Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • 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 non-aqueous ink compositions.
• an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixture of water and an organic solvent, or a non-aqueous ink composition in which a coloring material is dissolved or dispersed in an organic solvent that does not contain water. is widely used.
• Patent Document 1 discloses a technique related 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 recorded matter is excellent in abrasion resistance and coloring property, and that it is possible to prevent the generation of foreign substances in the container containing the dispersion.
• the non-aqueous ink composition may remain filled in the plastic container and/or the plastic supply body for a long period of time inside the device.
• the present inventors' studies have revealed that solid matter is generated by components contained in the non-aqueous ink composition.
• Such a non-aqueous ink composition for example, gels in a plastic container or supply body and increases its viscosity, or solid content precipitates in the plastic supply body, clogging the plastic supply body and causing a non-aqueous ink composition. In some cases, problems such as difficulty in coating may occur.
• the present invention provides a non-aqueous ink composition that can effectively suppress generation of solids even when the non-aqueous ink composition is applied to a substrate by an apparatus having a plastic container and/or a plastic supplier. intended to
• the present inventors have conducted extensive research, and found that the above problems can be solved by using a non-aqueous ink composition containing an organic solvent having a volatilization rate below a predetermined value in a storage test. I found that it can be done, and came to complete the present invention. Specifically, the present invention provides the following.
• organic solvent A contains at least one selected from the group consisting of glycol ether monoalkyls, cyclic esters, carbonate esters, and amide solvents.
• the non-aqueous ink composition of the present invention can effectively suppress generation of solid matter.
• the non-aqueous ink composition of the present invention is a non-aqueous ink composition that is applied to a substrate by an apparatus having a plastic container and/or a plastic supply, and contains an organic solvent A.
• the organic solvent A is characterized by having a volatilization rate of 15% by mass or less in the following storage test.
• a low-density polyethylene tube is filled with organic solvent A, sealed, and stored at 50°C for one week.
• the organic solvent contained in the non-aqueous ink composition permeates through the plastic that constitutes the container and the supply body, and is contained in the non-aqueous ink composition.
• Research by the present inventors has revealed that this is because the content of the organic solvent changes and some of the components contained in the non-aqueous ink composition precipitate.
• the components and the like contained in the non-aqueous ink composition refer to components such as pigments and resins contained in the non-aqueous ink composition, and materials (for example, plastic materials) are also included.
• the non-aqueous ink composition When solid matter is generated in such a non-aqueous ink composition, the non-aqueous ink composition gels and increases in viscosity, or solid content generated in the supply body clogs the plastic supply body, resulting in a non-aqueous ink composition. Problems such as difficulty in applying the ink composition may occur.
• a polyethylene tube hose manufactured by AS ONE (model number: 6-608-03, inner diameter 3 mm, outer diameter 5 mm) cut to 12 cm can be used.
• the plastic container means a plastic container that contains the non-aqueous ink composition
• the plastic supplier means a plastic supplier that supplies and applies the non-aqueous ink composition to the substrate.
• the plastic container is an ink cartridge containing a non-aqueous ink composition
• the plastic supply is a plastic tube connecting the ink cartridge and the inkjet head.
• Non-aqueous ink composition >>
• an ink jet recording apparatus equipped with a plastic feeder for example, a plastic tube
• the ink jet method through the plastic feeder is used.
• a non-aqueous ink composition to be ejected will be described as an example.
• non-aqueous ink composition means an ink composition that does not contain water (an oil-based ink composition), in which a coloring material is dissolved or dissolved in water or a mixture of water and an organic solvent. It differs from dispersed aqueous ink compositions.
• water-free does not take into account water that is unavoidably contained due to moisture in the air or additives.
• 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 preferably an ink composition that can obtain a recorded matter by drying (volatilizing) the organic solvent.
• a volatile component such as an organic solvent contained in the ink composition dries (volatilizes), and the residue deposits on the surface of the substrate to form a recorded matter. do.
• This ink composition is different from an active energy ray-curable ink composition that polymerizes and cures on a substrate upon irradiation with an active energy ray such as ultraviolet rays.
• An active energy ray-curable ink composition contains a polymerizable compound as an essential component, but an ink composition capable of obtaining a recorded matter by drying (volatilizing) an organic solvent contains an organic solvent. It is not necessary to contain a polymerizable compound as an essential component, and it may contain a polymerizable compound or may not contain a polymerizable compound.
