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WO2016181797A1 - Encre à base d'eau - Google Patents

Encre à base d'eau Download PDF

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Publication number
WO2016181797A1
WO2016181797A1 PCT/JP2016/062815 JP2016062815W WO2016181797A1 WO 2016181797 A1 WO2016181797 A1 WO 2016181797A1 JP 2016062815 W JP2016062815 W JP 2016062815W WO 2016181797 A1 WO2016181797 A1 WO 2016181797A1
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WO
WIPO (PCT)
Prior art keywords
water
mass
pigment
less
insoluble polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/062815
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English (en)
Japanese (ja)
Inventor
高宏 前田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015255303A external-priority patent/JP6031586B1/ja
Application filed by Kao Corp filed Critical Kao Corp
Priority to US15/570,123 priority Critical patent/US10227499B2/en
Priority to EP16792522.1A priority patent/EP3275949B1/fr
Priority to CN201680025515.4A priority patent/CN107532025B/zh
Priority to BR112017022872A priority patent/BR112017022872A2/pt
Publication of WO2016181797A1 publication Critical patent/WO2016181797A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention relates to a water-based ink and an ink jet recording method.
  • the ink jet recording method is a recording method in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle onto a recording medium and attaching them. This method is widely spread because it is easy to make full color and is inexpensive, and has many advantages such as the ability to use plain paper as a recording medium and non-contact with the substrate.
  • inks using pigments as colorants have been widely used in order to impart weather resistance and water resistance to printed matter.
  • techniques such as encapsulating the pigment with a polymer using a dispersant that modifies the surface of the pigment have been developed. Yes.
  • low water-absorbing coated paper such as offset coated paper, or polyvinyl chloride resin, polypropylene resin, polyester resin, etc.
  • a recording medium for commercial printing using a non-liquid-absorbing resin film When printing is performed on these low water-absorbing and non-water-absorbing recording media by the ink jet recording method, the liquid component is slowly absorbed or not absorbed, so it takes time to dry and the initial scratch resistance may be poor.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2008-260139
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2008-260139
  • As a method for obtaining a print an aqueous solution containing 5 to 30% by mass of glycol ether or alkanediol, having a surface tension of 20 to 30 mN / m, and containing 2 to 20% by mass of a fixing resin.
  • a recording method using ink is disclosed.
  • Patent Document 2 discloses an ink composition for ink jet which has storage stability and does not have a twist or bleeding of a printed matter on a water-non-water-absorbent substrate and has good scratch resistance.
  • the product contains pigment, water, organic solvent, pigment dispersant, resin, and silicone compound, the organic solvent contains at least one specific glycol monoalkyl ether, and the content of the ether is based on the total amount of the ink composition.
  • a water-based pigment ink composition is disclosed that is a water-dispersible resin having a glass transition point of 70 ° C. or higher in an amount of 10 to 30% by mass.
  • the present invention relates to a water-based ink containing a pigment, a water-insoluble polymer particle A containing a pigment, a water-insoluble polymer particle B containing no pigment, an organic solvent C, and water.
  • A is obtained by crosslinking water-insoluble polymer particles a containing a pigment in an aqueous medium, and water-insoluble polymer particles B are water-insoluble vinyl polymer particles, water-insoluble polyester resin particles, and water-insoluble.
  • One or more types selected from polyurethane resin particles, and the organic solvent C contains one or more types selected from diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether, and propylene glycol, and the total amount of diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether In water-based ink. And% by mass or more, boiling point of the content of the organic solvent exceeding 250 ° C. 5% by mass or less in aqueous ink, the content of water is 45 mass% or more, about water-based ink.
  • the present invention maintains a long-term storage stability and ejection stability during ink jet recording (printing), and even when printing on a non-water-absorbing recording medium, clear image quality without blurring or unevenness,
  • the present invention relates to a water-based ink and an ink jet recording method capable of improving scratch resistance, water resistance, solvent resistance, and substrate adhesion at a high level with a good balance.
  • non-water-absorbing is a concept including low liquid-absorbing property and non-water-absorbing property, and the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water is It means 0 g / m 2 or more and 2.5 g / m 2 or less.
  • the water-insoluble polymer particle B is at least one selected from water-insoluble vinyl polymer particles, water-insoluble polyester resin particles, and water-insoluble polyurethane resin particles
  • the organic solvent C contains at least one selected from diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether and propylene glycol, and the total amount of diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether is 0.8% by mass or more in the water-based ink.
  • the content of the organic solvent having a boiling point exceeding 250 ° C. is 5% by mass or less in the water-based ink, A water-based ink having a water content of 45% by mass or more.
  • the ink jet recording method which is 2.5 g / m 2 or more.
  • the present invention while maintaining long-term storage stability and ejection stability during ink jet recording (printing), clear image quality without blurring or unevenness even when printing is performed on a non-water-absorbing recording medium. Further, it is possible to provide a water-based ink and an ink jet recording method capable of improving the scratch resistance, water resistance, solvent resistance and substrate adhesion at a high level in a well-balanced manner.
  • the water-based ink of the present invention comprises a water-insoluble polymer particle A containing a pigment (hereinafter also referred to as “pigment-containing polymer particle A”) and a water-insoluble polymer particle B containing no pigment (hereinafter simply referred to as “water-insoluble polymer particle B”).
  • a water-based ink containing an organic solvent C and water, Water-insoluble polymer particles A containing pigment are obtained by crosslinking polymer particles a containing pigment (hereinafter also referred to as “pigment-containing polymer particles a”) in an aqueous medium
  • the water-insoluble polymer particle B is at least one selected from water-insoluble vinyl polymer particles, water-insoluble polyester resin particles, and water-insoluble polyurethane resin particles
  • the organic solvent C contains at least one selected from diethylene glycol monobutyl ether (hereinafter also referred to as “BDG”) and diethylene glycol monoisobutyl ether (hereinafter also referred to as “iBDG”), propylene glycol, and is a total of BDG and iBDG
  • BDG diethylene glycol monobutyl ether
  • iBDG diethylene glycol monoisobutyl ether
  • propylene glycol is a total of BDG and iBDG
  • the amount is 3% by mass
  • the water-based ink of the present invention can improve the image stability, scratch resistance, water resistance, solvent resistance and substrate adhesion to a non-water-absorbing recording medium at a high level in a well-balanced manner for a long period of time. It can be suitably used as a water-based ink for flexographic printing, gravure printing, or inkjet recording.
  • the aqueous ink of the present invention is preferably used as an aqueous ink for ink jet recording since it is excellent in continuous discharge stability in the ink jet system.
  • the present invention has excellent long-term storage stability, ejection stability during inkjet recording, and high levels of image quality, scratch resistance, water resistance, solvent resistance, and substrate adhesion to non-water-absorbent recording media. Can improve in a well-balanced manner. The reason is not necessarily clear, but is considered as follows.
  • the pigment-containing polymer particles A are obtained by crosslinking the pigment-containing polymer particles a, so that the swelling of the water-insoluble polymer particles A is suppressed even in the presence of the organic solvent C and the storage stability of the water-based ink is improved. It is done. Then, the pigment-containing polymer particles A and the water-insoluble polymer particles B that do not contain a pigment, which is a vinyl polymer particle, are used together as a fixing resin, so that the pigment-containing polymer particles A and the water-insoluble polymer particles B are phase-matched on the recording medium.
  • a water-insoluble polymer particle B which is a fixing resin, is dissolved and forms a film in which it is uniformly dispersed on the printing surface.
  • the scratch resistance, water resistance, solvent resistance and substrate adhesion improve at a high level in a well-balanced manner.
  • the pigment-containing polymer particles A and the water-insoluble polymer particles B are swollen or dissolved by the organic solvent C. It is considered that the affinity with the non-water-absorbing medium is improved without reducing the drying property of the water-based ink.
  • the wet-spreading property of the water-based ink on the non-water-absorbing medium is improved and a good image quality is obtained. If there are too many organic solvents having a boiling point exceeding 250 ° C. in the organic solvent C, the drying property of the water-based ink after image formation is lowered, and the organic solvent C is interposed between the pigment-containing polymer particles A and the water-insoluble polymer particles B. It is considered that the formation of a uniform film is inhibited.
  • the average particle diameter of the water-insoluble polymer particles A containing the pigment used in the present invention is preferably 40 nm or more, more preferably 50 nm or more, still more preferably 60 nm or more, and preferably 200 nm from the viewpoint of printing density. Hereinafter, it is more preferably 150 nm or less, and still more preferably 100 nm or less.
  • the average particle diameter of the pigment-containing polymer particles A can be measured by the method described in the examples.
  • the pigment used in the present invention is not particularly limited, and may be an organic pigment, an inorganic pigment, or a mixture thereof.
  • Organic pigments include anthraquinone pigments, quinacridone pigments, indigo pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, phthalocyanine pigments, quinophthalone pigments, diketo Examples thereof include one or more selected from condensed polycyclic pigments such as pyrrolopyrrole pigments, and azo pigments such as disazo pigments and condensed azo pigments.
  • quinacridone pigments examples include C.I. I. PR (Pigment Red) 122, PR192, PR202, PR207, PR209, and C.I. I. PV (Pigment Violet) 19 and the like, and C.I. I. PR122, and C.I. I.
  • the azo pigment include C.I. I. PY (Pigment Yellow) 74, PY151, PY154, PY155, PY180, PY213, and C.I. I.
  • PB Porous Blue
  • PB15 Porous Blue
  • PB15 Porous Blue
  • PB15 Porous Blue
  • PB15 PB15: 3
  • PB15: 4 PB15: 5
  • PG Porous Green
  • PG36 Pigment Green
  • PB15: 3 and PB15: 4 are more preferable.
  • Organic pigments include derivatives of organic pigments that are raw materials.
  • the pigment derivative can be prepared by performing a treatment for bonding a functional group such as a hydroxyl group, a carboxy group, a carbamoyl group, a sulfo group, a sulfonamide group, or a phthalimidomethyl group to the surface of the organic pigment.
  • a functional group such as a hydroxyl group, a carboxy group, a carbamoyl group, a sulfo group, a sulfonamide group, or a phthalimidomethyl group
  • inorganic pigments include metal oxides such as carbon black, alumina, and titanium dioxide. These inorganic pigments may be treated with a known hydrophobizing agent such as a titanium coupling agent, a silane coupling agent, or a higher fatty acid metal salt.
