Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5022—Organic solvents containing oxygen
• • 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
  • B41J2/135—Nozzles
  • B41J2/165—Prevention or detection of nozzle clogging, e.g. cleaning, capping or moistening for nozzles
  • B41J2/16517—Cleaning of print head nozzles
  • B41J2/16552—Cleaning of print head nozzles using cleaning fluids
• • 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
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/36—Inkjet printing inks based on non-aqueous solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents

Definitions

• the present invention relates to a maintenance liquid used for ink used in active energy ray curable ink jet printing.
• This maintenance liquid is used as a cleaning liquid used when cleaning the ink-jet ink, and is also used as a storage liquid filled in the head when the apparatus is stopped. That is, the present invention relates to a maintenance liquid having excellent cleaning properties and storage properties.
• the ink jet printing method is a method in which fine droplets of an ink composition are attached to a substrate to be printed to record images and characters, and is characterized in that no plate is used in the printing process.
• Other electrophotographic methods are well known as printing methods that do not use plates, but the inkjet printing method is considered to be superior in terms of device cost, running cost, printing speed, etc. Among them, the demand is further expanding. As the performance of inkjet heads has improved in recent years, attention has been focused on handling small lot printing in the existing printing market. In the printing market, productivity is important, and the single-pass method, which has a high printing speed, is mostly used.
• the cleaning liquid is required to have not only excellent cleaning properties but also storage suitability such as suppression of pigment aggregates (pigment dispersion stability) generated during ink cleaning that causes ejection failure and maintenance of water repellency of the nozzle plate. .
• the ink concentration becomes dilute when cleaning the ink, so that the dispersion of the pigment is broken and the discharge due to the clogging of the nozzles due to the pigment aggregates.
• the ink is stored in a thin state for a long period of time, and the risk of nozzle clogging increases in each stage.
• the pigment surface with broken dispersion has a very high surface free energy, and not only the pigment adheres to the ink flow path inside the printer or the head, but also firmly adheres to the nozzle plate surface. Cause water repellency to deteriorate.
• Patent Documents 1 and 2 as a study of the cleaning liquid, the surface conditioner has been used to express excellent cleaning properties and ejection properties, but the storability is not considered and the ink is dilute. It cannot withstand long-term storage in the state. These are aqueous cleaning liquids and are not suitable for use in active energy ray-curable inks.
• Patent Document 3 discloses that a dispersion resin is contained in a cleaning liquid to express cleaning performance and dispersion stability of a pigment contained in the ink.
• the pigment dispersion resin used in the active energy ray-curable ink is different from dispersion due to charge repulsion used in water or the like, and a dispersion resin having high adsorptivity is used. For this reason, if there is an excessive dispersion resin that is not adsorbed by the pigment in the maintenance liquid, the dispersion resin is adsorbed on the surface of the nozzle plate, the water repellency is deteriorated, and the ejection stability is significantly lowered.
• JP 2011-126147 A Japanese Patent No. 5027444 JP 2007-254550 A
• the present invention is a cleaning liquid used when cleaning ink used for active energy ray curable ink jet printing, and is a preservative liquid that fills the head when the apparatus is stopped, and has excellent cleaning properties. And a maintenance liquid having storability.
• the inventor uses at least one type of main liquid component, one type or more of a pigment dispersion resin, and one or more types of surface conditioners, and a cleaning solution and a storage solution for cleaning an active energy ray-curable inkjet ink.
• the present invention has been accomplished by finding that the above-mentioned problems can be solved.
• the present invention relates to the following inventions (1) to (9).
• a non-aqueous maintenance liquid for an active energy ray-curable inkjet ink containing a main liquid component, a pigment dispersion resin, and a surface conditioner
• a non-aqueous maintenance liquid for an active energy ray-curable inkjet ink wherein the main liquid component is an organic solvent and / or an active energy ray-curable compound.
• the surface conditioning agent comprises an acrylic, silicon or fluorine surface conditioning agent.
• the maintenance liquid as described above, wherein the surface conditioner comprises a silicon-based surface conditioner of polyether-modified dimethylsiloxane.
• the active energy ray-curable compound includes one or more selected from the group consisting of dipropylene glycol diacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, and phenoxyethyl acrylate. , The above maintenance liquid.