• the non-aqueous ink composition of the present invention does not have to be an inkjet non-aqueous ink composition that is ejected by an inkjet method, and may be used, for example, in a gravure method, a flexo method, a spray method, a screen method, a coater method, and the like.
• the inkjet method is a method in which a non-aqueous ink composition is ejected through an extremely thin plastic supply body (e.g., a plastic tube), so the inkjet ejection becomes difficult due to the generation of solid matter in the plastic tube. problem becomes more pronounced.
• the non-aqueous ink composition of the present invention is a non-aqueous ink composition that can effectively suppress the generation of solids. It is possible to effectively solve the problem that inkjet ejection becomes difficult due to the occurrence of substances, and enjoy the advantages of the inkjet ejection method.
• Organic solvent A is a solvent having a volatilization rate of 15% by mass or less in the following storage test.
• a low-density polyethylene tube is filled with organic solvent A, sealed, and stored at 50°C for one week.
• the volatilization rate in such a closed low-density polyethylene tube does not necessarily correlate with the volatility parameters of the organic solvent itself, such as boiling point, flash point, and evaporation enthalpy. This is because the permeability to plastics differs depending on the type of organic solvent, and the volatilization rate in a closed low-density polyethylene tube is rather due to the permeability to plastics. Specifically, the chemical structure of the organic solvent, It is a parameter resulting from molecular weight, compatibility, and the like.
• Organic solvents having a volatilization rate of 15% by mass or less in such a storage test include glycol ethers such as dipropylene glycol monomethyl ether (10% by mass) and triethylene glycol mono-n-butyl ether (3% by mass).
• Amide solvents such as monoalkyl, N,N-diethylformamide (11% by mass), N,N-diethylpropanamide (12% volatility), N,N-diethylacetamide (13% volatility), propylene Carbonic acid esters such as carbonate (1% by mass), cyclic esters such as ⁇ -butyrolactone (6% by mass), ⁇ -caprolactone (3% by mass) and the like can be mentioned.
• amide-based solvents such as N,N-diethylformamide and cyclic esters such as ⁇ -butyrolactone and ⁇ -caprolactone have a low volatility rate and, in addition, improve the printing performance of non-aqueous ink compositions on resin substrates.
• amide-based solvents such as N,N-diethylformamide are particularly preferred because they can effectively suppress bleeding.
• the amide-based solvent has a low volatilization rate in a closed space inside a plastic tube, it has a high volatilization rate in an open space. Therefore, by using an amide-based solvent as the organic solvent A, it is possible to effectively suppress the generation of solids and obtain a recorded matter with high recording drying property.
• the non-aqueous ink composition containing an amide-based solvent can suppress the occurrence of set-off (anti-blocking) on the back surface of the printed matter, and has good member suitability for inkjet recording devices. becomes.
• an alkylamide-based solvent as the amide-based solvent, the non-aqueous ink composition exhibits the above effects more effectively.
• R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms
• R 2 R 3 each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
• R 2 and R 3 in formula (1) are preferably alkyl groups having 1 to 4 carbon atoms, and more preferably alkyl groups having 2 to 4 carbon atoms.
• alkylamide solvents include N,N-diethylformamide, N,N-diethylacetamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diethylpropanamide, N , N-dipropylpropanamide, N-ethylformamide, N-ethylacetamide and the like.
• the content of the organic solvent A is not particularly limited, but the lower limit of the content of the organic solvent A is preferably in the range of 25 parts by mass or more with respect to 100 parts by mass of the solid content of the non-aqueous ink composition. It is more preferably in the range of 50 parts by mass or more, and even more preferably in the range of 60 parts by mass or more. This makes it possible to more effectively suppress the generation of solids contained in the non-aqueous ink composition.
• the upper limit of the content of the organic solvent A is not particularly limited. is more preferable, and the range of 150 parts by mass or less is even more preferable.
• the content of the organic solvent A with respect to the total amount of the non-aqueous ink composition depends on the content of solids contained in the non-aqueous ink composition, but the lower limit of the content of the organic solvent A is It is preferably in the range of 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total amount. .
• the upper limit of the content of the organic solvent A is preferably 85% by mass or less, more preferably 80% by mass or less, and 75% by mass or less with respect to the total amount of the non-aqueous ink composition. A range is more preferred.
• the solid content of the non-aqueous ink composition means the solid content of the non-aqueous ink composition, excluding the solvent, such as resins, coloring materials, dispersants, and surfactants.