  • black ink carbon black is preferred. Examples of carbon black include furnace black, thermal lamp black, acetylene black, channel black, and the like, and may be surface-treated.
  • the pigment content is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% in the aqueous ink from the viewpoint of increasing the printing density of the aqueous ink. It is at least 25% by mass, and is preferably at most 25% by mass, more preferably at most 10% by mass, still more preferably at most 7% by mass.
  • the pigment-containing polymer particle A is obtained by crosslinking the pigment-containing polymer particle a.
  • the water-insoluble polymer constituting the pigment-containing polymer particle a the water-insoluble polymer P1 is used from the viewpoint of improving the printing density of water-based ink. It is done.
  • the “water-insoluble polymer” refers to a polymer that has been dried at 105 ° C. for 2 hours and has reached a constant weight and dissolved in 100 g of water at 25 ° C., and its dissolved amount is 10 g or less.
  • the polymer preferably shows a dissolution amount of 5 g or less, more preferably 1 g or less.
  • the dissolution amount is the dissolution amount when the anionic group of the polymer is neutralized 100% with sodium hydroxide.
  • the polymer to be used include polyester, polyurethane, and vinyl polymer. From the viewpoint of storage stability of the water-based ink, one or more vinyl monomers selected from vinyl compounds, vinylidene compounds, and vinylene compounds are used. A vinyl polymer obtained by addition polymerization is preferred.
  • the water-insoluble polymer P1 a monomer mixture containing an ionic monomer (a) (hereinafter also referred to as “component (a)”) and a hydrophobic monomer (b) (hereinafter also referred to as “component (b)”),
  • component (a) an ionic monomer
  • component (b) a hydrophobic monomer
  • component (c) a vinyl polymer obtained by copolymerizing the nonionic monomer (c) (hereinafter also referred to as “component (c)”) (hereinafter also simply referred to as “monomer mixture”) is preferable.
  • This vinyl polymer has a structural unit derived from the component (a) and a structural unit derived from the component (b).
  • the water-insoluble polymer P1 preferably has a structural unit derived from the nonionic monomer (c) in addition to the structural unit derived from the component (a) and the structural unit derived from the component (b).
  • the ionic monomer (a) is used as a monomer component of the water-insoluble polymer P1 from the viewpoint of stably dispersing the pigment-containing polymer particles A in the water-based ink.
  • the ionic monomer (a) include an anionic monomer and a cationic monomer, and an anionic monomer is preferable.
  • the anionic monomer include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.
  • Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
  • Examples of the sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 3-sulfopropyl (meth) acrylate.
  • (meth) acrylate refers to acrylate and / or methacrylate. The same applies to the following.
  • Examples of the phosphoric acid monomer include vinyl phosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like.
  • anionic monomers from the viewpoint of dispersion stability of the anionic polymer particles in the water-based ink, a carboxylic acid monomer is preferable, acrylic acid and methacrylic acid are more preferable, and methacrylic acid is further preferable.
  • the hydrophobic monomer (b) is used as a monomer component of the water-insoluble polymer P1 from the viewpoint of dispersion stability of the aqueous dispersion.
  • the hydrophobic monomer (b) include one or more selected from alkyl (meth) acrylates, aromatic group-containing monomers, macromers, and the like.
  • the hydrophobic monomer (b) preferably contains a macromer.
  • the alkyl (meth) acrylate those having an alkyl group having 1 to 22 carbon atoms, preferably 6 to 18 carbon atoms are preferable.
  • “(iso or tertiary)” and “(iso)” mean both cases in which these groups are present and cases in which these groups are not present.
  • aromatic group-containing monomer a vinyl monomer having an aromatic group having 6 to 22 carbon atoms, which may have a substituent containing a hetero atom, is preferable. Are more preferable, and it is also preferable to use these in combination.
  • styrene monomer styrene, 2-methylstyrene, and divinylbenzene are preferable, and styrene is more preferable.
  • an aromatic group containing (meth) acrylate benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are preferable, and benzyl (meth) acrylate is more preferable.
  • the macromer is a compound having a polymerizable functional group at one end and a number average molecular weight of 500 to 100,000.
  • the monomer component of the water-insoluble polymer P1 Used as The polymerizable functional group present at one end is preferably an acryloyloxy group or a methacryloyloxy group, and more preferably a methacryloyloxy group.
  • the number average molecular weight of the macromer is preferably 1,000 to 10,000. The number average molecular weight is measured using polystyrene as a standard substance by gel chromatography using chloroform containing 1 mmol / L dodecyldimethylamine as a solvent.
  • an aromatic group-containing monomer-based macromer and a silicone-based macromer are preferable, and an aromatic group-containing monomer-based macromer is more preferable.
  • Examples of the aromatic group-containing monomer constituting the aromatic group-containing monomer-based macromer include the aromatic group-containing monomers, styrene and benzyl (meth) acrylate are preferable, and styrene is more preferable.
  • Specific examples of the styrenic macromer include AS-6 (S), AN-6 (S), HS-6 (S) (trade name of Toagosei Co., Ltd.) and the like.
  • Examples of the silicone macromer include organopolysiloxane having a polymerizable functional group at one end. Representative examples of the silicone macromer include those represented by the following formula.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • b represents a number of 5 to 60.
  • Examples of commercially available silicone macromers include Silaplane FM-0711, FM-0721 and FM-0725 manufactured by Chisso Corporation.
  • Nonionic monomer (c) The monomer mixture preferably further contains a nonionic monomer (c).
  • the commercially available component (c) include NK Ester M-20G, 40G, 90G, and 230G from Shin-Nakamura Chemical Co., Ltd., Bremer PE-90 and 200 from NOF Corporation. 350, PME-100, 200, 400, etc., PP-500, 800, etc., AP-150, 400, 550, 50PEP-300, 50POEP-800B, 43PAPE-600B (all of which are hydroxyl groups) Yes).
  • the above components (a) to (c) can be used alone or in combination of two or more.
  • the content of the component (a) and the component (b) in the monomer mixture (content as an unneutralized amount; the same applies hereinafter) or the component (a) in the water-insoluble polymer P1 during the production of the water-insoluble polymer P1 are as follows.
  • the content of the component (a) is preferably 3% by mass or more, more preferably 4% by mass or more, and further preferably 5% by mass or more from the viewpoint of stably dispersing the pigment-containing polymer particles A in the water-based ink. And, it is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.
  • the content of the component (b) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 40% by mass or more from the viewpoint of dispersion stability of the pigment-containing polymer particles A in the aqueous ink. Yes, and preferably 98% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
  • the content of the component (c) is 0% by mass or more, and when the component (c) is used, preferably 2% by mass or more from the viewpoint of dispersion stability of the pigment-containing polymer particles A in the aqueous ink. More preferably, it is 4 mass% or more, More preferably, it is 6 mass% or more, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.
  • the weight ratio of [(a) component / (b) component] in the monomer mixture that is, when there are two or more structural units derived from the hydrophobic monomer (b) (hydrophobic monomer (b) derived structural units)
  • the weight ratio of the structural unit derived from the salt-forming group-containing monomer (a) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0, from the viewpoint of dispersion stability of the pigment-containing polymer particles A in the aqueous ink and the printing density of the aqueous ink. 0.03 or more, and preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0.5 or less.
  • the water-insoluble polymer P1 is produced by copolymerizing a monomer mixture by a known polymerization method.
  • a solution polymerization method is preferable.
  • the solvent used in the solution polymerization method is not particularly limited, and examples thereof include one or more polar organic solvents selected from aliphatic alcohols having 1 to 8 carbon atoms, ketones, ethers, esters and the like.
  • aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ketones having 3 to 6 carbon atoms are preferable, and methyl ethyl ketone is more preferable.
  • a polymerization initiator or a polymerization chain transfer agent can be used.
  • the polymerization initiator is preferably an azo compound, more preferably 2,2′-azobis (2,4-dimethylvaleronitrile), and the polymerization chain transfer agent is preferably a mercaptan, more preferably 2 -Mercaptoethanol.
  • the polymerization temperature is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and preferably 90 ° C. or lower, more preferably 85 ° C. or lower.
  • the polymerization time is preferably 1 hour or longer, more preferably 1.5 hours or longer, and preferably 20 hours or shorter, more preferably 10 hours or shorter.
  • the polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
  • the water-insoluble polymer P1 is preferably used as it is as a polymer solution without removing the solvent used in the polymerization reaction.
  • the solid content concentration of the obtained water-insoluble polymer P1 solution is preferably 30% by mass or more, more preferably 35% by mass or more, and Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less.
  • the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation. The obtained polymer can remove unreacted monomers and the like by reprecipitation, membrane separation, chromatographic method, extraction method and the like.
  • the weight average molecular weight of the water-insoluble polymer P1 used in the present invention is preferably 5,000 or more, more preferably 1 from the viewpoint of the dispersion stability of the pigment-containing polymer particles A in the ink and the printing density of the water-based ink. 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, still more preferably 40,000 or more, and preferably 500,000 or less, more preferably 400,000 or less, still more preferably 300,000 or less, More preferably, it is 200,000 or less.
  • the measurement of a weight average molecular weight can be performed by the method as described in an Example.
  • Step (1) Step of obtaining a dispersion of water-insoluble polymer particles containing a pigment by dispersing a mixture containing the water-insoluble polymer P1, an organic solvent, a pigment, and water
  • Step (2) Step (1) Step of removing the organic solvent from the dispersion obtained in step 1 to obtain an aqueous dispersion of pigment-containing water-insoluble polymer particles a (pigment-containing polymer particles a)
  • Step (1) is a step of obtaining a dispersion of pigment-containing polymer particles A by dispersing a mixture containing the water-insoluble polymer P1, the organic solvent, the pigment, and water.
  • step (1) first, the water-insoluble polymer P1 is dissolved in an organic solvent, and then a pigment, water, and if necessary, a neutralizing agent, a surfactant, etc. are added to the obtained organic solvent solution and mixed.
  • a method of obtaining an oil-in-water type dispersion is preferred.
  • the organic solvent for dissolving the water-insoluble polymer P1 is not particularly limited, and includes aliphatic alcohols such as ethanol, isopropanol and isobutanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone, dibutyl ether, tetrahydrofuran and dioxane.
