耐候層を形成するための紫外線吸収剤や光安定化剤等を含むインク組成物、または接着性を有し、例えば基材と、箔などと、を接着させるためのインク組成物等が挙げられる。なお、これらのインク組成物は、色材を含有してもしていなくても良い。
本実施の形態に係るインク組成物において色材(顔料)を含有させる場合、必要に応じて分散剤を用いてもよい。分散剤としては、インク組成物において用いられている任意の分散剤を用いることができる。分散剤としては、高分子分散剤を用いるとよい。こうした分散剤としては、主鎖がポリエステル系、ポリアクリル系、ポリウレタン系、ポリアミン系、ポリカプロラクトン系などからなり、側鎖としてアミノ基、カルボキシル基、スルホン基、ヒドロキシル基などの極性基を有するものである。ポリアクリル系分散剤では、例えば、Disperbyk-2000、2001、2008、2009、2010、2020、2020N、2022、2025、2050、2070、2095、2150、2151、2155、2163、2164、BYKJET-9130、9131,9132,9133,9151(ビック・ケミー社製)、EfkaPX4310、PX4320、PX4330、PA4401、4402、PA4403、4570、7411、7477、PX4700、PX4701(BASF社製)、TREPLUS D-1200、D-1410、D-1420、MD-1000(大塚化学社製)、フローレンDOPA-15BHFS、17HF、22、G-700、900、NC-500、GW-1500(共栄社化学(株)製)、などが用いられる。ポリカプロラクトン系分散剤では、例えば、アジスパーPB821、PB822、PB881(味の素ファインテクノ(株)製)、ヒノアクトKF-1000、T-6000、T-7000、T-8000、T-8000E、T-9050(川研ファインケミカル(株)製)、Solsperse20000、24000、32000、32500、32550、32600、33000、33500、34000、35200、36000、37500、39000、71000、76400、76500、86000、88000、J180、J200(ルーブリゾール社製)、TEGO Dispers652、655、685、688、690(エボニック・ジャパン社製)などが用いられる。好ましい分散剤としては、BYKJET-9130、9131,9132,9133,9151、EfkaPX4310、PX4320、PX4330、PX4700、PX4701、Solsperse20000、24000、32000、33000、33500、34000、35200、39000、71000、76500、86000、88000、J180、J200、TEGO Dispers655、685、688、690などが用いられる。これらの単独、又はそれらの混合物を用いることができる。
本実施の形態に係るインク組成物において必要に応じて分散助剤を用いてもよい。分散助剤は色材(顔料)の表面に吸着し、官能基がインク組成物中の有機溶剤や分散剤との親和力を高め、分散安定性を向上させる。分散助剤としては、有機顔料残基に酸性基、塩基性基、中性基などの官能基を有する公知の顔料誘導体を用いることができる。
本実施の形態に係るインク組成物は、酸化防止剤や紫外線吸収剤等の安定剤、エポキシ化物等、多価カルボン酸、表面調整剤、スリップ剤、レベリング剤(アクリル系やシリコン系等)、消泡剤、pH調整剤、殺菌剤、防腐剤、防臭剤、電荷調整剤、湿潤剤等の公知の添加剤を任意成分として含んでもよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられる。具体的には、BHA(2,3-ブチル-4-オキシアニソール)、BHT(2,6-ジ-t-ブチル-p-クレゾール)等が例示される。また、紫外線吸収剤としてはベンゾフェノン系化合物、又はベンゾトリアゾール系化合物を用いることができる。また、エポキシ化物の具体例としては、エポキシグリセリド、エポキシ脂肪酸モノエステル、およびエポキシヘキサヒドロフタレートなどが例示され、具体的にはアデカサイザーO-130P、アデカサイザーO-180A(ADEKA社製)等が例示される。多価カルボン酸の具体例としては、クエン酸、マレイン酸などが例示される。
本実施の形態に係るインク組成物の粘度は、とくに限定されない。例えば、インクジェット吐出性、吐出安定性の点から、25℃での粘度が15.0mPa・s以下であることが好ましく、13.0mPa・sであることがより好ましく、10.0mPa・s以下であることがさらに好ましい。又、本実施の形態に係るインク組成物の粘度は、1.0mPa・s以上であることが好ましく、2.0mPa・s以上であることがより好ましく、3.0mPa・s以上であることがさらに好ましい。