• the organic solvent may contain organic solvents other than the organic solvent A described above.
• glycol ether dialkyl such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methylhexyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl Isopropyl ketone, ethyl ketone, eth
• cyclic saturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene, aromatic hydrocarbons such as benzene, toluene and xylene morpholines such as N-methylmorpholine, N-ethylmorpholine, and N-formylmorpholine, terpene-based solvents, and ether-based solvents. It is possible to list those that do not fall under the % or less solvent can. It is preferable to select a solvent with an appropriate HLB value according to the resin, dispersant, etc. to be combined.
• the non-aqueous ink composition according to the present embodiment may contain no resin, but may contain a resin.
• the fixability, water resistance and stretchability of the recording layer formed from the non-aqueous ink composition can be improved. Furthermore, the glossiness of the obtained recorded matter can be improved.
• the non-aqueous ink composition when the resin is contained in the non-aqueous ink composition, the content of solids contained in the non-aqueous ink composition increases, so that part of the solids contained in the non-aqueous ink composition precipitates.
• the non-aqueous ink composition according to the present embodiment contains the organic solvent A whose volatilization rate is below a predetermined value in a storage test, one part of the solid content It is possible to enjoy the advantage of containing a resin while effectively solving the problem that the part is deposited.
• resins include, but are not limited to, acrylic resins, polystyrene resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, polyethylene resins, polyurethane resins, Rosin-modified resin, phenolic resin, terpene-based resin, polyamide-based resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate-based copolymer, cellulose-based resin, silicone (silicon) resin, acrylamide-based resin, Epoxy resins, or copolymer resins or mixtures thereof can be used.
• acrylic resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, polyester resins, and polyurethane resins are preferred.
• 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 radically polymerizable monomer, or may be a copolymer of two or more selected radically polymerizable monomers.
• the acrylic resin preferable as the oil-based 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. Examples of commercially available (meth)acrylic resins include "Paraloid B99N", "Paraloid B60", “Paraloid B66” and "Paraloid B82" manufactured by Rohm and Haas.
• 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.
• vinyl chloride-vinyl acetate copolymer resins examples include "SOLBIN C”, “SOLBIN CL”, “SOLBIN CNL”, “SOLBIN CLL”, “SOLBIN CLL2”, and “SOLBIN C5R” from Nissin Chemical Industry Co., Ltd. ”, “SOLBIN TA2”, “SOLBIN TA3”, “SOLBIN A”, “SOLBIN AL”, “SOLBIN TA5R”, “SOLBIN M5” and the like, and used in the present invention.
• 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 cellulose-based resin is a resin with a cellulose skeleton that is obtained by biologically or chemically introducing functional groups using cellulose as a raw material.
• cellulose-based resins include cellulose acetate butyrate resins, cellulose acetate propionate resins, cellulose acetate alkylate resins such as cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. mentioned.
• Examples of the above cellulose resins include "CAB551-0.01", “CAB551-0.2", “CAB553-0.4", "CAB531-1", “CAB381-0.1", “CAB381-0.5", and “CAB381” available from EASTMAN. -2", “CAB381-20", “CAP504", and "CAP482-0.5".
• 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.
• Examples of the above polyester resin include "VYLON226", “VYLON270", “VYLON560”, “VYLON600”, “VYLON630”, “VYLON660”, “VYLON885", “VYLONGK250", “VYLONGK810", and “VYLON GK890” manufactured by Toyobo Co., Ltd. etc., and Unitika's product names such as “elitleUE-3200", “elitleUE-3285", “elitleUE-3320”, “elitleUE-9800” and “elitleUE-9885”.
• 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. Examples of the polyurethane-based resins include "Uriano KL-424", “Uriano KL-564", “Uriano KL-593", and “Uriano 3262” available from Arakawa Chemical Industries, Ltd., and "Pandex 372E” and "Uriano 372E” available from DIC.
• acrylic resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but they may be used in combination. is preferable, and it is more preferable to use a resin obtained by mixing an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin.
• the content ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin can be controlled so as to meet the requirements for color development, drying properties, coating properties, printability, etc. required for non-aqueous inks.
• the mixing ratio is not particularly limited and can be changed as appropriate.
• the weight average molecular weight (relative molecular mass) of the resin is not particularly limited, it is preferably 5,000 or more, more preferably 15,000 or more.
• the weight average molecular weight (relative molecular mass) is preferably 100,000 or less, more preferably 50,000 or less. Relative molecular weights of resins can be measured by conventional GPC (gel permeation chromatography).