• the maintenance liquid of the present invention can achieve excellent detergency and storability by containing at least one or more kinds of main liquid components, one or more kinds of pigment dispersion resins, and one or more kinds of surface conditioners. it can.
• the maintenance liquid of the present invention is a maintenance liquid for an active energy ray-curable inkjet ink containing at least one or more kinds of main liquid components, one or more kinds of pigment dispersion resins, and one or more kinds of surface conditioners.
• the maintenance liquid in the present invention can be used as a cleaning liquid or a storage liquid. Therefore, the maintenance liquid in the present invention means either or both of the cleaning liquid and the storage liquid. In this specification, the maintenance liquid may be simply referred to as a cleaning liquid.
• the cleaning liquid in the present invention is preferably used for cleaning the ink flow path and the head in the printer that ejects the energy ray curable inkjet ink from the head.
• Preservation liquid is a liquid that replaces the ink in the printer when it is not transported or printed over a long period of time, and is used to prevent ejection failures due to nozzle clogging due to hardened ink or aggregates of pigments. Is done.
• the main liquid component in the present invention a general organic solvent or an active energy ray-curable compound can be used. Moreover, an organic solvent and an active energy ray hardening-type compound can be used together as needed.
• the main liquid component is preferably contained in an amount of 85% by weight or more, more preferably 90% by weight or more with respect to 100% by weight of the maintenance liquid.
• organic solvent examples 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 acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol Propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol monobutyl ether propionate, diethylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether Terpropionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, ethylene glycol monoethyl ether butyrate,
• ethylene glycol monobutyl ether acetate diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, and tetraethylene glycol dimethyl ether are preferable.
• diethylene glycol monobutyl ether acetate, diethylene glycol Diethyl ether is more preferred.
• One or more organic solvents may be used as required.
• a monofunctional or bifunctional active energy ray-curable compound is suitable for setting the viscosity of the maintenance liquid suitable for cleaning.
• Specific examples include isobornyl acrylate, lauryl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, t-butyl acrylate, isobutyl acrylate, isooctyl acrylate, isostearyl.
• One or more active energy ray-curable compounds may be used as necessary. Among them, it is preferable to use any of 2-phenoxyethyl acrylate, dipropylene glycol diacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate from the viewpoint of viscosity, stability, and ink jet head member suitability.
• the active energy ray-curable compound is preferably contained in the maintenance liquid at 30% by weight or more. More preferably, it is 50 weight% or more, More preferably, it is 70 weight% or more.
• the viscosity of the cleaning liquid is desirably 50 mPa ⁇ s or less at 25 ° C. in order to obtain good cleaning power. Preferably, it is 5 to 30 mPa ⁇ s, more preferably 10 to 20 mPa ⁇ s.
• a maintenance liquid as a preservation
• the stability of the pigment dispersion is further improved and the effectiveness of the surface conditioner contained in the maintenance liquid is easily exhibited. It is possible to maintain a good balance of compatibility and maintain good printability with no missing nozzles.
• a pigment-dispersed resin is contained in order to improve the dispersibility of the pigment when washing the ink and the preservability as a preservation solution.
• the pigment-dispersed resin in the present invention is a resin that can disperse the pigment used in the active energy ray-curable inkjet ink, and is not particularly limited as long as it has the ability to disperse. It is desirable that the pigment-dispersed resin contained in
• pigment dispersion resin examples 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, Polymer 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 Nonylphenyl ether, stearylamine acetate, etc. can be used.
• pigment dispersion resin examples include BYK Chemie's “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101 ( Polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 168, 170, LPN 22252 (block copolymer having affinity for pigment) "," 400 ",” Bykumen "(high molecular weight unsaturated acid ester),” BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) " , “P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid and silico System) ",” Lactimon (silicon and long chain amine and unsaturated acid poly
• a basic dispersion resin having a basic functional group having affinity for the pigment a basic dispersion resin having a urethane skeleton, and a polyalkyleneimine pigment dispersion resin are preferably used.
• a basic dispersion resin having a basic functional group having affinity for the pigment a basic dispersion resin having a urethane skeleton, and a polyalkyleneimine pigment dispersion resin are preferably used.
• “BYK-LPN22252” manufactured by BYK Chemie and “Solsperse 32000, J-100, J-180” manufactured by Lubrizol are listed. Since these have good adsorptivity to pigments and particularly good dispersion stability, even if they are different from the pigment dispersion resin contained in the ink to be washed, they have good washing properties and storage stability.