本実施の形態に係るインク組成物の製造方法は、有機溶剤と、樹脂と、各種成分(例えば樹脂や色材等)とをペイントシェイカーを用いて混合することにより製造することができる。この際、ジルコニアビーズにて各成分を溶解又は分散させてもよい。なお必要に応じて、特定の溶媒に色材が分散された分散体を調整した後、他成分を加えてインク組成物を調整してもよい。なお、本実施の形態に係るインク組成物は、必要に応じて脱気処理するなどして所望の溶存酸素量や溶存窒素量に調整してもよい。
本実施の形態に係るインクセットは、上記のインク組成物を含むインクセットである。上記のインク組成物は、樹脂に由来する残留モノマーの含有量を2000ppm以下であることで、吐出安定性の低下を抑制し、かつインクジェットヘッドを構成する部材に対する部材適性も良好であることから、本実施の形態に係るインクセットにおいても吐出安定性の低下を抑制し部材適性も良好となる。
本実施の形態に係る記録方法は、上記のインク組成物を、基材の表面に塗布する記録方法である。上記のインク組成物は、樹脂に由来する残留モノマーの含有量を2000ppm以下であることで、吐出安定性の低下を抑制し、かつインクジェットヘッドを構成する部材に対する部材適性も良好であることから、本実施の形態に係るインク組成物を用いた記録方法においても吐出安定性の低下を抑制し部材適性も良好となって、画像再現性の高い記録物が得られる。
本実施の形態に係る記録物の製造方法は、上記のインク組成物を、基材の表面に塗布する記録方法である。上記のインク組成物は、樹脂に由来する残留モノマーの含有量を2000ppm以下であることで、吐出安定性の低下を抑制し、かつインクジェットヘッドを構成する部材に対する部材適性も良好であることから、本実施の形態に係る記録物の製造方法においても吐出安定性の低下を抑制し部材適性も良好となって、画像再現性の高い記録物が得られる。
本実施の形態に係る記録物は、基材と、基材上に形成されたインク組成物の層と、を備える。そして、インク組成物の層は、樹脂を含有し、樹脂に由来する残留モノマーの含有量は樹脂100質量部に対して4.0質量部以下であることを特徴とする。この記録物は、上記のインク組成物を、基材の表面にインクジェット吐出することで得られるものであり、上記のインク組成物は、吐出安定性の低下を抑制し部材適性も良好であるものであることから、本実施の形態に係る記録物においても画像再現性の高い記録物となる。
本実施の形態に係る記録方法に使用することのできる基材(記録媒体)としては、特に限定はされず、樹脂基材、金属板ガラスなどの非吸収性基材であっても、紙や布帛などの吸収性基材であっても、受容層を備える基材のような表面塗工が施された基材であってもよく、種々の基材を使用することができる。
記録層とは、上記のインク組成物に含まれる溶媒が揮発することにより形成される層であり、主に所望の画像を形成する層である。上記のインク組成物は、樹脂に由来する残留モノマーの含有量を2000ppm以下であることで、吐出安定性の低下を抑制し、かつインクジェットヘッドを構成する部材に対する部材適性も良好であることから、上記のインク組成物に含まれる溶媒が揮発することにより形成される記録層は、画像再現性の高い記録物が得られる。
本実施の形態に係る記録物は、さらに、インク組成物の層の上表面に所望の機能を有する層を備えてもよい。例えば、記録物に耐擦性や光沢性をさらに付与する目的で、樹脂、ワックスの少なくとも1つを含有するオーバーコート層が形成されていてもよい。また、フィラーを含有させ、又は膜厚をピクセル単位で変化させること等により、表面に凹凸感(マット面)を表現された層が形成されていてもよい。また、記録物に耐候性を付与するために、紫外線吸収剤や光安定化剤等を含む耐候層や光輝性顔料を含む光輝性層等が形成されていてもよい。
本実施の形態に係る装置は、上記のインク組成物を備えたインク吐出部を備え、上記のインク組成物を基材上に吐出する。この装置は、上記のインク組成物を、基材の表面に吐出することで記録物を製造する装置であり、上記のインク組成物は、吐出安定性の低下を抑制し部材適性も良好であるものであることから、本実施の形態に係る装置においても画像再現性の高い記録物が製造可能な装置となる。
(1)アクリル系樹脂