• the resin contained in the non-aqueous ink composition is preferably contained in a range of 0.05% by mass or more based on the total amount of the non-aqueous ink composition, although it depends on other components contained in the non-aqueous ink composition. , more preferably in the range of 0.1% by mass or more, and more preferably in the range of 0.5% by mass or more.
• the resin contained in the non-aqueous ink composition is preferably contained in a range of 20.0% by mass or less, more preferably 15.0% by mass or less, based on the total amount of the non-aqueous ink composition. It is more preferable to contain in the range of 10.0% by mass or less.
• the resin contained in the non-aqueous ink composition according to the present embodiment preferably has a resin having an intrinsic viscosity of 90 mL/g or more at 25°C in a range of 5% by mass or less in the total amount of the resin.
• a resin having a high intrinsic viscosity has a relatively low solubility in a solvent, so it tends to precipitate due to changes in the solvent composition such as volatilization, and is difficult to dissolve.
• the non-aqueous ink composition according to the present embodiment contains an organic solvent whose volatilization rate is a predetermined value or less in a storage test, thereby effectively suppressing deposition of solid content, and has an intrinsic viscosity of 90 mL. /g or more is in the range of 5% by mass or less in the total amount of the resin, the precipitation of the resin can be suppressed extremely effectively, and the ejection stability of the inkjet can be made extremely high.
• the intrinsic viscosity is the specific viscosity after the target resin is dispersed in a developing solvent and the molecules contained in the resin are separated by a column filled with granular gel in GPC (gel permeation chromatography) [ ⁇ SP ](( ⁇ 0 )/ ⁇ 0 ( ⁇ 0 : solvent viscosity, ⁇ : solution viscosity)) and concentration C are obtained, and the concentration C is set to 0 in the formula Lim ([ ⁇ SP ]/C). It can be obtained by interpolation (C ⁇ 0).
• the developing solvent is not particularly limited, for example, tetrahydrofuran can be used.
• the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C is preferably in the range of 4.0% by mass or less, more preferably 3.5% by mass or less, based on the total amount of the resin. The range of 2.5% by mass or less is even more preferable.
• the non-aqueous ink composition according to this embodiment may 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.
• Pigments that can be used in the non-aqueous ink composition according to the present embodiment are not particularly limited, and include organic pigments or 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. Note that the non-aqueous ink composition according to the present embodiment does not have to contain a coloring material.
• the dispersion stability of the pigment can be improved by using a dispersant or dispersion aid (pigment derivative) 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
• Dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigoids, fulgide dyes, nickel complex dyes, and Azulene dyes can be mentioned.
• inorganic pigments that can be used in the non-aqueous ink composition according to the present embodiment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, barium carbonate, silica, talc, clay, synthetic mica, and alumina. , zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (iron (III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, aluminum, titanium, indium, synthetic iron Examples include black and inorganic solid solution pigments.
• 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 non-aqueous ink composition according to the present embodiment can effectively suppress deposition of solid content by containing an organic solvent having a volatilization rate of less than a predetermined value in a storage test.
• the particle size is equal to or less than the above upper limit value, the ejection stability of inkjet can be made extremely high.
• 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 volume average particle diameters of the pigments contained in the respective non-aqueous ink compositions may be the same or different.
• the volume average particle diameter of the pigment contained in the cyan ink and the volume average particle diameter of the pigment contained in the magenta ink may be the same or different.
• the content of the pigment is not particularly limited as long as the desired image can be formed, and is appropriately adjusted. Specifically, it is preferably in the range of 0.05% by mass or more, more preferably in the range of 0.1% by mass or more, based on the total amount of the non-aqueous ink composition, although it varies depending on the type of pigment. It is preferably in the range of 20% by mass or less, more preferably in the range of 10% by mass or less, based on the total amount of the non-aqueous ink composition.
• the non-aqueous ink composition according to the present embodiment can effectively suppress the generation of solids by containing an organic solvent whose volatilization rate is below a predetermined value in a storage test.
• the deposition of the coloring material can be suppressed extremely effectively, and the ejection stability of the inkjet can be made extremely high.
• the non-aqueous ink composition according to the present embodiment is not particularly limited in the color to be recorded (printed), and coloring materials may be selected according to the intended color and used in combination. 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, in the ink set containing the non-aqueous ink composition according to the present embodiment, coloring materials of the same color may be selected.
