JP6123507B2 - Inkjet water-based ink, inkjet recording, inkjet recording method, and inkjet recording apparatus - Google Patents

Description

  The present invention relates to an aqueous inkjet ink, an inkjet recording, an inkjet recording method, and an inkjet recording apparatus.

  Inkjet printers have advantages such as low noise, low running cost, and easy color printing, and thus are widely used as digital signal output devices in general households.

  In recent years, inkjet technology has been used not only for such home use but also for industrial use such as a display, a poster, and a bulletin board.

  In such applications, non-porous substrates such as plastic films are used because porous substrates have problems with durability such as light resistance, water resistance, and abrasion resistance. Inks have been developed.

  As such an ink, for example, a solvent-based inkjet ink using an organic solvent as a vehicle and an ultraviolet curable inkjet ink mainly composed of a polymerizable monomer have been widely used.

  However, solvent-based ink-jet inks are not preferred from the viewpoint of environmental impact because they evaporate a large amount of solvent into the atmosphere, and UV curable ink-jet inks may have skin sensitization depending on the monomers used. Since the expensive ultraviolet irradiation device needs to be incorporated in the printer body, the field of application is limited.

  Against this background, recently, an ink-jet ink that can be directly printed on a non-porous substrate has been developed with a water-based ink-jet recording ink that has been used as a home-use ink-jet ink and has a low environmental impact. Yes. Examples of such attempts include, for example, Patent Document 1 and Patent Document 2.

  However, it has been pointed out that these water-based inks are generally inferior in image quality as compared with solvent-based inkjet inks.

  First of all, the ink does not penetrate into the non-porous substrate, so the ink on the substrate must be dried immediately, but it is added as water as the main solvent of water-based ink and as an additive. The water-soluble organic solvent has a problem that the drying property is deteriorated and is liable to cause poor drying. For this reason, when the printed matter is piled up or taken up, the ink shows through and so-called blocking occurs. May end up.

  In addition, many non-porous substrates are very glossy, and there is a need for inks that can provide high gloss so as not to impair the sense of unity as the recorded matter of the printed and non-printed parts when printed. However, unlike solvent-based inks in which the resin is dissolved in the ink, the particles are fused to form a coating film, so that the surface tends to become rough and the gloss tends to be impaired. Furthermore, with regard to image fastness, sufficient properties are not obtained with respect to scratch resistance and ethanol resistance, and higher performance is required.

Patent Document 3 includes a water-based resin dispersion mainly composed of self-dispersing carbon black, polyvinyl alcohol, and urethane resin as an ink having improved print quality, scratch resistance, and clogging. An ink for ink jet recording is disclosed.
However, none of the examples of Patent Document 3 has a reference in which polyvinyl alcohol is added, and glycerin is added to any of the examples. However, for non-porous substrates such as plastic films, etc. Therefore, there is a problem that the drying property is deteriorated and the drying is liable to occur.

Patent Document 4 discloses an ink for ink-jet recording characterized by containing a self-dispersing or resin-dispersed pigment and a resin having a silanol group as an ink capable of achieving both scratch resistance and ink storage stability. Has been.
However, in Patent Document 4, there is a problem that non-porous substrates such as plastic films are deteriorated in drying properties and easily cause poor drying.

Patent Document 5 discloses an ink jet recording ink containing silanol-modified polyvinyl alcohol as an ink having improved scratch resistance and glossiness.
However, in Patent Document 5, it is essential to eject the ink after ejecting the pretreatment liquid to the planned printing position by the ink jet recording method, which is different from the water-based ink for ink jet used in the ink jet recording method including the heating step. .

The object of the present invention has been made in view of such circumstances, and an object thereof is to solve the above problems.
That is, an object of the present invention is to provide an ink that exhibits good drying properties even when printed on a non-porous substrate and has a high gloss, scratch resistance, and ethanol resistance in the printed portion.

  As a result of intensive studies, the present inventors have found that the above-mentioned problem occurs when an ink-jet aqueous ink characterized by containing water, a water-soluble organic solvent, a pigment, polycarbonate urethane resin fine particles, and polyvinyl alcohol is used. Has been found to be solved, and the present invention has been achieved.