• the pigment dispersion resin is preferably contained in the cleaning liquid in an amount of 0.01% by weight to 10% by weight, more preferably 0.02% by weight to 5% by weight, and still more preferably 0.05% by weight to 3% by weight. It is as follows. Even if the pigment dispersion resin is present in a small amount of about 0.01% by weight in the cleaning liquid, the pigment dispersion stabilizing effect is exhibited when the ink is diluted, and the detergency and storage stability are improved. When the pigment-dispersed resin amount is 0.02% by weight or more, the dispersion of the pigment is further stabilized, the continuous discharge property is improved, and good printability with no nozzle omission can be maintained.
• the amount of the pigment dispersion resin is more than 5% by weight, an excess of the pigment dispersion resin that is not adsorbed by the pigment adheres to the surface of the nozzle plate of the head and causes water repellency to deteriorate.
• a surface conditioner is used in order to maintain good nozzle plate water repellency and maintain printing suitability.
• a surface conditioner is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Although it has a hydrophilic group, its solubility in water is low, and when added to an ink composition, its surface tension is reduced. It is something to be made.
• the surface conditioner in the present invention is a resin or compound that lowers the surface tension of the maintenance liquid by 0.5 mN / m or more when 1 wt% is added to the cleaning liquid.
• an acrylic surface conditioning agent such as an acrylic copolymer, polyether-modified polydimethylsiloxane, polyether-modified polymer.
• polyester modified polydimethylsiloxane polyester modified methylalkylsiloxane
• polyether modified polymethylalkylsiloxane polyether modified polymethylalkylsiloxane
• aralkyl modified polymethylalkylsiloxane hydroxyl group containing polyester modified polydimethylsiloxane
• acrylic group containing polyester modified polydimethyl Siloxane hydroxyl group-containing polyether-polyester-modified polydimethylsiloxane
• acrylic group-containing polyetherester-modified polydimethylsiloxane polyether-modified polysilos Offspring polymers
• surface modifier silicon such as a silicon-modified acrylate
• fluorine-based surface control agent such as fluorine-modified acrylic polymers
• These surface conditioners may be used alone or in combination of two or more as required.
• the surface conditioner By including the surface conditioner in the maintenance liquid, good cleanability and storage stability are exhibited. Although the principle is not clear, when the ink is diluted with the maintenance liquid, the dispersant adsorbed on the pigment is desorbed, and an aggregate of the pigment and an excessive dispersion resin not adsorbed on the pigment are generated. The aggregate of pigment and excess pigment dispersion resin may cause clogging of nozzles and ink flow paths.
• the surface conditioning agent is included in the maintenance liquid, the surface conditioning agent is oriented on the nozzle plate or the wall surface of the ink flow path, and the dispersion is broken and aggregated, or excess dispersion resin that does not adsorb to the pigment is on the nozzle plate surface or ink.
• silicon-based and fluorine-based surface conditioners exhibit good adhesion prevention properties.
• polyether-modified dimethylsiloxane which is a silicon-based surface conditioner, is preferable from the viewpoints of surface tension reducing ability, compatibility with curable compounds, and compatibility with inkjet ink compositions.
• the amount of the surface conditioner in the maintenance liquid in the present invention is preferably 0.01% by weight or more and 10% by weight or less, more preferably 0.2% by weight or more and 10% by weight or less, and further preferably 1% by weight. % To 10% by weight.
• the surface conditioner By including 0.01% by weight or more of the surface conditioner in the maintenance liquid, good cleaning properties are exhibited. Further, when the addition amount is large, for example, when 0.05% by weight or more is included, pigments, excess dispersion resin, etc. Adhesion to nozzles and ink flow paths can be suppressed, and continuous ejection after washing and storage stability are excellent. If the surface conditioning agent is contained in the maintenance liquid in an amount of 10% by weight or more, the viscosity becomes high and the maintenance liquid becomes unsuitable.
• the maintenance liquid in the present invention can use a polymerization inhibitor.
• an active energy ray-curable compound is used as the main liquid component of the maintenance liquid, an increase in the viscosity of the maintenance liquid can be prevented and good storage stability can be obtained by using a polymerization inhibitor.