  • aliphatic alcohols such as ethanol, isopropanol and isobutanol
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone
  • dibutyl ether dibutyl ether
  • tetrahydrofuran and dioxane examples thereof include organic solvents having 2 to 8 carbon atoms such as ethers and esters.
  • organic solvents having 2 to 6 carbon atoms are preferable, and ketones such as acetone, methyl
  • the organic solvent used in the polymerization may be used as it is.
  • the water-insoluble polymer P1 may be neutralized with a neutralizing agent.
  • a neutralizing agent for example, when the water-insoluble polymer P1 is an anionic polymer and a neutralizing agent is used, the dispersion is preferably neutralized so that the pH of the dispersion is 7 to 11.
  • the neutralizing agent include bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and various amines.
  • the anionic polymer may be neutralized in advance.
  • the degree of neutralization of the anionic group of the water-insoluble polymer P1 is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, and preferably 300% or less. More preferably, it is 200% or less, and more preferably 150% or less.
  • the degree of neutralization is obtained by dividing the molar equivalent of the neutralizing agent by the molar amount of the ionic group of the water-insoluble polymer P1.
  • the pigment content is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less.
  • the content of the organic solvent is preferably 10% by mass or more, and preferably 70% by mass or less, more preferably 50% by mass or less.
  • the content of the water-insoluble polymer P1 is preferably 2% by mass or more, more preferably 3% by mass or more, and preferably 40% by mass or less, more preferably 20% by mass or less. Water is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 70% by mass or less.
  • the weight ratio of the pigment content to the water-insoluble polymer P1 content is preferably 50/50 to 90/10, and preferably 60/40 to 80 More preferably, it is / 20.
  • the average particle size of the pigment-containing polymer particles A can be atomized only by the main dispersion until the desired particle size is obtained.
  • the main dispersion is further performed by applying a shear stress to the pigment containing polymer particles It is preferable to control the average particle size of the polymer particles A to a desired particle size.
  • the temperature in the dispersion in the step (1) is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 5 ° C. or higher, and preferably 40 ° C. or lower, more preferably 30 ° C. or lower.
  • the dispersion time is preferably 1 hour or more, more preferably 2 hours or more, and preferably 30 hours or less, more preferably 25 hours or less.
  • a generally used mixing and stirring device such as an anchor blade or a disper blade, particularly a high-speed stirring and mixing device is preferable.
  • means for applying the shear stress of the present dispersion include a kneader such as a roll mill and a kneader, a high-pressure homogenizer such as a microfluidizer (trade name), a media type disperser such as a paint shaker and a bead mill.
  • Examples of commercially available media dispersers include Ultra Apex Mill (trade name, manufactured by Kotobuki Industries Co., Ltd.), Pico Mill (trade name, manufactured by Asada Tekko Co., Ltd.), and the like. A plurality of these devices can be combined. Among these, it is preferable to use a high-pressure homogenizer from the viewpoint of reducing the particle diameter of the pigment-containing polymer particles A.
  • a more preferable dispersion method is preferably pre-dispersion using a disper or the like and then high-pressure dispersion treatment.
  • “high pressure dispersion” means dispersion at a dispersion pressure of 20 MPa or more.
  • the dispersion pressure is preferably 50 MPa or more, more preferably 100 MPa or more, still more preferably 120 MPa or more, preferably 250 MPa or less, more preferably 200 MPa or less, from the viewpoint of reducing the particle size and the efficiency of dispersion treatment.
  • Step (2) is a step of removing the organic solvent from the dispersion obtained in step (1) to obtain an aqueous dispersion of pigment-containing polymer particles a.
  • An aqueous dispersion of the pigment-containing polymer particles a can be obtained by removing the organic solvent by a known method.
  • the organic solvent in the aqueous dispersion containing the obtained pigment-containing polymer particles a is preferably substantially removed, but may remain as long as the object of the present invention is not impaired.
  • the amount of the residual organic solvent is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. If necessary, the dispersion can be heated and stirred before the organic solvent is distilled off.
  • Examples of the organic solvent removing device include a batch simple distillation device, a vacuum distillation device, a thin film distillation device such as a flash evaporator, a rotary distillation device, and a stirring evaporation device.
  • the temperature of the dispersion for removing the organic solvent can be appropriately selected depending on the type of the organic solvent to be used, but is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, more preferably 30 ° C. or higher, under reduced pressure.
  • the temperature is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and still more preferably 65 ° C. or lower.
  • the removal of the organic solvent is performed until the concentration of the non-volatile component (solid content) of the dispersion from which the organic solvent has been removed is preferably 18% by mass or more, more preferably 20% by mass or more, and even more preferably 22% by mass or more. Preferably, it is preferably carried out until 60% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.
  • the obtained aqueous dispersion of pigment-containing polymer particles a is one in which the solid content of pigment-containing polymer particles a is dispersed in water as the main medium.
  • the form of the polymer particles is not particularly limited as long as the particles are formed of at least the pigment and the water-insoluble polymer P1.
  • the particle form in which the pigment is encapsulated in the polymer the particle form in which the pigment is uniformly dispersed in the polymer, the particle form in which the pigment is exposed on the polymer particle surface, and the like, and mixtures thereof are also included.
  • a particle form in which at least a part of the pigment is encapsulated in the water-insoluble polymer P1 in other words, a particle form in which at least a part of the pigment is coated with the water-insoluble polymer P1 is preferable.
  • Step (3) is a step of mixing the aqueous dispersion containing the pigment-containing polymer particles a obtained in step (2) and a crosslinking agent, and crosslinking to obtain an aqueous dispersion containing the pigment-containing polymer particles A. .
  • a crosslinking agent By performing the step (3), when the obtained water dispersion is blended in the ink, in addition to suppressing the swelling of the water-insoluble polymer P1 as the pigment dispersion resin with respect to the organic solvent C, it is a fixing resin.
  • the crosslinking treatment include a method in which the mixture of the aqueous dispersion and the crosslinking agent is reacted with stirring at 60 ° C. or higher, preferably 65 ° C. or higher.
  • the crosslinking agent a compound having in the molecule two or more functional groups that react with the ionic groups of the pigment-containing polymer particles a is preferable. From the viewpoint of improving the storage stability by controlling the molecular weight of the polymer, Compounds having 2 to 6 in it are preferred.
  • the molecular weight of the crosslinking agent is preferably 120 or more, more preferably 150 or more, and preferably 2000 or less, more preferably 1500, from the viewpoint of easy reaction and storage stability of the resulting crosslinked polymer particles. Hereinafter, more preferably 1000 or less.
  • the crosslinking agent has a dissolution amount of preferably 50 g or less, more preferably 40 g or less, still more preferably 30 g or less when dissolved in 100 g of water at 25 ° C. It is.
  • the functional group of the cross-linking agent include one or more selected from a hydroxyl group, an epoxy group, an aldehyde group, an amino group, a carboxy group, an oxazoline group, and an isocyanate group.
  • a compound having an epoxy group is preferred.
  • the epoxy equivalent (g / eq) is preferably 90 or more, more preferably 100 or more, still more preferably 110 or more, from the viewpoint of efficiently surface-crosslinking the water-insoluble polymer P1. From the viewpoint of storage stability of the resulting crosslinked polymer particles, it is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less.
  • the measurement of an epoxy equivalent can be performed by the method as described in an Example.
  • Compounds having two or more epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylol.
  • Polyglycidyl ethers such as propane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether, etc., but ethylene glycol diglycidyl Ether and trimethylolpropane polyglycidyl ether It is more preferable.
  • Examples of commercially available cross-linking agents include Denacol EX series manufactured by Nagase ChemteX Corporation, Epiol BE manufactured by NOF Corporation, and B Series.
  • the amount of the crosslinking agent used is preferably from 0.3 / 100 to 50/100, and preferably from 1/100 to 100/50 by weight ratio of [crosslinking agent / water-insoluble polymer P1], from the viewpoint of the storage stability of the aqueous dispersion and the aqueous ink. 40/100 is more preferable, and 3/100 to 25/100 is still more preferable. Further, the amount of the crosslinking agent used is preferably 0.1 mmol or more, more preferably 0.3 mmol or more, and still more preferably 0.1 mmol or more, in terms of the amount of ionic groups per 1 g of the water-insoluble polymer P1.
  • the pigment-containing polymer particles A obtained by the crosslinking treatment preferably contain 0.3 mmol or more of ionic groups neutralized with a base, more preferably 0.5 mmol or more, per 1 g of the polymer. , 1.5 mmol or less is preferable.
  • the crosslinking rate of the pigment-containing polymer particles A is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and preferably 80 mol% or less, more preferably 60 mol%. Hereinafter, it is more preferably 50 mol% or less.
  • the crosslinking rate is obtained by dividing the number of moles of reactive groups of the crosslinking agent by the number of moles of reactive groups (for example, ionic groups) that can react with the crosslinking agent of the pigment-containing polymer particles a.
  • the content (solid content) of the pigment-containing polymer particles A in the water-based ink is preferably 3.0% by mass or more, more preferably 4.0 from the viewpoint of improving image quality and substrate adhesion to a non-water-absorbing medium.
  • % By mass or more, more preferably 6.0% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 9.0% by mass. It is as follows.
  • the content of the water-insoluble polymer P1 in the water-based ink in the water-based ink is preferably 1.0% by mass or more, more preferably 2.0% by mass, from the viewpoint of improving image quality and substrate adhesion to a non-water-absorbing medium. % Or more, more preferably 3.0% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5.0% by mass or less.
  • the water-insoluble polymer particles B containing no pigment are at least one selected from water-insoluble vinyl polymer particles, water-insoluble polyester resin particles, and water-insoluble polyurethane resin particles.
  • the water-insoluble polymer P2 constituting B is preferably at least one selected from a water-insoluble acrylic polymer, a water-insoluble polyester, and a water-insoluble polyurethane. Among these, water-insoluble acrylic polymer particles using a water-insoluble acrylic polymer are more preferable.
  • the “water-insoluble polymer” has the same definition as in the water-insoluble polymer P1.
