WO2010027053A1 - インキ組成物 - Google Patents
インキ組成物 Download PDFInfo
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- WO2010027053A1 WO2010027053A1 PCT/JP2009/065512 JP2009065512W WO2010027053A1 WO 2010027053 A1 WO2010027053 A1 WO 2010027053A1 JP 2009065512 W JP2009065512 W JP 2009065512W WO 2010027053 A1 WO2010027053 A1 WO 2010027053A1
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- average molecular
- ink composition
- general formula
- molecular weight
- resin
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
Definitions
- the present invention relates to a pigment ink composition capable of realizing excellent printing stability, printed material performance, and drying property.
- inkjet printing that prints images and characters by using fine ink droplets ejected from the nozzles of an inkjet head has recently been developed as an inkjet printer that can handle A-0 size.
- Ink jet printing inks that are excellent in water resistance, weather resistance, and friction resistance have been actively developed against the background of the increase in usage environment.
- ink-jet printing inks used for the sign industry are mainly solvent ink-jet inks that use organic solvents as the solvent, instead of water-based ink-jet inks in which colorants such as water-soluble dyes are added to general water. in use.
- solvent ink-jet inks that use organic solvents as the solvent
- colorants such as water-soluble dyes are added to general water.
- a pigment having excellent weather resistance a binder resin that firmly adheres the pigment to the sheet surface
- a pigment ink composition containing an organic solvent capable of dissolving the binder resin is considered suitable.
- Patent Documents 1 to 3 when selecting a binder resin, it is common to select one of various types of resin so that it can be stably ejected from an inkjet head and sufficient printed material resistance and drying properties can be realized.
- Patent Documents 1 to 3 if a resin that improves the ejection stability from the ink jet head is selected, the coating film resistance and drying properties deteriorate, and if a resin that improves the coating film resistance and drying properties is selected, the ejection stability deteriorates. Therefore, it has been difficult to develop an ink-jet ink that improves all the performance.
- the present invention has been made in view of the above problems, and its purpose is to provide a pigment ink composition, particularly an inkjet ink composition, that can achieve excellent printing stability, printed matter resistance, and drying properties. is there.
- the present invention includes at least a pigment, an organic solvent, and two or more kinds of binder resins having different weight average molecular weights (Mw), and the binder resin having the smallest weight average molecular weight (Mw) among the two or more kinds of binder resins used.
- the present invention relates to an ink composition characterized by satisfying the general formulas (1), (2), and (3) where ⁇ is ⁇ and ⁇ is a binder resin having a weight average molecular weight (Mw) larger than ⁇ .
- the present invention relates to an ink composition characterized in that the relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of two or more kinds of binder resins contained is in the range of the general formula (4).
- the present invention relates to an ink composition wherein two or more kinds of binder resins are vinyl chloride resin and / or acrylic resin.
- the present invention relates to an ink composition
- an ink composition comprising any one or more of the solvents represented by general formula (5) to general formula (8) as an organic solvent.
- R 10 COOR 11 (Wherein R 2, R 5 and R 8 are each independently an ethylene group or a propylene group, R 1 , R 3 , R 4 and R 6 are each independently an alkyl group having 1 to 4 carbon atoms, R 7 R 9 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 10 is a 2-hydroxyethyl group, R 11 is an alkyl group having 1 to 8 carbon atoms, and Z is an integer of 1 to 3 .) Furthermore, at least one of the two or more types of binder resins contained is an acrylic resin, which is synthesized in an organic solvent having a boiling point of 60 ° C.
- the present invention relates to an ink composition characterized in that a part of the organic solvent contains a nitrogen-containing, sulfur-containing, or lactone solvent.
- the present invention relates to an ink composition characterized by containing a dispersant in the ink composition.
- the present invention relates to an ink composition that is an inkjet ink.
- a pigment ink composition capable of realizing excellent printing stability, printed matter performance, and drying property,
- an inkjet ink composition is provided.
- the ink composition of the present invention comprises a pigment ink composition comprising a pigment having excellent weather resistance, a binder resin for firmly adhering the pigment to the surface of a print medium, and an organic solvent capable of dissolving the binder resin. It is.
- binder resin having excellent adhesion to the surface of the printing medium examples include acrylic resins, styrene-acrylic resins, styrene-maleic resins, rosin resins, rosin ester resins, ethylene-vinyl acetate resins, petroleum Resin, coumarone indene resin, terpene phenol resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid Resin, fumaric acid resin, vinyl chloride resin and the like can be used.
- the resin examples include BR-50, BR-52, MB-2539, BR-60, BR-64, BR-73, BR-75, MB-2389, BR-80, BR- manufactured by Mitsubishi Rayon Co., Ltd. 83, BR-87, BR-105, BR-106, BR-107, BR-110, BR-113, MB-2660, MB-2952, MB-3015, MB-7033, BR-115, MB-2478, BR-116, Wilber Ellis A-12, A-21, B-38, B-60, B-65, B-66, B-67, B-99N, DM-55, manufactured by Dow Chemicals Yuker Solutions vinyl resins VYHD, VYHH, VMCA, VROH, VYLF-X, Nisshin Chemical's sorbine resins CL, CNL, C5R, TA3, TA5R, manufactured by Wacker Nyl resin E15 / 45, H14 / 36, H40 /
- the resin is preferably contained in the ink in an amount of 0.1 to 20% by weight.
