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WO2012042968A1 - Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre contenant celui-ci, et matériau imprimé - Google Patents

Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre contenant celui-ci, et matériau imprimé Download PDF

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Publication number
WO2012042968A1
WO2012042968A1 PCT/JP2011/061849 JP2011061849W WO2012042968A1 WO 2012042968 A1 WO2012042968 A1 WO 2012042968A1 JP 2011061849 W JP2011061849 W JP 2011061849W WO 2012042968 A1 WO2012042968 A1 WO 2012042968A1
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WO
WIPO (PCT)
Prior art keywords
ink
isocyanate group
group
mass
binder
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
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PCT/JP2011/061849
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English (en)
Japanese (ja)
Inventor
定 永浜
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.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2011553202A priority Critical patent/JP5029932B2/ja
Publication of WO2012042968A1 publication Critical patent/WO2012042968A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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

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 cross-linked in the particles as the binder and have a high molecular weight.
  • the use of the modified resin particles was considered and could be solved by the investigation.
  • the present invention relates to a binder for ink jet printing ink, which is dispersed in an aqueous medium (B), an ink for ink jet printing containing 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 composite resin particles (A) formed by reacting the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2) other than the isocyanate group-containing polyurethane (a1), and the polyamine (a3) are formed into an aqueous medium. It is the binder for inkjet printing inks disperse
  • the composite resin particles (A) used in the present invention are formed by a cross-linking reaction between the isocyanate group-containing polyurethane (a1), polyisocyanate (a2), and polyamine (a3).
  • the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2), and the polyamine (a3) are crosslinked by the isocyanate group [X1] of the isocyanate group-containing polyurethane (a1) and the polyisocyanate (a2). This is a reaction between an isocyanate group [X2] and an amino group [Y] of the polyamine (a3).
  • the isocyanate group [X1] of the isocyanate group-containing polyurethane (a1) and the isocyanate group [X2] of the polyisocyanate (a2) are converted into those of the polyamine (a3). It is a reaction capable of forming a urea bond by reacting with each of the amino groups [Y].
  • 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 cross-linked structure is formed in the particles, it is difficult to cause swelling of the particles due to the aqueous medium (B) and the like, and as a result, the ink ejection stability is excellent without being impaired. It is possible to impart abrasion resistance 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 molar ratio of the isocyanate group [X1] of the isocyanate group-containing polyurethane (a1) and the isocyanate group [X2] of the polyisocyanate (a2) [isocyanate group [X1] / isocyanate Group [X2]] is preferably in the range of 0.1 to 20, more preferably 0.1 to 9, and the amino group [Y], the isocyanate group [X1] and the isocyanate group [X2]
  • the total molar ratio [amino group [Y] / ⁇ sum of isocyanate group [X1] and isocyanate group [X2] ⁇ ] is preferably in the range of 0.3 to 3.
  • the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2), and the polyamine (a3) were mixed and subjected to a crosslinking reaction within the range of The use of the is preferable for both the excellent discharge stability and storage stability of the ink, and excellent
  • the composite resin particles (A) part or all of the polyisocyanate (a2) and the polyamine (a3) are inherently contained in the resin particles (a) formed by the isocyanate group-containing polyurethane (a1). And it is preferable to use what cross-linked in the said resin particle (a). As the composite resin particles (A), all of the polyisocyanate (a2) and polyamine (a3) are not present in the polyurethane (a1) resin particles (a), or one of them is not subjected to a crosslinking reaction.
  • the polyisocyanate (a2) And 90% by mass or more of the total mass of the polyamine (a3) is preferably present in the composite resin particles (A) and subjected to a crosslinking reaction, and more preferably 95% by mass or more.
  • composite resin particles (A) those having a hydrophilic group are preferably used from the viewpoint of being stably dispersed in the aqueous medium (B).
  • the composite resin particles (A) those having a hydrophilic group as the isocyanate group-containing polyurethane (a1) are used, and the resin particles (a) formed by the polyurethane (a1) are used. It is preferable to use those in which a part or all of the polyisocyanate (a2) and the polyamine (a3) are present and cross-linked within the resin particles (a). Also when using what has a hydrophilic group as said composite resin particle (A), all of said polyisocyanate (a2) and polyamine (a3) are in said polyurethane (a1) resin particle (a) similarly to the above.
