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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—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
  • C09D11/02—Printing inks
  • C09D11/14—Printing inks based on carbohydrates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
  • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
• • 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

Definitions

• the present invention relates to a non-aqueous ink composition, an inkjet recording method, and a method for producing a printed matter.
• an ink composition a non-aqueous ink composition in which various coloring materials are dissolved or dispersed in a mixed solution with an organic solvent is widely used. Characters and images can be obtained by applying this ink composition directly or via another layer to a substrate such as paper by an inkjet method or the like, adhering the ink composition, and drying the non-aqueous ink composition.
• Patent Document 1 discloses a technique relating to an inkjet ink containing colored resin particles containing a resin, a nonionic surfactant, and a non-aqueous solvent. This Patent Document 1 describes that the printed matter is excellent in scratch resistance and color development, and that foreign matter can be prevented from being generated in the container of the dispersion.
• the present invention provides a non-aqueous ink composition which is excellent in printing performance such as continuous ejection stability, has good storage stability, has good color development property, and can obtain a printed matter having excellent resistance.
• the purpose is to do.
• the present inventors have conducted extensive research in order to solve the above-mentioned problems, and as a result, by controlling the content of the resin exhibiting a predetermined intrinsic viscosity in the non-aqueous ink composition containing the resin, the above-mentioned problems. We have found that it is possible to solve the problem, and have completed the present invention.
• the organic solvent contains at least one selected from the group consisting of a glycol ether solvent, an amide solvent, a lactone solvent, and a carbonate solvent.
• An inkjet recording method for ejecting the non-aqueous ink composition according to any one of (1) to (4) onto the surface of a medium by an inkjet method.
• a method for producing a printed matter which comprises a step of ejecting the non-aqueous ink composition according to any one of (1) to (4) onto the surface of a medium by an inkjet method.
• a non-aqueous ink composition capable of obtaining a printed matter having excellent printing performance such as continuous ejection stability, good storage stability, good color development, and excellent resistance.
• the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition that contains an organic solvent, a coloring material, and a resin and is ejected by an inkjet method.
• the non-aqueous ink composition means an ink composition containing an organic solvent produced without intentionally containing water, unlike an aqueous ink composition containing water as a main component. ..
• the resin contains at least one selected from the group consisting of an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, and a cellulosic resin, and the resin has an inherent viscosity at 25 ° C. It is characterized in that the amount of resin of 90 mL / g or more is 5% by mass or less in the total amount of the resin.
• the specific viscosity in the present specification is the specific viscosity [ ⁇ SP ] after the target resin is dispersed in a developing solvent and the molecules contained in the resin are separated by a column packed with granular gel in GPC (gel permeation chromatography). (( ⁇ - ⁇ 0 ) / ⁇ 0 ( ⁇ 0 : solvent viscosity, ⁇ : solution viscosity)) and the concentration C were obtained, and the concentration C was extrapolated to 0 in the formula Lim ([ ⁇ SP ] / C) (C). ⁇ 0) It can be obtained by doing.
• the developing solvent is not particularly limited, but for example, tetrahydrofuran can be used.
• Such an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, and a resin containing a cellulose resin exhibit a plurality of intrinsic viscosities, and a resin having an intrinsic viscosity of 90 mL / g or more is 5% by mass in the total amount of the resin. It has been clarified by the studies of the present inventors that the ejection stability and the like when ejected by the inkjet method is lowered by including the resin in a ratio of more than%.
• the non-aqueous ink composition is controlled so that the content of the resin having an intrinsic viscosity at 25 ° C. of 90 mL / g or more is 5% by mass or less in the total amount of the resin, the printing performance such as continuous ejection stability can be improved. It is possible to obtain a printed matter having excellent and good storage stability, good color development property, and excellent resistance.
• the content of the resin having an intrinsic viscosity of 90 mL / g or more at 25 ° C. may be 5.0% by mass or less based on the total amount of the resin, but is preferably 4.0% by mass or less, preferably 3.5% by mass. It is more preferably less than or equal to, and most preferably 2.5% by mass or less.
• the lower limit of the content of the resin having an intrinsic viscosity of 90 mL / g or more at 25 ° C. is not particularly limited, and for example, even if it is 0% by mass in the total amount of the resin, the effect of the present invention can be obtained. Among them, if the content of the resin having an intrinsic viscosity of 90 mL / g or more at 25 ° C.