• a dispersant may be used as necessary in the non-aqueous ink composition according to the present embodiment. Any dispersant used in non-aqueous ink compositions can be used as the dispersant.
• a polymer dispersant is preferably used as the dispersant. 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.
• polycaprolactone-based dispersants it is preferable to use polycaprolactone-based dispersants.
• an amide solvent such as N,N-diethylformamide
• the dispersibility of the pigment in the ink composition containing the amide solvent such as N,N-diethylformamide is effectively dispersed. This makes it possible to effectively suppress the formation of solids in the non-aqueous ink composition.
• the content of the dispersant is not particularly limited, but the lower limit of the content of the dispersant is preferably in the range of 0.1% by mass or more, and in the range of 0.5% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is in the range of 0.8% by mass or more.
• the content of the dispersant is not particularly limited, but the lower limit of the content of the dispersant is preferably in the range of 5.0% by mass or more, and in the range of 4.0% by mass or more, based on the total amount of the non-aqueous ink composition. More preferably, it is in the range of 3.0% by mass or more. This makes it possible to effectively disperse the dispersibility of the pigment in the ink composition and effectively suppress the generation of solids in the non-aqueous ink composition.
• a dispersing aid may be used as necessary in the non-aqueous 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 affinity with the organic solvent and dispersant in the non-aqueous ink composition, thereby improving 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.
• a surfactant in the non-aqueous ink composition according to the present embodiment, for the purpose of suppressing volatilization and solidification of the ink composition in devices such as nozzles and tubes, and resolubility when solidified, A surfactant may be added for the purpose of reducing the surface tension and improving the wettability with the recording medium (substrate).
• acetylene glycol-based surfactants include Surfynol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan), Olfine (registered trademark) STG, E1010 (all manufactured by Nissin Chemical Co., Ltd.) and the like are exemplified.
• the surfactant is not limited to the above, and any anionic, cationic, amphoteric or nonionic surfactant can be used, and may be appropriately selected according to the purpose of addition.
• the non-aqueous ink composition according to the present embodiment contains stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface modifiers, slip agents, leveling agents (acrylic, silicone, etc.). ), antifoaming agents, pH adjusters, bactericides, preservatives, deodorants, charge control agents, wetting agents, and other known additives as optional components.
• stabilizers such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface modifiers, slip agents, leveling agents (acrylic, silicone, etc.).
• antifoaming agents such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface modifiers, slip agents, leveling agents (acrylic, silicone, etc.).
• antifoaming agents such as antioxidants and ultraviolet absorbers, epoxides and the like, polyvalent carboxylic acids, surface modifiers, slip agents, leveling agents
• 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 ink composition according to the present embodiment is produced by mixing an organic solvent containing organic solvent A with a volatilization rate of 15% by mass or less and each main component (for example, a resin, a coloring material, etc.) using a paint shaker. can be manufactured by At this time, each component may be dispersed with zirconia beads. Note that the non-aqueous ink composition according to the present embodiment may be adjusted to a desired dissolved oxygen content and dissolved nitrogen content by performing a deaeration treatment or the like, if necessary.
• each main component for example, a resin, a coloring material, etc.
• 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. 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.
• an inert gas e.g., nitrogen gas
• the recording method according to the present embodiment is a recording method in which the above non-aqueous ink composition is ejected onto the surface of a substrate by an inkjet method.
• the above-mentioned non-aqueous ink composition can effectively suppress generation of solid matter, and in the recording method according to the present embodiment, the generation of solid matter in the plastic feeder, the wetted part, etc. It is possible to effectively solve the problem that inkjet ejection becomes difficult.
• a method of ejecting ink by an inkjet method may be a piezo method using a piezoelectric element or a thermal method using a heating element, and is not particularly limited.
• the non-aqueous ink composition that has landed on the substrate (recording medium) by a heating mechanism provided in the inkjet recording apparatus. Accordingly, by drying the non-aqueous ink composition that has landed on the base material (recording medium), it is possible to improve the surface drying property and blocking resistance of the recorded matter.
• an amide solvent such as N,N-diethylformamide
• a recorded matter having excellent surface drying properties can be obtained.
• the drying speed of the organic solvent contained in the non-aqueous ink composition can be increased, and the production speed of recorded matter can be further improved. The same applies to the method of manufacturing a printed matter, which will be described later.