  • Some of them are present in the shell layer of the resin particles (a) without being present or cross-linking reaction, or in the aqueous medium (B) independently of the composite resin particles (A). It may be present, but 90% by mass or more of the total mass of the polyisocyanate (a2) and the polyamine (a3) is preferably present in the composite resin particles (A) and subjected to a crosslinking reaction, What is more than the mass% is more preferable.
  • an anionic group As the hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used. Among these, an anionic group or a cationic group is more preferable, and an anionic group is particularly preferable. preferable.
  • 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 15 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) those having an acid value of 1 mgKOH / g to 70 mgKOH / g are preferably used from the viewpoint of maintaining good storage stability and ejection stability.
  • the acid value is preferably derived from an acid group such as a carboxyl group that the isocyanate group-containing polyurethane (a1) can have.
  • the isocyanate group-containing polyurethane (a1) used for the production of the composite resin particles (A) will be described.
  • isocyanate group-containing polyurethane (a1) those having an isocyanate group [X1] as a functional group capable of reacting with an amino group [Y] of a polyamine (a3) described later are used.
  • polyurethane (a1) those having the isocyanate group [X1] at the molecular one end, both ends or molecular side chains of the polyurethane (a1) can be used.
  • the isocyanate group equivalent of the polyurethane (a1) is preferably in the range of 500 to 50,000.
  • the isocyanate group-containing polyurethane (a1) is preferably one having a hydrophilic group from the viewpoint of imparting good water dispersion stability to the composite resin particles (A).
  • an anionic group As the hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used. Among these, an anionic group or a cationic group is more preferable, and an anionic group is particularly preferable. .
  • a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used.
  • 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 etc. can be used, for example.
  • the hydrophilic group is preferably present in the range of 50 to 2000 mmol / kg, and preferably in the range of 150 to 1500 mmol / kg, with respect to the whole isocyanate group-containing polyurethane (a1). It is more preferable in giving.
  • the isocyanate group-containing polyurethane (a1) it is possible to use a polyurethane having a weight average molecular weight of 1,000 to 100,000, which has excellent alcohol resistance as well as excellent scratch resistance and alkali resistance. It is preferable for forming a printed image and imparting good ink ejection stability, and more preferably having a weight average molecular weight in the range of 1,000 to 50,000.
  • the isocyanate group-containing polyurethane (a1) can be produced, for example, by reacting the polyol (a1-1) and the polyisocyanate (a1-2) with a chain extender or the like, if necessary, as raw materials. it can.
  • polyether polyol for example, polyether polyol, polyester polyol, polyester ether polyol, polycarbonate polyol and the like can be used. Among these, it is more preferable to use a polyether polyol in order to improve the storage stability of the binder for ink jet printing ink.
  • polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, 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.
  • polyoxytetramethylene glycol or polyoxypropylene glycol as the polyether polyol in order to improve ink ejection stability.
  • polyoxytetramethylene glycol or polyoxypropylene glycol as the polyether polyol, those having a number average molecular weight of 300 to 2,000 are preferably used, and those having a number average molecular weight of 800 to 1500 are excellent in ink ejection stability, scratch resistance and alcohol resistance. And more preferable.
  • polyester polyol examples include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ⁇ -caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyester obtained by the above, copolymerized polyesters thereof, and the like can be used.
  • the low molecular weight polyol for example, ethylene glycol, propylene glycol and the like can be used.
  • polycarboxylic acid for example, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof can be used.
  • polyester ether polyol for example, a reaction product of a polyether polyol obtained by adding the alkylene oxide to the initiator and a polycarboxylic acid can be used.
  • the initiator and the alkylene oxide the same ones exemplified as those usable when the polyether polyol is produced can be used.
  • said polycarboxylic acid the thing similar to what was illustrated as what can be used when manufacturing the said polyester polyol can be used.
  • polycarbonate polyol for example, those obtained by reacting a carbonic acid ester and a polyol, or those obtained by reacting phosgene with bisphenol A or the like 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, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-
  • the polyether polyol, polyester polyol, polyester ether polyol, and polycarbonate polyol are used in a total range of 15% by mass to 85% by mass with respect to the total mass of raw materials used for the production of the isocyanate group-containing polyurethane (a1). It is preferable.