  • the water-insoluble acrylic polymer used in the present invention includes (meth) acrylic acid-derived structural units, and (meth) acrylic acid esters, vinyl chloride, and vinyl acetate. Polymers containing structural units derived from one or more selected monomers are preferred. Examples of monomers that give structural units derived from (meth) acrylic acid include acrylic acid and methacrylic acid. As a monomer which gives the structural unit derived from (meth) acrylic acid ester, (meth) acrylic acid ester containing an alkyl group and (meth) acrylic acid ester containing an aromatic group can be mentioned.
  • the (meth) acrylic acid ester containing an alkyl group those having an alkyl group having 1 to 22 carbon atoms are preferable.
  • the (meth) acrylic acid ester containing an aromatic group include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
  • the glass transition temperature of the acrylic polymer is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 30 ° C. or higher, even more preferably 50 ° C. or higher, from the viewpoint of substrate adhesion.
  • the temperature is preferably 90 ° C. or less, more preferably 85 ° C. or less, still more preferably 80 ° C. or less, and still more preferably 75 ° C. or less.
  • the water-insoluble acrylic polymer particles those synthesized appropriately may be used, or commercially available products may be used.
  • Water-insoluble acrylic polymer particles can be produced by copolymerizing a mixture of (meth) acrylic acid and (meth) acrylic acid ester by a known polymerization method.
  • the polymerization method preferably includes an emulsion polymerization method and a suspension polymerization method, and more preferably an emulsion polymerization method.
  • a polymerization initiator can be used.
  • the polymerization initiator include persulfates and water-soluble azo polymerization initiators, and persulfates such as ammonium persulfate and potassium persulfate are preferable.
  • a surfactant can be used.
  • the surfactant examples include nonionic surfactants, anionic surfactants, and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of improving the dispersion stability of the resin particles.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers, and the like, which improve the dispersion stability of resin particles. From the viewpoint, polyoxyethylene alkyl ether is preferable.
  • the polymerization temperature is preferably 50 ° C. or higher and 90 ° C. or lower
  • the polymerization time is preferably 1 hour or longer and 20 hours or shorter.
  • the polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
  • the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation.
  • the obtained polymer can remove unreacted monomers and the like by reprecipitation, membrane separation, chromatographic method, extraction method and the like.
  • the water-insoluble polymer particles B are preferably used as an aqueous dispersion (emulsion) of polymer particles containing water as a main dispersion medium without removing the solvent used in the polymerization reaction, from the viewpoint of compoundability in water-based ink. .
  • the solid content concentration of the dispersion of the water-insoluble acrylic polymer particles is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably from the viewpoint of blending with the pigment-containing polymer particles A and the water-based ink. It is 60 mass% or less, More preferably, it is 50 mass% or less.
  • the weight average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 200,000 or more, from the viewpoint of adhesion to the base material and from the viewpoint of improving the image quality when printed on a non-water-absorbing recording medium. More preferably, it is 500,000 or more, and preferably 2,500,000 or less, more preferably 1,000,000 or less.
  • Average particle size of water-insoluble acrylic polymer particles In addition, the average particle diameter of the water-insoluble acrylic polymer particles in the dispersion containing the water-insoluble acrylic polymer particles or in the water-based ink is the storage stability of the water-based ink.
  • the concentration is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, and preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 130 nm. It is as follows. The average particle size of the water-insoluble acrylic polymer particles is measured by the method described in the examples.
  • Water-insoluble acrylic polymer particles Commercially available dispersions of water-insoluble acrylic polymer particles include, for example, “NeocryA-1127” (manufactured by DSM Coating Resins, anionic self-crosslinking water-based vinyl resin), “Johncrill 390” (manufactured by BASF Japan Ltd.), etc.
  • Acrylic resin such as “Johncrill 7100”, “Johncrill 734”, “Johncrill 538” (above, manufactured by BASF Japan Ltd.), “ViniBran 701” (manufactured by Nissin Chemical Industry Co., Ltd.), etc. Examples include emulsions of vinyl chloride and acrylic resins.
  • Examples of the form of the water-insoluble acrylic polymer particles include a dispersion in which water-insoluble acrylic polymer particles are dispersed in water, and may contain a dispersant such as a surfactant as necessary.
  • the aqueous dispersion of water-insoluble acrylic polymer particles also acts as a fixing emulsion in order to fix the ink droplets ejected from the ink jet nozzles to the recording medium and obtain an image having excellent uniformity.
  • the content of the water-insoluble polymer particles B in the dispersion containing the water-insoluble acrylic polymer particles is preferably 10% by mass or more from the viewpoint of dispersion stability of the water-insoluble polymer particles B and convenience when blending the ink. 20 mass% or more is more preferable, 30 mass% or more is still more preferable, 70 mass% or less is preferable, 60 mass% or less is more preferable, and 55 mass% or less is still more preferable.
  • the water-insoluble polyester used in the present invention can be obtained by polycondensation of at least an alcohol component and a carboxylic acid component.
  • the alcohol component which is a raw material monomer for polyester, preferably contains an aromatic diol from the viewpoint of fixability after drying.
  • the aromatic diol is preferably an alkylene oxide adduct of bisphenol A.
  • the alkylene oxide adduct of bisphenol A means the entire structure in which an oxyalkylene group is added to 2,2-bis (4-hydroxyphenyl) propane.
  • the alkylene oxide adduct of bisphenol A is preferably a compound represented by the following general formula (I).
  • OR 1 and R 2 O are both oxyalkylene groups, preferably each independently an oxyalkylene group having 1 to 4 carbon atoms, more preferably an oxyethylene group or an oxyethylene group.
  • x and y correspond to the number of added moles of alkylene oxide.
  • the average value of the sum of x and y is preferably 2 or more. Further, from the same viewpoint, the average value of the sum of x and y is preferably 7 or less, more preferably 5 or less, and still more preferably 3 or less.
  • x OR 1 and y R 2 O may be the same or different from each other, but are preferably the same from the viewpoint of adhesion to the substrate.
  • the alkylene oxide adduct of bisphenol A may be used alone or in combination of two or more.
  • the alkylene oxide adduct of bisphenol A is preferably a propylene oxide adduct of bisphenol A or an ethylene oxide adduct of bisphenol A, and more preferably a propylene oxide adduct of bisphenol A.
  • the content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably from the viewpoint of the fixing property of the ink to the recording medium. It is 70 mol% or more, and the upper limit is preferably 100 mol% or less.
  • the alcohol component that is a raw material monomer for polyester may contain the following alcohol components.
  • examples of the alcohol component of the raw material monomer derived from the structural unit of the polyester resin include, for example, ethylene glycol, propylene glycol (1,2-propanediol).
  • the carboxylic acid component which is a raw material monomer for polyester includes carboxylic acids, anhydrides of those acids, and alkyl (1 to 3 carbon atoms) esters thereof.
  • carboxylic acid component aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and trivalent or higher polyvalent carboxylic acid are preferable, from the viewpoint of substrate adhesion and reactivity with the alcohol component.
  • An aromatic dicarboxylic acid and an aliphatic dicarboxylic acid are more preferable, and an aliphatic dicarboxylic acid is still more preferable.
  • aromatic dicarboxylic acid phthalic acid, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
  • aliphatic dicarboxylic acid examples include unsaturated aliphatic dicarboxylic acid and saturated aliphatic dicarboxylic acid, and unsaturated aliphatic dicarboxylic acid is preferable from the viewpoint of adhesion to the substrate and reactivity with the alcohol component.
  • unsaturated aliphatic dicarboxylic acid fumaric acid and maleic acid are preferable from the same viewpoint, and fumaric acid is more preferable.
  • the saturated aliphatic dicarboxylic acid is preferably adipic acid or succinic acid (succinic acid may be substituted with an alkyl group and / or alkenyl group).
  • succinic acid may be substituted with an alkyl group and / or alkenyl group.
  • alicyclic dicarboxylic acid cyclohexane dicarboxylic acid, decalin dicarboxylic acid, and tetrahydrophthalic acid are preferable.
  • Trimellitic acid and pyromellitic acid are preferable as the trivalent or higher polyvalent carboxylic acid.
  • the said carboxylic acid component may be individual or 2 or more types may be contained.
  • the polyester is obtained by condensation polymerization of the alcohol component and the carboxylic acid component.
  • the preferred structure and preferred content of the alcohol component and the carboxylic acid component are as described above.
  • Polyester can be produced, for example, by subjecting the alcohol component and the carboxylic acid component to condensation polymerization at a temperature of 180 ° C. or higher and 250 ° C. or lower using an esterification catalyst as necessary in an inert gas atmosphere. it can.
  • the polyester preferably has a sharp molecular weight distribution, and is preferably subjected to polycondensation using an esterification catalyst.
  • esterification catalyst examples include metal compounds such as tin catalyst, titanium catalyst, antimony trioxide, zinc acetate, and germanium dioxide. From the viewpoint of the reaction efficiency of the esterification reaction in the synthesis of the polyester, a tin catalyst is preferable.
  • tin catalyst dibutyltin oxide, tin (II) di (2-ethylhexane) ate, and salts thereof are preferably used, and tin (II) di (2-ethylhexane) ate is more preferably used.
  • an esterification cocatalyst such as gallic acid may be further used. Further, radical polymerization inhibitors such as 4-t-butylcatechol and hadroquinone may be used in combination.
  • the softening point of the polyester is preferably 80 ° C or higher, more preferably 85 ° C or higher, more preferably 90 ° C or higher.
  • the upper limit thereof is preferably 170 ° C. or lower, more preferably 145 ° C. or lower, and further preferably 125 ° C. or lower.
  • the glass transition temperature (Tg) of the polyester is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and the upper limit thereof is preferably 95 ° C. or lower, more preferably 90 ° C. or lower.
  • the acid value of the polyester is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and its upper limit. Is preferably 40 mgKOH / g or less, more preferably 37 mgKOH / g or less, and still more preferably 35 mgKOH / g or less.
  • the glass transition temperature, softening point, and acid value can all be obtained by appropriately adjusting the type of monomer used, the blending ratio, the temperature of condensation polymerization, and the reaction time.
  • the polyester resin particles can be efficiently produced by a method having the following step (1 ′) and step (2 ′) as an aqueous dispersion.
  • Step (1 ′) Step of obtaining a dispersion by dispersing a mixture containing polyester, organic solvent, neutralizing agent, and water
  • Step (2 ′) From the dispersion obtained in Step (1 ′) A step of obtaining a method for obtaining an aqueous dispersion of polyester resin particles by removing an organic solvent
  • the above steps (1 ′) and (2 ′) do not use a pigment in the production of the pigment-containing polymer particles A described above. Except this, it is the same as the step (1) and the step (2).