• the recording method using the ink composition of the present invention As a specific embodiment of the recording method using the ink composition of the present invention, a recording method in which ink is ejected onto the surface of a base material by an ink jet method has been described, but the recording method using the ink composition of the present invention is described. is not limited to the inkjet method, and may be a recording method in which the surface of the substrate is coated by, for example, a gravure method, a flexographic method, a spray method, a screen method, or a coater method. The same applies to the method of manufacturing a printed matter, which will be described later.
• Method for producing recorded matter ⁇ A recording method using the above ink composition can also be defined as a method for producing a recorded matter. In the method of manufacturing a printed matter according to the present embodiment, it is possible to effectively solve the problem of difficulty in ink jet ejection due to the generation of solid matter in the plastic supply body, the wetted part, or the like.
• the base material (recording medium) that can be used in the recording method according to the present embodiment is not particularly limited, and non-materials such as resin base materials (including those whose surface is mainly made of resin), metal plate glass, etc. It may be an absorbent substrate, an absorbent substrate such as paper or fabric, or a surface-coated substrate such as a substrate having a receiving layer. material can be used.
• the non-aqueous ink composition is a non-aqueous ink composition that does not contain water, it is preferable that the surface is mainly made of a resin.
• the above non-aqueous ink composition contains an alkylamide-based solvent (a) that exhibits permeability to a resin substrate, bleeding of printing on a medium (recording medium) whose surface is made of a resin is prevented. less and the print becomes clearer.
• resins include polyvinyl chloride-based polymers, acryl, PET, polycarbonate, PE, and PP.
• 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 non-aqueous ink composition containing a large amount of the organic solvent A which has a low volatility rate in the low-density polyethylene tube
• bleeding may occur in the print. Therefore, for example, when the content of the organic solvent A is in the range of 60 parts by mass or more with respect to 100 parts by mass of the solid content of the non-aqueous ink composition, a substrate (recording medium) having a receiving layer is used. By using it, such bleeding can be effectively suppressed.
• the organic solvent A is an amide solvent such as N,N-diethylformamide or an organic solvent A other than a cyclic ester such as ⁇ -butyrolactone or ⁇ -caprolactone
• the organic solvent A may be an amide solvent or a cyclic ester. Bleeding is relatively likely to occur in printing compared to a non-aqueous ink composition containing. Therefore, when forming a recording layer from a non-aqueous ink composition containing such an amide-based solvent or organic solvent A other than a cyclic ester, it is possible to use a substrate (recording medium) having a receiving layer. Especially preferred. As a result, bleeding can be effectively suppressed in the same manner as a non-aqueous ink composition containing an amide-based solvent or a cyclic ester as the organic solvent A.
• the recording layer is a layer formed by volatilization of the solvent contained in the non-aqueous ink composition, and is a layer that forms a desired image.
• the layer formed by evaporating the solvent contained in the non-aqueous ink composition may be formed from a plurality of layers.
• a layer of color ink (for example, yellow, magenta, cyan, black) of the above non-aqueous ink composition may be formed on the substrate.
• the recorded matter according to this embodiment may further include a layer having a desired function on the upper surface of the recording layer.
• a layer having a desired function on the upper surface of the recording 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 bright layer containing a bright pigment, a white layer containing a white material, etc. may be formed. .
• the recorded matter including the recording layer formed with the above non-aqueous ink composition has been described.
• the above non-aqueous ink composition may be ejected to form a layer having a desired function.
• a layer having a desired function may be formed by ejecting the above non-aqueous ink composition on the recording layer formed with the above non-aqueous ink composition.
• Inkjet recording device A conventionally known inkjet recording apparatus that ejects the above non-aqueous ink composition by an inkjet method can be used.
• an inkjet printer such as VersaArt RE-640 manufactured by Roland DG Co., etc. can be used.
• an on-carriage type and serial printer type inkjet recording apparatus will be described. It may be an off-carriage type inkjet recording device fixed to the head, or a line printer type inkjet recording device in which the ink composition is ejected onto the recording medium (substrate) without moving the inkjet head. good.
• the inkjet recording apparatus preferably includes a heating mechanism and a fixing mechanism for fixing the substrate.
• the organic solvent contained in the non-aqueous ink composition is dried by controlling the substrate surface temperature with a heating mechanism provided in the inkjet recording apparatus and drying the non-aqueous ink composition that has landed on the substrate (recording medium). can be volatilized, and the surface drying property is improved.