  • a hydrophilic group-containing polyol can be used for the purpose of introducing the hydrophilic group into the isocyanate group-containing polyurethane (a1).
  • hydrophilic group-containing polyol a polyol having a hydrophilic group other than the polyether polyol, polyester polyol, polyester ether polyol and polycarbonate polyol can be used.
  • an anionic group-containing polyol, a cationic group-containing polyol can be used.
  • a polyol and a nonionic group-containing polyol can be used, and among them, an anionic group-containing polyol and a cationic group-containing polyol are preferably used, and an anionic group-containing polyol is particularly preferably used.
  • anionic group-containing polyol for example, 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.
  • carboxyl group-containing polyester polyol obtained by making the said carboxyl group-containing polyol and various polycarboxylic acids react can also be 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, and the polyether polyol.
  • dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof
  • the polyether polyol examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the polyether polyol.
  • the carboxyl group-containing polyol or sulfonic acid group-containing polyol is preferably used in the range where the acid value of the isocyanate group-containing polyurethane (a1) is 1 mgKOH / g to 70 mgKOH / g, and is 10 mgKOH / g to 40 mgKOH / g. It is particularly preferable to use in a range.
  • the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said isocyanate group containing polyurethane (a1).
  • 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 for neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, NaOH, KOH, and 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 preferably partially or completely neutralized with an acidic compound such as formic acid, acetic acid, phosphoric acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.
  • an acidic compound such as formic acid, acetic acid, phosphoric acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.
  • the tertiary amino group as the cationic group is preferably partly or entirely quaternized.
  • the quaternizing agent for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and dimethyl sulfate is preferably used.
  • nonionic group-containing polyol polyalkylene glycol having a structural unit derived from ethylene oxide can be used.
  • the hydrophilic group-containing polyol is preferably used in the range of 1% by mass to 50% by mass with respect to the total mass of raw materials used for the production of the isocyanate group-containing polyurethane (a1).
  • polyol (a1-1) other polyols having a relatively low molecular weight can be used as necessary in addition to those described above.
  • the other polyol has a molecular weight of about 100 to 500, and for example, ethylene glycol or propylene glycol can be used.
  • aliphatic cyclic structure-containing polyols such as 1,4-cyclohexanediol, cycloheptanediol, and cyclohexanedimethanol can be used.
  • Examples of the polyisocyanate (a1-2) that can be used for the production of the isocyanate group-containing polyurethane (a1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and crude diphenylmethane.
  • Aromatic polyisocyanates such as diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Isocyanate There may be used a polyisocyanate having an alicyclic structure.
  • 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.
  • the polyisocyanate (a1-2) is preferably a single polyisocyanate rather than a multimer such as nurate.
  • the isocyanate group-containing polyurethane (a1) can be produced, for example, by reacting the polyol (a1-1) and the polyisocyanate (a1-2) in the absence of a solvent or in the presence of an organic solvent.
  • the reaction is preferably performed in the range of about 40 ° C. to 100 ° C. for about 1 hour to 10 hours.
  • a chain extender When a chain extender is used as necessary, it may be used by mixing with the polyol (a1-1) or the polyisocyanate (a1-2).
  • the reaction between the polyol (a1-1) and the polyisocyanate (a1-2) is, for example, that the equivalent ratio of the isocyanate group of the polyisocyanate (a1-2) to the hydroxyl group of the polyol (a1-1) is , Preferably in the range of 0.8 to 2.5, more preferably in the range of 0.9 to 1.5.
  • Examples of the organic solvent that can be used in producing the isocyanate group-containing polyurethane (a1) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; and acetates such as ethyl acetate and butyl acetate.
  • Nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more.
  • a chain extender can be used as needed for the purpose of enlarging the molecular weight from a viewpoint of improving abrasion resistance.
  • the chain extender for example, an isocyanate group-containing polyurethane prepolymer is prepared by reacting the polyol (a1-1) with the polyisocyanate (a1-2) in the absence of a solvent or in the presence of an organic solvent.