  That is, the present invention is an inkjet water-based ink used in an inkjet recording system including a heating step, which contains water, a water-soluble organic solvent, a pigment, polycarbonate-based urethane resin fine particles, and modified polyvinyl alcohol. An aqueous inkjet ink characterized by being one or two selected from silanol-modified polyvinyl alcohol and carboxyl-modified polyvinyl alcohol.

  According to the present invention, it is possible to provide an ink that exhibits good drying properties even when printed on a non-porous substrate and has a high gloss, scratch resistance, and ethanol resistance in the printed portion.

It is the schematic which shows the structure in one Embodiment of the inkjet recording device which can implement suitably the ink which concerns on this invention. It is another schematic diagram showing a configuration in an embodiment of an ink jet recording apparatus that can suitably implement the ink according to the present invention.

  The water-based ink for ink-jet according to the present invention (hereinafter sometimes simply referred to as “ink”) is a water-based ink for ink-jet recording used in an ink-jet recording system including a heating step, and includes water, water-soluble organic solvents, pigments, and polycarbonate-based inks. It contains urethane resin fine particles and modified polyvinyl alcohol, and the modified polyvinyl alcohol is one or two selected from silanol-modified polyvinyl alcohol and carboxyl-modified polyvinyl alcohol.

Hereinafter, the water-based ink for ink jet, the ink jet recorded material, the ink jet recording method, and the ink jet recording apparatus according to the present invention will be described.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

  The water-soluble organic solvent added to the water-based ink generally has a boiling point higher than that of water and is difficult to dry. Therefore, in order to obtain drying properties, it is necessary to add an organic solvent having a relatively low boiling point. However, when quick drying is required, the resin film formation is generally too fast, so that a sufficiently uniform coating film cannot be formed, resulting in poor film strength and glossiness.

  As a result of continuously studying the relationship between the existing resin and the water-soluble organic solvent, the inventors of the present invention can form a uniform film by using a polycarbonate urethane resin and a water-soluble organic solvent and using polyvinyl alcohol. I found out that

  In particular, the polycarbonate-based urethane resin is excellent in water resistance, heat resistance, abrasion resistance, and weather resistance due to the high cohesive strength of the carbonate group, and is suitable for printed matter used in harsh environments such as outdoor applications. As a result, after a specific water-soluble organic solvent is printed as an ink together with polycarbonate urethane resin emulsion particles and polyvinyl alcohol, it promotes moderate drying and fusion between resin emulsions, thereby forming a uniform film. This makes it possible to obtain a high gloss on the printed portion, and to exhibit scratch resistance and ethanol resistance.

  Next, other components of the ink of the present invention will be described. The ink component of the present invention comprises at least water, a water-soluble organic solvent, a pigment, polycarbonate urethane resin fine particles, and polyvinyl alcohol, and if necessary, a surfactant, antiseptic and fungicide, rust inhibitor, pH It may contain a conditioner or the like.

(Polycarbonate urethane resin fine particles)
First, the polycarbonate-based urethane resin fine particles used in the present invention will be described. The polycarbonate-type urethane resin in this invention points out what is obtained by making a polycarbonate polyol and polyisocyanate react.

  As said polycarbonate polyol, what is obtained by transesterifying a carbonate ester and a polyol in presence of a catalyst, for example, and the thing obtained by making phosgene and bisphenol A react can be used.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol to be reacted with the carbonate ester include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane. Low molecular diol compounds such as diol, neopentyl glycol, 1,4-cyclohexanediol, polyethylene glycol, polypropylene glycol, and the like can be used.

  The polyisocyanate that can be used in the present invention can be used without particular limitation. For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6- Tolylene diisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl Aromatic polyisocyanate compounds such as 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate; Tylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Aliphatic polyisocyanate compounds such as proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate; isophorone diisocyanate ( IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated) Alicyclic polycyanate compounds such as TDI), bis (2-isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. These may be used alone or in combination of two or more.