• One or two polymerization inhibitors such as phenothiazine, hydroquinone, p-methoxyphenol, t-butylcatechol, pyrogallol, butylhydroxytoluene, 2,6-di-tert-butyl-4-methylphenol as required
• the above can be used.
• BHT Swanox manufactured by Seiko Chemical Co., Ltd., 2,6-di-tert-butyl-4-methylphenol
• phenothiazine manufactured by Seiko Chemical Co., Ltd.
• the cleaning liquid of the present invention preferably contains 0.01 to 5% by weight of a polymerization inhibitor.
• the active energy ray-curable inkjet ink in the present invention includes at least a colorant, a polymerizable monomer, and a photopolymerization initiator, and may include a pigment dispersion resin, a surface conditioner, a polymerization inhibitor, and a solvent as necessary. it can.
• the polymerizable monomer used in the active energy ray-curable inkjet ink in the present invention the monofunctional and bifunctional active energy ray-curable compounds shown above can be used. Moreover, a polyfunctional monomer can be used as needed.
• polyfunctional monomers include trimethylolpropane triacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphoric acid triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, caprolactone-modified tri Methylolpropane triacrylate, propoxylate glyceryl triacrylate, trimethylolpropane oligoacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethylisocyanurate) tri Acrylate, tri (meth) allyl isocyanurate Trimethylolpropane triacrylate, hydroxypivalate trimethylolpropane triacrylate, ethoxylated phosphate triacryl
• Bifunctional and polyfunctional monomers may be used alone or in combination of two or more as required.
• the polymerizable monomer used in the active energy ray-curable inkjet ink it is preferable to use any of 2-phenoxyethyl acrylate, dipropylene glycol diacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate.
• an oligomer or prepolymer can be used for the active energy ray-curable inkjet ink in the present invention.
• the active energy ray-curable inkjet ink in the present invention may contain the organic solvent shown above.
• the active energy ray described in the present invention refers to an energy ray that affects the electron orbit of an irradiated object such as an electron beam, ultraviolet ray, and infrared ray, and can trigger a polymerization reaction such as radical, cation, and anion.
• the energy ray is not limited to this as long as it induces a reaction.
• pigments are often used particularly in terms of weather resistance.
• achromatic pigments such as carbon black, titanium oxide, calcium carbonate, or chromatic organic pigments can be used.
• organic pigments include insoluble azo pigments such as Toluidine Red, Toluidine Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red, soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, alizarin, indanthrone, and thioindigo.
• vat dyes such as maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, isoindolinone yellow , Isoindolinone organic pigments such as isoindolinone orange, pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioy Digo-based organic pigments, condensed azo-based organic pigments, benzimidazolone-based organic pigments, quinophthalone-based organic pigments such as quinophthalone yellow, isoindoline-based organic pigments such as isoindoline yellow, and other pigments such as flavanthrone yellow and acylamide yellow Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dian
• organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, C.I. I.
• carbon black examples include “Special BLCAK 350, 250, 100, 550, 5, 4, 4A, 6” “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, manufactured by Degussa. "45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G", “REGAL400R, 660R, 330R, 250R", “MOGUL E, L”, manufactured by Mitsubishi Chemical Corporation “MA7, 8, 11, 77, 100, 100R, 100S, 220, 230” “# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, include # 650
• titanium oxide examples include “Taipaque CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58-” manufactured by Ishihara Sangyo Co., Ltd.
• the pigment used in the active energy ray-curable inkjet ink in the present invention is preferably contained in the ink in the range of 0.1 to 30% by weight in order to obtain a sufficient concentration and sufficient light resistance.
• the above-described pigment dispersion resin to the active energy ray-curable inkjet ink in the present invention. It is preferably contained in an amount of 01 to 20% by weight.
• an acidic derivative of an organic pigment is preferably blended at the time of pigment dispersion in order to further improve the dispersibility of the pigment and the storage stability of the ink.
• photopolymerization initiator in the active energy ray-curable inkjet ink of the present invention include 4- (methylphenylthio) phenyl] phenylmethanone, benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,4,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1,2-octanedione, 1- (4- (phenylthio) -2,2- (O-benzoyloxime)), oligo (2-hydroxy-2-methyl) -1- (4- (1-Methylvinyl) phenyl) propano 1-hydroxycyclohexyl
• a sensitizer as necessary.
• Specific examples are ethyl-4-dimethylaminobenzoate, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzyl.