• the solid filling becomes good. From the viewpoint of solid filling property, it is most preferable that the content of the resin having an intrinsic viscosity at 25 ° C. of 90 mL / g or more is 1.0% by mass or more in the total amount of the resin. If the content of the resin having an intrinsic viscosity of 90 mL / g or more at 25 ° C. exceeds 5.0% by mass in the total amount of the resin, the solid filling deteriorates, and if it becomes 8.2% by mass or more, unevenness is observed in the solid printed portion. Will be able to.
• the content of the resin having an intrinsic viscosity of 100 mL / g or more at 25 ° C. is control the content of the resin having an intrinsic viscosity of 100 mL / g or more at 25 ° C. to a predetermined amount, and the content of the resin having an intrinsic viscosity of 100 mL / g or more at 25 ° C. is 3.0% by mass or less in the total amount of the resin. It is preferably 2.0% by mass or less, and more preferably 2.0% by mass or less.
• the lower limit of the content of the resin having an intrinsic viscosity of 100 mL / g or more at 25 ° C. is not particularly limited and may be, for example, 0% by mass based on the total amount of the resin, but the intrinsic viscosity at 25 ° C.
• the content of the above resin is 0.2% by mass or more in the total amount of the resin, satellite droplets are generated in the ink droplets of the non-aqueous ink composition ejected by the inkjet method, and the solid filling when printing the image is performed. It will be good. From the viewpoint of solid filling property, it is most preferable that the content of the resin having an intrinsic viscosity at 25 ° C. of 100 mL / g or more is 0.5% by mass or more in the total amount of the resin.
• the resin, the organic solvent, the coloring material, and other additives contained in the non-aqueous ink composition according to the present embodiment will be described.
• the non-aqueous ink composition of the present embodiment contains a resin.
• the resin contains at least one selected from the group consisting of an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, and a cellulosic resin. Discharge stability, water resistance and solvent resistance can be improved by containing at least one selected from the group consisting of acrylic resins, vinyl chloride-vinyl acetate copolymer resins, and cellulosic resins. can.
• These acrylic resins, vinyl chloride-vinyl acetate copolymer resins, and cellulosic resins are binder resins that form a so-called coating film, and are distinct from polymer dispersants that disperse coloring materials (pigments). Will be done.
• the acrylic resin is not particularly limited as long as it is contained as the main component of the monomer constituting the (meth) acrylic acid ester monomer.
• the acrylic resin may be a homopolymer of one kind of radically polymerizable monomer, or may be any of a copolymers in which two or more kinds of radically polymerizable monomers are selected and used.
• the preferable acrylic resin as the oil-based ink composition according to the above form is a polymer of methyl methacrylate alone, 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 vinyl chloride-vinyl acetate copolymer resin is a polymer of a vinyl chloride monomer and a vinyl acetate monomer.
• Examples of the vinyl chloride vinyl acetate-based copolymer resin include vinyl chloride vinyl acetate copolymer, vinyl chloride / vinyl acetate / maleic acid copolymer, vinyl chloride / vinyl acetate / vinyl alcohol copolymer, and vinyl chloride / vinyl acetate. / Hydroxyalkyl acrylate copolymers and the like, and mixtures thereof.
• the vinyl chloride-vinyl acetate copolymer resin can be obtained by polymerizing a vinyl chloride monomer and a vinyl acetate monomer.
• the polymerization method may be any conventionally known polymerization method.
• the method of polymerization is preferably emulsion polymerization or suspension polymerization, and more preferably suspension polymerization.
• Cellulose-based resin is a resin having a cellulosic skeleton obtained by biologically or chemically introducing a functional group using cellulose as a raw material.
• a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin, a cellulose acetate resin, a nitrocellulose resin and a mixture thereof can be used.
• a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin, a cellulose acetate resin, a nitrocellulose resin and a mixture thereof can be used.
• a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin,
• acrylic resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins may be used alone, but it is preferable to use a mixture of the two, and the acrylic resin and chloride are used. It is more preferable to use a resin in which a vinyl-vinyl acetate copolymer resin is mixed.
• a resin in which a vinyl-vinyl acetate copolymer resin is mixed it is possible to control so as to satisfy the requirements such as color development, drying property, coating material properties, printability, etc. required for the non-aqueous ink.