  Since the ink in the present invention is also suitably used in outdoor applications such as posters and signboards, it requires a coating film with extremely high long-term weather resistance. From this viewpoint, an aliphatic or cycloaliphatic diisocyanate is used. It is preferable to do. Furthermore, in the present invention, it is preferable to add at least one alicyclic diisocyanate, which makes it easy to obtain the desired coating strength.

  Among these, isophorone diisocyanate and dicyclohexylmethane diisocyanate can be suitably used, and the ratio of the alicyclic diisocyanate is preferably 60% or more of the total isocyanate compound.

  In the present invention, the polycarbonate urethane fine particles may be added in the form of a resin emulsion dispersed in an aqueous medium. In that case, the resin solid content in the resin emulsion is preferably 20% by weight or more, and if it is less than 20% by weight, it is not preferable because it is difficult to design a formulation when making an ink.

  The urethane resin fine particles at this time desirably have an average particle diameter in the range of 10 to 350 nm from the viewpoints of liquid storage stability and ejection stability when converted into ink.

  In addition, when dispersing the urethane fine particles in the aqueous medium, a forced emulsification type using a dispersant can be used, but since the dispersant may remain in the coating film and lower the strength, A so-called self-emulsifying type having an anionic property can be suitably used. In that case, it is preferable to contain an anionic group in an acid value range of 20 to 100 in order to impart excellent scratch resistance and chemical resistance.

  In addition, as the anionic group, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used. Among them, a carboxylate group or a sulfonate partially or completely neutralized with a basic compound or the like. It is preferable to use a group for maintaining good water dispersion stability.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. And metal base compounds.

  When the forced emulsification method is used, as the surfactant, any of a nonionic surfactant and an anionic surfactant can be used. However, the nonionic surfactant is preferable because it has better water resistance.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, sorbitan fatty acid ester , Polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, polyalkylene glycol (meth) acrylate and the like. Preferably, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned.

  As an anionic surfactant, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, methyl taurate, sulfosuccinate, ether sulfonate, ether carboxylate, Fatty acid salts, naphthalenesulfonic acid formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, alkylamine oxides and the like are preferable, and polyoxyethylene alkyl ether sulfates, sulfosuccinates and the like are preferable.

  The addition amount of the surfactant is preferably 0.1 to 30% by weight, more preferably 5 to 20% by weight with respect to the urethane resin. If it exceeds 30% by weight, the excess emulsifier more than necessary to form a urethane resin emulsion will significantly reduce the adhesion and water resistance. This is not preferable because it is likely to cause blocking.

  In addition, the urethane resin emulsion in the present invention may contain other water-soluble organic solvents, preservatives, leveling agents, antioxidants, light stabilizers, ultraviolet absorbers, and the like as necessary.

Next, the manufacturing method of the polycarbonate-type urethane resin fine particle in this invention is demonstrated. As the production method, any of the methods generally used in the past can be used, and examples thereof include the following methods.
First, in the absence of a solvent or in the presence of an organic solvent, the polycarbonate polyol and the polyisocyanate are reacted at an equivalent ratio in which an isocyanate group becomes excessive to produce an isocyanate-terminated urethane prepolymer.
Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with the neutralizing agent as necessary, and then reacted with a chain extender, and finally the organic solvent in the system is removed as necessary. Can be obtained.

  In this case, usable organic solvents include, for example, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, acetates such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, dimethylformamide, N- Examples include amides such as methylpyrrolidone and 1-ethyl-2-pyrrolidone, and these may be used alone or in combination of two or more.

  As the chain extender, polyamines and other active hydrogen atom-containing compounds can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamine, polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine, hydrazines such as hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazide, adipic dihydrazide Further, dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide can be used.

  Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, Glycols such as methylene glycol, glycerin, sorbitol, bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, phenols such as hydroquinone, In addition, water and the like can be used alone or in combination of two or more within a range in which the storage stability of the coating agent of the present invention does not decrease.

  The ink of the present invention can be used satisfactorily by performing heat treatment because the residual solvent is reduced and the adhesiveness is improved, and the polycarbonate-based urethane resin fine particles have high heat resistance.

  The polycarbonate-based urethane resin fine particles used in the present invention may not necessarily have a minimum film-forming temperature of room temperature or lower. However, when heating is performed, it is desirable that the minimum film-forming temperature is at least the heating temperature or lower.

