WO2012035827A1 - Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre le contenant, et matière imprimée - Google Patents

Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre le contenant, et matière imprimée Download PDF

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Publication number
WO2012035827A1
WO2012035827A1 PCT/JP2011/061847 JP2011061847W WO2012035827A1 WO 2012035827 A1 WO2012035827 A1 WO 2012035827A1 JP 2011061847 W JP2011061847 W JP 2011061847W WO 2012035827 A1 WO2012035827 A1 WO 2012035827A1
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Prior art keywords
polyurethane
ink
group
mass
binder
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PCT/JP2011/061847
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English (en)
Japanese (ja)
Inventor
定 永浜
北田　満
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Dic株式会社
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Priority to JP2011553182A priority Critical patent/JP5029931B2/ja
Publication of WO2012035827A1 publication Critical patent/WO2012035827A1/fr

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Classifications

    • 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
    • B41M5/0023—Digital printing methods characterised by the inks used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant

Definitions

  • the present invention relates to an ink binder usable for ink jet printing and an ink for ink jet printing including the same.
  • the ink has good ejection stability and storage stability. Scratch resistance at a level that can prevent discoloration and deterioration of the printed image due to missing pigment due to friction that can occur when external force is applied to the surface of the printed image without damaging, and glass cleaner.
  • durability such as chemical resistance at a level that does not cause bleeding or discoloration of a printed image when various cleaning agents adhere to the surface of the printed image.
  • the ink having excellent scratch resistance is obtained by, for example, reacting an organic diisocyanate with a diol having a polyoxyethylene structure in an inkjet recording ink containing a pigment, an aqueous resin, and an aqueous medium.
  • An ink for inkjet recording which is a polyurethane resin, has a carboxyl group and has a specific acid value, a number average molecular weight, and a specific amount of the polyoxyethylene structure is known ( For example, see Patent Document 1.)
  • the image obtained by printing using the ink jet recording ink had a certain degree of scratch resistance, such as preventing the pigment from dropping off due to rubbing between papers.
  • an image obtained by printing using the ink jet recording ink has a problem in that, for example, when an alkaline cleaning agent or the like adheres to the surface, the printing surface is floated or smeared.
  • the ink for ink jet printing that can form a printed image that has both excellent scratch resistance and excellent alkali resistance without impairing the good ejection stability and storage stability of the ink is industrially
  • an ink for ink jet printing provided with the ink jet ink and a binder for ink jet printing ink that can be used for producing the ink have not yet been found.
  • the problem to be solved by the present invention is that a printed image having excellent durability such as scratch resistance and alkali resistance can be formed without impairing the good ejection stability and storage stability of the ink.
  • the improvement in the scratch resistance may be realized by using a resin having a higher molecular weight than the conventional one as a binder for ink jet printing ink. Thought.
  • the resin absorbs an aqueous medium and swells, thereby significantly reducing the ejection stability and storage stability of the ink, and clogging of the ink ejection nozzle and the ink ejection direction. In some cases, the occurrence of abnormalities and the generation of aggregates may occur.
  • the improvement in ejection stability and storage stability could be realized by using a relatively low molecular weight binder, but in such a case, the scratch resistance, alkali resistance, and the like are reduced. There was a case.
  • the present inventors have increased the molecular weight by crosslinking in the particles as the binder. Investigation was proceeded with the idea that the above problems could be solved by using the resin particles.
  • the present invention is an inkjet printing ink characterized in that the composite resin particles (A) formed by the reaction of the polyurethane (a1) and the epoxy compound (a2) are dispersed in the aqueous medium (B).
  • the present invention relates to a binder, an ink for inkjet printing including the binder, and a printed matter.
  • the ink for ink jet printing containing the ink jet printing ink binder of the present invention can remove the pigment even when a strong external force is applied without impairing the good ejection stability or storage stability of the ink. It is possible to maintain a high-definition printed image without causing it, and can provide scratch resistance comparable to silver salt photographs and excellent alkali resistance.
  • by photo printing by inkjet printing or high-speed printing by inkjet printing The obtained printed matter can be used in various scenes including outdoor advertising.
  • the present invention provides a binder for ink jet printing ink, wherein the composite resin particles (A) formed by reacting polyurethane (a1) and epoxy compound (a2) are dispersed in an aqueous medium (B). is there.
  • the composite resin particle (A) used in the present invention is formed by a cross-linking reaction between the polyurethane (a1) and the epoxy compound (a2).
  • the crosslinking reaction between the polyurethane (a1) and the epoxy compound (a2) is performed between the functional group [X] of the polyurethane (a1) and the epoxy group [Y] of the epoxy compound (a2). It is a reaction.
  • the functional group [X] of the polyurethane (a1) may be any functional group that can react with the epoxy group [Y], and examples thereof include a carboxyl group, a carboxylate group, and an amino group. . Among these, a carboxyl group or a carboxylate group is preferable for obtaining a printed material excellent in durability such as alkali resistance.
  • the composite resin particles (A) it is preferable to use composite resin particles that are cross-linked at high density inside the particles from the viewpoint of imparting even better scratch resistance and the like. If the composite resin particles, since a crosslinked structure is formed in the particles, the particles are less likely to swell due to an aqueous medium or the like, and as a result, excellent scratch resistance without impairing ink ejection stability. It is possible to impart sex and the like.
  • the degree of crosslinking in the composite resin particles (A) can be evaluated by the gel fraction of the composite resin particles (A), and it is more preferable to use those having a gel fraction of 70% by mass or more. It is preferable for imparting more excellent scratch resistance, and more preferably 85% by mass to 100% by mass.
  • the gel fraction is based on the mass of the film before the immersion. It can be shown by the ratio of the mass of the residue of the film that remains without being eluted in methyl ethyl ketone.
  • a film having a length of 3 cm, a width of 3 cm and a thickness of 150 ⁇ m is prepared using the composite resin particles (A), and the mass (M) thereof is measured.
  • the residue of the film that did not dissolve in methyl ethyl ketone was separated by filtration through a 300 mesh wire mesh, and the residue was dried at 108 ° C. for 1 hour.
  • the gel fraction can be calculated by using the values of the masses (M) and (N) and calculating based on the formula [(N) / (M)] ⁇ 100.