100℃に保たれたジエチレングリコールメチルエチルエーテル300g中に、メタクリル酸メチル150g及びメタクリル酸ブチル50gと所定量(表1に記載の量)のt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤)との混合物を1.5時間かけて滴下した。滴下終了後、合成樹脂[1]~[4]、[6]、[7]においてはt-ブチルパーオキシ-2-エチルヘキサノエート(重合開始剤)0.5gを表1に記載の回数追添加し、100℃で表1に記載した時間反応させた後冷却して、無色透明のメタクリル酸メチルの重合体溶液を得た。その後、合成樹脂[2]~[7]においては、ジエチレングリコールメチルエチルエーテルを追加して固形分35%のアクリル樹脂溶液を得た。一方で合成樹脂[1]においてはこの重合体溶液をヘキサン中に滴下し再沈殿、乾燥させることで、アクリル樹脂を得た。このアクリル樹脂を再度ジエチレングリコールメチルエチルエーテルに溶解し、固形分35%のアクリル樹脂溶液を得た。
撹拌装置を備えたオートクレーブに、窒素置換後、脱イオン水100質量部、メタノール40質量部、塩化ビニル32質量部、酢酸ビニル5質量部、グリシジルメタクリレート0.2質量部、ヒドロキシプロピルアクリレート3.55質量部、ヒドロキシプロピルメチルセルロース(懸濁剤)を0.1質量部、ジ-2-エチルヘキシルパーオキシジカーボネート(重合開始剤)を0.026質量部、ジ-3,5,5-トリメチルヘキサノールパーオキサイド(重合開始剤)0.58gを仕込み、窒素ガス雰囲気下に撹拌しながら63℃に昇温し、63℃に到達直後に塩化ビニル48質量部を6時間で、グリシジルメタクリレート0.6質量部、ヒドロキシプロピルアクリレート10.65部を混合したものを5.4時間で連続圧入し、共重合反応させた。オートクレーブ内圧が0.3MPaになった時点で残圧を抜き、冷却して樹脂スラリーを取り出し、ろ過、乾燥して塩化ビニル系共重合樹脂を得た。得られた樹脂をインク組成と同比率の混合溶剤中に溶解させ(固形分20%)、60℃で表2に記載された時間撹拌を続けた。
テレフタル酸104質量部、イソフタル酸104質量部、エチレングリコール79質量部、ネオペンチルグリコール89質量部、テトラブチルチタネート0.1質量部を丸底フラスコに仕込み、4時間かけて240℃まで徐々に昇温し、留出物を系外に除きながらエステル化反応を行った。エステル化反応終了後30分かけて10mmHgまで減圧、温度を250℃まで昇温し初期重合を行った。その後1mmHg以下で1時間後期重合を行い、ポリエステル系樹脂を得た。得られたポリエステル樹脂にジエチレングリコールメチルエチルエーテルを追加して固形分35%のポリエステル樹脂溶液を得た。
ポリカーボネートジオール(プラクセルCD-220:ダイセル製)192.5質量部とイソホロンジイソシアネート(IPDI:エボニック製)41.6質量部、γ-ブチロラクトン(GBL)100質量部を丸底フラスコに入れ均一に混合後、T100BHJ(触媒)0.01質量部とγ-ブチロラクトン(GBL)0.09質量部の混合液を入れ75℃で3時間反応させて末端にイソシアネート基をもつプレポリマーを得た。これにγ-ブチロラクトン(GBL)を250質量部投入し均一に溶解後、3アミノメチル3,5,5トリメチルシクロヘキシルアミン(IPD:エボニック製)12質量部をγ-ブチロラクトン(GBL)100質量部に溶解した鎖伸長剤溶液を添加し60℃でさらに40分撹拌した。その後モノイソプロパノールアミン(MIPA:ダイセル製)3.8質量部をγ-ブチロラクトン(GBL)50質量部に溶解した反応停止剤を添加し、最後にγ-ブチロラクトン(GBL)を250質量部添加して固形分25.0%のポリウレタン溶液を得た。
それぞれの有機溶剤、樹脂、表面調整剤(界面活性剤)、分散剤、顔料を下記表の割合になるように実施例及び比較例のインク組成物を作製した。具体的には、ペイントシェイカーを用いてジルコニアビーズにて顔料および分散剤を有機溶剤中に分散させた顔料分散体を作製し、各成分が下記表の割合になるようにインク組成物を調製した。単位は質量%である。
(1)粘度安定性(加温保管)
実施例及び比較例のインク組成物について粘度安定性(加温保管)を評価した。具体的には、まず実施例及び比較例のインク組成物について初期粘度(Va)を測定した。その後、およそ25mlを容量30mlの褐色ガラスびんへ入れ密栓した試料を、60℃、保管期間を42日とし、保管試験後の実施例及び比較例のインク組成物について再度同様の条件で保管後粘度(Vb)を測定した。そして、初期粘度(Va)及び保管後粘度(Vb)から、(Vb-Va)/Va×100(単位は%)を計算し、粘度変化率を求めた。なお、インク組成物の粘度は、落球式粘度計(アントンパール社製AMVn)を用いて、25℃の条件下で測定した。(表中、「粘度安定性(加温保管)」と表記)。
評価基準
評価5:粘度変化率が3%未満である。
評価4:粘度変化率が3%以上5%未満である。
評価3:粘度変化率が5%以上8%未満である。
評価2:粘度変化率が8%以上10%未満である。
評価1:粘度変化率が10%以上である。