  The minimum film-forming temperature of the polycarbonate-based urethane resin emulsion comprising polycarbonate-based urethane resin fine particles contained in water or water and a solvent is preferably 0 ° C. or higher and lower than the heating temperature by 5 ° C. or higher. The temperature is preferably 25 ° C or higher and lower than the heating temperature by 10 ° C or higher.

In general, the lower the film-forming temperature is, the better the film-forming property is. However, when the minimum film-forming temperature is too low, the glass transition point of the resin is low and sufficient film strength cannot be obtained.
The minimum film-forming temperature is the lowest temperature at which a transparent continuous film is formed when a polycarbonate urethane resin emulsion is cast thinly on a metal plate such as aluminum and the temperature is raised. In the temperature range below the minimum film-forming temperature, the polycarbonate-based urethane resin emulsion is in a liquid state or a white powder.

Further, the polycarbonate-based urethane resin used in the present invention preferably has a surface hardness of 100 N / mm ² or more, and when satisfying this, the ink of the present invention forms a tough coating film and has a higher scratch resistance. Can be obtained.

  The surface hardness in the present invention can be measured, for example, by the following method. After applying a polycarbonate urethane resin emulsion on a slide glass so that the film thickness becomes 10 μm, the resin film formed by drying at 100 ° C. for 30 minutes is used with a micro surface hardness tester (FISCHERSCOPE HM2000, manufactured by Fischer), Berkovich The indentation depth when the indenter is pushed in with a load of 9.8 mN can be obtained and measured as the Martens hardness described in ISO14577-2002.

  In the ink of the present invention, the polycarbonate-based urethane resin fine particles are preferably added in an amount of 0.5 to 10% in terms of solid content in the ink, more preferably 1 to 8%, and further preferably 3 to 8%. It is. When the addition amount is less than 0.5%, the image fastness is inferior because a coating film is not sufficiently formed with respect to the pigment, and when the addition amount exceeds 10%, the viscosity becomes too high and the discharge becomes difficult. .

  The ink of the present invention may contain a resin other than the polycarbonate-based urethane resin fine particles, but 50% or more of the resin added to the ink in order to sufficiently satisfy the effects of the invention is preferably a polycarbonate-based urethane resin, More preferably, 70% or more is polycarbonate-based urethane resin.

  Examples of resin fine particles that can be contained in addition to the polycarbonate urethane resin fine particles include acrylic resin fine particles, polyolefin resin fine particles, vinyl acetate resin fine particles, vinyl chloride resin fine particles, fluororesin fine particles, polyether resin fine particles, and polyester resin fine particles. Is mentioned.

(Polyvinyl alcohol)
Next, the polyvinyl alcohol used in the present invention will be described.
Polyvinyl alcohol, when used in combination with polycarbonate-based urethane resin fine particles, increases the bonding strength between the resins by filling the gaps between the resin fine particles and improves the surface smoothness, thereby improving image quality and scratch resistance. Can be improved.

Examples of the polyvinyl alcohol include silanol-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, and acetoacetyl-modified polyvinyl alcohol.
In particular, it is preferable to use silanol-modified polyvinyl alcohol because the above-described effects can be remarkably obtained without impairing the storage stability of the ink. Polyvinyl alcohol may be used alone or in combination of two or more.

Moreover, R1130, R2105 (made by Kuraray) etc. are mentioned as a commercial item of silanol modified polyvinyl alcohol.
Examples of commercially available products of carboxyl-modified polyvinyl alcohol include T330H (manufactured by Nippon Synthetic Chemical Co., Ltd.).

  In addition, a resin other than silanol-modified polyvinyl alcohol may be used in combination as long as the storage stability and ejection stability of the ink are not impaired. For example, various water-soluble polymers, emulsions thereof, latex, and the like may be used as appropriate. Can do.

  The degree of saponification of polyvinyl alcohol is not particularly limited as long as it is in a water-soluble range, but is generally selected from the range of 80 to 100 mol%. Since the ink of the present invention is a water-based ink, the range of 98 to 99 mol% called a completely saponified product is more preferable.