- the addition amount is 0.1% by weight or less in the ink, the adhesion to the surface of the printing medium is poor, and the resistance of the coating film is reduced.
- the addition amount is 20% by weight or more, the ink viscosity is too high, and thus the printability is high. Since it falls, it is not preferable.
- Acrylic resins, styrene-acrylic resins, and vinyl chloride resins are preferable from the viewpoint of the resistance of the printed material, and acrylic resins and styrene-acrylic resins are more preferable from the viewpoint of drying properties.
- the resin used as the binder resin has good printed matter resistance and drying properties when the weight average molecular weight (Mw) is large, but is the most important performance as an inkjet ink, and has the ink ejection stability from the inkjet head. It will get worse.
- the weight average molecular weight (Mw) of the binder resin is small, the discharge stability is good, but the printed matter resistance and drying property are deteriorated. For this reason, it has been difficult to develop an ink-jet ink that improves all three of these performances.
- the present inventors have realized that excellent printing stability, printed matter performance, and drying property can be achieved by using two or more types of binder resins having different weight average molecular weights (Mw). Knowing that a pigment ink composition for inkjet recording can be produced, the present invention has been completed.
- two or more kinds of binder resins having different weight average molecular weights (Mw) are used in order to produce a pigment ink composition for inkjet recording capable of realizing excellent printing stability, printed matter resistance, and drying property.
- the two or more types of binder resins to be used preferably include a binder resin ⁇ having the smallest weight average molecular weight (Mw) and one or more binder resins ⁇ having a weight average molecular weight (Mw) larger than Mw ⁇ . This is because the binder resin ( ⁇ ) having a small weight average molecular weight excellent in ink ejection stability and the binder resin ( ⁇ ) having a large weight average molecular weight excellent in printed material performance and drying property are used in combination. The purpose is to improve all three performances.
- the weight average molecular weight of ⁇ is Mw ⁇ and the weight average molecular weight of ⁇ is Mw ⁇
- the relationship between the weight average molecular weights (Mw) of two or more binder resins used in the present invention is Mw ⁇ Mw ⁇ ⁇ 10.
- Mw ⁇ -Mw ⁇ ⁇ 15,000 is more preferable, and Mw ⁇ -Mw ⁇ ⁇ 20,000 is particularly preferable.
- the relationship between the weight average molecular weights (Mw) of two or more types of binder resins used is in the range of Mw ⁇ -Mw ⁇ ⁇ 20,000, it is possible to produce an ink with excellent ejection stability, printed material performance, and drying properties. If the area is Mw ⁇ -Mw ⁇ ⁇ 10,000, it is difficult to improve all these three performances.
- the relationship between the weight average molecular weights (Mw) of two or more kinds of binder resins is preferably in the range of 1,000 ⁇ Mw ⁇ ⁇ 30,000 and 20,000 ⁇ Mw ⁇ ⁇ 100,000, The region of 000 ⁇ Mw ⁇ ⁇ 30,000 and 20,000 ⁇ Mw ⁇ ⁇ 50,000 is particularly preferred.
- Mw ⁇ ⁇ 1,000 the printed film becomes brittle and cracks when printed, and when Mw ⁇ > 30,000, the discharge stability deteriorates. Further, when Mw ⁇ ⁇ 20,000, excellent printed material performance / drying properties cannot be realized, and when Mw ⁇ > 100,000, the ink jet head cannot be ejected.
- the relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of two or more binder resins is preferably in the region of 1 ⁇ Mw / Mn ⁇ 3, more preferably 1 ⁇ Mw / Mn ⁇ 2. .5, and more preferably 1 ⁇ Mw / Mn ⁇ 2.3.
- the ink can be easily dissolved in a solvent and can stably discharge ink from the inkjet head.
- Mw / Mn> 3 the binder resin is difficult to dissolve in the solvent, and the ink ejection stability is deteriorated.
- vinyl chloride resin and / or acrylic resin can be used for the two or more kinds of binder resins contained.
- a vinyl chloride resin that is excellent in printed gloss and film stretchability and an acrylic resin that is excellent in drying properties of the printed material it is excellent in printed matter without show-through (blocking) even in an inkjet printer with a high printing speed. Can be obtained.
- the main solvent used in the present invention preferably has a boiling point of 150 ° C. or higher. If the boiling point is too low, when used as an inkjet ink, drying on the nozzles is accelerated, causing clogging.
- the flash point is preferably 61 ° C. or higher. When the flash point is less than 61 ° C, dangerous goods in the case of ship transportation under international transport laws and regulations are classified as highly flammable liquids and are restricted during transportation and transportation. More preferably, the flash point is 70 ° C. or higher. When the temperature exceeds 70 ° C., it is classified as a hazardous material type 4 and type 3 petroleum under the Fire Service Law, and restrictions on manufacturing, transportation, transportation and storage are reduced.
- solvents represented by the following general formulas (5) to (8) there are solvents represented by the following general formulas (5) to (8).