• An amine that does not cause an addition reaction with the polymerizable component such as amine and 4,4′-bis (diethylamino) benzophenone, can also be used in combination.
• the radical photopolymerization initiator and the sensitizer which are excellent in solubility in the ultraviolet curable compound and do not inhibit the ultraviolet transmittance.
• the said sensitizer is an example and is not limited to this.
• the photopolymerization initiator and sensitizer are preferably contained in an amount of 2 to 25% by weight based on the polymerizable monomer. If it is less than 2% by weight, the curing rate is remarkably deteriorated. If it is more than 25% by weight, not only the curing rate is different from that of 10% by weight, but also a dissolution residue may occur. Even if the undissolved residue is melted, there is a problem that the viscosity of the ink is increased and the inkjet dischargeability is deteriorated.
• the surface conditioner shown above it is preferable to use the surface conditioner shown above as necessary.
• the surface conditioner is preferably contained in the active energy ray-curable inkjet ink in an amount of 0.001 to 5% by weight. If it is less than 0.001% by weight, the wetting spread is poor, and if it is more than 5% by weight, the surface conditioner cannot be fully oriented at the ink interface, and only a certain effect is exhibited.
• phenothiazine, hydroquinone, p-methoxyphenol, t-to increase the viscosity stability of the ink with the passage of time, the discharge property after the passage of time, and the on-machine viscosity stability in the recording apparatus.
• One or more polymerization inhibitors such as butylcatechol, pyrogallol and butylhydroxytoluene can be used as required.
• the cleaning liquid and the active energy ray-curable inkjet ink composition in the present invention may be filtered with a filter having a pore size of 3 ⁇ m or less, preferably 1 ⁇ m or less after dissolution of the photopolymerization initiator. preferable.
• the active energy ray-curable inkjet ink of the present invention preferably has an electric conductivity of 10 ⁇ S / cm or less in a piezo head and does not cause electrical corrosion inside the head.
• the continuous type it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.
• pigment dispersion resin Solsperse 32000 (manufactured by Lubrizol, polyethyleneimine basic dispersion resin) 15.0 parts monomer: dipropylene glycol diacrylate (manufactured by BASF) 55.0 parts
• the above material was stirred with a high-speed mixer or the like until uniform, and then the obtained mill base was dispersed with a horizontal sand mill for about 1 hour to prepare a pigment dispersion.
• 10.0 parts of the prepared pigment dispersion and the following materials were combined, stirred for 3 hours using a rotary disper while heating to 45 ° C., and filtered through a 1 ⁇ m membrane filter to prepare ink M1.
• Monomer Dipropylene glycol diacrylate (manufactured by BASF) 17.0 parts 2- (2-vinyloxyethoxy) ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) 40.0 parts N-vinylcaprolactam (BASF) 20.0 parts
• ink W1 (Preparation of ink W1)
• the pigment used in the ink M1 was changed to a titanium oxide pigment (“PF-740” manufactured by Ishihara Sangyo Co., Ltd.), and a pigment dispersion was prepared in the same procedure.
• Ink W1 was prepared in the same manner as M1, except that the amount of the pigment dispersion obtained was 30.0 parts and the N-vinylcaprolactam used in ink M1 was not added.
• Example 1 to Example 10 Next, in the formulation shown in Table 1, each component listed in the table is added with stirring sequentially from the top, and stirred for 30 minutes using a rotary disper while heating to 45 ° C., and a 1 ⁇ m membrane filter. Filtration was performed to obtain a maintenance liquid. Detergency evaluation and storage stability evaluation were performed using the obtained maintenance liquid and the ink composition.
• the numerical values shown in Tables 1 to 3 indicate the blending ratio (% by weight) of each component.
• Examples 11 to 22 In the same manner as in Examples 1 to 10, a maintenance liquid was prepared according to the formulation shown in Table 2, and cleaning performance and storage stability were evaluated.
• ⁇ Detergency evaluation> (Detergency test) 5 g of ink was placed in a 30 ml glass petri dish and uniformly spread on the inner surface of the petri dish, and then the ink was discarded. 5 g of maintenance liquid was put into the petri dish soiled with ink, and evenly spread on the inner surface of the petri dish. The petri dish was evaluated when the petri dish was washed and the maintenance liquid was discarded three times. The evaluation criteria are as follows. ⁇ : Almost no ink color residue ⁇ : Slight ink color residue ⁇ : Ink color residue
• nozzle missing refers to a phenomenon in which ink is not ejected from the nozzles due to clogging of foreign matters such as ink aggregates in the nozzles and ink flow paths.