  • An isocyanate group-containing polyurethane (a1) can be produced by producing a polymer and then reacting the polyurethane with a chain extender.
  • chain extender that can be used for producing the isocyanate group-containing polyurethane (a1)
  • polyamine other active hydrogen atom-containing compounds, and the like
  • chain extender that can be used for producing the isocyanate group-containing polyurethane (a1)
  • polyamine other active hydrogen atom-containing compounds, and the like
  • 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 isocyanate group-containing 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.
  • the isocyanate group-containing polyurethane (a1) obtained above is the total mass of raw materials used in the production of the composite resin particles (A), that is, the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2), and the It is preferably used in the range of 50% by mass to 99% by mass and more preferably in the range of 80% by mass to 95% by mass with respect to the total mass of the polyamine (a3).
  • the polyisocyanate (a2) is a compound having two or more isocyanate groups, and refers to a compound other than the isocyanate group-containing polyurethane (a1).
  • polyisocyanate (a2) examples include aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.
  • aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.
  • aliphatic or alicyclic polyisocyanates such as hexane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or those A dimer or the like, generally those referred to as cyanurate and can be used a mixture thereof.
  • said polyisocyanate (a2) the thing in which two or more nurate partly formed the urethane bond, and the mixture containing it can be used.
  • polyisocyanates (a2) it is preferable to use a nurate form, and more specifically, a dimer to pentamer form is more preferable. It is preferable to use a body to a pentamer in order to achieve both the ejection stability and storage stability of the ink and the scratch resistance and alkali resistance.
  • the polyisocyanate (a2) a mixture of various polyisocyanates described above may be used.
  • the average number of isocyanate groups in the mixture is preferably in the range of 2 to 6.
  • the average number of isocyanate groups is an average value calculated based on the mass of each polyisocyanate and the number of functional groups.
  • the nurate body can be produced, for example, by reacting the aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, or the like in the presence of a plasticizer and a catalyst.
  • plasticizer for example, in an inert solvent such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane, or diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, trimellitic acid ester, etc. can be used. .
  • an inert solvent such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane, or diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, trimellitic acid ester, etc.
  • a tertiary amine, a quaternary ammonium compound, a Mannich base, an alkali metal of a fatty acid, an alcoholate, or the like can be used.
  • polyisocyanate (a2) it is preferable to use a polyisocyanate (a2) having a number average molecular weight of 300 to 5,000 in order to achieve both the ejection stability and storage stability of the ink and the scratch resistance and alkali resistance. .
  • the polyisocyanate (a2) is inherent in the resin particles (a) formed by the isocyanate group-containing polyurethane (a1), and is crosslinked with the polyurethane (a1) or the polyamine (a3).
  • the polyisocyanate (a2) alone has a hydrophobicity level that cannot be stably dispersed in the aqueous medium (B).
  • the content of the hydrophilic group in the polyisocyanate (a2) is preferably less than 50 mmol / kg, preferably 25 mmol / kg or less, and particularly preferably 0 mmol / kg. .
  • the polyisocyanate (a2) is used in the range of 0.5% by mass to 20% by mass with respect to the total mass of the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2), and the polyamine (a3). It is preferable to achieve both the ejection stability and storage stability of the ink and the scratch resistance and alkali resistance, and more preferably 0.5 to 10% by mass.
  • the polyamine (a3) is a compound having two or more amino groups [Y], and the isocyanate group-containing polyurethane (a1) or the polyisocyanate (a2) has an isocyanate group [X1] or [X2]. It can react.
  • the amino group [Y] is preferably a primary amino group or a secondary amino group from the viewpoint of promptly crosslinking with the isocyanate group [X1] or the isocyanate group [X2].
  • the reaction of the amino group [Y] with the isocyanate group [X1] or the isocyanate group [X2] proceeds to form the composite resin particles (A), thereby improving the ink ejection stability and storage stability. It is possible to obtain an ink jet printing ink binder capable of forming a printed image having excellent durability such as scratch resistance and alkali resistance without damaging.