  • the composite resin particles (A) it is preferable to use those having a hydrophilic group as described above from the viewpoint of being stably dispersed in the aqueous medium (B).
  • hydrophilic group an anionic group, a cationic group, and a nonionic group can be used, and it is more preferable to use an anionic group.
  • a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used. Among them, a part or all of the carboxyl group and the sulfonic acid group are formed by a basic compound or the like. It is preferable to use a neutralized carboxylate group or sulfonate group in order to impart good water dispersion stability.
  • a tertiary amino group can be used, and as the nonionic group, for example, a polyethylene oxide chain can be used.
  • the hydrophilic group is preferably present in the range of 1 mmol / kg to 2000 mmol / kg, and preferably in the range of 15 mmol / kg to 1500 mmol / kg with respect to the entire composite resin particle (A). It is more preferable when obtaining a binder for ink jet printing ink having good properties and ejection stability.
  • the composite resin particles (A) preferably have an average particle diameter in the range of 10 nm to 1000 nm from the viewpoint of maintaining good storage stability and ejection stability. More preferably, it has a particle size.
  • the average particle diameter refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, as will be described later in Examples.
  • the composite resin particles (A) are preferably those having an acid value of 1 mgKOH / g to 50 mgKOH / g from the viewpoint of maintaining good storage stability and ejection stability.
  • the said acid value originates in the acid group which a polyurethane (a1) has.
  • a step (I) of producing a polyurethane (a1) by reacting a polyol, a polyisocyanate and, if necessary, a chain extender, and the polyurethane A method including the step (II) of producing a composite resin particle (A) by reacting a1) with the epoxy compound (a2) may be mentioned.
  • Examples of the polyurethane (a1) include a reaction with the epoxy group [Y] of the epoxy compound (a2) among polyurethanes obtained by reacting the polyol, polyisocyanate, and a chain extender, if necessary. What has functional group [X] provided with property can be used.
  • a carboxyl group, a carboxylate group, an amino group, and the like can be used as the functional group [X].
  • a method for producing the polyurethane (a1) having the functional group [X] specifically, a polyol (a1-1) or polyisocyanate (a1-2) having no functional group [X]
  • a functional group A method of producing the polyurethane (a1) by reacting the group [X] -containing compound with a chain extender as necessary may be mentioned.
  • Examples of the functional group [X] -containing compound used when introducing the functional group [X] into the polyurethane (a1) include a polyol having the functional group [X] and a polyisocyanate having the functional group [X]. Can be used. When using the polyol having the functional group [X] or the polyisocyanate having the functional group [X], the polyol (a1-1) or polyisocyanate (a1-2) not having the functional group [X] is used. ) Is not necessarily used. However, a polyol having a functional group [X] or a polyisocyanate having a functional group [X] is used from the viewpoint of imparting various properties such as good storage stability in an aqueous medium and excellent scratch resistance of a printed image.
  • polys (a1-1) and polyisocyanates (a1-2) in combination.
  • examples of the method for producing the polyurethane (a1) using the polyol having the functional group [X] and the polyisocyanate having the functional group [X] include, for example, the polyol having the functional group [X] and the functional group [X And a polyol (a1-1) or polyisocyanate (a1-2) that does not have a functional group [X] and a chain extender, if necessary.
  • the polyurethane (a1) in which the functional group [X] is introduced into the molecular side chain or molecular end can be obtained.
  • Examples of the polyol having the functional group [X] include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolvaleric acid. Can be used. Among them, it is preferable to use 2,2′-dimethylolpropionic acid in order to obtain composite resin particles (A) having excellent dispersion stability.
  • the polyol having the functional group [X] is a total mass of raw materials that can be used in the production of the polyurethane (a1), specifically, the polyol (a1-1), the polyisocyanate (a1-2), and the functional group.
  • the group [X] -containing compound and the chain extender are used, it is preferably used in the range of 0.5% by mass to 35% by mass with respect to the total mass including the chain extender.
  • the functional group [X] -containing compound polyamine or the like can be used. Specifically, a urethane prepolymer having an isocyanate group or a hydroxyl group at the molecular terminal is produced by reacting the polyol (a1-1) or polyisocyanate (a1-2), and then the molecular terminal of the urethane prepolymer is produced.
  • the functional group [X] can be introduced into the molecular terminal of the polyurethane (a1) by reacting the isocyanate group or hydroxyl group present in the compound with a compound having the functional group [X] such as the polyamine.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4.
  • Diamines such as' -dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxy Propylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-he Samethylene bishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-
  • the acid group is present in a range where the acid value of the polyurethane (a1) is 1 mgKOH / g to 70 mgKOH / g. preferable.
  • polyol (a1-1) that can be used for the production of the polyurethane (a1)
  • various polyols other than the polyol having the functional group [X] can be used.
  • polyurethane (a1) it is preferable to use one having a hydrophilic group from the viewpoint of imparting good storage stability of the composite resin particles (A) in the aqueous medium (B).
  • the hydrophilic group can be introduced into the polyurethane (a1) by using a hydrophilic group-containing polyol as the polyol (a1-1).
  • hydrophilic group-containing polyol for example, an anionic group-containing polyol, a cationic group-containing polyol, a nonionic group-containing polyol, and the like can be used, and it is particularly preferable to use an anionic group-containing polyol. It is preferable for maintaining the storage stability.
  • anionic group-containing polyol for example, an anionic group-containing polyol such as a carboxyl group-containing polyol or a sulfonic acid group-containing polyol can be used.
  • carboxyl group-containing polyol examples include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and the like. Among them, it is preferable to use 2,2′-dimethylolpropionic acid.
  • a carboxyl group-containing polyester polyol obtained by reacting the carboxyl group-containing polyol with various polycarboxylic acids or lactones, a vinyl polymer having two or more hydroxyl groups at one end, and the like can also be used.
  • vinyl polymer having two or more hydroxyl groups at one end include vinyl monomers containing a carboxyl group in the presence of thioglycerin such as 3-mercapto-1,2-propanediol. Those obtained by polymerization can be suitably used.
  • sulfonic acid group-containing polyol examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof; Polyester polyol obtained by reacting can be used.
  • the anionic group is preferably partially or completely neutralized with a basic compound or the like in order to develop good water dispersibility.
  • Examples of basic compounds that can be used when neutralizing the anionic group include ammonia, triethylamine, morpholine, organic amines such as monoethanolamine and diethylethanolamine having a boiling point of 100 ° C. or higher, NaOH, KOH, LiOH A metal hydroxide containing etc. can be used.