  • the order of mixing the polyester, the organic solvent, the neutralizing agent, and water is premixed with the polyester and the organic solvent, preferably the polyester is dissolved in the organic solvent, and then the neutralizing agent is added. It is preferable to add water while stirring.
  • the neutralizing agent ammonia is preferable.
  • a dispersion method similar to the method for producing an aqueous dispersion of pigment particles may be used, but it is preferable to disperse only by stirring.
  • the volume median particle size of the polyester resin particles obtained by the above method is preferably 5 nm or more and 200 nm or less.
  • This volume median particle size is more preferably 10 nm or more, further preferably 50 nm or more, and still more preferably 80 nm or more, from the viewpoint of improving the ink dischargeability. From the viewpoint of improving the fixability, it is more preferably 150 nm or less, more preferably 130 nm or less, and further preferably 120 nm or less.
  • Examples of the form of the water-insoluble polyester resin particles include a dispersion in which water-insoluble polyester resin particles are dispersed in water, and may contain a dispersant such as a surfactant as necessary.
  • the aqueous dispersion of water-insoluble polyester resin particles also functions as a fixing emulsion in order to fix the ink droplets ejected from the ink jet nozzles to the recording medium and obtain an image having excellent uniformity.
  • the content of the water-insoluble polymer particles B in the dispersion containing the water-insoluble polyester resin particles is preferably 10% by mass or more from the viewpoint of the dispersion stability of the water-insoluble polymer particles B and the convenience when blending the ink. More preferably, it is more preferably 30% by mass or more, more preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less.
  • the water-insoluble polyurethane used in the present invention (hereinafter also simply referred to as “polyurethane”) was synthesized by reacting an organic compound having two or more active hydrogen atoms, a polyisocyanate, and a dialkanol carboxylic acid. Thereafter, the carboxyl group in polyurethane A can be obtained by neutralizing with a neutralizing agent and dispersing in water. More specifically, the synthesis of polyurethane A can be performed by addition reaction of polyol, diisocyanate, and dialkanol carboxylic acid. In the above addition reaction, if necessary, a chain extender or a reaction terminator may be used in combination.
  • polyurethane A is reacted by a multi-stage method to synthesize a urethane prepolymer, and then this prepolymer is mixed with water while neutralizing with a neutralizing agent to cause a water elongation reaction and simultaneously dispersed in water.
  • a neutralizing agent to cause a water elongation reaction and simultaneously dispersed in water.
  • it is easy to adjust the viscosity and distill off the solvent, which is suitable for production.
  • a particulate polyurethane having an average particle size of 0.01 to 1 ⁇ m can be obtained in the form of an emulsion.
  • Diisocyanates include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, chain aliphatic isocyanates such as trimethylhexamethylene diisocyanate, lysine diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene.
  • Diisocyanates hydrogenated xylylene diisocyanates, isophorone diisocyanates, aliphatic isocyanates having a cyclic structure such as 4,4'-dicyclohexylmethane diisocyanate, aromatic isocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, and modified products of these diisocyanates ( Carbodiimide, uretdione, ureitoimine-containing modified products, etc.) And the like. Of these, aliphatic diisocyanates are preferred.
  • the polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule, but polycarbonate polyol, polyester polyol, and polyether polyol are preferable, and polycarbonate polyol is more preferable. That is, the water-insoluble polyurethane is more preferably a polycarbonate-based polyurethane, and the water-insoluble polyurethane resin particles are more preferably a polycarbonate-based polyurethane resin particle.
  • the polycarbonate polyol can be obtained by reacting a carbonate compound and a diol.
  • the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, diethylene carbonate, and the like.
  • diol examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol optionally substituted with a lower alcohol, Aliphatic diols such as 1,6-hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, and the like, cycloaliphatic diols such as hydrogenated xylylene glycol, and aromatic diols such as xylylene glycol Is mentioned.
  • Aliphatic diols such as 1,6-hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecaned
  • aliphatic diols are preferred, and carbon chain lengths such as 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, heptanediol, octanediol, and nonanediol are preferred. 4 to 9 aliphatic diols are more preferred.
  • the polyester polyol can be obtained by condensing a low molecular weight diol and a dicarboxylic acid.
  • the low molecular weight diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol and the like, and ethylene glycol, propylene glycol, 1,4-butanediol and the like are preferable.
  • dicarboxylic acid examples include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and brassic acid, and aromatic dibasic acids such as isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
  • aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and brassic acid
  • aromatic dibasic acids such as isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
  • Examples include basic acids, but aliphatic dibasic acids are preferable, and dibasic acids having a methylene chain length of 4 to 8 such as adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are more preferable.
  • a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, etc. may be used alone or in combination of two or more by using a compound having an active hydrogen atom as a catalyst.
  • examples thereof include polymers obtained by mixing and ring-opening polymerization. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • reaction solvent for polyol and diisocyanate examples include acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, toluene, xylene, and the like. From the viewpoint of emulsifying the reaction product, acetone, methyl ethyl ketone, ethyl acetate, and the like are preferable.
  • the dialkanol carboxylic acid is a component for introducing an anionic hydrophilic group for stably dispersing the polyurethane in water, and examples thereof include dimethylolacetic acid and dimethylolpropionic acid.
  • An aqueous dispersion can be obtained by neutralizing these carboxylic acids with a neutralizing agent.
  • the neutralizing agent include alkylamines such as butylamine and triethylamine, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and inorganic bases such as morpholine, ammonia and sodium hydroxide.
  • the reaction product of the polyol and the diisocyanate can be further increased in molecular weight using a known chain extender if necessary.
  • the chain extender include polyols and polyamines, and examples of the reaction terminator include monoalcohols and monoamines.
  • the acid value of polyurethane is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and 50 mgKOH / g or less from the viewpoint of water dispersibility.
  • Examples of the form of the water-insoluble polyurethane resin particles include a dispersion in which water-insoluble polyurethane resin particles are dispersed in water, and may contain a dispersant such as a surfactant as necessary.
  • the aqueous dispersion of water-insoluble polyester resin particles also functions as a fixing emulsion in order to fix the ink droplets ejected from the ink jet nozzles to the recording medium and obtain an image having excellent uniformity.
  • the content of the water-insoluble polymer particles B in the dispersion containing the water-insoluble polyurethane resin particles is preferably 10% by mass or more from the viewpoint of the dispersion stability of the water-insoluble polymer particles B and the convenience when blending the ink.
  • the dispersion of commercially available water-insoluble polyurethane resin particles that can be used include NeoRez R-9603 manufactured by DSM Coating Resins.
  • the content (solid content) of the water-insoluble polymer particles B in the water-based ink is preferably 1.0% by mass or more, more preferably 1.6%, from the viewpoint of improving image quality and substrate adhesion to a non-water-absorbing medium.
  • the mass ratio of the pigment to the water-insoluble polymer particle B [pigment / water-insoluble polymer particle B] is preferably from the viewpoint of improving the image quality and substrate adhesion to the non-water-absorbing medium and improving the printing density. 3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, still more preferably 0.7 or more, and preferably 4.0 or less, more preferably 3.0 or less, still more preferably It is 2.5 or less, more preferably 2.0 or less.
  • Organic solvent C contains one or more selected from diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether (hereinafter also referred to as “alkylene glycols”) and propylene glycol, and the total amount of diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether is
  • alkylene glycols diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether
  • the content of the organic solvent in the water-based ink is 0.8% by mass or more and the boiling point exceeds 250 ° C. is 5% by mass or less in the water-based ink.
  • the total content of one or more selected from diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether is preferably 3% by mass or more, more preferably 5% by mass or more in the water-based ink. From the viewpoint of stability and image quality improvement, the content is preferably 20% by mass or less, more preferably 10% by mass or less in the water-based ink. When the total amount is less than 0.8% by mass, sufficient wettability with respect to the substrate cannot be obtained, image quality is deteriorated, and white stripes may be generated.
  • the organic solvent C contains propylene glycol as an organic solvent other than the above alkylene glycols.
  • the organic solvent C contained in the water-based ink is only alkylene glycols, the image quality deteriorates because droplets are difficult to be generated when the water-based ink is ejected from the printer, and mist and satellite are easily generated.
  • storage stability tends to deteriorate.
  • the content of propylene glycol in the water-based ink is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, still more preferably 28% by mass or more, and preferably 38%.
  • the content of the organic solvent C is preferably 40% by mass or more, more preferably 50% by mass with respect to the total amount of water and the organic solvent C. From the viewpoint of the storage stability of the water-based ink, it is preferably 80% by mass or less, more preferably 75% by mass or less.
  • the organic solvent C can be used in combination with other organic solvents other than the above alkylene glycols and propylene glycol, but the content of the organic solvent having a boiling point exceeding 250 ° C. is 5% by mass or less, preferably 3% in the water-based ink.
  • the organic solvent does not contain an organic solvent having a boiling point exceeding 250 ° C., more preferably 1% by mass or less, more preferably 1% by mass or less.
  • the organic solvent having a boiling point exceeding 250 ° C. increases, the solvent tends to remain between the substrate and the printing surface, which acts as a mold release agent, and the substrate adhesion, water resistance, and solvent resistance tend to deteriorate. is there.
  • the organic solvent used in combination is more preferably liquid in a 25 ° C. environment.
  • Use of an organic solvent that is not liquid in a 25 ° C. environment increases water retention on the recording medium and is difficult to remove by evaporation. There is a tendency to greatly deteriorate the solvent resistance.
  • organic solvents include aliphatic diols having 2 to 6 carbon atoms having a hydroxy group bonded to a secondary carbon atom, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Examples thereof include glycol ethers such as propyl ether and diethylene glycol monoisopropyl ether, and ⁇ -butyrolactone.
  • the number of carbon atoms having a hydroxy group bonded to a secondary carbon atom is 2 to 6, preferably 3 carbon atoms.
  • An aliphatic diol of 5 or less is preferred.
  • aliphatic diols having 3 or 4 carbon atoms selected from 1,2-propanediol, 1,2-butanediol, and 1,3-butanediol are more preferable, and 1,2-butanediol is more preferable.