  • polyamine (a3) examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3, Diamines such as 3′-dimethyl-4,4′-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethyl Aminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydra
  • a polyamine having 3 or more amino groups it is preferable to use a polyamine having 3 or more amino groups, and the amino group is more preferably a primary amino group.
  • the amino group is more preferable to use diethylenetriamine or the polyoxyalkylenetriamine because it has three primary amines having high reactivity with the isocyanate group.
  • the polyamine (a3) is inherent in the resin particles (a) formed by the isocyanate group-containing polyurethane (a1), and is crosslinked with the polyurethane (a1) or the polyisocyanate (a2).
  • the polyamine (a3) alone has a hydrophobicity at a level that cannot be stably dispersed in the aqueous medium (B).
  • the content of hydrophilic groups other than amino groups in the polyamine (a3) is preferably less than 50 mmol / kg, preferably 25 mmol / kg or less, and 0 mmol / kg. Is particularly preferred.
  • the amino group in the polyamine (a3) reacts immediately with the isocyanate groups [X1] and [X2] in the aqueous medium (B) to form a urea bond, thereby substantially imparting water dispersibility. Does not contribute.
  • the polyamine (a3) is used in the range of 0.5% by mass to 30% by mass with respect to the total mass of the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2), and the polyamine (a3). It is preferable to achieve both the ejection stability and storage stability of the ink and the scratch resistance and alkali resistance, and more preferably 0.5 to 15% by mass.
  • the aqueous medium (B) used in the ink jet printing ink binder of the present invention is one in which the composite resin particles (A) can be dispersed.
  • 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) when used as a solvent, the aqueous medium (B) can be continuously used as a solvent for the binder for inkjet printing ink of the present invention.
  • the aqueous medium (B) is preferably contained in an amount of 40 to 90% by mass, and more preferably 50 to 85% by mass with respect to the total amount of the binder for ink jet printing ink.
  • the [Method 1] includes, for example, a step (I) for producing a mixture of the isocyanate group-containing polyurethane (a1) and the polyisocyanate (a2), and the mixture and the aqueous medium (B) are mixed and dispersed. And the step (II) of producing composite resin particles (A) in which the dispersion and the polyamine (a3) are mixed and crosslinked in the particles.
  • Method 2 includes the step (IV) for producing a mixture of the isocyanate group-containing polyurethane (a1) and the polyisocyanate (a2), and the aqueous medium (B) and the polyamine separately from the step (IV).
  • (A3) is mixed with the step (V) to obtain a mixture, and the mixture obtained in the step (IV) and the mixture obtained in the step (V) are mixed to obtain an isocyanate group-containing polyurethane (a1).
  • This is a method comprising a step (VI) of producing an aqueous dispersion of composite resin particles (A) in which the polyisocyanate (a2) or the polyamine (a3) is crosslinked in the formed resin particles.
  • Step (I) in [Method 1] is a step in which the isocyanate group-containing polyurethane (a1) obtained above and the polyisocyanate (a2) are mixed to obtain a mixture thereof.
  • the organic solvent solution of the isocyanate group-containing polyurethane (a1) and the polyisocyanate (a2) may be mixed.
  • the organic solvent is preferably removed by a method such as distillation after the production of the ink jet ink binder of the present invention.
  • Step (II) in [Method 1] is a mixture of the isocyanate group-containing polyurethane (a1) obtained in the step (I) and the polyisocyanate (a2), and an aqueous medium (B),
  • This is a step of producing a dispersion in which the isocyanate group-containing polyurethane (a1) and the polyisocyanate (a2) are dispersed in an aqueous medium (B).
  • the polyisocyanate (a2) may not be stably dispersed in the aqueous medium (B) alone. In such a case, part or all of the polyisocyanate (a2) may be present in a localized state in the resin particles formed by the isocyanate group-containing polyurethane (a1).
  • the isocyanate group-containing polyurethane (a1) contained in the mixture has the hydrophilic group
  • Step (III) in [Method 1] is a step of producing a composite resin particle (A) obtained by mixing and crosslinking the dispersion obtained in the step (II) and the polyamine (a3).
  • the polyamine (a3) may be partly or wholly localized in the resin particles formed by the isocyanate group-containing polyurethane (a1).