- R 10 COOR 11 (Wherein R 2, R 5 and R 8 are each independently an ethylene group or a propylene group, R 1 , R 3 , R 4 and R 6 are each independently an alkyl group having 1 to 4 carbon atoms, R 7 , R 9 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 10 represents a 2-hydroxyethyl group, R 11 represents an alkyl group having 1 to 8 carbon atoms, and Z represents an integer of 1 to 4 .)
- Solvents corresponding to general formula (5) include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether a
- glycol monoacetates such as dirate glycol, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol monomethyl ether butyrate and dipropylene glycol monomethyl ether butyrate.
- Solvents corresponding to general formula (6) include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, ethylene glycol propionate.
- glycol dipropionate ethylene glycol dibutyrate, diethylene glycol acetate propionate, diethylene glycol butyrate, diethylene glycol propionate butyrate, diethylene glycol dipropionate, diethylene glycol dibutyrate, propylene glycol acetate propionate, propylene glycol acetate Butyrate, propylene glycol Cole propionate butyrate, propylene glycol dipropionate, propylene glycol dibutyrate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyrate, dipropylene glycol propionate butyrate, dipropylene glycol dipropionate, di There are glycol diacetates such as propylene glycol dibutyrate.
- Solvents corresponding to the general formula (7) include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl.
- glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl.
- Ether diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol n-propyl ether, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, there is a glycol ether such as tetraethylene glycol diethyl ether.
- Examples of the solvent corresponding to the general formula (8) include esters such as methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.
- (poly) ethylene glycol diether solvents and (poly) ethylene glycol monoether monoester solvents are preferred from the viewpoints of resin solubility and drying on the nozzle.
- Specific examples include ethylene glycol monobutyl ether acetate and diethylene glycol diethyl ether.
- Diethylene glycol diethyl ether is particularly preferred from the viewpoint of low odor.
- diethylene glycol diethyl ether In consideration of safety and health, it is particularly preferable to use diethylene glycol diethyl ether, from the viewpoint of harmfulness such as acute toxicity, mutagenicity, carcinogenicity, and reproductive toxicity.
- At least one of the two or more types of binder resins used in the present invention is an acrylic resin.
- the acrylic resin is synthesized in an organic solvent having a boiling point of 60 ° C. to 150 ° C., and then a boiling point of 150 ° C. by a stripping method. It is preferable to substitute and use at least one of the above (poly) alkylene glycol derivatives.
- the gloss and density of the printed product tend to decrease.
- the (poly) alkylene glycol derivative works as a chain transfer agent, and a structure derived from the (poly) alkylene glycol derivative is generated in a part of the resin, resulting in a decrease in the reaction rate and the refractive index of the resin. This is presumed to be uneven.
- the acrylic resin obtained by the stripping method has a high reaction rate and can be suitably used as a raw material for the ink composition by avoiding these problems.
- These (poly) alkylene glycol derivatives having a boiling point of 150 ° C. or higher include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol.
- Dibutyl ether dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono Chirueteru, tripropylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, glycol ethers such as tetraethylene glycol diethyl ether.
- solvents may be used alone or in combination of two types.
- (poly) ethylene glycol diether solvents and (poly) ethylene glycol monoether monoester solvents are preferred from the viewpoints of resin solubility and drying properties on the nozzle.
- Specific examples include ethylene glycol monobutyl ether acetate and diethylene glycol diethyl ether.
- Diethylene glycol diethyl ether is particularly preferred from the viewpoint of low odor.
- organic solvent having a boiling point of 60 ° C. to 150 ° C. a hydrocarbon solvent, an ester solvent, a ketone solvent, an alcohol solvent, a glycol solvent, and the like can be used. As described above, chain transfer is performed during the polymerization. It is preferable to use a hydrocarbon solvent, an ester solvent or a ketone solvent that does not work as an agent.
- the boiling point of the organic solvent it is preferable to use an organic solvent having a temperature of 60 ° C. to 150 ° C. from the viewpoint of polymerization temperature and ease of stripping.
- hydrocarbon solvents examples include n-hexane (boiling point 68.7 ° C), n-heptane (boiling point 98.4 ° C), n-octane (boiling point 125.6 ° C), isooctane (boiling point 99.3 ° C), cyclohexane (Boiling point 80.7 ° C), methylcyclohexane (boiling point 110.9 ° C), benzene (boiling point 80.1 ° C), toluene (boiling point 110.6 ° C), o-xylene (boiling point 144, 4 ° C), m-xylene (Boiling point 139.1 ° C.), p-xylene (boiling point 138.4 ° C.), ethylbenzene (boiling point 136.2 ° C.) and the like.
- ester solvents examples include propyl formate (boiling point 81.3 ° C.), formate-n-butyl (boiling point 106.8 ° C.), isobutyl formate (boiling point 98 ° C.), amyl formate (boiling point 130.4 ° C.), ethyl acetate ( Boiling point 77.1 ° C), Acetic acid-n-propyl (boiling point 101.6 ° C), Isopropyl acetate (boiling point 89.0 ° C), Acetic acid-n-butyl (boiling point 126.5 ° C), Isobutyl acetate (boiling point 118.3 ° C) ° C), sec-butyl acetate (boiling point 112.5 ° C), acetic acid-n-amyl (boiling point 147.6 ° C), isoamyl acetate (boiling point
- ketone solvents examples include methyl ethyl ketone (boiling point 79.6 ° C.), methyl-n-propyl ketone (boiling point 103.3 ° C.), methyl-n-butyl ketone (boiling point 127.5 ° C.), methyl isobutyl ketone (boiling point 115.9 ° C.).