  • An aliphatic diol selected from 1,3-butanediol is more preferable.
  • glycol ethers diethylene glycol monomethyl ether is more preferable.
  • the water used in the water-based ink of the present invention is preferably pure or ultrapure water such as ion exchange water and distilled water.
  • the water content is 45% by mass or more, preferably 48% by mass or more, and more preferably 50% by mass or more in the water-based ink from the viewpoint of reducing the amount of the organic solvent used and improving the dischargeability. And 75% by mass or less.
  • a surfactant is preferably added as a surface tension adjusting agent from the viewpoint of improving image quality and ejection stability.
  • the surfactant include a nonionic surfactant, a silicone-based surfactant, and a fluorine-based surfactant, and a nonionic surfactant is more preferable. Any nonionic surfactant may be used as long as it can be used in water-based inks.
  • polyoxyalkylene alkyl ether surfactants and acetylene glycol surfactants are preferable, and surfactants of alkylene oxide adducts of alcohols having 6 to 30 carbon atoms are more preferable. preferable.
  • a surfactant of an alkylene oxide adduct of an alcohol having 6 to 30 carbon atoms and an acetylene glycol type More preferably, a surfactant is used in combination.
  • the alcohol preferably has 8 or more carbon atoms, more preferably 10 or more, still more preferably 12 or more, and is preferably 24 or less, more preferably 22 or less, still more preferably 20 or less.
  • an ethylene oxide adduct, an adduct of ethylene oxide and propylene oxide is preferable from the same viewpoint as described above, and an adduct of ethylene oxide, that is, polyoxyethylene alkyl ether is more preferable.
  • the content of the surfactant in the water-based ink is preferably 0.05% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 3.0%.
  • the aqueous ink of the present invention may be added with a pH adjuster such as amines, a fungicide, a preservative, a chelating agent such as ethylenediaminetetraacetic acid, a rust inhibitor, an antioxidant, etc. It can be used as a water-based ink for flexographic printing, gravure printing, or ink-jet recording, preferably water-based ink for ink-jet recording. Moreover, it is preferable that the water-based ink of the present invention does not contain a radical initiator and / or a polymerizable monomer, for example, from the viewpoint of safety in printing applications for food packages.
  • a pH adjuster such as amines, a fungicide, a preservative, a chelating agent such as ethylenediaminetetraacetic acid, a rust inhibitor, an antioxidant, etc. It can be used as a water-based ink for flexographic printing, gravure printing, or ink-jet recording, preferably water
  • the ink jet recording method of the present invention is a method of recording on a recording medium using the water-based ink, and the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water is 0 g / m 2 or more. 0.5 g / m 2 or less.
  • the recording medium used has a water absorption of 0 g / m 2 or more and 2.5 g / m 2 or less when the contact time between the recording medium and pure water is 100 msec.
  • Such a substrate examples include one or more selected from polyester films, polyvinyl chloride films, polypropylene films, polyethylene films, nylon films, and the like. These films may be subjected to surface treatment such as corona treatment as necessary.
  • Examples of generally available films include Lumirror T60 (manufactured by Toray Industries, Inc., polyethylene terephthalate, thickness 125 ⁇ m, water absorption 2.3 g / m 2 ), PVC80BP (manufactured by Lintec Corporation, polyvinyl chloride, water absorption 1 .4 g / m 2 ), KAINUS KEE70CA (manufactured by Lintec Corporation, polyethylene), Yupo SG90 PAT1 (manufactured by Lintec Corporation, polypropylene), Bonile RX (manufactured by Kojin Film & Chemicals Co., Ltd., nylon) and the like.
  • the said water absorption is measured by the method as described in an Example.
  • an ink jet recording apparatus used in the ink jet recording method there are a thermal type and a piezo type.
  • the piezo method is less heated and volatilized during printing, and can be printed without impairing the performance of the water-based ink.
  • an image can be formed by the ink jet recording method using the aqueous ink after heating the recording medium.
  • the heating temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of fixability, and preferably 100 ° C.
  • heating may be performed after image formation.
  • the heating temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of fixability, and preferably 100 ° C. or lower, more preferably 80 ° C., from the viewpoint of suppressing modification of the recording medium and from the viewpoint of energy suppression.
  • it is 60 degrees C or less more preferably.
  • the heating time is preferably 10 seconds or more, more preferably 60 seconds or more, and still more preferably 120 seconds or more from the viewpoint of improving drying, and from the viewpoint of suppressing the modification of the recording medium and from the viewpoint of energy suppression, It is 300 seconds or less, more preferably 200 seconds or less.
  • the present invention further discloses the following water-based ink and ink jet recording method with respect to the above-described embodiments.
  • the water-insoluble polymer particle A containing a pigment is obtained by crosslinking the water-insoluble polymer particle a containing a pigment with a compound having two or more epoxy groups in the molecule, ⁇ 1>
  • a monomer mixture in which the water-insoluble polymer P1 constituting the water-insoluble polymer particles a containing a pigment contains an ionic monomer (a) and a hydrophobic monomer (b), preferably a nonionic monomer (c).
  • the content of the component (a) in the water-insoluble polymer P1 is preferably 3% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, and preferably 40% by mass.
  • the water-based ink according to ⁇ 3> more preferably 30% by mass or less, and further preferably 25% by mass or less.
  • the content of the component (b) in the water-insoluble polymer P1 is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 40% by mass or more, and preferably 98% by mass.
  • the water-based ink according to ⁇ 3> or ⁇ 4> more preferably 80% by mass or less, and still more preferably 70% by mass or less.
  • the content of the component (c) in the water-insoluble polymer P1 is 0% by mass or more, preferably 2% by mass or more, more preferably 4% by mass or more, and further preferably 6% by mass or more.
  • the epoxy equivalent (g / eq) of the compound having two or more epoxy groups in the molecule is preferably 90 or more, more preferably 100 or more, still more preferably 110 or more, and preferably 1000 or less.
  • the molecular weight of the compound having two or more epoxy groups in the molecule is preferably 120 or more, more preferably 150 or more, and preferably 2000 or less, more preferably 1500 or less, and still more preferably 1000 or less.
  • the amount of the compound having two or more epoxy groups in the molecule is preferably 0.3 / 100 to 50/100, more preferably 1 / in weight ratio of [crosslinking agent / water-insoluble polymer P1].
  • the amount of the compound having two or more epoxy groups in the molecule is preferably the polymer in terms of the amount of ionic groups per gram of the water-insoluble polymer P1 constituting the pigment-containing water-insoluble polymer particle a. In an amount that reacts with 0.1 mmol or more, more preferably 0.3 mmol or more, more preferably 0.5 mmol or more, and preferably 20 mmol or less, more preferably 15 mmol or less of the ionic group of the polymer.
  • the water-based ink according to any one of the above ⁇ 3> to ⁇ 10>, which is an amount that reacts with 10 mmol or less, more preferably 5 mmol or less, and even more preferably 1.0 mmol or less.
  • the pigment-containing polymer particles A obtained by crosslinking treatment contain 0.3 mmol or more, preferably 0.5 mmol or more, of ionic groups neutralized with a base per 1 g of the polymer, and 1.5 mmol
  • the crosslinking rate of the water-insoluble polymer particles A containing the pigment is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and preferably 80 mol% or less.
  • the average particle size of the water-insoluble polymer particles A containing the pigment is preferably 40 nm or more, more preferably 50 nm or more, still more preferably 60 nm or more, and preferably 200 nm or less, more preferably 150 nm or less, More preferably, the water-based ink according to any one of ⁇ 1> to ⁇ 13>, which is 100 nm or less.
  • the glass transition temperature of the water-insoluble polymer P2 constituting the water-insoluble polymer particles B containing no pigment is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, still more preferably 30 ° C. or higher, and still more preferably.
  • the water-based ink according to any one of the above.
  • the average particle size of the water-insoluble polymer particles B containing no pigment is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, and preferably 300 nm or less, more preferably 200 nm or less, The water-based ink according to any one of ⁇ 1> to ⁇ 16>, further preferably 150 nm or less, and still more preferably 130 nm or less.
  • the content of propylene glycol in the water-based ink is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 38% by mass or less.
  • the content of the organic solvent having a boiling point of more than 250 ° C. in the water-based ink is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably the boiling point is 250 ° C.
  • the pigment content in the water-based ink is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 25% by mass or less, more preferably
  • the content (solid content) of the water-insoluble polymer particles A containing the pigment in the water-based ink is preferably 3.0% by mass or more, more preferably 4.0% by mass or more, and further preferably 6.0%.
  • ⁇ 1> to ⁇ % preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 9.0% by mass or less.
  • the content of the water-insoluble polymer P1 in the aqueous ink in the aqueous ink is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and further preferably 3.0% by mass or more.
  • the content of the water-insoluble polymer particles B in the water-based ink is preferably 1.0% by mass or more, more preferably 1.6% by mass or more, still more preferably 2.4% by mass or more, and further preferably 3 0.0 mass% or more, more preferably 3.5 mass% or more, and preferably 7.0 mass% or less, more preferably 6.5 mass% or less, still more preferably 6.0 mass% or less,
  • the mass ratio of the pigment to the water-insoluble polymer particle B [pigment / water-insoluble polymer particle B] is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.6 or more, and still more preferably. Is 0.7 or more, and preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, and still more preferably 2.0 or less, ⁇ 1> to ⁇ 23>
  • the water-based ink according to any one of the above.
  • the content of the organic solvent C in the water-based ink is preferably 40% by mass or more, more preferably 50% by mass or more with respect to the total amount of water and the organic solvent C, and preferably The water-based ink according to any one of ⁇ 1> to ⁇ 24>, which is 80% by mass or less, more preferably 75% by mass or less.
  • the total content of one or more selected from diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether is preferably 3% by mass or more, more preferably 5% by mass or more in the aqueous ink, and in the aqueous ink.
  • the water-based ink according to any one of ⁇ 1> to ⁇ 25> preferably 20% by mass or less, more preferably 10% by mass or less.
  • the water content in the water-based ink is 45% by mass or more, preferably 48% by mass or more, more preferably 50% by mass or more, and 75% by mass or less.
  • a nonionic surfactant preferably a polyoxyalkylene alkyl ether type surfactant, an acetylene glycol surfactant, more preferably an alkylene oxide adduct of an alcohol having 6 to 30 carbon atoms.