  • a tertiary amino group-containing polyol for example, a tertiary amino group-containing polyol can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies per molecule, and a secondary amine can be used. A polyol obtained by reacting with can be used.
  • the cationic group is partially or entirely neutralized with an acidic compound such as formic acid, acetic acid, phosphoric acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, or dimethyl sulfate, diethyl sulfate, methyl It may be quaternized with a quaternizing agent such as chloride or ethyl chloride.
  • an acidic compound such as formic acid, acetic acid, phosphoric acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, or dimethyl sulfate, diethyl sulfate, methyl
  • a quaternizing agent such as chloride or ethyl chloride.
  • nonionic group-containing polyol polyalkylene glycol having a structural unit derived from ethylene oxide can be used.
  • the hydrophilic group-containing polyol includes the polyol (a1-1), the polyisocyanate (a1-2), the functional group [X] -containing compound, and the chain extender, which are raw materials that can be used in the production of the polyurethane (a1). Is preferably used in the range of 1% by mass to 45% by mass with respect to their total mass.
  • examples of the polyol having the functional group [X] as the functional group [X] -containing compound and the hydrophilic group-containing polyol partially overlap.
  • 2,2-dimethylolpropionic acid can introduce a carboxyl group as a hydrophilic group into the polyurethane (a1), while introducing a carboxyl group as the functional group [Y] into the polyurethane (a1). .
  • the carboxyl group introduced into the polyurethane (a1) for the purpose of increasing the crosslinking density in the particles by reacting with the epoxy group [Y] of the epoxy compound (a2) acts as the functional group [X].
  • a polyol such as 2,2-dimethylolpropionic acid used for introducing a carboxyl group into the polyurethane (a1) for the purpose is used as the functional group.
  • the polyol having the group [X] is exemplified.
  • the composite resin particle (A) in order to improve the water dispersion stability of the composite resin particle (A), it is a carboxyl group introduced as an anionic group, and does not react with the epoxy group [Y], so that the composite resin particle (A)
  • the carboxyl group remaining in the solvent and the carboxylate group formed by further neutralization act as a hydrophilic group, and therefore, used for introducing a carboxyl group into the polyurethane (a1) for this purpose.
  • An anionic group-containing polyol such as 2-dimethylolpropionic acid is exemplified as the hydrophilic group-containing polyol.
  • the cationic group-containing polyol that can be used for the hydrophilic group-containing polyol is the same as the anionic group-containing polyol.
  • polyol (a1-1) used for the production of the polyurethane (a1) in addition to the hydrophilic group-containing polyol, other polyols can be used in combination as required.
  • the other polyols examples include polyether polyols, polyester polyols, and polycarbonate polyols other than the polyol having the functional group [X] and the hydrophilic group-containing polyol.
  • the use of the polyether polyol imparts excellent scratch resistance and alkali resistance without impairing excellent ink storage stability and ink ejection properties. Is preferable.
  • polyether polyol examples include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator. .
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.
  • alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
  • polyether polyol it is preferable to use polyoxytetramethylene glycol or polyoxypropylene glycol from the viewpoint of obtaining a binder for inkjet printing ink capable of imparting excellent ejection stability of the ink.
  • polyether polyol that can be used as the other polyol, it is preferable to use a polyether polyol having a number average molecular weight of 600 to 5,000, and more preferably 800 to 3,000.
  • the polyether polyol preferably the polyether polyol having a number average molecular weight of 600 to 5000, is the polyol (a1-1) and the polyisocyanate (a1-2), which are raw materials that can be used in the production of the polyurethane (a1).
  • the content is preferably in the range of 15% by mass to 80% by mass with respect to the total mass thereof.
  • polycarbonate polyol for example, those obtained by reacting a carbonate and a polyol can be used.
  • carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
  • polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4 , 4'-biphenol, etc.
  • the molecular weight of the dihydroxy compound, polyethylene glycol, polypropylene glycol, and polyether polyols such as polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate, may be used polyester polyols such as polycaprolactone and the like.
  • polyester polyol examples include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ⁇ -caprolactone, and the like. Copolyester of the above can be used.
  • the low molecular weight polyol for example, ethylene glycol, propylene glycol and the like can be used.
  • polycarboxylic acid examples include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.
  • the other polyol it is preferable to use an aliphatic cyclic structure-containing polyol in addition to the above-mentioned ones in order to improve the scratch resistance of the printed matter.
  • Examples of the aliphatic cyclic structure-containing polyol include cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1 , 0,2,6] decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] no Nandimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanedi
  • the aliphatic cyclic structure-containing polyol having a molecular weight of 100 to 500 includes the polyol (a1-1), the polyisocyanate (a1-2) and the functional group which are raw materials that can be used for the production of the polyurethane (a1).
  • the content is preferably in the range of 0.5 to 35% by mass with respect to the total mass thereof.
  • ethylene glycol for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1 , 7-heptanediol and the like can be used.
  • polyisocyanate (a1-2) that can be used for the production of the polyurethane (a1) those having no functional group [X] can be used.
  • those having no functional group [X] can be used.
  • polyisocyanates having aliphatic polyisocyanate or an alicyclic structure can be used.
  • an aliphatic polyisocyanate from the viewpoint of preventing yellow discoloration, and from the viewpoint of further improving the scratch resistance and alkali resistance in addition to the above-mentioned discoloration prevention, an aliphatic cyclic structure-containing polyisocyanate. Is preferably used.
  • the polyurethane (a1) can be produced, for example, by mixing and reacting a polyol and polyisocyanate in the absence of a solvent or in the presence of an organic solvent.
  • the polyurethane (a1) includes the polyol (a1-1), the polyisocyanate (a1-2), functional groups such as the functional group [X] -containing polyol and the functional group [X] -containing polyisocyanate. It can be produced by mixing and reacting with a group [X] -containing compound.
  • the organic solvent is preferably removed by a method such as distillation when the polyurethane (a1) is made aqueous.
  • a urethane prepolymer having a hydroxyl group or an isocyanate group at the molecular end is prepared by reacting the polyol (a1-1) and the polyisocyanate (a1-2) in advance in the absence of a solvent or in the presence of an organic solvent. Then, the urethane prepolymer and the functional group [X] -containing compound such as the polyamine are mixed and reacted to produce the polyurethane (a1) having the functional group [X] at the molecular terminal. Also in this case, when the organic solvent is used, the organic solvent is preferably removed by a method such as distillation when the polyurethane (a1) is made aqueous.