  • composite resin particles (A) in which the isocyanate group-containing polyurethane (a1), the polyisocyanate (a2), and the polyamine (a3) are cross-linked in the resin particles can be formed.
  • a curing agent or A curing catalyst may be used in combination.
  • 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 ink binder for ink-jet printing 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.
  • the composite resin particle (A) is in the range of 10% by mass to 60% 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 50% 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, particularly in the case of forming a higher gloss image such as photographic image quality, the range of 80 to 500 nm. It is more preferable that
  • 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.
  • Example 1 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 141.4 parts by mass of polyoxypropylene glycol having a number average molecular weight of 1000, 11.9 parts by mass of 2,2-dimethylolpropionic acid, and 76.6 parts by mass of isophorone diisocyanate was reacted in the presence of 25.5 parts by mass of methyl ethyl ketone as an organic solvent for 5 hours to obtain an isocyanate group-containing polyurethane (a1-I).
  • Example 2 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 141.3 parts by mass of polyoxypropylene glycol having a number average molecular weight of 1000, 11.8 parts by mass of 2,2-dimethylolpropionic acid, and 76.6 parts by mass of isophorone diisocyanate was reacted in the presence of 25.5 parts by mass of methyl ethyl ketone as an organic solvent for 5 hours to obtain an isocyanate group-containing polyurethane (a1-II).
  • the aqueous dispersion of the composite resin particles (A′-2) is aged and desolvated to have an acid value of 19.5, a gel fraction of 85% by mass to 100% by mass, and an average particle size of 50 nm to A binder for ink jet printing ink having a nonvolatile content of 25% by mass, in which 500 nm composite resin particles (A-2) were dispersed in water, was obtained.
  • Example 3 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 126.9 parts by mass of polyoxypropylene glycol having a number average molecular weight of 1000, 10.6 parts by mass of 2,2-dimethylolpropionic acid, and 68.8 parts by mass of isophorone diisocyanate was reacted in the presence of 22.9 parts by mass of methyl ethyl ketone as an organic solvent for 5 hours to obtain an isocyanate group-containing polyurethane (a1-III).
  • the acid value is 20
  • the gel fraction is 85 mass% to 100 mass%
  • the average particle diameter is 70 nm to 700 nm.
  • a binder for inkjet printing ink having a non-volatile content of 25% by mass in which the composite resin particles (A-3) were dispersed in water was obtained.
  • Example 4 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 141.4 parts by mass of polyoxytetramethylene glycol having a number average molecular weight of 1000 and 11.9 parts by mass of 2,2-dimethylolpropionic acid And 76.6 parts by mass of isophorone diisocyanate were reacted for 5 hours in the presence of 25.5 parts by mass of methyl ethyl ketone as an organic solvent to obtain an isocyanate group-containing polyurethane (a1-IV).
  • Example 5 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 144.9 parts by mass of polyoxypropylene glycol having a number average molecular weight of 1000, 12.2 parts by mass of 2,2-dimethylolpropionic acid, and 78.5 parts by mass of isophorone diisocyanate was reacted in the presence of 26.2 parts by mass of methyl ethyl ketone as an organic solvent for 5 hours to obtain an isocyanate group-containing polyurethane (a1-V).
  • the composite resin particles (x) having an acid value of 20 and a gel fraction of 40% by mass to 70% by mass and an average particle size of 50 nm to 500 nm are dissolved in water.
  • a binder for ink jet printing ink having a dispersed nonvolatile content of 25% by mass was obtained.
  • the reaction is terminated by adding 1.8 parts by mass of methanol, and further, 164.9 parts by mass of methyl ethyl ketone is added as a diluent solvent, 500.0 parts by mass of an organic solvent solution of polyurethane having an acid value of 24 (nonvolatile content: 50% by mass) was obtained.
  • 10.8 parts by mass of triethylamine is added to the polyurethane organic solvent solution to neutralize part or all of the carboxyl groups of the polyurethane, and further 739.2 parts by mass of water is added and stirred sufficiently.
  • an aqueous dispersion of polyurethane (y ′) was obtained.
  • the polyurethane (y) having an acid value of 24, a gel fraction of 1% by mass to 30% by mass and an average particle size of 10 nm to 100 nm is obtained by aging and removing the aqueous dispersion of the polyurethane (y ′).