• the evaluation criteria are as follows. ⁇ : No nozzle omission ⁇ : Nozzle omission 1 to 2 ⁇ : Nozzle omission 3 to 10 x: Nozzle omission 11 or more
• ⁇ Preservation evaluation> (Dispersion stability test) An ink diluted solution obtained by diluting the ink to 0.1% by weight with a maintenance solution was put in a glass bottle and aged for one month at 45 ° C., and the sedimentation degree of the pigment after the aging was evaluated.
• the evaluation criteria are as follows. ⁇ : Pigment hardly settles ⁇ : Pigment slightly settles ⁇ : Most pigment settles
• Nozzle plate water repellency test Immerse the nozzle plate of the head (Kyocera KJ-4A) in the ink diluted to 0.1% by weight with the maintenance liquid. After 45 months at 45 ° C, remove the cleaning liquid with a dry cloth. Thereafter, the contact angle between the surface of the nozzle plate and 1 ⁇ L of water was measured to confirm the water repellency of the nozzle plate.
• the evaluation criteria are as follows. ⁇ : Contact angle of water is 90 ° or more ⁇ : Contact angle of water is 80 ° or more and less than 90 ° ⁇ : Contact angle of water is 70 ° or more and less than 80 ° ⁇ : Contact angle of water is less than 70 °
• Examples 1 to 22 are examples containing a main liquid component, a pigment-dispersing resin, and a surface conditioner, and are good in any of cleaning properties, continuous ejection properties, dispersion stability, nozzle plate water repellency, and storage stability. Results were obtained.
• Examples 2 to 4, 7 to 9, and 11 to 16 include the same pigment dispersion resin as the ink, and the pigment dispersion resin amount is 0.02% by weight or more, so that the pigment dispersion resin is adsorbed to the pigment. Shows better dispersion stability.
• Examples 2 to 3, 7 to 9, and 11 to 16 since the amount of the pigment dispersion resin is 5% by weight or less, the amount of the excess pigment dispersion resin that is not adsorbed to the pigment is small, and good nozzle plate water repellency is achieved. Is maintained.
• Examples 7 to 10, 13, 14, 16, 20 to 22 contain 30% by weight or more of the active energy ray-curable compound used in the ink. It is excellent in compatibility, works effectively, and exhibits good continuous discharge properties.
• the surface conditioner was used in an amount of 0.2% by weight or more and 10% by weight or less, which shows better nozzle plate water repellency. Further, in Example 14, the amount of the surface conditioning agent contained 1% by weight or more and 10% by weight or less, and the active energy ray-curable compound was used, and further excellent cleaning properties, continuous ejection properties, and storage stability were obtained. Show. Examples 17 to 22 use Solsperse J-100, Solsperse J-180, and LPN 22252, which are basic dispersion resins, as the pigment dispersion resin in the cleaning liquid. Even if they are different, they show better dispersion stability. Further, Examples 20 to 22 are used in combination with the active energy ray-curable compound and show better continuous discharge properties.
• Comparative Example 1 does not contain a pigment-dispersing resin and a surface conditioner, each test result is significantly inferior.
• Comparative Examples 2 to 3 contain a pigment-dispersed resin, but do not contain a surface conditioner and have poor cleanability. In addition, the adsorption of the pigment and excess pigment dispersion resin to the nozzle plate cannot be prevented, and the storage stability is poor. Since Comparative Example 4 does not contain a pigment-dispersed resin, it has good short-term evaluation as a cleaning liquid having a cleaning property and continuous discharge property. However, as a storage solution for dispersion stability, nozzle plate water repellency, storage stability, and the like. The long-term aging evaluation of is significantly worse.
• the main liquid component, the pigment-dispersing resin, and the surface conditioner are indispensable conditions for obtaining a maintenance liquid having excellent detergency and storage stability.
• the present invention is a cleaning liquid used when cleaning ink used for active energy ray curable ink jet printing, and is a preservative liquid that fills the head when the apparatus is stopped, and has excellent cleaning properties. And can be used as a maintenance liquid for inkjet printing in industrial applications and industrial applications.

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