  The amount of polyvinyl alcohol added is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of ink. When used in combination with resin fine particles, a sufficient image quality improvement effect can be obtained at 0.1% by weight or more. If it is less than 0.1% by weight, a sufficient image quality improvement effect cannot be obtained, and if it exceeds 10% by weight, the storage stability of the ink may be lowered.

(Pigment)
As the pigment, both inorganic pigments and organic pigments can be used.
Carbon black produced by known methods such as contact method, furnace method, thermal method in addition to titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow as inorganic pigments Etc. can be used.
Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments). , Dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acid dye chelates), nitro pigments, nitroso pigments, aniline black, etc. .

  Of these pigments, those having good affinity with the solvent are preferably used. Further, the amount of the pigment added as a coloring material in the ink composition is preferably about 0.1 to 10% by weight, more preferably about 1 to 10% by weight. In general, when the pigment concentration is increased, the image density is increased and the image quality is improved. However, the reliability such as fixing property, ejection stability, and clogging tends to be adversely affected.

  Specific examples of pigments preferably used in the present invention include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11). And metal pigments such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).

  Further, for CI color, CI pigment yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 81, 83, 95, 97, 98 , 100, 101, 104, 108, 109, 110, 117, 120, 138, 150, 153, CI Pigment Orange 5, 13, 16, 17, 36, 43, 51, CI Pigment Red 1, 2, 3, 5 17, 22, 23, 31, 38, 48: 2, 48: 2 (permanent red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1. (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219, CI pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, CI pigment blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.

In addition, a self-dispersing pigment that can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the surface of the pigment (for example, carbon) can be used.
Further, a pigment may be included in a microcapsule so that the pigment can be dispersed in water. This can be paraphrased as resin fine particles containing pigment particles. In this case, it is not necessary for all pigments blended in the ink to be enclosed or adsorbed in the resin fine particles, and the pigments may be dispersed in the ink as long as the effects of the present invention are not impaired.

  In the case of dispersing a pigment using a dispersant, any conventionally known one can be used. Examples thereof include a polymer dispersant and a water-soluble surfactant.

  The particle diameter of the pigment is not particularly limited, but it is preferable in the present invention to use a pigment ink having a particle diameter of 20 to 150 nm in terms of the maximum frequency in terms of the maximum number. When the particle diameter exceeds 150 nm, not only the pigment dispersion stability as the ink composition is deteriorated, but also ejection stability is deteriorated, and image quality such as image density is lowered, which is not preferable. If the particle size is less than 20 nm, the storage stability of the ink composition and the jetting characteristics of the printer are stable. However, dispersing to such a fine particle size is complicated by the dispersion operation and classification operation. In particular, it becomes difficult to produce a recording liquid.

(Water-soluble organic solvent)
Next, although a water-soluble organic solvent is demonstrated, in this invention, the solvent seed | species used in particular is not restrict | limited.
Specifically, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3- Methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1, Polyhydric alcohols such as 3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Polyhydric alcohol alkyl ethers such as coal monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, 2 -Pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide Amides such as N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine and triethylamine, dimethyl sulfoxide, sulfolane, Sulfur-containing compounds such methiodide ethanol, propylene carbonate, and ethylene carbonate and the like.

  Among these, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, from the viewpoint of obtaining an ink having good compatibility with the polycarbonate-based urethane resin and more excellent film forming properties. 1,3-butanediol and 2,3-butanediol are particularly preferable, and high gloss is easily obtained.

  The total amount of the water-soluble organic solvent contained in the entire ink is preferably in the range of 20 to 70% by weight, and more preferably in the range of 30 to 60% by weight. When the total amount is 20% by weight or less, the ink is easily dried, and thus sufficient ejection stability may not be obtained. When the total amount exceeds 70% by weight, the viscosity may become too high to be ejected. .

  Further, it is preferably a water-soluble organic solvent having a boiling point of less than 220 ° C. Among them, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 2 In the case of containing at least one selected from the group consisting of 1,3-butanediol, higher gloss is obtained, which is more preferable. Moreover, when the water-soluble organic solvent whose boiling point exceeds 250 degreeC is not included, since drying property improves further, it is preferable.