• the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin are mixed, the mixing ratio is not particularly limited and can be appropriately changed.
• the content of the vinyl chloride-vinyl acetate copolymer resin is preferably 80:20 to 20:80, preferably 70:30 to 30. : 70 is more preferable.
• the content of the acrylic resin, vinyl chloride-vinyl acetate copolymer resin, and cellulosic resin is preferably 90% by mass or more, more preferably 95% by mass or more, and 99% by mass, based on the total amount of the resin. The above is more preferable.
• the weight average molecular weight (relative molecular mass) of the resin is preferably 5000 or more, and more preferably 15000 or more.
• the weight average molecular weight (relative molecular weight) is preferably 100,000 or less, and more preferably 50,000 or less.
• the relative molecular weight of the resin can be measured by ordinary GPC (gel permeation chromatography).
• the resin contained in the non-aqueous ink composition is preferably contained in a proportion of 3.0% by mass or more, more preferably 5.0% by mass or more, based on the total amount of the non-aqueous ink composition. It is more preferable to contain it in a proportion of 5.5% by mass or more.
• the resin contained in the non-aqueous ink composition is preferably contained in a proportion of 13.0% by mass or less, more preferably 11.0% by mass or less, based on the total amount of the non-aqueous ink composition. It is more preferably contained in a proportion of 8.5% by mass or less.
• the resin contained in the non-aqueous ink composition having an intrinsic viscosity of 90 mL / g or more is preferably 0.35% by mass or less, and preferably 0.25% by mass or less, based on the total amount of the non-aqueous ink composition. Is more preferable, and 0.20% by mass or less is further preferable.
• the resin contained in the non-aqueous ink composition having an intrinsic viscosity of 90 mL / g or more is preferably 0% by mass or more, more preferably 0.10% by mass or more, based on the total amount of the non-aqueous ink composition.
• the ink composition is not particularly limited and may be, for example, 0% by mass in the total amount of the ink composition, but the intrinsic viscosity at 25 ° C. is 90 mL.
• the content of the resin of / g or more is 0.1% by mass or more in the total amount of the ink composition, satellite droplets are generated in the ink droplets of the non-aqueous ink composition ejected by the inkjet method and the image is printed. The solid filling is good.
• the resin contained in the non-aqueous ink composition having an intrinsic viscosity of 100 mL / g or more is preferably 0.20% by mass or less, more preferably 0.15% by mass or more, based on the total amount of the non-aqueous ink composition. It is preferably 0.10% by mass or more, and more preferably 0.10% by mass or more.
• the lower limit of the content of the resin having an intrinsic viscosity of 100 mL / g or more at 25 ° C. is not particularly limited and may be, for example, 0% by mass in the total amount of the ink composition, but the intrinsic viscosity at 25 ° C. is 100 mL.
• the content of the resin having an intrinsic viscosity of 90 mL / g or more in the total amount of the ink composition is "the content of the resin having the intrinsic viscosity of 90 mL / g or more in the total amount of the resin" and "the content of the resin in the total amount of the ink composition". It can be calculated by the product of "quantity”.
• the non-aqueous ink composition When a plurality of types of resins are contained in the non-aqueous ink composition, it can be obtained by adding the contents of 90 mL / g or more of the resins contained in each resin. The same applies to the content of the resin having an intrinsic viscosity of 100 mL / g or more in the total amount of the ink composition.
• the resin contained in the non-aqueous ink composition of the present embodiment may contain a resin other than an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, and a cellulosic resin.
• resins include polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, polyethylene resins, urethane resins, rosin-modified resins, phenyl resins, terpene resins, polyamide resins, and vinyltoluene- ⁇ -methylstyrene copolymer weights.
• ethylene-vinyl acetate-based copolymer silicone (silicon) resin, acrylamide resin, epoxy resin, or a copolymer resin or mixture thereof can be used.
• a resin other than the acrylic resin, the vinyl chloride-vinyl acetate copolymer resin, and the cellulosic resin it is a polymer dispersant that disperses the coloring material (pigment) contained in the non-aqueous ink composition. May be good.
• the main chain is composed of polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaprolactone-based, etc.
• the side chain is a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group.
• polyacrylic dispersants include 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 BIC Chemie) are used.
• polycaprolactone-based dispersant for example, azisper PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) are used.