• the fixing mechanism for fixing the base material makes it possible to dry the non-aqueous ink composition while the base material (recording medium) is fixed. Uniformity can be suppressed. This makes it possible to effectively dry the non-aqueous ink composition that has landed on the substrate (recording medium).
• the heating mechanism provided in the inkjet recording apparatus may be a pre-heater, a platen heater, an after-heater, or the like, or may be a mechanism for blowing warm air onto the recorded matter. Also, a plurality of these heating mechanisms may be combined.
• the surface temperature of the substrate heated by the heating mechanism is not particularly limited as long as the organic solvent contained in the non-aqueous ink composition can be volatilized, and the lower limit of the surface temperature of the substrate is 20° C. or higher. , more preferably 30° C. or higher, and even more preferably 40° C. or higher.
• the upper limit of the surface temperature of the substrate is preferably 70° C. or lower, more preferably 60° C. or lower, and even more preferably 50° C. or lower.
• 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 inkjet head that ejects the above non-aqueous ink composition may be a piezo inkjet head using a piezoelectric element or a thermal inkjet head using a heating element, and is not particularly limited.
• the inkjet recording apparatus includes a plastic container (ink cartridge, bottle, etc.) that stores the non-aqueous ink composition and a plastic supply body (plastic tube) that connects the inkjet head that ejects the non-aqueous ink composition. ), and the above non-aqueous ink composition may be ejected through the plastic supplier (plastic tube) by an inkjet method.
• the above non-aqueous ink composition can effectively suppress the generation of solids by containing an organic solvent having a volatilization rate of less than a predetermined value in a storage test, and such a plastic container and / or It can be suitably used in an ink jet recording apparatus equipped with a plastic feeder.
• Materials constituting the plastic container and/or the plastic supply body are not particularly limited, but include polyolefin resin, ethylene propylene diene rubber, nylon, polyurethane, PTFE, and the like, and polyethylene resin, ethylene propylene diene. It is preferable to use rubber, and among these, it is particularly preferable to use low density polyethylene resin.
• an ink circulation mechanism for circulating the non-aqueous ink composition within the inkjet recording apparatus.
• the above non-aqueous ink composition can effectively suppress the generation of solid matter, and can improve ejection stability when ejected by an inkjet method. By ejecting the non-aqueous ink composition from an inkjet recording apparatus having an ink circulation mechanism, it is possible to achieve extremely good ejection stability.
• the inkjet recording apparatus is a device capable of ejecting a plurality of non-aqueous ink compositions
• these storage mechanism, plastic tube, and ink circulation mechanism are provided for all mechanisms for ejecting a plurality of non-aqueous ink compositions. It may be absent, and it may be provided for at least one non-aqueous ink composition.
• the non-aqueous ink composition according to the present embodiment can 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.
• the inkjet printer may or may not have a winding mechanism for the recording medium (base material), a drying mechanism for drying the surface of the base material, and an ink circulation mechanism.
• the inkjet recording apparatus is described as an example of a recording apparatus that applies (discharges) the non-aqueous ink composition
• the recording apparatus that applies (discharges) the non-aqueous ink composition is limited to the inkjet recording apparatus.
• the above non-aqueous ink composition may be applied by a recording apparatus used in a gravure, flexo, spray, screen, or coater recording method.
• a recording apparatus may include an ink circulation mechanism.
• 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 30,000 to 105,000 (this The mass of the polymerization initiator used is shown in the following Table 1. In Table 1, it is described as "initiator amount").
• Table 1 shows the weight-average molecular weight (relative molecular mass) of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin) and the ratio of resins having an intrinsic viscosity of 90 mL/g or more at 25°C.
• the weight average molecular weight (relative molecular mass) was measured by GPC (gel permeation chromatography).
• the ratio of the resin with an intrinsic viscosity of 90 mL / g or more is determined by connecting a viscosity detector (ViscoStar III manufactured by WYATT) and a refractive index detector (Optilab T-rEX manufactured by WYATT) to a Shimadzu SEC (GPC) system, Using tetrahydrofuran as a developing solvent, the sample was first passed through a column heated to 40°C in the Shimadzu SEC (GPC) system, and then cooled to 25°C. ⁇ SP ] was determined, the concentration C was determined by a refractive index detector, and the intrinsic viscosity was determined by extrapolating the concentration C to 0 in Lim ([ ⁇ SP ]/C).
• Non-aqueous ink compositions of Examples and Comparative Examples were prepared according to the proportions of each component shown in the table below. Specifically, each component was dispersed with zirconia beads using a paint shaker to prepare a non-aqueous ink composition. The unit is % by mass.