実施例及び比較例のインク組成物について粘度安定性(加温保管)を評価した。具体的には、上記の「粘度安定性(加温保管)」において、保管条件を常温から5℃/min.の昇温速度で60℃まで昇温させて、保管試験を60℃3日で行った後、-5℃/min.の降温速度で-20℃まで降温させて-20℃3日間保管を行い、再び5℃/min.の昇温速度で常温まで昇温する内容を1サイクルとしたものを4サイクルに変更させて行ったこと以外同様に初期粘度(Va)及び保管後粘度(Vb)を求め、(Vb-Va)/Va×100(単位は%)を計算し、粘度変化率を求めた。評価基準は、上記「粘度安定性(加温保管)」と同様の基準で評価した。(表中、「粘度安定性(ヒートサイクル)」と表記)。
実施例及び比較例のインク組成物について吐出安定性を評価した。実施例及び比較例のインク組成物について吐出安定性を評価した。具体的には、インクジェットプリンター(VersaCAMM VS300i、ローランドDG(株)製)に加温保管(60℃、42日保管)後の実施例及び比較例のインク組成物を充填して、双方向の高速印刷モード(360x360dpi)、基材表面温度40℃で、記録媒体(糊付きポリ塩化ビニルフィルム(IMAGin JT5829R:MACtac社製)に細線を印刷し、ドット抜け、飛行曲がり、インクの飛び散りの有無を目視およびルーペ(×25)で確認して評価した(表中、「吐出安定性(加温保管)」と表記)。
評価基準
評価5:目視およびルーペで確認した際、細線が正しく再現できている。
評価4:目視で細線が正しく再現できている。
評価3:わずかに細線に曲がりが見られる。
評価2:着弾位置がずれており、曲がりが見られる。
評価1:着弾位置のずれが酷く、細線を表現できない。
実施例及び比較例のインク組成物について吐出安定性を評価した。具体的には、具体的には、上記の「吐出安定性(加温保管)」において、保管条件を常温から5℃/min.の昇温速度で60℃まで昇温させて、保管試験を60℃3日で行った後、-5℃/min.の降温速度で-20℃まで降温させて-20℃3日間保管を行い、再び5℃/min.の昇温速度で常温まで昇温する内容を1サイクルとしたものを4サイクルに変更させて行ったこと以外同様の条件、評価基準で吐出安定性の評価を行った。(表中、「吐出安定性(ヒートサイクル)」と表記)。
実施例及び比較例のインク組成物について部材適性(接着剤の硬化物)を評価した。具体的には、インクジェットヘッドの部材に使用されるエポキシ接着剤(2液硬化型エポキシ接着剤「1500」、セメダイン(株)製)を60℃1日乾燥させた硬化物、0.2gを、実施例及び比較例のインク組成物に浸漬して、60℃で1週間放置して、浸漬試験を行い、硬化物の重量変化を測定した(表中、「プリンター部材適性試験1」と表記)。
評価基準
評価5:重量変化率が3%未満で、エポキシ接着剤の材質の劣化がない。
評価4:重量変化率が3%以上5%未満で、エポキシ接着剤の材質の劣化がない。
評価3:重量変化率が5%以上10%未満で、エポキシ接着剤の材質の劣化がない。
評価2:重量変化率が10%以上15%未満で、エポキシ接着剤の材質の劣化がない。
評価1:重量変化率が15%以上及び/又は、エポキシ接着剤の材質の劣化がある。
実施例及び比較例のインク組成物について部材適性(ヘッドキャップ部材)を評価した。具体的には、インクジェットヘッドの部材に使用されるシリコン系樹脂(一液型液状ゴム「KE1831」、信越化学社製)を120℃10分乾燥させた硬化物、0.2gを、実施例及び比較例のインク組成物に浸漬して、60℃で1週間放置して、浸漬試験を行い、硬化物の重量変化を測定した(表中、「プリンター部材適性試験2」と表記)。
評価基準
評価5:重量変化率が5%未満で、シリコン系樹脂の材質の劣化がない。
評価4:重量変化率が5%以上10%未満で、シリコン系樹脂の材質の劣化がない。
評価3:重量変化率が10%以上15%未満で、シリコン系樹脂の材質の劣化がない。
評価2:重量変化率が15%以上20%未満で、シリコン系樹脂の材質の劣化がない。
評価1:重量変化率が20%以上及び/又は、シリコン系樹脂の材質の劣化がある。
Claims (18)
- 樹脂と、有機溶剤と、を含み、インクジェット法によって吐出されるインク組成物であって、
前記樹脂は、アクリル系樹脂、又は塩化ビニル-酢酸ビニル共重合体樹脂の少なくとも1つ以上を含有し、
前記樹脂に由来する残留モノマーの含有量はインク組成物全量中2000ppm以下である
インク組成物。 - 前記樹脂は、さらに、塩化ビニル系樹脂、酢酸ビニル系樹脂、ポリエステル系樹脂、及びポリウレタン系樹脂からなる群より選択される少なくとも1つ以上の重合体又は共重合体を含む
請求項1に記載のインク組成物。 - 前記樹脂は、アクリル系樹脂を含有し、
前記アクリル系樹脂の含有量は、前記インク組成物に含まれる樹脂全量中30質量%以上100質量%以下の範囲である