- organic solvents it is more preferable to use toluene, ethyl acetate, or methyl ethyl ketone from the viewpoint of cost.
- the addition of a nitrogen-containing, sulfur-containing or lactone-based solvent can dissolve the surface of the printing medium, so that the fixing property can be obtained. , Weather resistance and the like can be improved. Examples include 3-methyloxazolidinone, 3-ethyloxazolidinone, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -caprolactone, and the like.
- the addition amount is preferably 1 to 20%, preferably 1 to 10%, more preferably 3 to 9%. If these nitrogen-containing or lactone-based solvents are used excessively, problems are caused from the viewpoint of erosion to the printer member, which is not preferable.
- Examples of the printing medium of the present invention include a polyvinyl chloride resin sheet, a polyolefin-based sheet, glass, metal and the like, and a polyvinyl chloride resin sheet is particularly preferable.
- pigments used for printing ink, paint, and the like can be used.
- these pigments are represented by color index, Pigment Black 7, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49 , 52, 53, 57, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151 , 154, 155, 166, 168, 180, 185, 213, Pigment Orange 36, 43, 51, 5 , Such as 59,61,71,74, and the like.
- carbon black any carbon black such as neutral, acidic and basic can be
- a dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink.
- the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Molecular copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Phenyl ether, stearylamine acetate, etc.
- the pigment is dispersed and stabilized by the interaction with the dispersant, it is preferable to use a pigment containing a basic group which is a pigment adsorption site, and a basic containing at least one of a primary amine or a secondary amine. More preferably, a dispersant is used.
- polyester-based basic dispersants and acrylic urethane urea-based basic dispersants are most preferable from the viewpoints of solubility in solvents and storage stability of the dispersion.
- Specific examples of the basic dispersant include Solspurs 11200, Solspurs 13240, Solspers 16000, Solspers 18000, Solspers 20000, Solspurs 26000, Solspers 28000, Solspers 31845, Solspers 32500, Solspers 32550, Solspers 32600, Solspers 33000, manufactured by Lubrizol.
- polyester-based basic dispersant examples include Solspers 13940, 17000, 24000, and 32000 manufactured by Lubrizol, and Ajisper PB821, PB822, PB823, PB824, and PB827 manufactured by Ajinomoto Fine-Techno Co., Ltd. These can be used according to the kind of pigment and solvent.
- the dispersant is preferably contained in the ink in an amount of 0.1 to 10% by weight.
- various additives such as a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, an antioxidant, and a hydrolysis inhibitor can be used.
- Examples of the printing method of the ink composition of the present invention include gravure printing, flexographic printing, silk screen printing, inkjet printing, and the like, and an inkjet printing method is particularly preferable.
- the ink composition of the present invention is prepared by first dispersing a pigment in a single or mixed solvent with a resin or a dispersant using a paint shaker, sand mill, roll mill, medialess disperser, etc. It is manufactured by diluting with the solvent of the invention.
- part represents “part by weight”.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by using TSKgelsuper HZM-N columns (manufactured by Tosoh Corp.) in duplicate and using GPC (Tosoh Corp., HLC-8220 GPC) at a flow rate of 0.35 ml / min. And the molecular weight in terms of polystyrene when THF is used as the developing solvent.
- Diethylene glycol diethyl ether (DEDG) was added to adjust the solid content to 20% to obtain a vinyl polymer (A-1) solution having two free hydroxyl groups in one end region.
- the weight average molecular weight (Mw) was 5,800
- the number average molecular weight (Mn) was 3,700
- Mw / Mn was 1.57.
- Diethylene glycol diethyl ether (DEDG) was added to adjust the solid content to 20% to obtain a vinyl polymer (A-2) solution having two free hydroxyl groups in one end region.
- the weight average molecular weight (Mw) was 39,000
- the number average molecular weight (Mn) was 19,000
- Mw / Mn was 2.17.
- the mixture was further reacted at 110 ° C. for 1 hour, 0.3 parts of AIBN was added three times every hour, and the reaction was further continued at 110 ° C. for 1 hour, followed by cooling to reduce the solid content of the resin solution. It was measured.
- 200 parts of diethylene glycol diethyl ether (DEDG) was added to the reaction vessel, and the temperature was raised to 80 ° C. When the temperature reached 80 ° C., a vacuum pump was attached, and stripping was started at a reduced pressure of 60 torr, and the stripping was terminated when the solid content reached 56.2%.
- DEDG diethylene glycol diethyl ether
- Diethylene glycol diethyl ether (DEDG) was added to adjust the solid content to 20% to obtain a vinyl polymer (A-3) solution.
- the weight average molecular weight (Mw) was 5,400
- the number average molecular weight (Mn) was 2,800
- Mw / Mn was 1.93.
- This reaction solution was a colorless and transparent polycarbonate urethane resin (A-4) having a solid content of 50%, a weight average molecular weight (Mw) of 62,300, a number average molecular weight (Mn) of 28,300, and an Mw / Mn of 2 .20.