  • the reaction between the polyol and polyisocyanate used for the production of the polyurethane (a1) is, for example, such that the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol is in the range of 0.8 to 2.5. Preferably, it is carried out, more preferably in the range of 0.9 to 1.5.
  • the polyol and polyisocyanate include the polyol (a1-1) and polyisocyanate (a1-2), the functional group [X] -containing polyol, the functional group [X] -containing polyisocyanate, and the like.
  • Examples of the organic solvent that can be used in producing the polyurethane (a1) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; acetonitrile and the like. Nitriles; amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more.
  • the chain extender can be used as necessary for the purpose of increasing the molecular weight from the viewpoint of improving the scratch resistance.
  • the chain extender for example, the polyol (a1-1), the polyisocyanate (a1-2) and the functional group [X] -containing compound are reacted in the absence of a solvent or in the presence of an organic solvent.
  • the polyurethane (a1) can be produced by reacting the polyurethane with a chain extender.
  • the organic solvent is preferably removed by a method such as distillation when the polyurethane (a1) is made aqueous.
  • chain extender that can be used when producing the polyurethane (a1), polyamine, other active hydrogen atom-containing compounds, and the like can be used.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; disuccinate Dorazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid
  • Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose.
  • Glycols such as methylene glycol, glycerin and sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used.
  • the chain extender is used, for example, in such a range that the equivalent of the amino group and active hydrogen atom-containing group of the chain extender is 1.9 or less (equivalent ratio) with respect to the equivalent of the isocyanate group of the polyurethane. It is preferable to use within the range of 0.3 to 1.0 (equivalent ratio).
  • the polyurethane obtained using the chain extender has a urea bond in the molecule, it can be suitably used for forming a printed image having excellent scratch resistance.
  • the polyurethane tends to lower the alcohol resistance due to the influence of the urea bond
  • the polyurethane (a1) is used when forming a printed image excellent in the alcohol resistance as well as the scratch resistance and alkali resistance.
  • a polyurethane obtained without using a chain extender a polyurethane obtained by limiting the amount of use to a minimum, specifically, the proportion of urea bonds contained in the polyurethane is 10% by mass It is preferable to use the following.
  • polyurethane (a1) obtained by the above method it is preferable to use a polyurethane having a weight average molecular weight in the range of 10,000 to 200,000 in order to obtain sufficient alkali resistance, scratch resistance and alcohol resistance. It is more preferable to use those in the range of 20000 to 80,000.
  • the dispersion of the polyurethane (a1) produced by the above method into the aqueous medium (B) can be carried out by the following method when the polyurethane (a1) is a hydrophilic group-containing polyurethane, for example.
  • Method 1 After neutralizing or quaternizing some or all of the hydrophilic groups of the polyurethane (a1) produced by the above method, the aqueous medium (B) is added and dispersed in water. Accordingly, a method of producing an aqueous dispersion of polyurethane (a1) by supplying and reacting the chain extender accordingly.
  • Polyurethane obtained by reacting polyol (a1-1) and polyisocyanate (a1-2) and, if necessary, the chain extender are charged into a reaction vessel in a batch or divided.
  • the polyurethane (a1) is produced by chain extension reaction, and then the hydrophilic group which the obtained polyurethane (a1) may have is neutralized or quaternized, and then an aqueous medium.
  • a method for producing an aqueous dispersion of polyurethane (a1) by adding (B) and dispersing in water.
  • an organic solvent is used in the production of the polyurethane (a1)
  • an aqueous dispersion of the polyurethane (a1) is produced by the methods 1 and 2, and then the organic solvent is distilled as necessary. It is preferable to remove by.
  • a hydrophilic group As said polyurethane (a1), when dispersing the said polyurethane (a1) in an aqueous medium (B), the following emulsifier etc. can be used. . Even when a hydrophilic group-containing polyurethane is used as the polyurethane (a1), an emulsifier may be used as necessary in the [Method 1] to [Method 2]. In addition, when water is dissolved or dispersed, a machine such as a homogenizer may be used as necessary.
  • emulsifier examples include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • Anionic emulsifiers; cationic amines such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts It is below.
  • an anionic or nonionic emulsifier it is basically preferable to use an anionic or nonionic emulsifier.
  • a hydrophilic group-containing compound may be used as an aid for assisting the water dispersibility of the polyurethane (a1).
  • hydrophilic group-containing compound an anionic group-containing compound, a cationic group-containing compound, an amphoteric group-containing compound, or a nonionic group-containing compound can be used, but the excellent storage stability of the ink of the present invention is maintained. Therefore, it is preferable to use a nonionic group-containing compound.
  • the nonionic group-containing compound includes a group having at least one active hydrogen atom in the molecule and consisting of a repeating unit of ethylene oxide, and a group consisting of a repeating unit of ethylene oxide and another repeating unit of alkylene oxide.
  • a compound having at least one functional group selected from the group can be used.
  • polyoxyethylene glycol or polyoxyethylene-polyoxypropylene having a number average molecular weight of 300 to 20,000 containing at least 30% by mass of repeating units of ethylene oxide and containing at least one active hydrogen atom in the polymer
  • Nonionic group-containing compounds such as copolymer glycols, polyoxyethylene-polyoxybutylene copolymer glycols, polyoxyethylene-polyoxyalkylene copolymer glycols or monoalkyl ethers thereof, or polyester polys obtained by copolymerizing these It is possible to use compounds such as ether polyols.
  • step (II) for producing the composite resin particles (A) by reacting the polyurethane (a1) obtained above and the epoxy compound (a2) will be described.
  • the reaction between the polyurethane (a1) and the epoxy compound (a2) is a reaction between the functional group [X] of the polyurethane (a1) and the epoxy group [Y] of the epoxy compound (a2). .
  • epoxy compound (a2) for example, a novolac type, a cresol type, a phenol type, a bisphenol A type, a bisphenol F type, or the like can be used.
  • aliphatic polyglycidyl ether or bisphenol diglycidyl ether can be used as the epoxy compound (a2) because it can impart excellent scratch resistance without impairing the ejection stability of the ink. preferable.
  • Examples of the aliphatic polyglycidyl ether include cyclohexanedimethanol diglycidyl ether, cyclohexanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, Diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polypropylene glycol diglycidyl ether, and the like can be used.
  • bisphenol diglycidyl ether for example, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, or the like can be used.
  • the epoxy compound (a2) it is preferable to use an epoxy compound having an epoxy equivalent of 100 to 2000 from the viewpoint of forming a sufficient crosslinking point for imparting excellent scratch resistance. It is more preferable to use one having an epoxy equivalent of 100 to 500 in order to impart excellent scratch resistance.