請求項1又は2に記載のインク組成物。 - 前記樹脂の含有量は、インク組成物全量中1.0質量%以上20.0質量%以下の範囲である
請求項1から3のいずれかに記載のインク組成物。 - 前記樹脂の重量平均分子量Mwは、10000以上60000以下の範囲である
請求項1から4のいずれかに記載のインク組成物。 - 前記有機溶剤は、下記式(1)で表されるグリコールエーテル系溶剤を含有する
請求項1から5のいずれかに記載のインク組成物。
Ra-(-O-Rb)n-O-Rc・・・(1)
(式(1)中、Ra、Rcは、それぞれ独立して、水素または炭素数1以上8以下の分岐しても良いアルキル基であり、Rbは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。) - 前記グリコールエーテル系溶剤は、下記式(2)で表されるグリコールエーテルモノアルキルを含有する
請求項6に記載のインク組成物。
Rd-(-O-Re)n-O-H・・・(2)
(式(2)中、Rd、は、炭素数1以上8以下の分岐しても良いアルキル基であり、Reは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。) - 前記グリコールエーテル系溶剤は、下記式(3)で表されるグリコールエーテルジアルキルを含有する
請求項6又は7に記載のインク組成物。
Rf-(-O-Rg)n-O-Rh・・・(3)
(式(3)中、Rf、Rhは、それぞれ独立して、炭素数1以上8以下の分岐しても良いアルキル基であり、Rgは炭素数1以上4以下の分岐しても良いアルキレン基を表す。nは1以上6以下の整数を表す。) - 請求項1から13のいずれかに記載のインク組成物を含む
インクセット。 - 請求項1から14のいずれかに記載のインク組成物を基材上に吐出する
記録方法。 - 請求項1から14のいずれかに記載のインク組成物を基材上に吐出する工程を含む
記録物の製造方法。 - 請求項1から14のいずれかに記載のインク組成物を備えたインク吐出部を備え、
請求項1から14のいずれかに記載のインク組成物を基材上に吐出する
装置。 - 基材と、
前記基材上に形成されたインク組成物の層と、
を備え、
前記インク組成物の層は、樹脂を含有し、
前記樹脂は、アクリル系樹脂、又は塩化ビニル-酢酸ビニル共重合体樹脂の少なくとも1つ以上を含有し、
前記樹脂に由来する残留モノマーの含有量は樹脂100質量部に対して4.0質量部以下である
記録物。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18/689,816 US20240384119A1 (en) | 2021-10-21 | 2022-10-12 | Ink composition, ink set, recording method, method for producing recorded matter, and recorded matter |
| CN202280060165.0A CN117957289A (zh) | 2021-10-21 | 2022-10-12 | 油墨组合物、油墨组、记录方法、记录物的制造方法和记录物 |
| EP22883446.1A EP4421135A1 (en) | 2021-10-21 | 2022-10-12 | Ink composition, ink set, recording method, method for producing recorded matter, and recorded matter |
| JP2023554583A JPWO2023068142A1 (ja) | 2021-10-21 | 2022-10-12 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021172307 | 2021-10-21 | ||
| JP2021-172307 | 2021-10-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023068142A1 true WO2023068142A1 (ja) | 2023-04-27 |
Family
ID=86059188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/038071 Ceased WO2023068142A1 (ja) | 2021-10-21 | 2022-10-12 | インク組成物、インクセット、記録方法、記録物の製造方法、及び記録物 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20240384119A1 (ja) |