(water)
There is no restriction | limiting in particular as water used for this invention, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. There is no restriction | limiting in particular in water content in the ink for inkjet recording, According to the objective, it can select suitably.

(Surfactant)
In the ink of the present invention, a surfactant may be added for the purpose of ensuring wettability to media. The addition amount of the surfactant is preferably 0.1% by weight to 5% by weight as an active ingredient in the ink. If the amount is less than 0.1% by weight, the wettability to the non-porous substrate becomes insufficient, so that the image quality is deteriorated. If the amount exceeds 5% by weight, non-ejection due to easy foaming occurs.

If the said restrictions are satisfy | filled, the surfactant to be used can be used without limitation.
As the surfactant, any of amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used. However, polyoxyethylene alkylphenyl is used because of the dispersion stability of the coloring material and the image quality. Nonionic series such as ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, ethylene oxide adduct of acetylene alcohol A surfactant is desirably used. Depending on the formulation, it is possible to use (or use alone) a fluorine-based surfactant or a silicone-based surfactant.

(Other additives)
Examples of other additives include antiseptic / antifungal agents, rust preventives, pH adjusters and the like.
Examples of antiseptic / antifungal agents include 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and the like.
Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite and the like.
As the pH adjuster, any substance can be used as long as it can adjust the pH to a desired value without adversely affecting the ink to be prepared. Examples include hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate, quaternary ammonium hydroxides and diethanolamine. And amines such as triethanolamine, ammonium hydroxide, quaternary phosphonium hydroxide and the like.

  The ink composition of the present invention is prepared by dissolving the above-described constituents in an aqueous medium and further stirring and mixing as necessary. The stirring and mixing can be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser or the like, but the present invention is not affected by the production method.

  The ink of the present invention is capable of printing with high image quality even on a non-porous substrate, but in order to form an image with higher image quality and higher abrasion resistance and adhesiveness, and also for high-speed printing conditions. It is more desirable to heat the recorded matter so that it can cope.

  The heating temperature can be changed according to the type and amount of the water-soluble organic solvent contained in the ink and the minimum film-forming temperature of the resin to be added, and can also be changed according to the type of the substrate to be printed. it can. The heating temperature is preferably high from the viewpoints of drying property and film-forming temperature. However, if the heating temperature is too high, the substrate to be printed is damaged, or non-ejection occurs due to warming up to the ink head. This is not preferable because it may be

(Inkjet recording device)
The ink jet recording apparatus of the present invention includes at least a printing unit that prints on a recording medium and a heating unit that heats the printed matter. Also, energy is applied to the water-based ink for ink jet, the ink flying means for flying the ink to record an image, and the non-porous substrate which is a plastic film such as vinyl chloride resin film, PET film, polycarbonate film, and other There may be a conveyance unit that conveys the recording medium.

  The ink flying means is means for forming an image by applying a stimulus to the aqueous ink of the present invention and causing the ink to fly. The ink flying means is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include various recording heads (ink discharge heads), and particularly a head having a plurality of nozzle rows and a liquid storage. It is preferable to have a sub-tank that contains the liquid supplied from the tank for supplying the liquid to the head.

  The sub tank includes negative pressure generating means for generating a negative pressure in the sub tank, atmospheric release means for releasing the inside of the sub tank to the atmosphere, and detection means for detecting the presence or absence of ink based on a difference in electrical resistance. What has is preferable.

  There is no restriction | limiting in particular as said irritation | stimulation, According to the objective, it can select suitably, A heat | fever (temperature), a pressure, a vibration, light, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  Examples of the means for generating the stimulus include a heating device, a pressurizing device, a piezoelectric element (sometimes referred to as a piezo element), a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a heating resistor, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, For example, an electrostatic actuator using an electrostatic force may be used.

  There is no restriction | limiting in particular as an aspect of ink flying, According to the kind etc. of said stimulation, it can select. For example, when the stimulus is “heat”, thermal energy corresponding to the recording signal is applied to the ink in the recording head using, for example, a thermal head, and bubbles are generated in the ink by the thermal energy. And a method of ejecting and ejecting ink as droplets from the nozzle holes of the recording head.

  Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting ink as droplets from the nozzle holes of the recording head.

  In the present invention, it is preferable to apply a voltage to the piezo element so as to fly the ink. Since the piezo method does not generate heat, it is advantageous for flying ink containing resin, and is an effective method with less nozzle clogging, particularly when ink containing a small amount of wetting agent is used.

  In order to prevent nozzle omission, it is preferable to perform a blank scan by applying a voltage having a strength that does not eject ink to the piezo element. Furthermore, it is preferable to perform an operation of discharging ink to the ink reservoir before reaching the empty scan for one page printing.

Further, it is preferable to have a scraping means for scraping off the ink fixed to the empty discharge receptacle. As the scraping means, either a wiper or a cutter is preferable.
Further, the ink jet recording apparatus of the present invention may have a transport unit for transporting the recording medium. As the transport unit, a known transport unit such as a transport roller or a transport belt can be used.

  Further, the ink jet recording apparatus of the present invention has a heating means for fixing ink droplets on a recording medium such as a non-porous substrate. As the heating means, one or more of many known heating devices can be used. Examples include forced air heating, radiation heating, conduction heating, high-frequency drying, and microwave drying apparatuses, and these may be used alone or in combination of two or more.

  Here, an aspect of the ink jet recording apparatus of the present invention will be described with reference to the drawings. In addition, although demonstrated below using a non-porous base material, in this invention, it is not limited to a non-porous base material.

FIG. 1 is a schematic view showing an example of the ink jet recording apparatus of the present invention.
The ink jet recording apparatus shown in FIG. 1 has an apparatus main body 101, a paper feed tray 102 for loading a non-porous substrate mounted on the apparatus main body 101, and an image recorded (formed) mounted on the apparatus main body 101. A paper discharge tray 103 for stocking non-porous substrates and an ink cartridge loading unit 104 are provided. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 200. In FIG. 1, reference numeral 111 denotes an upper cover, and 112 denotes a front surface.

  In the apparatus main body 101, as shown in FIG. 2, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on left and right side plates (not shown). Then, the scanning is moved by a main scanning motor (not shown).

  The carriage 133 has a plurality of ink ejection openings of a recording head 134 including four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

  As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.

  In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub tank 135 is supplied with ink from the ink set from the ink cartridge 200 of the present invention loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown) and replenished.

  On the other hand, the nonporous substrate stacking unit 141 is used as a sheet feeding unit for feeding the nonporous substrate 142 loaded on the nonporous substrate stacking unit (pressure plate) 141 of the sheet feeding tray 102. A half-moon roller (sheet feeding roller 143) that separates and feeds the base material 142 one by one, and a sheet separation roller 144 made of a material having a large friction coefficient are provided opposite to the sheet feeding roller 143. It is biased toward the roller 143 side.

  A conveying belt 151 for electrostatically adsorbing and conveying the non-porous substrate 142 as a conveying unit for conveying the non-porous substrate 142 fed from the sheet feeding unit below the recording head 134. A counter roller 152 for transporting the non-porous base material 142 fed from the paper supply unit via the guide 145 between the transport belt 151 and a non-porous base material 142 fed substantially vertically upward Is provided with a conveyance guide 153 for changing the direction of the belt by approximately 90 ° and following the conveyance belt 151, and a tip pressure roller 155 urged toward the conveyance belt 151 by the pressing member 154. A charging roller 156 is provided as charging means for charging the surface 151.

  The conveyor belt 151 is an endless belt, is stretched between a heater-type conveyor roller 157 and a tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a non-porous substrate adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE). And a back layer (medium resistance layer, earth layer) which is made of the same material as the surface layer and is subjected to resistance control by carbon. A heater-type guide member 161 is disposed on the back side of the conveyance belt 151 so as to correspond to a printing area by the recording head 134.

  Note that a separation claw 171 for separating the non-porous substrate 142 from the transport belt 151 and a discharge roller 172 serve as a discharge unit for discharging the non-porous substrate 142 recorded by the recording head 134. And the paper discharge roller 173, the non-porous substrate 142 is dried with hot air by the fan heater 174, and then output to the paper discharge tray 103 below the paper discharge roller 172.