  • the reaction between the functional group [X] and the epoxy group [Y] can be performed, for example, by mixing the polyurethane (a1) obtained in the step (I) and the epoxy compound (a2).
  • a method in which the organic solvent solution or aqueous dispersion of the polyurethane (a1) obtained in the step (I) and the epoxy compound (a2) are mixed can be mentioned.
  • the mixing may be performed before or after neutralizing the hydrophilic group of the polyurethane (a1), or may be performed at any time before or after the organic solvent is removed.
  • the reaction between the functional group [X] and the epoxy group [Y] varies depending on the type of the epoxy compound (a2) used, but is preferably in the range of 50 ° C. to 150 ° C., more preferably 65 ° C. to 100 ° C. Therefore, it is preferably carried out with stirring for about 1 to 10 hours.
  • the polyurethane (a1) and the epoxy compound (a2) have a molar ratio of the functional group [X] of the polyurethane (a1) and the epoxy group [Y] of the epoxy compound (a2) [epoxy group [Y ] / Functional group [X]] is preferably mixed and reacted in the range of 1/20 to 1/1, and mixed and reacted in the range of 1/5 to 4/5.
  • the functional group [X] is capable of acting as a hydrophilic group such as the carboxyl group or amino group
  • the viewpoint of maintaining excellent storage stability of the resulting composite resin particle (A) from the above, it is preferable that the molar ratio [epoxy group [Y] / functional group [X]] is mixed within the range of 1/20 to 9/10, and the reaction is performed, and the mixture is preferably mixed within the range of 1/5 to 4/5. It is more preferable to react.
  • an epoxy group [Y] and unreacted functional group [X] can be made to remain as a hydrophilic group, and the said composite resin particle (B) in an aqueous medium (B) ( The storage stability of A) can be improved.
  • composite resin particles (A) are dispersed in the aqueous medium (B) used in the ink jet printing ink binder of the present invention.
  • Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof.
  • the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
  • the aqueous medium (B) is continuously used. be able to.
  • the aqueous medium (B) is preferably contained in an amount of 40% by mass to 90% by mass, and more preferably 50% by mass to 85% by mass with respect to the total amount of the binder for ink jet printing ink.
  • a curing agent or a curing catalyst may be used in combination as required so long as the storage stability and the ink ejection property are not deteriorated.
  • Examples of the curing agent include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, a polyisocyanate, and the like.
  • Examples of the curing catalyst include lithium hydroxide. Sodium hydroxide, potassium hydroxide and the like can be used.
  • the polyurethane composition containing the composite resin particles (A) and the aqueous medium (B) obtained by the above method can dramatically improve the scratch resistance and alkali resistance of the printed matter, it is exclusively for inkjet printing. It can be suitably used for an ink binder.
  • the composite resin particle (A) is in the range of 10% by mass to 50% by mass with respect to the total amount of the binder for ink jet printing ink from the viewpoint of achieving both the storage stability of the ink, excellent scratch resistance and alkali resistance. It is preferably contained in the range of 15% by mass to 40% by mass.
  • the ink for inkjet printing of the present invention contains the above-mentioned binder for ink-jet printing ink, pigments and dyes, and other various additives as required.
  • the pigment known and commonly used inorganic pigments and organic pigments can be used.
  • the inorganic pigment for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite and the like can be used.
  • organic pigments examples include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, Organic pigments such as diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used.
  • These pigments can be used in combination of two or more. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.
  • the dye examples include azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, Naphthoquinone dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane, and the like can be used.
  • azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, Naphthoquinone dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes,
  • additives examples include polymer dispersants, viscosity modifiers, wetting agents, antifoaming agents, surfactants, preservatives, pH adjusting agents, chelating agents, plasticizers, ultraviolet absorbers, and antioxidants.
  • acrylic resins and the like that have been used as binders for conventional ink jet printing inks can be used.
  • polymer dispersant for example, an acrylic resin, a styrene-acrylic resin, or the like can be used, and any of a random type, a block type, and a graft type can be used.
  • an acid or a base may be used in combination to neutralize the polymer dispersant.
  • the ink for inkjet printing can be prepared, for example, by the following manufacturing method.
  • An ink precursor composed of an aqueous dispersion of a pigment or dye is prepared by mixing the pigment or dye, the aqueous medium and, if necessary, the additive using various dispersing devices;
  • the ink precursor containing the pigment used in the ink production method described in (2) above can be prepared, for example, by the following method.
  • (I) A pigment obtained by mixing a kneaded product obtained by pre-kneading additives such as a pigment and a polymer dispersing agent using a two-roll or a mixer with an aqueous medium using various dispersing devices.
  • a method for preparing an ink precursor comprising an aqueous dispersion containing (Ii) After the pigment and the polymer dispersant are mixed using various dispersing devices, the polymer dispersant is deposited on the surface of the pigment by controlling the solubility of the polymer dispersant, and further dispersed.
  • a method of preparing an ink precursor comprising an aqueous dispersion containing a pigment by mixing them using an apparatus (Iii) The pigment and the additive are mixed using various dispersing devices, and then the mixture and the resin emulsion are mixed using the dispersing device to prepare an ink precursor composed of an aqueous dispersion containing the pigment. how to.
  • Examples of the dispersing device that can be used in the production of the ink for inkjet printing include, for example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer.
  • an ultrasonic homogenizer a high-pressure homogenizer
  • a paint shaker a ball mill, a roll mill
  • a sand mill a sand grinder
  • a dyno mill a disperse mat
  • SC mill and a nanomizer.
  • two or more types can be used in combination.
  • the coarse particles having a particle diameter of approximately 250 nm or more may be present.
  • the coarse particles may cause clogging of printer nozzles and the like, and may deteriorate ink discharge characteristics. Therefore, the coarse particles may be coarsened by a method such as centrifugation or filtration after the preparation of the aqueous dispersion of the pigment or after the preparation of the ink. It is preferred to remove the particles.
  • the ink for ink jet printing obtained above preferably has a volume average particle diameter of 1000 nm or less, and preferably has a volume average particle diameter of 300 nm or less, and more particularly like photographic image quality. In the case of forming a high gloss image, the range of 80 to 120 nm is more preferable.
  • the ink for ink jet printing is 0.2% by mass to 10% by mass of the hydrophilic group-containing polyurethane (A) and 50% by mass to 95% by mass of the aqueous medium (B) with respect to the whole ink for ink jet printing.
  • %, Pigment or dye is preferably contained in an amount of 0.5 to 15% by mass.