| EP (1) | EP4421135A1 (ja) |
| JP (2) | JPWO2023068142A1 (ja) |
| CN (1) | CN117957289A (ja) |
| TW (1) | TW202323451A (ja) |
| WO (1) | WO2023068142A1 (ja) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51119784A (en) * | 1975-03-28 | 1976-10-20 | Rhone Poulenc Ind | Method of degasing vinylchloride base polymer |
| JPS5225890A (en) * | 1975-08-22 | 1977-02-26 | Denki Kagaku Kogyo Kk | Process for producing vinyl chloride copolymers |
| JPS546089A (en) * | 1977-06-16 | 1979-01-17 | Toyo Ink Mfg Co Ltd | Preparation of aqueous acrylic resin dispersion |
| JP2002265831A (ja) * | 2001-03-13 | 2002-09-18 | Ricoh Co Ltd | インク組成物及びそれを使用する記録方法 |
| JP2007131838A (ja) * | 2005-10-11 | 2007-05-31 | Sekisui Chem Co Ltd | アクリル系重合体の製造方法、アクリル系重合体、アクリル系粘着組成物及び粘着テープ |
| JP2007169492A (ja) | 2005-12-22 | 2007-07-05 | Seiko Epson Corp | インクジェット記録用油性インク組成物 |
| JP2017031272A (ja) * | 2015-07-30 | 2017-02-09 | サカタインクス株式会社 | 非水性インクジェット用インク組成物 |
| JP2018095688A (ja) * | 2016-12-09 | 2018-06-21 | サカタインクス株式会社 | 非水性インクジェット用インク組成物 |
| WO2021201149A1 (ja) * | 2020-03-31 | 2021-10-07 | 株式会社Dnpファインケミカル | 非水性インク組成物、インクジェット記録方法及び印刷物の製造方法 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1469046A4 (en) * | 2001-12-25 | 2005-03-16 | Konishiroku Photo Ind | Aqueous ink and its preparation |
| JP2003342507A (ja) * | 2002-05-30 | 2003-12-03 | Konica Minolta Holdings Inc | 水性インク、水性インクの製造方法及びそれを用いた画像形成方法 |
| JP5163847B2 (ja) * | 2004-05-06 | 2013-03-13 | Jsr株式会社 | 硬化性樹脂組成物、保護膜およびその形成方法 |
| JP2006077177A (ja) * | 2004-09-10 | 2006-03-23 | Fuji Xerox Co Ltd | インクジェット記録用分散液、インクジェット記録用インク及びインクジェット記録装置 |
| JP2009007560A (ja) * | 2007-05-28 | 2009-01-15 | Mitsubishi Chemicals Corp | 着色硬化性樹脂組成物、カラーフィルタ、液晶表示装置及び有機elディスプレイ |
| JP2009001691A (ja) * | 2007-06-22 | 2009-01-08 | The Inctec Inc | インクジェット記録用油性インク組成物 |
| US8177356B2 (en) * | 2007-11-14 | 2012-05-15 | Konica Minolta Ij Technologies, Inc | Non-aqueous ink-jet ink and ink-jet recording method |