- This reaction solution was a colorless and transparent polyester urethane resin (A-5) having a solid content of 50%, a weight average molecular weight (Mw) of 62,000, a number average molecular weight (Mn) of 27,700, and an Mw / Mn of 2 .24.
- This reaction solution is a colorless and transparent polyether urethane resin (A-6) having a solid content of 50%, the weight average molecular weight (Mw) is 64,100, the number average molecular weight (Mn) is 29,200, and Mw / Mn is 2.24.
- the reaction vessel was heated to 100 ° C., reacted for 3 hours, cooled to 40 ° C., and dropped into a mixed solution of 35.9 parts of methyliminobispropylamine and 876.6 parts of diethylene glycol diethyl ether over 30 minutes. Then, after further reaction for 1 hour, the reaction was terminated by cooling to room temperature. The solid content was adjusted to 30% to obtain a pale yellow transparent solution of the dispersant (B-1).
- the amine value of the dispersant (B-1) was 48.0 mg KOH / g.
- Table 1 shows the binder resins used in Examples and Comparative Examples, which are obtained by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of commercially available binder resins and calculating Mw / Mn. To do.
- Pigment Dispersion A was prepared with the following composition. This dispersion was prepared by adding a pigment and a dispersant into an organic solvent, stirring until uniform with a high speed mixer or the like, and dispersing the obtained mill base with a horizontal sand mill for about 1 hour.
- LIONOL BLUE FG-7400G phthalocyanine pigment manufactured by Toyo Ink Manufacturing Co., Ltd.
- Azisper PB821 pigment dispersant manufactured by Ajinomoto Fine Techno Co.
- 12.50 parts ethylene glycol monobutyl ether acetate 52.50 parts In the same manner as in Production Example 1, Pigment Dispersion B was prepared.
- Pigment Dispersion D was prepared.
- ELFTEX 415 (Carbot carbon black) 35.00 parts
- Dispersant: B-1 solid content 30% DEDG varnish) 46.67 parts
- NMP N-methyl-2-pyrrolidone
- GBL gamma butyrolactone ⁇ -CL: epsilon caprolactone
- MOZ 3-methyl-2-oxazolidinone
- EOZ 3-ethyl-2-oxazolidinone
- DMSO dimethyl sulfoxide
- BGAc ethylene glycol monobutyl ether Acetate
- DEDG Diethylene glycol diethyl ether
- MEDG Diethylene glycol methyl ethyl ether
- DMTeG Tetraethylene glycol dimethyl ether
- the ink compositions of Examples 1 to 14 using only those specified in the present invention for the selection of the binder resin in the ink are all in print stability, print performance and drying property. Excellent.
- Comparative Examples 1, 6, and 12 use only one or two types having a small weight average molecular weight (Mw), so that the printing stability is good, but the printed matter performance and drying property are good.
- Mw weight average molecular weight
- Comparative Examples 5, 8, 9, 10, and 11 use a resin having a weight average molecular weight (Mw) that is too large or Mn / Mw of 3 or more, the printed material performance and drying properties are good. As a result, the printing stability was inferior.
- Comparative Examples 2, 3, 4, and 7 have a large weight average molecular weight (Mw) such as vinyl polymer A-2 having a weight average molecular weight (Mw) of 39000 and resin 3 (VYHD) having a weight average molecular weight (Mw) of 48000. Since the binder resin was used alone, the printing stability at low temperature and low humidity was lost, resulting in poor printing stability.
- Mw weight average molecular weight
- VYHD resin 3
- the evaluation method is shown below.
- the printed surface showed no noticeable change 4, the test piece was colored, and the printed surface was slightly discolored 3, but it was peeled off but the substrate was visible 2 was evaluated as 1 and the ink was peeled off and the substrate could be seen more than half.