• Preferred dispersants are polyester-based dispersants, such as Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 (manufactured by Kawaken Fine Chemical Co., Ltd.), Solspace 20000, and the like.
• the organic solvent can disperse or dissolve each component contained in the non-aqueous ink composition according to the present embodiment.
• alkyl alcohols having 1 to 5 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol and n-pentanol;
• Monohydric alcohols such as 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, 3-methoxy-n-butanol; 1-dimethylformamide, dimethylacetamide , 3-methoxypropanamide, 3-butoxypropanamide, N, N-dimethyl-3-methoxypropanamide, N, N-dibutyl-3-methoxypropanamide, N, N-dibutyl-3-methoxypropanamide, N, N-d
• Monoalkyl ethers diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, di Dialkyl ethers of polyhydric alcohols such as propylene glycol dimethyl ether and dipropylene glycol diethyl ether; monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyl Alkanolamines such as diethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-
• organic solvents it is preferable to contain at least one selected from the group consisting of glycol ether solvents, amide solvents, lactone solvents, and carbonate solvents.
• glycol ether-based solvent examples include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, ethylene glycol butyl ether acetate, diethylene glycol methyl butyl ether, diethyl bricol dibutyl ether, triethylene glycol methyl butyl ether, and tetraethylene glycol.
• Examples thereof include dimethyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monobutyl ether.
• amide-based solvent examples include ⁇ -methoxypropionamide, ⁇ -butoxypropionamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.
• lactone-based solvent examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, ⁇ -undecalactone, and ⁇ -valerolactone.
• the coloring material contained in the non-aqueous ink composition of the present embodiment is not particularly limited and may be dye-based or pigment-based, but the printed matter has water resistance and light resistance. It is preferable to use a pigment-based coloring material from the viewpoint of good resistance to the like.
• the pigments that can be used in the ink composition of the present embodiment are not particularly limited, and examples thereof include organic pigments and inorganic pigments used in conventional ink compositions. These may be used alone or in combination of two or more.
• 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, dioxazine-based organic pigments, nickel-azo pigments, and isoindolinone.
• Organics such as organic pigments, pyranthron organic pigments, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindolin organic pigments, quinacridone solid solution pigments, perylene solid solution pigments, etc.
• the solid solution pigment and other pigments include carbon black and the like.
• Lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, inorganic solid solution pigments, etc. can.
• the average dispersed particle size of the pigment that can be contained is not particularly limited as long as it can develop a desired color.
• the number average particle size is preferably in the range of 5 nm or more, preferably 20 nm or more, from the viewpoint of good dispersibility and dispersion stability of the pigment and sufficient coloring power. More preferably, it is more preferably 30 nm or more.
• the number average particle size is preferably in the range of 300 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. If the number average particle size is less than or equal to the above lower limit, the light resistance may decrease. In this embodiment, the number average particle size of the pigment was measured at a measurement temperature of 25 ° C. using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., model: FPAR-1000).
• the content of the pigment that can be used is not particularly limited as long as a desired image can be formed, and is appropriately adjusted. Specifically, although it varies depending on the type of pigment, it is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more, based on the total amount of the non-aqueous ink composition. It is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total amount of the non-aqueous ink composition. When the content of the pigment is within the range of 0.05% by mass or more or 20% by mass or less, the balance between the dispersion stability of the pigment and the coloring power can be excellent.
• surfactant In the non-aqueous ink composition of the present embodiment, for the purpose of suppressing volatilization of the ink composition in a device such as a nozzle portion or a tube, preventing solidification, and resolubility when solidified, and surface tension.
• a surfactant may be added for the purpose of reducing the amount of ink and improving the wettability with the recording medium.
• polyether-modified silicone examples thereof include BYK-347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by Big Chemie Japan) and the like as acetylene glycol-based surfactants.
• Specific examples include Surfinol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan Co., Ltd.), Orfin (registered trademark) STG, E1010 (all manufactured by Nisshin Kagaku Co., Ltd.) and the like. Will be done.
• the surfactant is not limited to the above, and any of anionic, cationic, amphoteric or nonionic surfactants can be used and may be appropriately selected according to the purpose of addition. Further, if necessary, other components may be further contained.
• a medium that can be used for the non-aqueous ink composition of the present embodiment a medium whose surface is mainly made of resin is preferably used.