| EP2990441B1 (en) * | 2013-04-22 | 2020-03-04 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous emulsion solution, coloring agent composition containing said aqueous solution, aqueous inkjet ink, and method for producing aqueous emulsion solution |
| JP6596983B2 (ja) * | 2015-07-01 | 2019-10-30 | セイコーエプソン株式会社 | インクジェットインク組成物 |
| WO2018061581A1 (ja) * | 2016-09-29 | 2018-04-05 | 富士フイルム株式会社 | インクジェット用液体組成物、及び、インクジェット記録方法 |
| JPWO2020004228A1 (ja) * | 2018-06-26 | 2021-08-02 | 富士フイルム株式会社 | インク、インクカートリッジ、インクセット、インクジェットプリンタ及びインクジェット捺染方法 |
| JP2022072990A (ja) * | 2020-10-30 | 2022-05-17 | 株式会社パイロットコーポレーション | 摩擦具及び熱変色性筆記具 |
-
2022
- 2022-10-12 WO PCT/JP2022/038071 patent/WO2023068142A1/ja not_active Ceased
- 2022-10-12 CN CN202280060165.0A patent/CN117957289A/zh active Pending
- 2022-10-12 JP JP2023554583A patent/JPWO2023068142A1/ja active Pending
- 2022-10-12 JP JP2022164197A patent/JP7288545B2/ja active Active
- 2022-10-12 US US18/689,816 patent/US20240384119A1/en active Pending
- 2022-10-12 EP EP22883446.1A patent/EP4421135A1/en active Pending
- 2022-10-14 TW TW111138955A patent/TW202323451A/zh unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51119784A (en) * | 1975-03-28 | 1976-10-20 | Rhone Poulenc Ind | Method of degasing vinylchloride base polymer |
| JPS5225890A (en) * | 1975-08-22 | 1977-02-26 | Denki Kagaku Kogyo Kk | Process for producing vinyl chloride copolymers |
| JPS546089A (en) * | 1977-06-16 | 1979-01-17 | Toyo Ink Mfg Co Ltd | Preparation of aqueous acrylic resin dispersion |
| JP2002265831A (ja) * | 2001-03-13 | 2002-09-18 | Ricoh Co Ltd | インク組成物及びそれを使用する記録方法 |
| JP2007131838A (ja) * | 2005-10-11 | 2007-05-31 | Sekisui Chem Co Ltd | アクリル系重合体の製造方法、アクリル系重合体、アクリル系粘着組成物及び粘着テープ |
| JP2007169492A (ja) | 2005-12-22 | 2007-07-05 | Seiko Epson Corp | インクジェット記録用油性インク組成物 |
| JP2017031272A (ja) * | 2015-07-30 | 2017-02-09 | サカタインクス株式会社 | 非水性インクジェット用インク組成物 |
| JP2018095688A (ja) * | 2016-12-09 | 2018-06-21 | サカタインクス株式会社 | 非水性インクジェット用インク組成物 |
| WO2021201149A1 (ja) * | 2020-03-31 | 2021-10-07 | 株式会社Dnpファインケミカル | 非水性インク組成物、インクジェット記録方法及び印刷物の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202323451A (zh) | 2023-06-16 |