  • the water-based ink according to any one of ⁇ 1> to ⁇ 27> further comprising an agent and an acetylene glycol surfactant.
  • ⁇ 29> The water-based ink according to any one of ⁇ 1> to ⁇ 28>, which does not contain a radical initiator and / or a polymerizable monomer.
  • ⁇ 30> The water-based ink according to any one of ⁇ 1> to ⁇ 29>, which is for inkjet recording.
  • An ink jet recording method for recording on a recording medium using a water-based ink wherein the water-based ink includes water-insoluble polymer particles A containing a pigment, water-insoluble polymer particles B not containing a pigment, and an organic solvent C.
  • Water-insoluble polymer particles A containing water and a pigment are obtained by crosslinking water-insoluble polymer particles a containing a pigment in an aqueous medium, and water-insoluble polymer particles B are It is a vinyl polymer particle, the organic solvent C contains at least one selected from diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether, and propylene glycol, and the total amount of diethylene glycol monobutyl ether and diethylene glycol monoisobutyl ether is 3 in the aqueous ink. And the boiling point is 250 ° C.
  • the excess organic solvent content is 5% by mass or less in the water-based ink, the water content is 45% by mass or more, and the water absorption amount of the recording medium at a contact time of 100 msec between the recording medium and pure water is 0 g. / m 2 or more 2.5 g / m 2 or less, the ink jet recording method.
  • the recording medium is one or more selected from a polyester film, a polyvinyl chloride film, a polypropylene film, a polyethylene film, a nylon film, and the like.
  • the heating temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and preferably 100 ° C. or lower, more preferably. Is 80 ° C. or lower, more preferably 60 ° C. or lower, the inkjet recording method according to ⁇ 32> or ⁇ 33>.
  • Heating is performed after image formation, and the heating temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 60 ° C. or lower.
  • the inkjet recording method according to any one of ⁇ 32> to ⁇ 34>.
  • the heating time is preferably 10 seconds or more, more preferably 60 seconds or more, still more preferably 120 seconds or more, and preferably 300 seconds or less, more preferably 200 seconds or less, ⁇ 35>
  • the amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
  • (7) Glass transition temperature of resin Using a differential scanning calorimeter (trade name: Pyris 6 DSC, manufactured by Perkin Elmer), the temperature was raised to 200 ° C., and the temperature was cooled to 0 ° C. at a rate of temperature reduction of 10 ° C./min. The sample is heated at a heating rate of 10 ° C / min, and the glass transition takes place at the intersection of the baseline extension below the maximum peak temperature of endotherm and the tangent that indicates the maximum slope from the peak rise to the peak apex. Points.
  • the aqueous dispersion was freeze-dried at ⁇ 10 ° C. for 9 hours using a freeze dryer “FDU-2100” manufactured by Tokyo Rika Kikai Co., Ltd. A sample was used.
  • the pigments, water dispersion of water-insoluble polymer particles B, organic solvent C, and surfactant used in the following production examples, preparation examples, examples and comparative examples are as follows.
  • [Pigment] Copper phthalocyanine pigment (Fastgen Blue TGR-SD, manufactured by DIC Corporation)
  • B-1 Water-insoluble acrylic emulsion (Vinyl Blanc 701, manufactured by Nissin Chemical Industry Co., Ltd., vinyl chloride / acrylic resin emulsion, solid content concentration 30.0%), average particle size 57.2 nm
  • B-2 Water-insoluble acrylic resin emulsion (NeoCryl A-1127, DSM Coating Resins, solid content concentration 44.0%), average particle size 63.0 nm
  • B-3 Water-insoluble polyester resin emulsion obtained by the following method 3718 g of polyoxypropylene (2.2) adduct of bisphenol A, 1282 g of fumaric acid, 25 g of di (2-ethylhexanoic acid) tin (esterification catalyst), gallic 0.25 g of acid (esterification co-catalyst) was placed in a 10 L
  • polyester resin had a softening point of 100.9 ° C., a glass transition temperature of 58.5 ° C., and an acid value of 22.4 mgKOH / g.
  • 200 g of the obtained polyester resin is dissolved in 200 g of methyl ethyl ketone (MEK), and 3.26 g of 25% ammonia water and 467 g of ion-exchanged water are added thereto as a neutralizing agent, and a disper blade is used at 10 ° C. to 15 ° C.
  • MEK methyl ethyl ketone
  • the mixture was stirred and mixed at 2000 rpm for 15 minutes to obtain a dispersion of polyester resin particles (solid content concentration 40%).
  • B-4 Water-insoluble polyurethane resin emulsion (NeoRez R-9603, manufactured by DSM Coating Resins, solid content concentration 34%, acid value 32 mg KOH / g), average particle size 34.7 nm
  • BX1 Water-soluble styrene / acrylic acid polymer emulsion (Johncrill 690, manufactured by BASF Japan, solid content concentration 20%, weight average molecular weight 16500, acid value 240 mgKOH / g)
  • BX2 water-soluble urethane resin emulsion (Acryt WBR-016U, manufactured by Taisei Fine Chemical Co., Ltd., solid content concentration 30.0%), average particle diameter 19.7 nm
  • BDG diethylene glycol monobutyl ether, boiling point 230 ° C.
  • IBDG diethylene glycol monoisobutyl ether, boiling point 220 ° C.
  • Propylene glycol boiling point 187 ° C ⁇ 1,2-butanediol, boiling point 190 °C 1,3-butanediol, boiling point 207 ° C
  • MDG Diethylene glycol monomethyl ether, boiling point 194 ° C.
  • BTG triethylene glycol monobutyl ether, boiling point 304 ° C. -Glycerin, boiling point 290 ° C, manufactured by Kao Corporation
  • Organic solvents other than glycerin are manufactured by Wako Pure Chemical Industries, Ltd.
  • Nonionic surfactant A Emulgen 120, manufactured by Kao Corporation, polyoxyethylene lauryl ether, nonionic surfactant B: Surfynol 104PG-50, manufactured by Kawaken Fine Chemicals, acetylene glycol surfactant, propylene glycol Solution of non-ionic surfactant
  • Production Example 1 Production of water-insoluble polymer P1 solution
  • the monomers, organic solvent (methyl ethyl ketone), and polymerization chain transfer agent (2-mercaptoethanol) shown in “Initially charged monomer solution” shown in Table 1 are added and mixed. Then, nitrogen gas replacement was performed to obtain an “initially charged monomer solution”.
  • the mixed solution in the reaction vessel was stirred at 77 ° C. for 0.5 hour.
  • a polymerization initiator solution in which 0.6 part of the polymerization initiator was dissolved in 27.0 parts of methyl ethyl ketone was prepared, added to the mixed solution, and aged by stirring at 77 ° C. for 1 hour.
  • the polymerization initiator solution was further prepared, added and aged for 5 times.
  • the reaction solution in the reaction vessel was maintained at 80 ° C. for 1 hour, and methyl ethyl ketone was added to obtain a solution of the water-insoluble polymer P1 (solid content concentration 40.8%).
  • the obtained water-insoluble polymer P1 had a weight average molecular weight of 52,700.
  • Preparation Example 1 (Preparation of pigment dispersion A-1C) (1) Step 1 157.6 g of the water-insoluble polymer a solution (solid content concentration 40.8%) obtained in Production Example 1 was mixed with 60.7 g of methyl ethyl ketone (MEK) to obtain a MEK solution of water-insoluble polymer a.
  • MEK methyl ethyl ketone
  • the MEK solution of the water-insoluble polymer a is charged into a 2 L volume of the disper, and while stirring at 1400 rpm, 446.9 g of ion-exchanged water, 22.3 g of 5N aqueous sodium hydroxide, and 1.7 g of 25% aqueous ammonia.
  • Step 2 Place 1000 g of the dispersion-treated product obtained in step 1 into a 2 L eggplant flask, add 400 g of ion-exchanged water (solid content concentration 15.0% by mass), and use a rotary distillation apparatus “Rotary evaporator N-1000S” (Tokyo Rika Kikai Co., Ltd.) Was used for 3 hours at a pressure of 0.09 MPa in a warm bath adjusted to 32 ° C. at a rotation speed of 50 rpm to remove the organic solvent. Furthermore, the warm bath was adjusted to 62 ° C., the pressure was lowered to 0.07 MPa, and the mixture was concentrated to a solid content concentration of 25.0 mass%.
  • the obtained concentrate was put into a 500 ml angle rotor, and centrifuged at 7000 rpm for 20 minutes using a high-speed cooling centrifuge “himac CR22G” (manufactured by Hitachi Koki Co., Ltd., set temperature: 20 ° C.). Filtration through a 5 ⁇ m membrane filter “Minisart” (manufactured by Sartorius) gave a pigment dispersion a.
  • the mixture was filtered through the 5 ⁇ m filter, and ion-exchanged water was further added so that the solid content concentration was 22.0% by mass to obtain pigment dispersion A-1C (crosslinking rate: 40 mol%). .
  • the average particle diameter of the water-insoluble polymer particles A-1C containing the pigment was 93.1 nm.
  • Preparation Example 2 (Preparation of pigment dispersion A-2C) Ion-exchanged water 49.6 g was added to 400 g of pigment dispersion a (copper phthalocyanine 68.6 g, water-insoluble polymer a 29.4 g) obtained in Step 2 of Preparation Example 1, and Proxel LVS (Arch Chemicals Japan Co., Ltd.).
  • Preparation Examples 3 to 7 (Preparation of pigment dispersions A-3M, A-4M, A-5Y, A-6Y, A-7B)
  • the pigments were respectively 2 types of magenta pigments; PR122 (manufactured by Dainichi Seika Kogyo Co., Ltd.) and PR150 (manufactured by Fuji Color Co., Ltd.), 2 types of yellow pigments; PY74 (manufactured by Sanyo Color Co., Ltd.) and PY155 Pigment dispersions A-3M and A-4M (magenta pigment dispersions), A-5Y and A in the same manner as in Preparation Example 1, except that the pigments were changed to (Clariant), black pigments; PB7 (Cabot). -6Y (yellow pigment dispersion) and A-7B (black pigment dispersion) were obtained.