• resin a polyvinyl chloride polymer, acrylic, PET, polycarbonate, PE, PP and the like are used.
• it is suitable for application to a medium made of a polyvinyl chloride-based polymer having a hard or soft surface.
• examples of the medium whose surface is made of a polyvinyl chloride polymer include a polyvinyl chloride base material (film or sheet).
• the inkjet recording method using the non-aqueous ink composition of the present embodiment is an inkjet recording method in which the non-aqueous ink composition is ejected by an inkjet method and recorded on a medium.
• recording is performed on the medium using an inkjet recording apparatus equipped with an inkjet head cleaning system. Since the non-aqueous ink composition of the present embodiment has good ejection stability, drying property of printed matter, and blocking resistance, the productivity of printed matter using the inkjet recording method can be improved.
• a printed matter can also be produced using the non-aqueous ink composition of the present embodiment.
• the non-aqueous ink composition of the present embodiment in this method for producing a printed matter, it is possible to obtain a high-quality printed matter having good color-developing property and excellent resistance.
• the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average molecular weight of methyl methacrylate (acrylic resin) to be 15,000 to 120,000 (this).
• the mass of the polymerization initiator used at this time is shown in Table 1 below. In Table 1, it is referred to as "initiator amount").
• Hydroxypropyl acrylate 3.55 parts, hydroxypropyl methyl cellulose (suspension agent) 0.1 parts, di-2-ethylhexyl peroxydicarbonate (polymerization initiator) 0.026 parts, di-3,5,5 -Prepare a predetermined amount of trimethylhexanol peroxide (polymerization initiator), raise the temperature to 63 ° C while stirring in a nitrogen gas atmosphere, and immediately after reaching 63 ° C, add 48 parts of vinyl chloride in 6 hours to 0.6 glycidyl methacrylate. A mixture of 10.65 parts of hydroxypropyl acrylate was continuously press-fitted for 5.4 hours to cause a copolymerization reaction.
• the amount of the polymerization initiator di-3,5,5-trimethylhexanol peroxide was changed to control the polymerization average molecular weight of the vinyl chloride-vinyl acetate copolymer resin to be 40,000 to 75,000 ().
• the mass of the polymerization initiator used at this time is shown in Table 1 below. In Table 1, it is referred to as "initiator amount").
• Cellulose-based resin A commercially available cellulosic resin (CAB551-0.01, CAB553-0.4 of EASTMAN CHEMICAL) was used.
• Table 1 shows the weight average molecular weight (relative molecular mass) of each resin (polyester polymer dispersant, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin) and the intrinsic viscosity at 25 ° C. of 90 mL / g.
• the ratio of the above resin and the ratio of the resin having an intrinsic viscosity at 25 ° C. of 100 mL / g or more are shown.
• the weight average molecular weight (relative molecular weight) was measured by GPC (gel permeation chromatography).
• the proportion of resin with intrinsic viscosity of 90 mL / g or more is determined by the Shimadzu SEC (GPC) system with a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T- manufactured by WYATT). rEX) is connected, and tetrahydroflan is used as the developing solvent.
• the sample is passed through a column heated to 40 ° C, and then the passage cooled to 25 ° C is viscous.
• the specific viscosity [ ⁇ SP ] was determined by the detector, the concentration C was determined by the refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP] / C).
• Non-aqueous ink compositions were produced so as to have the composition ratios (parts by mass) shown in Tables 2 and 3. Specifically, a non-aqueous ink composition was prepared by dispersing each component with zirconia beads using a paint shaker.
• the numbers in parentheses for each resin mean the content of the resin having an intrinsic viscosity of 90 mL / g or more in the total amount of the resin.
• a mixed solvent of 80% by mass of diethylene glycol diethyl ether, 10% by mass of methyl ethyl diglycol, and 10% by mass of gamma butyrolactone (a solvent containing a glycol ether solvent and a lactone solvent) was used.
• Solid filling confirmation test> The solid filling was evaluated for the non-aqueous ink compositions of Examples and Comparative Examples. Specifically, printing was performed using the non-aqueous ink compositions of Examples and Comparative Examples using an inkjet printer, and it was confirmed that the solid printed portion was filled (white spots) (in the table, "solid". Notated as "buried”). (Evaluation criteria) ⁇ : Uneven printing and white spots were not observed, and the solid part was sufficiently filled with ink (dot diameter was sufficiently widened). ⁇ : There was slight unevenness, but the solid part was filled. X: The solid part was not sufficiently filled, and unevenness was observed.