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Abstract
Description
一般式(2) 1,000<Mwα<30,000
一般式(3) 20,000<Mwβ<100,000
ここで、αの重量平均分子量をMwα、βの重量平均分子量をMwβとする。
更に、含まれる2種類以上のバインダー樹脂が塩化ビニル系樹脂および/またはアクリル系樹脂であることを特徴とするインキ組成物に関する。
一般式(6) R4CO(OR5)ZOCOR6
一般式(7) R7(OR8)ZOR9
一般式(8) R10COOR11
(式中、R2、R5、R8、それぞれ独立してエチレン基又はプロピレン基、R1、R3、R4、R6はそれぞれ独立して炭素数1~4のアルキル基、R7、R9はそれぞれ独立して水素原子又は炭素数1~4のアルキル基、R10は2-ヒドロキシエチル基、R11は炭素数1~8のアルキル基、Zは1~3の整数を表す。)
更に、含まれる2種類以上のバインダー樹脂のうち少なくとも1種類以上がアクリル系樹脂であり、沸点60℃~150℃の有機溶剤中で合成した後、ストリッピング法により沸点150℃以上の(ポリ)アルキレングリコール誘導体の少なくとも1つに置換して用いることを特徴とする請求項1ないし請求項4いずれか記載のインキ組成物に関する。
一般式(6) R4CO(OR5)ZOCOR6
一般式(7) R7(OR8)ZOR9
一般式(8) R10COOR11
(式中、R2、R5、R8、それぞれ独立してエチレン基又はプロピレン基、R1、R3、R4、R6はそれぞれ独立して炭素数1~4のアルキル基、R7、R9はそれぞれ独立して水素原子又は炭素数1~4のアルキル基、R10は2-ヒドロキシエチル基、R11は炭素数1~8のアルキル基、Zは1~4の整数を表す。)
一般式(5)に該当する溶剤としては、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノメチルエーテルプロピオネート、エチレングリコールモノエチルエーテルプロピオネート、エチレングリコールモノブチルエーテルプロピオネート、ジエチレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールモノエチルエーテルプロピオネート、ジエチレングリコールモノブチルエーテルプロピオネート、プロピレングリコールモノメチルエーテルプロピオネート、ジプロピレングリコールモノメチルエーテルプロピオネート、エチレングリコールモノメチルエーテルブチレート、エチレングリコールモノエチルエーテルブチレート、エチレングリコールモノブチルエーテルブチレート、ジエチレングリコールモノメチルエーテルブチレート、ジエチレングリコールモノエチルエーテルブチレート、ジエチレングリコールモノブチルエーテルブチレート、プロピレングリコールモノメチルエーテルブチレート、ジプロピレングリコールモノメチルエーテルブチレート等のグリコールモノアセテート類がある。
(ビニル重合体:A-1の製造)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、メチルメタクリレート 500部、チオグリセロール 18.5部と、トルエン 518.5部を仕込み、窒素ガスで置換した。反応容器内を90℃に加熱して、AIBN 0.50部を添加した後7時間反応した後、冷却して樹脂溶液の固形分を測定した。次いで反応容器にジエチレングリコールジエチルエーテル(DEDG)を600部加えて80℃まで温度を上げた。80℃になったら真空ポンプを取り付け、60torrの減圧度でストリッピングを開始し、固形分が56.2%になったところでストリッピングを終了した。
(ビニル重合体:A-2の製造)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、メチルメタクリレート 500部、チオグリセロール 3.2部と、トルエン 503.2部を仕込み、窒素ガスで置換した。反応容器内を90℃に加熱して、AIBN 0.50部を添加した後7時間反応した後、冷却して樹脂溶液の固形分を測定した。次いで反応容器にジエチレングリコールジエチルエーテル(DEDG)を600部加えて80℃まで温度を上げた。80℃になったら真空ポンプを取り付け、60torrの減圧度でストリッピングを開始し、固形分が56.2%になったところでストリッピングを終了した。
(ビニル重合体:A-3の製造)
反応容器にトルエン 100部を入れ、容器に窒素ガスを注入しながら110℃に加熱して、同温度でメチルメタクリレート 100部、及び2,2’-アゾビスイソブチロニトリル(AIBN) 6.0部の混合物を2時間かけて滴下することにより重合反応を行った。
(ポリカーボネートウレタン樹脂:A-4の製造)
撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた4口フラスコにクラレポリオールC-590(2官能ポリカーボネートジオール、株式会社クラレ製) 100.0部、イソホロンジイソシアネート(商品名:IPDI、エボニックデグサジャパン株式会社製) 38.7部、ジエチレングリコールジエチルエーテル(DEDG) 138.7部、触媒としてジブチル錫ジラウレート 0.014部を仕込み、100℃まで徐々に昇温し2時間反応を行った。
(ポリエステルウレタン樹脂:A-5の製造)
撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた4口フラスコにクラレポリオールP-510(2官能ポリエステルジオール、株式会社クラレ製) 100.0部、イソホロンジイソシアネート(商品名:IPDI、エボニックデグサジャパン株式会社製) 38.7部、ジエチレングリコールジエチルエーテル(DEDG) 138.7部、触媒としてジブチル錫ジラウレート0.014部を仕込み、100℃まで徐々に昇温し2時間反応を行った。
(ポリエーテルウレタン樹脂:A-6の製造)
撹拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた4口フラスコにPP-400(2官能ポリエーテルジオール、三洋化成工業株式会社製) 100.0部、イソホロンジイソシアネート(商品名:IPDI、エボニックデグサジャパン株式会社製) 48.3部、ジエチレングリコールジエチルエーテル(DEDG) 148.3部、触媒としてジブチル錫ジラウレート0.015部を仕込み、100℃まで徐々に昇温し2時間反応を行った。
(分散剤:B-1の合成方法)