  • the ink for ink jet printing of the present invention obtained by the above method can be used exclusively for ink jet printing using an ink jet printer, for example, ink jet printing on a substrate such as paper, plastic film, metal film or sheet. be able to.
  • the ink jet method is not particularly limited, but a known method such as a continuous jet type (charge control type, spray type, etc.) or an on-demand type (piezo type, thermal type, electrostatic suction type, etc.) should be applied. Can do.
  • the printed matter printed using the ink for ink jet printing of the present invention has excellent scratch resistance, it is difficult to cause deterioration of a printed image due to lack of pigments and the like, and has excellent alkali resistance. Since it has a high color density image, it can be prevented by bleed or the like due to adhesion of alkaline detergent to the printed image surface, and can be obtained, for example, by photographic printing by inkjet printing or high-speed printing by inkjet printing. It can be used for various purposes such as printed materials.
  • the reaction was terminated by adding 7.8 parts by mass of methanol, and 563.7 parts by mass of methyl ethyl ketone was added as a diluting solvent.
  • An organic solvent solution of polyurethane having a valence of 20 (nonvolatile content 50% by mass) 2000 parts by mass was obtained.
  • the acid value is a theoretical value calculated based on the amount of acid group-containing compound such as 2,2-dimethylolpropionic acid used in the production of polyurethane. In the following Examples and Comparative Examples, the acid value was calculated by the same method as described above unless otherwise specified.
  • Example 1 By adding 7.3 parts by mass of a 20% by mass aqueous ammonia solution to 483.8 parts by mass of the polyurethane organic solvent solution obtained in Preparation Example 1, some or all of the carboxyl groups of the polyurethane are neutralized, and An aqueous dispersion of polyurethane (a1-I) was obtained by adding 977.2 parts by mass of water and stirring sufficiently. To the obtained aqueous dispersion of polyurethane (a1-I), 8.1 parts by mass of an epoxy resin (“Epiclon 850” manufactured by DIC Corporation, bisphenol A type diglycidyl ether, epoxy equivalent 188) was added, and 80 ° C. For 6 hours to obtain an aqueous dispersion of composite resin particles (AI).
  • an epoxy resin (“Epiclon 850” manufactured by DIC Corporation, bisphenol A type diglycidyl ether, epoxy equivalent 188) was added, and 80 ° C.
  • the aqueous dispersion of the composite resin particles (AI) is subjected to aging and solvent removal, whereby composite resin particles having an acid value of 10 and a gel fraction of 85 to 100% by mass and an average particle size of 10 to 70 nm are obtained.
  • An ink-jet printing ink binder having a nonvolatile content of 25% by mass in which (AI) was dispersed in water was obtained.
  • Example 2 By adding 7.5 parts by mass of a 20% by mass aqueous ammonia solution to 493.4 parts by mass of the organic solvent solution of polyurethane obtained in Preparation Example 1, some or all of the carboxyl groups of the polyurethane are neutralized, and An aqueous dispersion of polyurethane (a1-II) was obtained by adding 972.4 parts by mass of water and stirring sufficiently. To an aqueous dispersion of the obtained polyurethane (a1-II), 3.3 parts by mass of an epoxy resin (“Epiclon 850” manufactured by DIC Corporation, bisphenol A type diglycidyl ether, epoxy equivalent 188) was added, and 80 ° C.
  • an epoxy resin (“Epiclon 850” manufactured by DIC Corporation, bisphenol A type diglycidyl ether, epoxy equivalent 188) was added, and 80 ° C.
  • aqueous dispersion of composite resin particles (A-II) For 6 hours to obtain an aqueous dispersion of composite resin particles (A-II). Next, the aqueous dispersion of the composite resin particles (A-II) is aged and removed to remove the composite resin particles having an acid value of 16 and a gel fraction of 80 to 98% by mass and an average particle size of 10 to 70 nm. A binder for ink jet printing ink having a nonvolatile content of 25% by mass in which (A-II) was dispersed in water was obtained.
  • Example 3 By adding 7.2 parts by mass of a 20% by mass aqueous ammonia solution to 474.6 parts by mass of the polyurethane organic solvent solution obtained in Preparation Example 1, some or all of the carboxyl groups of the polyurethane are neutralized, and An aqueous dispersion of polyurethane (a1-III) was obtained by adding 981.9 parts by mass of water and stirring sufficiently. To the obtained aqueous dispersion of polyurethane (a1-III), 12.7 parts by mass of epoxy resin (“Epiclon 850”, bisphenol A type diglycidyl ether, epoxy equivalent 188, manufactured by DIC Corporation) was added, and 80 By reacting at 6 ° C.
  • epoxy resin (“Epiclon 850”, bisphenol A type diglycidyl ether, epoxy equivalent 188, manufactured by DIC Corporation) was added, and 80 By reacting at 6 ° C.
  • an aqueous dispersion of composite resin particles (A-III) was obtained.
  • the aqueous dispersion of the composite resin particles (A-III) is aged and removed to remove the composite resin particles having an acid value of 4 and a gel fraction of 90 to 100% by mass and an average particle size of 10 to 70 nm.
  • An ink-jet printing ink binder having a nonvolatile content of 25% by mass in which (A-III) was dispersed in water was obtained.
  • Example 4 137.1 parts by mass of polyether polyol ("Exenol 2020” polypropylene glycol manufactured by Asahi Glass Co., Ltd., number average molecular weight 2000) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube and a stirrer, 2-methylolpropionic acid 11.3 parts by mass, 1,4-cyclohexanedimethanol 17.9 parts by mass and isophorone diisocyanate 67.8 parts by mass in the presence of 100.3 parts by mass of methyl ethyl ketone as the organic solvent for 5 hours Reacted.
  • polyether polyol Polyether polyol
  • aqueous dispersion of polyurethane (a1-IV) was obtained by adding part by mass and stirring sufficiently.
  • an epoxy resin (“Epiclon 850”, bisphenol A type diglycidyl ether, epoxy equivalent 188, manufactured by DIC Corporation) was added. By reacting at 6 ° C.
  • an aqueous dispersion of composite resin particles (A-IV) was obtained.
  • the aqueous dispersion of the composite resin particles (A-IV) is aged and removed to remove the composite resin particles having an acid value of 16 and a gel fraction of 75 to 98% by mass and an average particle size of 20 to 200 nm.
  • An ink-jet printing ink binder having a nonvolatile content of 25% by mass in which (A-IV) was dispersed in water was obtained.
  • Example 5 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol ("Exenol 2020" polypropylene glycol manufactured by Asahi Glass Co., Ltd., number average molecular weight 2000) 146.9 parts by mass, 2, 29.3 parts by mass of 2-dimethylolpropionic acid, 0.3 parts by mass of 1,4-cyclohexanedimethanol and 65.4 parts by mass of isophorone diisocyanate were added in the presence of 103.7 parts by mass of methyl ethyl ketone as an organic solvent for 5 hours. Reacted.
  • polyether polyol Polyether polyol
  • the reaction is terminated by adding 1.9 parts by mass of methanol, and 136.3 parts by mass of methyl ethyl ketone is added as a diluent solvent, so that polyurethane An organic solvent solution having an acid value of 50 was obtained.
  • 18.3 parts by mass of a 20% by mass aqueous ammonia solution was added to the total amount of the polyurethane organic solvent solution obtained above to neutralize part or all of the carboxyl groups of the polyurethane, and water 975.0
  • An aqueous dispersion of polyurethane (a1-V) was obtained by adding part by mass and stirring sufficiently.
  • the reaction is terminated by adding 2.4 parts by mass of methanol, and 283.3 parts by mass of methyl ethyl ketone is added as a diluent solvent. 1000.0 parts by mass of an organic solvent solution of polyurethane with a valence of 20 (nonvolatile content: 50% by mass) was obtained.