• the volatilization rate was measured in advance by a storage test. Specifically, a polyethylene tube hose (model number: 6-608-03, inner diameter: 3 mm, outer diameter: 5 mm) cut to 12 cm from AS ONE was filled with an organic solvent, and pinch cocks were placed at 1 cm from both ends of the tube. The container was sealed with a Hoffman clamp, stored at 50° C. for 1 week, and the volatilization amount (% by mass) of the organic solvent was determined.
• the non-aqueous ink compositions of Examples and Comparative Examples were evaluated for suitability for members (suitability for members of inkjet heads). 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 (denoted as “member suitability” 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.
• Ejection stability was evaluated for the non-aqueous ink compositions of Examples and Comparative Examples. Specifically, in the same manner as in the above cleaning recovery evaluation, a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) was printed in a bidirectional high-speed printing mode (360 x 760 dpi) at a substrate surface temperature of 40 ° C. Solids and fine lines were printed by continuous printing, and the presence or absence of missing dots, flight deflection, and ink scattering was visually observed, and the number of occurrences was counted. Evaluation criteria Evaluation 5: Within the 24-hour test period, dot dropout, flight deflection, or ink scattering occurred less than 10 times.
• Evaluation 4 During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 10 times or more and less than 20 times.
• Evaluation 3 During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 20 times or more and less than 30 times.
• Evaluation 2 During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 30 times or more and less than 40 times.
• Evaluation 1 During the test period of 24 hours, dot missing, flight deflection, or ink scattering occurred 40 times or more.
• MFDG is dipropylene glycol monomethyl ether.
• BCG is triethylene glycol mono-n-butyl ether.
• PC propylene carbonate
• ECL in the table is ⁇ -caprolactone.
• DMDG diethylene glycol dimethyl ether
• DEDG diethylene glycol diethyl ether
• DMFDG dipropylene glycol dimethyl ether
• EDGmMEA ethylene glycol monomethyl ether acetate
• EDGmBEA ethylene glycol monobutyl ether acetate
• PEGMEA propylene glycol monomethyl ether acetate
• Solsperse 32000 is a polycaprolactone-based dispersant manufactured by Lubrizol.
• Solsperse 33000 is a polycaprolactone-based dispersant manufactured by Lubrizol.
• the non-aqueous ink compositions of Examples containing an organic solvent having a volatility rate of volatilization in the storage test of not more than a predetermined amount did not generate solids even in the tube volatility test.
• the cleaning recoverability is also good, and it can be seen that the deposition of solids can be effectively suppressed.
• the ejection stability by inkjet is also good, and the non-aqueous ink compositions of Examples are difficult to eject by inkjet due to the generation of solids in the plastic feeder, which can be a problem in the inkjet ejection method. It can be seen that the problem can be effectively solved.
• the content of Examples 2 to 8 in the range of 25 parts by mass or more with respect to 100 parts by mass of the solid content produced less gel in the tube volatility test.
• the non-aqueous ink compositions of Examples 4 to 7, which have a range of 60 parts by mass or more with respect to 100 parts by mass of solid content have good results in all tests, and the effect of the present invention is particularly good. It can be seen that it is playing
• non-aqueous ink compositions of Examples 29 to 39 in which the content of the resin having an intrinsic viscosity of 90 mL/g or more at 25°C was changed, 5 resins having an intrinsic viscosity of 90 mL/g or more at 25°C were included in the total amount of the resin.
• the non-aqueous ink compositions of Examples in the range of less than or equal to 5% by mass exhibited particularly high inkjet ejection stability even compared to the non-aqueous ink compositions of Examples in the range of more than 5% by mass. .
• the non-aqueous ink composition of the comparative example which does not contain the organic solvent A, generated solid matter in the tube volatility test, and the cleaning recoverability was also deteriorated.
• the ejection stability in inkjet was also deteriorated. From this, it can be seen that the non-aqueous ink compositions of the comparative examples do not exhibit the effects of the present invention.
• Example 17 Example 17, and Comparative Example 1, the tube volatility was evaluated in the same manner as the tube volatility test described above, except that the material of the plastic tube was changed to Teflon (registered trademark) and polypropylene. In addition, cleaning recoverability was similarly evaluated except that the material of the plastic tube provided in the inkjet recording apparatus was changed.
• PE polyethylene
• EPDM ethylene propylene diene rubber
• PP polypropylene

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