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、ビニル重合体(A-1)の固形分50%溶液 1037部と、イソホロンジイソシアネート 76.0部と、ジエチレングリコールジエチルエーテル 75.8部と、触媒としてジブチル錫ジラウレート 0.22部を仕込み、窒素ガスで置換した。反応容器内を100℃に加熱して、3時間反応した後、40℃まで冷却して、メチルイミノビスプロピルアミン 35.9部、ジエチレングリコールジエチルエーテル 876.6部の混合液に30分かけて滴下し、さらに1時間反応した後、室温まで冷却して反応を終了した。固形分を30%に調整し、分散剤(B-1)の淡黄色透明溶液を得た。分散剤(B-1)のアミン価48.0mg KOH/gであった。
実施例、比較例にて使用されるバインダー樹脂として、市販されているバインダー樹脂の重量平均分子量(Mw)、数平均分子量(Mn)を測定し、Mw/Mnを算出したものを表1に記載する。
顔料)35.00部
・アジスパーPB821(味の素ファインテクノ社製 顔料分散剤)12.50部
・エチレングリコールモノブチルエーテルアセテート 52.50部
更に、下記のような配合で製造例1と同様に、顔料分散体Bを作成した。
・アジスパーPB821(味の素ファインテクノ社製 顔料分散剤)12.8部
・ジエチレングリコールジエチルエーテル 55.2部
更に、下記のような配合で製造例1と同様に、顔料分散体Cを作成した。
・ソルスパーズ24000GR(ルーブリゾール社製 顔料分散剤)16.50部
・ ジエチレングリコールエチルメチルエーテル 53.50部
更に、下記のような配合で製造例1と同様に、顔料分散体Dを作成した。
・分散剤:B-1(固形分30% DEDGワニス) 46.67部
・ ジエチレングリコールジエチルエーテル 18.33部
表2のような配合で実施例1~14、比較例1~12のインキを作成した。
NMP:N-メチル-2-ピロリドン
GBL:ガンマブチロラクトン
ε-CL:イプシロンカプロラクトン
MOZ:3-メチル-2オキサゾリジノン
EOZ:3-エチル-2-オキサゾリジノン
DMSO:ジメチルスルホキシド
BGAc:エチレングリコールモノブチルエーテルアセテート
DEDG:ジエチレングリコールジエチルエーテル
MEDG:ジエチレングリコールメチルエチルエーテル
DMTeG:テトラエチレングリコールジメチルエーテル
実施例1~14、比較例1~12で得られたインキ組成物について、25℃環境下にて(株)セイコーアイ・インフォテック製 ソルベントインクインクジェットプリンターColor Painter 64S Plusにて、表面が無処理のポリ塩化ビニル樹脂シートに50時間連続印刷し、ドット抜け、飛行曲がり又はインクの飛び散りの発生頻度を評価した。この際、印刷時の環境温度,湿度を管理し、中温中湿=気温:23度,湿度:60~70% 低温低湿=気温:15℃以下 湿度:40%以下の2つの環境にて実験を行った。表には、50時間連続印刷後ノズルチェックパターンを印字し、ドット抜け、飛行曲がり又はインクの飛び散りが何箇所あるかを確認し、その数を記載した。
実施例1~14、比較例1~12で得られたインキ組成物について、(株)セイコーアイ・インフォテック製 ソルベントインクインクジェットプリンターColor Painter 64S Plusにて、表面が無処理のポリ塩化ビニル樹脂シートに印刷し、印刷面をラビングテスター(テスター産業製、型式AB301)にて耐アルコール性を評価。評価条件としては試験用布片(金巾3号)にてエタノール/水=70/30で希釈した液を1滴たらし加重200g、50往復で実施し、塗布面が全く剥ぎ取られなかったものを5、試験用布片に着色が見られたが、印刷面には目立った変化の見られないものを4、試験片が着色、印刷面にも若干の色落ちが見られるものを3、剥ぎ取られたが基材が見えたものを2、インキが剥ぎ取られ、基材が半分以上見えるものを1と評価した。
実施例1~14、比較例1~12で得られたインキ組成物について、(株)セイコーアイ・インフォテック製 ソルベントインクインクジェットプリンターColor Painter 64S Plusにて、表面が無処理のポリ塩化ビニル樹脂シートに印刷し、印刷面をラビングテスター(テスター産業製、型式AB301)にて耐ガゾリン性を評価。評価条件としては試験用布片(金巾3号)にてガゾリンを1滴たらし加重200g、10往復で実施し、塗布面が全く剥ぎ取られなかったものを5、試験用布片に着色が見られたが、印刷面には目立った変化の見られないものを4、試験片が着色、印刷面にも若干の色落ちが見られるものを3、剥ぎ取られたが基材が見えたものを2、インキが剥ぎ取られ、基材が半分以上見えるものを1と評価した。
実施例1~14、比較例1~12で得られたインキ組成物について、(株)セイコーアイ・インフォテック製 ソルベントインクインクジェットプリンターColor Painter 64S Plusにて、表面が無処理のポリ塩化ビニル樹脂シートに印刷し、60°光沢計にて光沢を評価した。
実施例1~14、比較例1~12で得られたインキ組成物について、25℃環境下にて(株)セイコーアイ・インフォテック製 ソルベントインクインクジェットプリンターColor Painter 64S Plusにて、表面が無処理のポリ塩化ビニル樹脂シートにCyan,Magenta,Yellowの3色印字にて印字率100,200,300%のベタ印刷を行い、40℃で乾燥するまでの時間を計測した。具体的には、10秒毎に触手試験を行い、手にインキが付着しなくなる時間を計測した。
Claims (8)
- 少なくとも顔料,有機溶剤および重量平均分子量(Mw)が異なる2種類以上のバインダー樹脂を含み、使用されている2種類以上のバインダー樹脂のうち重量平均分子量(Mw)が最も小さいバインダー樹脂をα,これよりも重量平均分子量(Mw)が大きく、かつ一般式(3)を満たすバインダー樹脂をβとした場合、一般式(1),(2)を満たすことを特徴とするインキ組成物。
一般式(1) Mwβ - Mwα ≧ 10,000
一般式(2) 1,000<Mwα<30,000
一般式(3) 20,000<Mwβ<100,000
ここで、樹脂αの重量平均分子量をMwα、樹脂βの重量平均分子量をMwβとする。 - 更に、含まれる2種以上のバインダー樹脂の、それぞれの重量平均分子量(Mw)と数平均分子量(Mn)の関係が、一般式(4)の範囲であることを特徴とする請求項1記載のインキ組成物。
一般式(4) 1 < Mw/Mn < 3 - 更に、含まれる2種類以上のバインダー樹脂が塩化ビニル系樹脂および/またはアクリル系樹脂であることを特徴とする請求項1または2記載のインキ組成物。
- 更に、有機溶剤として一般式(5)ないし一般式(8)で表される溶剤のいずれか1つ以上を含むことを特徴とする請求項1ないし3いずれか記載のインキ組成物。
一般式(5) R1CO(OR2)ZOR3
一般式(6) R4CO(OR5)ZOCOR6