  • Example 6 By adding 7.3 parts by mass of a 20% by mass aqueous ammonia solution to 483.8 parts by mass of the polyurethane organic solvent solution obtained in Preparation Example 2, part or all of the carboxyl groups of the polyurethane are neutralized, and An aqueous dispersion of polyurethane (a1-VI) was obtained by adding 197.2 parts by mass of water and stirring sufficiently. To the obtained aqueous dispersion of polyurethane (a1-VI), 8.1 parts by mass of an epoxy resin (“Epiclon 850”, bisphenol A type diglycidyl ether, epoxy equivalent 188, manufactured by DIC Corporation) was added. By reacting at 6 ° C.
  • an epoxy resin (“Epiclon 850”, bisphenol A type diglycidyl ether, epoxy equivalent 188, manufactured by DIC Corporation) was added.
  • an aqueous dispersion of composite resin particles (A-VI) was obtained.
  • composite resin particles having an acid value of 10 and a gel fraction of 85 to 100% by mass and an average particle diameter of 10 to 70 nm are obtained.
  • An ink-jet printing ink binder having a nonvolatile content of 25% by mass in which (A-VI) was dispersed in water was obtained.
  • Example 7 By adding 5.9 parts by mass of a 20% by mass aqueous ammonia solution to 485.2 parts by mass of the polyurethane organic solvent solution obtained in Preparation Example 1, some or all of the carboxyl groups of the polyurethane are neutralized, and An aqueous dispersion of polyurethane (a1-VII) was obtained by adding 976.5 parts by mass of water and stirring sufficiently. To the obtained aqueous dispersion of polyurethane (a1-VII), 7.4 parts by mass of an epoxy resin (“CR-5L” manufactured by DIC Corporation, aliphatic polyglycidyl ether, epoxy equivalent 171) was added, and 80 ° C.
  • an epoxy resin (“CR-5L” manufactured by DIC Corporation, aliphatic polyglycidyl ether, epoxy equivalent 171) was added, and 80 ° C.
  • aqueous dispersion of composite resin particles (A-VII) For 6 hours to obtain an aqueous dispersion of composite resin particles (A-VII). Next, by aging and removing the aqueous dispersion of the composite resin particles (A-VII), a composite having an acid value of 10 and a gel fraction of 85% by mass to 100% by mass and an average particle size of 10 nm to 70 nm is obtained. A binder for ink jet printing ink having a nonvolatile content of 25% by mass in which resin particles (A-VII) were dispersed in water was obtained.
  • the weight average molecular weight of the polyurethane was measured using a gel permeation chromatograph (GPC method). Specifically, the binder for inkjet printing ink obtained above was coated on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to prepare a semi-dry coating film. The obtained coating film was peeled off from the glass plate, and 0.4 g of the coating film dissolved in 100 g of tetrahydrofuran was used as a measurement sample.
  • GPC method gel permeation chromatograph
  • HLC-8220 As a measuring device, a high performance liquid chromatograph HLC-8220 type manufactured by Tosoh Corporation was used. As a column, Tosoh Corporation column TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) was used in combination.
  • Standard polystyrenes manufactured by Showa Denko KK and Toyo Soda Co., Ltd.
  • molecular weight samples molecular weights: 44.48 million, 425,000, 288,000, 2750,000, 1.85 million, 860,000, 450,000, 411,000, 35.
  • Calibration curves were created using 50,000, 190,000, 160,000, 96,000, 50,000, 37,000, 198,000, 196,000, 5570, 4000, 2980, 2030, 500). .
  • Tetrahydrofuran was used as the eluent and sample solution, and the weight average molecular weight was measured using a RI detector with a flow rate of 1 mL / min, a sample injection amount of 500 ⁇ L, and a sample concentration of 0.4%.
  • the average particle diameter of the composite resin particles (A) was a 50% median diameter on a volume basis, and was measured using a Microtrac UPA250 particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method.
  • the ion-exchanged water heated to 60 ° C. with a total amount of 8000 g was added to the kneaded material in 2 hours to obtain a colored resin composition having a nonvolatile content of 37.9% by mass.
  • aqueous pigment dispersion precursor 18 kg was added to a bead mill (Nanomill NM-G2L manufactured by Asada Tekko Co., Ltd., beads ⁇ : 0.3 mm zirconia beads, bead filling amount: 85%, cooling water temperature: 10 ° C., Rotating speed: 2660 rev / min), the bead mill passing liquid is centrifuged at 13000 G ⁇ 10 minutes, and then filtered through a filter having an effective pore size of 0.5 ⁇ m to thereby obtain a water-based quinacridone pigment. A dispersion was obtained. The concentration of the quinacridone pigment in this aqueous pigment dispersion was 14.9% by mass.
  • Example 1 to 7 and Comparative Examples 1 and 2 binders for ink jet printing inks and Preparation Example 1 were used so that the concentration of the quinacridone pigment was 4% by mass and the concentration of polyurethane was 1% by mass.
  • the obtained quinacridone pigment, 2-pyrrolidinone, triethylene glycol monobutyl ether, glycerin, surfactant (Surfinol 440, manufactured by Air Products) and ion-exchanged water were mixed and stirred according to the following blending ratio. By doing so, an ink for inkjet printing was prepared.
  • the ink is sealed in a glass container such as a screw tube, a heating test is performed for 4 weeks with a thermostat at 70 ° C., and the viscosity and particle diameter of the ink after the heating test are measured by the same method as described above. did.
  • Viscosity change rate is less than 2% ⁇ : Viscosity change rate is 2% or more and less than 5% ⁇ : Viscosity change rate is 5% or more
  • a diagnostic page was printed using a Photomart D5360 (manufactured by Hewlett Packard) in which a black ink cartridge was filled with the ink for inkjet printing, and the state of the nozzle was confirmed.
  • 20 pages of solid printing with a printing density setting of 100% in an area of 18 cm ⁇ 25 cm per page were continuously performed, and then a diagnostic page was printed again to check the state of the nozzles.
  • the change in the state of the nozzles before and after continuous solid printing was evaluated as the ink ejection property. The evaluation criteria are described below.
  • the printed matter for evaluation was dried at room temperature for 10 minutes, the printed surface was scratched with a nail under a load of about 5 kg, and the rubbing condition such as the color of the printed surface was visually evaluated according to the following evaluation criteria. .
  • the ejection stability of ink was insufficient, the printed matter for evaluation could not be obtained, and those that could not be evaluated were marked with “-” in the table.
  • E850 indicates bisphenol A type diglycidyl ether, epoxy equivalent 188 (Epiclon 850), which is an epoxy resin manufactured by DIC Corporation.
  • CR-5L indicates an aliphatic polyglycidyl ether which is an epoxy resin manufactured by DIC Corporation, and an epoxy equivalent of 171.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention vise à procurer un liant pour une encre d'impression à jet d'encre apte à former une image imprimée ayant une très longue durée de vie, par exemple une résistance à l'abrasion et une résistance aux alkalis, sans détérioration de la stabilité à l'éjection favorable, de la stabilité de stockage, etc., de l'encre, et sur une encre d'impression à jet d'encre contenant le liant. A cet effet, l'invention porte sur un liant pour une encre d'impression à jet d'encre, dans lequel liant des particules de résine composites (A) formées par la réaction d'un polyuréthane (a1) avec un composé époxy (a2) sont dispersés dans un milieu aqueux (B), sur une encre d'impression à jet d'encre le contenant, et sur une matière imprimée.
PCT/JP2011/061847 2010-09-17 2011-05-24 Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre le contenant, et matière imprimée WO2012035827A1 (fr)