  • a binder for inkjet printing ink having a nonvolatile content of 25% by mass dispersed in water was obtained.
  • 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 min, 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 5 and Comparative Examples 1 and 2 the ink-jet printing ink binders and Preparation Example 1 were prepared 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
  • 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 of 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.
  • “Molar ratio 1” in Tables 1 and 2 indicates that the isocyanate group [X1] of the isocyanate group-containing polyurethane (a1) constituting the composite resin particle (A) and the isocyanate group [X2] of the polyisocyanate (a2). ] And the molar ratio [isocyanate group [X1] / isocyanate group [X2]].
  • the “molar ratio 2” in Tables 1 and 2 is the molar ratio of the amino group [Y] and the total of the isocyanate group [X1] and the isocyanate group [X2] [amino group [Y] / ⁇ isocyanate. Group [X1] and isocyanate group [X2] total ⁇ ].

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

La présente invention résout le problème de production de : un liant pour des encres pour impression à jet d'encre qui sont capables de former des images imprimées ayant une durabilité, telle qu'une résistance aux rayures et une résistance aux alcalis extrêmement élevées, tout en conservant des propriétés intactes comprenant une stabilité de distribution et une stabilité à la conservation satisfaisantes ; et une encre pour impression à jet d'encre contenant le liant. Ce liant pour des encres pour impression à jet d'encre est caractérisé en ce qu'il comprend un milieu aqueux (B) et, dispersé dans celui-ci, des particules de résine composite (A) formées par des réactions entre un polyuréthane contenant un groupe isocyanate (a1), un polyisocyanate (a2) autre que le polyuréthane contenant un groupe isocyanate (a1), et une polyamine (a3). L'invention concerne en outre un matériau imprimé.
PCT/JP2011/061849 2010-09-29 2011-05-24 Liant pour encre d'impression à jet d'encre, encre d'impression à jet d'encre contenant celui-ci, et matériau imprimé Ceased WO2012042968A1 (fr)

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JP2015025122A (ja) * 2013-06-20 2015-02-05 キヤノン株式会社 インク、インクカートリッジ、及びインクジェット記録方法

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JPH03128912A (ja) * 1989-06-14 1991-05-31 Ici Americas Inc 水分散性ポリウレタンの水性分散物
JPH04249517A (ja) * 1990-05-09 1992-09-04 Dainippon Ink & Chem Inc 架橋ウレタン−尿素樹脂分散体およびその製造法
JP2004285344A (ja) * 2003-03-04 2004-10-14 Seiko Epson Corp 顔料分散水性記録液および印刷物
WO2009143433A1 (fr) * 2008-05-23 2009-11-26 E. I. Du Pont De Nemours And Company Dispersants de polyuréthane à terminaison d’urée

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JP2006282760A (ja) * 2005-03-31 2006-10-19 Seiko Epson Corp インク組成物、これを用いたインクジェット記録方法及び記録物
JP2008266595A (ja) * 2007-03-29 2008-11-06 Dic Corp 顔料分散液及びインクジェット記録用水性インク
JP5196235B2 (ja) * 2008-01-25 2013-05-15 株式会社リコー インクジェット用記録インク、インクカートリッジ、インクジェットプリント装置、及び画像形成方法

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Publication number Priority date Publication date Assignee Title
JPH03128912A (ja) * 1989-06-14 1991-05-31 Ici Americas Inc 水分散性ポリウレタンの水性分散物
JPH04249517A (ja) * 1990-05-09 1992-09-04 Dainippon Ink & Chem Inc 架橋ウレタン−尿素樹脂分散体およびその製造法
JP2004285344A (ja) * 2003-03-04 2004-10-14 Seiko Epson Corp 顔料分散水性記録液および印刷物
WO2009143433A1 (fr) * 2008-05-23 2009-11-26 E. I. Du Pont De Nemours And Company Dispersants de polyuréthane à terminaison d’urée

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Publication number Priority date Publication date Assignee Title
JP2015025122A (ja) * 2013-06-20 2015-02-05 キヤノン株式会社 インク、インクカートリッジ、及びインクジェット記録方法

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