| US20240384119A1 (en) | 2024-11-21 |
| JP7288545B2 (ja) | 2023-06-07 |
| EP4421135A1 (en) | 2024-08-28 |
| CN117957289A (zh) | 2024-04-30 |
| JP2023062679A (ja) | 2023-05-08 |
| JPWO2023068142A1 (ja) | 2023-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US12338356B2 (en) | Nonaqueous ink composition, and recording method and recorded matter manufacturing method using same | |
| JP7175410B1 (ja) | インク組成物、インクセット、記録物、記録方法、及び記録物の製造方法 | |
| JP7741650B2 (ja) | インクセット、記録物、記録方法、及び記録物の製造方法 | |
| JP7288545B2 (ja) | インク組成物、インクセット、記録方法、記録物の製造方法、及び記録物 | |
| CN116888225B (zh) | 非水性油墨组合物、使用该非水性油墨组合物的记录方法以及记录物的制造方法 | |
| JP7168808B1 (ja) | インク組成物、インクセット、記録方法、記録物の製造方法、及び記録物 | |
| JP7204963B2 (ja) | 記録方法及びその記録方法に用いられるインク組成物 | |
| JP7741651B2 (ja) | インクセット、記録物、記録方法、及び記録物の製造方法 | |
| WO2022211028A1 (ja) | 非水性インク組成物、記録方法、及び記録物の製造方法 | |
| JP7110507B1 (ja) | 非水性インク組成物、それを用いた記録方法、及び記録物の製造方法 | |
| JP7229415B2 (ja) | 非水性インク組成物、それを用いた記録方法、及び記録物の製造方法 | |
| JP7161569B2 (ja) | 非水性インク組成物、それを用いた記録方法、及び記録物の製造方法 | |
| JP7698449B2 (ja) | 非水性インク組成物、それを用いた記録方法及び記録物の製造方法 | |
| JP7031035B1 (ja) | 非水性インク組成物、それを用いた記録方法及び記録物の製造方法 | |
| JP7031036B1 (ja) | 非水性インク組成物、それを用いた記録方法及び記録物の製造方法 | |
| JP2022157934A (ja) | 非水性インク組成物、インクジェット記録方法及び印刷物の製造方法 | |
| WO2022259743A1 (ja) | インク組成物、インクセット、記録物、記録方法、及び記録物の製造方法 | |
| JP2022188479A (ja) | インク組成物、インクセット、記録物、記録方法、及び記録物の製造方法 | |
| WO2023054474A1 (ja) | 非水系粘着性組成物、記録方法、記録物の製造方法、組成物のセット、装置、及び記録物 | |
| WO2023127740A1 (ja) | インクセット | |
| WO2023054472A1 (ja) | 非水系粘着性組成物、記録方法、記録物の製造方法、組成物のセット、及び記録物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22883446 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 202280060165.0 Country of ref document: CN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 18689816 Country of ref document: US |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2023554583 Country of ref document: JP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2022883446 Country of ref document: EP |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2022883446 Country of ref document: EP Effective date: 20240521 |