  • Preparation Example 8 (Preparation of pigment dispersion AX) To the pigment dispersion a 400 g obtained in Step 2 of Preparation Example 1 (copper phthalocyanine 68.6 g, water-insoluble polymer a 29.4 g) was added 44.6 g of ion-exchanged water, and Proxel LVS (Arch Chemicals Japan Co., Ltd.). (Product: antifungal agent, effective 20%) 0.89 g was added and stirred at 70 ° C. for 2 hours.
  • the mixture was filtered through the 5 ⁇ m filter, and ion-exchanged water was further added so that the solid content concentration was 22.0% by mass to obtain pigment dispersion AX (color material not cross-linked).
  • the average particle diameter of the water-insoluble polymer particles X containing the pigment was 91.7 nm.
  • Example 1 (1) Manufacture of water-based ink 1 Water-insoluble acrylic emulsion B-1 (Vinyl Blanc 701) 13 to 26.0 g of pigment dispersion A-1C obtained in Preparation Example 1 (4.00 g of pigment, 1.71 g of resin) 13 .3 g (resin 4.00 g, water 9.33 g), propylene glycol 30 g, diethylene glycol monobutyl ether (BDG) 5 g, Emulgen 120 0.5 g, Surfynol 104PG50 0.5 g, and ion-exchanged water 24.7 g are added and mixed.
  • BDG diethylene glycol monobutyl ether
  • Examples 2 to 21 and Comparative Examples 1 to 15 (1) Production of water-based inks 2 to 36 Pigment dispersions (A-1C to A-7B or AX), water-insoluble polymer particles B, or water-soluble polymer particles obtained with the formulation shown in Tables 2 and 3 The resulting dispersion, an organic solvent, a surfactant, ion-exchanged water, and the like were mixed, and the resulting mixture was filtered through the 1.2 ⁇ m membrane filter to obtain aqueous inks 2 to 36. (2) Evaluation of water-based inks 2 to 36 Except that the water-based ink 1 obtained in Example 1 (1) was changed to the water-based inks 2 to 36 obtained in the above (1), it was the same as in Example 1. A printed matter was obtained. The obtained water-based ink and printed matter were evaluated by the following methods.
  • ⁇ Storage stability> The water-based ink was stored in a 60 ° C. environment for 28 days, and the change rate of the cumulant average particle size of the pigment dispersion measured using a particle size measuring device ELSZ-2000S manufactured by Otsuka Electronics Co., Ltd. Average particle diameter after storage / average particle diameter before storage) was measured. Further, an ink viscosity at 25 ° C. was measured using an E-type viscometer manufactured by Toki Sangyo Co., Ltd., and the rate of change in viscosity (viscosity after storage / viscosity before storage) was evaluated. Based on these results, storage stability was evaluated according to the following evaluation criteria.
  • A- Change rate of average particle size is within ⁇ 10% and change rate of viscosity is within ⁇ 10%
  • B Average particle size change rate is within ⁇ 15% and viscosity change rate is within ⁇ 15%
  • C Average particle size change rate is within ⁇ 20% and viscosity change rate is within ⁇ 20%
  • D Average The change rate of the particle diameter is ⁇ 20% or more, or the change rate of the viscosity is ⁇ 20% or more. If the evaluation is A or A ⁇ , the storage stability is sufficient.
  • B- Ink peeled parts can be confirmed in some areas of 3/4 or less of the test part.
  • ⁇ Solvent resistance (ethanol) resistance A 10% to 100% ethanol solution in increments of 5% is soaked in a Johnson cotton swab from Johnson & Johnson, and the final printed material of polyvinyl chloride is subjected to a load of 5g and rubbed the printed surface 10 times. The ethanol concentration when there was no change in the printed surface was measured, and the solvent resistance was evaluated according to the following evaluation criteria.
  • ⁇ Base material adhesion> Evaluation was carried out by a cross cut test method according to JIS 5400. That is, using a cutter knife on the printed surface of the final printed matter of polyvinyl chloride, make 11 cuts that reach the substrate, make 100 grids, and strongly bond the cello tape (registered trademark) to the grids. The edge of the substrate was peeled off at an angle of 45 °, the state of the grid was compared with the state before the test, and the substrate adhesion was evaluated according to the following evaluation criteria.
  • the water-based inks of Examples 1 to 21 of the present invention have a long-term storage stability and a higher ink-jet recording time than the water-based inks of Comparative Examples 1 to 15.
  • High level of clear image quality, scratch resistance, water resistance, solvent resistance and substrate adhesion without blurring or unevenness even when printing on non-water-absorbing recording media while maintaining ejection stability It can be seen that it can be improved in a balanced manner.

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Abstract

[1] L'invention concerne une encre à base d'eau comprenant : des particules de polymère insoluble dans l'eau contenant un pigment A; des particules de polymère à base de vinyle insoluble dans l'eau B; et un solvant organique C. Les particules de polymère insoluble dans l'eau A sont obtenues par réticulation; les particules de polymère insoluble dans l'eau B sont un ou plusieurs types de particules de polymère insoluble dans l'eau choisis parmi des particules de polymère à base de vinyle insoluble dans l'eau ou similaire; et le solvant organique C comprend un ou plusieurs type de solvant organique choisis parmi l'éther monobutylique de diéthylène glycol et l'éther monoisobutylique de diéthylène glycol, et le propylène glycol, la quantité totale d'éther monobutylique de diéthylène glycol et d'éther monoisobutylique de diéthylène glycol étant de 0,8 % en masse ou plus, la teneur en solvant organique ayant un point d'ébullition supérieur à 250 °C étant de 5 % en masse ou moins, et la teneur en eau étant de 45 % en masse ou plus. [2] L'invention concerne également un procédé d'enregistrement par jet d'encre pour l'enregistrement sur un support d'enregistrement mettant en œuvre l'encre à base d'eau décrite ci-dessus. Cette encre à base d'eau présente une excellente stabilité au stockage à long terme et stabilité d'éjection pendant un enregistrement par jet d'encre, et permet une amélioration bien équilibrée de la qualité d'image sur un support d'enregistrement n'absorbant pas l'eau, de la solidité au frottement, de la résistance à l'eau, de la résistance aux solvants et de l'adhérence au substrat, à des niveaux élevés.
PCT/JP2016/062815 2015-05-08 2016-04-22 Encre à base d'eau Ceased WO2016181797A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/570,123 US10227499B2 (en) 2015-05-08 2016-04-22 Water-based ink
EP16792522.1A EP3275949B1 (fr) 2015-05-08 2016-04-22 Encre à base d'eau
CN201680025515.4A CN107532025B (zh) 2015-05-08 2016-04-22 水性油墨
BR112017022872A BR112017022872A2 (pt) 2015-05-08 2016-04-22 tinta à base de água

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015096036 2015-05-08
JP2015-096036 2015-05-08
JP2015255303A JP6031586B1 (ja) 2015-05-08 2015-12-25 水系インク
JP2015-255303 2015-12-25

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EP3950146A4 (fr) * 2019-03-28 2022-05-18 FUJIFILM Corporation Encre à jet d'encre pour substrat imperméable, procédé d'impression d'image et procédé de production de stratifié
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EP3904473A4 (fr) * 2018-12-26 2022-09-21 Kao Corporation Encre aqueuse pour impression à jet d'encre
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US11180671B2 (en) 2017-07-03 2021-11-23 Kao Corporation Aqueous ink
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WO2019013173A1 (fr) * 2017-07-10 2019-01-17 花王株式会社 Encre à base d'eau destinée à une impression à jet d'encre
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JP2019119890A (ja) * 2017-12-28 2019-07-22 花王株式会社 水系顔料分散体
WO2019132023A1 (fr) * 2017-12-28 2019-07-04 花王株式会社 Dispersion aqueuse de pigment
WO2019132024A1 (fr) * 2017-12-28 2019-07-04 花王株式会社 Dispersion aqueuse de pigment
JP2019119788A (ja) * 2017-12-28 2019-07-22 花王株式会社 水系顔料分散体
JP7137211B2 (ja) 2017-12-28 2022-09-14 花王株式会社 水系顔料分散体
EP3875551A4 (fr) * 2018-10-30 2022-07-27 Kao Corporation Encre aqueuse pour impression à la plaque
CN113195650A (zh) * 2018-12-18 2021-07-30 花王株式会社 水性凹版油墨
EP3901224A4 (fr) * 2018-12-18 2022-09-14 Kao Corporation Encre de gravure à base d'eau
EP3904473A4 (fr) * 2018-12-26 2022-09-21 Kao Corporation Encre aqueuse pour impression à jet d'encre
EP3904474A4 (fr) * 2018-12-26 2022-09-14 Kao Corporation Encre aqueuse pour impression à jet d'encre
EP3950146A4 (fr) * 2019-03-28 2022-05-18 FUJIFILM Corporation Encre à jet d'encre pour substrat imperméable, procédé d'impression d'image et procédé de production de stratifié
US12054624B2 (en) 2019-03-28 2024-08-06 Fujifilm Corporation Inkjet ink for impermeable base material, image recording method, and method of producing laminate
JP2020196777A (ja) * 2019-05-31 2020-12-10 ブラザー工業株式会社 インクジェット記録用水性インク及びインクジェット記録方法
JP2020196778A (ja) * 2019-05-31 2020-12-10 ブラザー工業株式会社 インクジェット記録用水性インク
WO2020241196A1 (fr) * 2019-05-31 2020-12-03 ブラザー工業株式会社 Encre à l'eau pour impression à jet d'encre
EP3978248A4 (fr) * 2019-05-31 2023-02-01 Brother Kogyo Kabushiki Kaisha Encre aqueuse pour impression à jet d'encre et procédé d'impression à jet d'encre
JP7298308B2 (ja) 2019-05-31 2023-06-27 ブラザー工業株式会社 インクジェット記録用水性インク及びインクジェット記録方法
WO2020241195A1 (fr) * 2019-05-31 2020-12-03 ブラザー工業株式会社 Encre aqueuse pour impression à jet d'encre et procédé d'impression à jet d'encre
US12378428B2 (en) 2019-05-31 2025-08-05 Brother Kogyo Kabushiki Kaisha Water-based ink for ink-jet recording
CN116568516A (zh) * 2020-10-26 2023-08-08 花王株式会社 喷墨记录用水性油墨
EP4234252A4 (fr) * 2020-10-26 2024-09-04 Kao Corporation Encre à base d'eau pour une impression à jet d'encre

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