一般式(7) R7(OR8)ZOR9
一般式(8) R10COOR11
(式中、R2、R5、R8、それぞれ独立してエチレン基又はプロピレン基、R1、R3、R4、R6はそれぞれ独立して炭素数1~4のアルキル基、R7、R9はそれぞれ独立して水素原子又は炭素数1~4のアルキル基、R10は2-ヒドロキシエチル基、R11は炭素数1~8のアルキル基、Zは1~3の整数を表す。) - 更に、含まれる2種類以上のバインダー樹脂のうち少なくとも1種類以上がアクリル系樹脂であり、沸点60℃~150℃の有機溶剤中で合成した後、ストリッピング法により沸点150℃以上の(ポリ)アルキレングリコール誘導体の少なくとも1つに置換して用いることを特徴とする請求項1ないし請求項4いずれか記載のインキ組成物。
- 更に、有機溶剤の一部に、含窒素系または含硫黄系またはラクトン系溶剤を含有することを特徴とする請求項1ないし5いずれか記載のインキ組成物。
- 更に、インキ組成物中に分散剤を含有することを特徴とする請求項1ないし6いずれか記載のインキ組成物。
- 請求項1ないし請求項7いずれか記載のインクジェットインキ。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09811578.5A EP2341109B1 (en) | 2008-09-05 | 2009-09-04 | Ink composition |
| BRPI0918771-5A BRPI0918771B1 (pt) | 2008-09-05 | 2009-09-04 | Composição de tinta |
| US13/062,348 US20110230603A1 (en) | 2008-09-05 | 2009-09-04 | Ink composition |
| US14/832,192 US20150353749A1 (en) | 2008-09-05 | 2015-08-21 | Ink composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008228848A JP2010059364A (ja) | 2008-09-05 | 2008-09-05 | インキ組成物 |
| JP2008-228848 | 2008-09-05 | ||
| JP2008-301093 | 2008-11-26 | ||
| JP2008301093A JP2010126585A (ja) | 2008-11-26 | 2008-11-26 | 非水性インキ組成物 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/062,348 A-371-Of-International US20110230603A1 (en) | 2008-09-05 | 2009-09-04 | Ink composition |
| US14/832,192 Division US20150353749A1 (en) | 2008-09-05 | 2015-08-21 | Ink composition |
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| Publication Number | Publication Date |
|---|---|
| WO2010027053A1 true WO2010027053A1 (ja) | 2010-03-11 |
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| PCT/JP2009/065512 Ceased WO2010027053A1 (ja) | 2008-09-05 | 2009-09-04 | インキ組成物 |
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|---|---|
| US (2) | US20110230603A1 (ja) |
| EP (1) | EP2341109B1 (ja) |
| KR (1) | KR101614012B1 (ja) |
| BR (1) | BRPI0918771B1 (ja) |
| WO (1) | WO2010027053A1 (ja) |
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| JP6357751B2 (ja) | 2013-10-02 | 2018-07-18 | 東洋インキScホールディングス株式会社 | 溶剤系インクジェットインキ |
| EP3164456A1 (en) | 2014-07-03 | 2017-05-10 | Corning Incorporated | Jet ink composition, method and coated article |
| TWI686354B (zh) * | 2015-01-27 | 2020-03-01 | 日商住友金屬礦山股份有限公司 | 近紅外線吸收微粒子分散液及其製造方法、使用近紅外線吸收微粒子分散液之防偽油墨組成物、及使用近紅外線吸收微粒子之防偽印刷物 |
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- 2009-09-04 WO PCT/JP2009/065512 patent/WO2010027053A1/ja not_active Ceased
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- 2009-09-04 KR KR1020117007482A patent/KR101614012B1/ko active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| US20150353749A1 (en) | 2015-12-10 |
| KR20110055709A (ko) | 2011-05-25 |
| EP2341109A4 (en) | 2014-01-22 |
| EP2341109A1 (en) | 2011-07-06 |
| BRPI0918771A2 (pt) | 2015-12-01 |
| EP2341109B1 (en) | 2017-11-29 |
| KR101614012B1 (ko) | 2016-04-20 |
| BRPI0918771B1 (pt) | 2019-03-26 |
| US20110230603A1 (en) | 2011-09-22 |
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