Priority Applications (1)

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JP2011553182A JP5029931B2 (ja) 2010-09-17 2011-05-24 インクジェット印刷用インクの製造方法及び印刷物

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JP2010209239 2010-09-17
JP2010-209239 2010-09-17

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WO2012035827A1 true WO2012035827A1 (fr) 2012-03-22

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Country Status (3)

Country Link
JP (1) JP5029931B2 (fr)
TW (1) TW201233564A (fr)
WO (1) WO2012035827A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017021278A1 (fr) * 2015-08-03 2017-02-09 Agfa Graphics Nv Liquides aqueux pour l'impression à jet d'encre
JP2018131509A (ja) * 2017-02-14 2018-08-23 理想科学工業株式会社 油性インクジェットインク
WO2019009210A1 (fr) * 2017-07-03 2019-01-10 花王株式会社 Encre aqueuse
EP3395852A4 (fr) * 2015-12-25 2019-08-21 Kao Corporation Dispersion aqueuse de pigment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111344363B (zh) * 2017-11-22 2021-07-09 Dic油墨株式会社 水性液体墨及印刷物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09104834A (ja) * 1995-08-09 1997-04-22 Dainippon Ink & Chem Inc 水性顔料分散体の製造方法、および水性着色剤組成物
JP2004300223A (ja) * 2003-03-31 2004-10-28 Toyo Ink Mfg Co Ltd 水性ポリウレタン樹脂および該樹脂を用いた印刷インキ
JP2005225948A (ja) * 2004-02-12 2005-08-25 Seiko Epson Corp 顔料分散液およびこれを用いたインク組成物
JP2007501871A (ja) * 2003-08-07 2007-02-01 ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー 光架橋性ポリウレタン

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09104834A (ja) * 1995-08-09 1997-04-22 Dainippon Ink & Chem Inc 水性顔料分散体の製造方法、および水性着色剤組成物
JP2004300223A (ja) * 2003-03-31 2004-10-28 Toyo Ink Mfg Co Ltd 水性ポリウレタン樹脂および該樹脂を用いた印刷インキ
JP2007501871A (ja) * 2003-08-07 2007-02-01 ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー 光架橋性ポリウレタン
JP2005225948A (ja) * 2004-02-12 2005-08-25 Seiko Epson Corp 顔料分散液およびこれを用いたインク組成物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017021278A1 (fr) * 2015-08-03 2017-02-09 Agfa Graphics Nv Liquides aqueux pour l'impression à jet d'encre
CN107922760A (zh) * 2015-08-03 2018-04-17 爱克发有限公司 水性喷墨印刷液体
US10619294B2 (en) 2015-08-03 2020-04-14 Agfa Nv Aqueous inkjet printing liquids
EP3395852A4 (fr) * 2015-12-25 2019-08-21 Kao Corporation Dispersion aqueuse de pigment
US10968358B2 (en) 2015-12-25 2021-04-06 Kao Corporation Aqueous pigment dispersion
JP2018131509A (ja) * 2017-02-14 2018-08-23 理想科学工業株式会社 油性インクジェットインク
WO2019009210A1 (fr) * 2017-07-03 2019-01-10 花王株式会社 Encre aqueuse
US11180671B2 (en) 2017-07-03 2021-11-23 Kao Corporation Aqueous ink

Also Published As

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TW201233564A (en) 2012-08-16
JPWO2012035827A1 (ja) 2016-05-26
JP5029931B2 (ja) 2012-09-19

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