• ⁇ Within the test period of 24 hours, the occurrence of missing dots, flight bending, or ink splattering was 10 times or more and less than 20 times.
• X Within the test period of 24 hours, the occurrence of missing dots, flight bending, or ink splattering was 20 times or more.
• Coating film abrasion resistance test The coating film abrasion resistance of the non-aqueous ink compositions of Examples and Comparative Examples was evaluated. Specifically, a printed matter (solid printing) is produced using the non-aqueous ink compositions of Examples and Comparative Examples using an inkjet printer, and the printed surface of the printed matter is loaded with a test cloth piece at a load of 200 g and 50 reciprocations. The scratch resistance was evaluated by rubbing and visually. (Indicated as "coating film abrasion resistance" in the table).
• OD value (color development) test> The OD value (color development) was evaluated for the non-aqueous ink compositions of Examples and Comparative Examples. Specifically, a printed matter (solid printing) was produced using the non-aqueous ink compositions of Examples and Comparative Examples using an inkjet printer, and the OD value was measured (in the table, "OD value (color development)". labels). The OD value was determined by measuring the reflection density using X-Rite eXact (manufactured by X-Rite Co., Ltd.) under the conditions of a viewing angle of 2 °, a measurement range of 4 mm ⁇ , and a D65 light source.
• X-Rite eXact manufactured by X-Rite Co., Ltd.
• ⁇ The OD value was 2.5 or more.
• ⁇ The OD value was 2.0 or more and less than 2.5.
• X The OD value was less than 2.0.
• the non-aqueous ink composition contains 5% by mass or less of the resin having an intrinsic viscosity of 90 mL / g or more at 25 ° C., the printing performance such as continuous ejection stability is excellent and good. It can be seen that a printed matter having storage stability, good color development, and excellent resistance can be obtained.
• the content of the resin having an intrinsic viscosity of 90 mL / g or more at 25 ° C. is 1.0% by mass or more and 5.0% by mass or less in the total amount of the resin.
• the solid filling was good as compared with other examples and comparative examples.
• Comparative Examples 2, 4 and 7 in which the content of the resin of 90 mL / g or more was 8.2% by mass or more in the total amount of the resin unevenness was observed in the solid printed portion.
• non-aqueous ink composition 2 The non-aqueous ink compositions of Examples 17 to 33 and Comparative Examples 8 to 11 were produced so as to have the composition ratio (part by mass) shown in Table 4. Specifically, a non-aqueous ink composition was prepared by dispersing each component with zirconia beads using a paint shaker.
• the numbers in parentheses for each resin mean the content of the resin having an intrinsic viscosity of 90 mL / g or more in the total amount of the resin.
• the solvent contained in the non-aqueous ink compositions of Examples 17 to 27 and Comparative Examples 8 to 10 is a mixed solvent of 80% by mass of diethylene glycol diethyl ether, 10% by mass of methyl ethyl diglycol, and 10% by mass of gamma-butyrolactone. It was used.
• the solvents contained in the non-aqueous ink compositions of Examples 28 to 33 and Comparative Example 11 are 80% by mass of diethylene glycol diethyl ether, 10% by mass of methyl ethyl diglycol, and 3-methoxy-N, N-dimethylpropane.
• a mixed solvent of 10% by mass of amide solvent containing glycol ether solvent and amide solvent was used.
• non-aqueous ink composition 2 The non-aqueous ink compositions of Examples 17 to 33 and Comparative Examples 8 to 11 were tested in the same manner as in Evaluation 1 of the non-aqueous ink composition described above.
• ⁇ The OD value was 1.6 or more.
• ⁇ The OD value was 1.2 or more and less than 1.6.
• X The OD value was less than 1.2.
• the contained organic solvent is a mixed solvent of 80% by mass of diethylene glycol diethyl ether, 10% by mass of methyl ethyl diglycol, and 10% by mass of 3-methoxy-N, N-dimethylpropanamide (glycol ether solvent and amide solvent).
• the non-aqueous ink compositions of Examples 28 to 33 changed to (solvent containing) are similarly excellent in printing performance such as continuous ejection stability, have good storage stability, and have good color development. However, it can be seen that a printed matter having excellent resistance can be obtained.

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