  A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the non-porous substrate 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.

  In the inkjet recording apparatus of the present invention, the non-porous substrate 142 is separated and fed one by one from the sheet feeding unit, and the non-porous substrate 142 fed substantially vertically upward is guided by the guide 145, It is sandwiched between the transport belt 151 and the counter roller 152 and transported. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °.

  At this time, the conveyance belt 151 is charged by the charging roller 156, and the non-porous substrate 142 is electrostatically attracted to the conveyance belt 151 and conveyed. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped non-porous substrate 142 to record one line, and the non-porous substrate is recorded. After the material 142 is conveyed by a predetermined amount, the next line is recorded. Upon receiving a recording end signal or a signal indicating that the rear end of the non-porous substrate 142 has reached the recording area, the recording operation is completed, and the non-porous substrate 142 is discharged onto the discharge tray 103.

  Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  The ink jet recording apparatus of the present invention can be applied to various types of recording by the ink jet recording method, and is particularly preferably applied to, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. Can do.

(Recorded material)
The recorded matter of the present invention has information or an image recorded on a recording medium using the ink of the present invention. There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, a plain paper, glossy paper, special paper, cloth, a film, an OHP sheet etc. are mentioned.

  The ink of the present invention can provide an image having good gloss and image fastness, particularly when applied to a non-porous substrate. The non-porous substrate is not particularly limited, but is somewhat water like a recording medium made of a hydrophobic resin that hardly absorbs water such as polyvinyl chloride, PET, polypropylene, polyethylene, polycarbonate, or a printing paper such as coated paper. For example, there may be mentioned a recording medium that absorbs water but has a slow absorption speed and causes trouble without drying of the water-based ink in the printing process of ordinary ink jet printing in a normal temperature and humidity environment.

  The said recorded matter may be used individually by 1 type, and may use 2 or more types together. The recorded matter obtained by the present invention has high glossiness, excellent scratch resistance, etc., and can be suitably used for various applications.

(Recording method)
The recording method of the present invention preferably includes a printing step of printing on a recording medium using the aqueous inkjet ink of the present invention, and a heating step of heating the printed matter.

  There is no restriction | limiting in particular as a heating means used at the process of heating, As mentioned above, for example, the apparatus for forced air heating, radiation heating, conduction heating, high frequency drying, and microwave drying etc. are mentioned. These may be used alone or in combination of two or more.

  As described above, the heating temperature can be changed according to the type and amount of the water-soluble organic solvent contained in the ink and the minimum film-forming temperature of the resin to be added, and further according to the type of substrate to be printed. Can also be changed. The heating temperature is preferably high from the viewpoints of drying property and film-forming temperature. However, if the heating temperature is too high, the substrate to be printed is damaged, or non-ejection occurs due to warming up to the ink head. This is not preferable because it may be

  Hereinafter, the present invention will be described with reference to examples and comparative examples. In addition, this invention is not limited to the Example illustrated here.

<Preparation of polycarbonate urethane resin emulsion A>
In a reaction vessel into which a stirrer, a reflux condenser and a thermometer were inserted, 1500 g of polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate), 220 g of 2,2-dimethylolpropionic acid (DMPA) and dipropylene glycol 1347 g of dimethyl ether (bp 171 ° C.) was charged under a nitrogen stream and heated to 60 ° C. to dissolve DMPA.

  1,445 g of 4,4′-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. and subjected to urethanization for 5 hours to obtain an isocyanate-terminated urethane prepolymer.

  The reaction mixture was cooled to 80 ° C., 4340 g was extracted from the mixture in which 149 g of triethylamine was added and mixed, and added to a mixed solution of 5400 g of water and 15 g of triethylamine with vigorous stirring.

  Next, 1500 g of ice was added, 626 g of 35% by weight 2-methyl-1,5-pentanediamine aqueous solution was added to carry out chain extension reaction, and the solvent was distilled off so that the solid content concentration became 30%. Urethane resin emulsion A (urethane resin component 30%, water 64%, dipropylene glycol dimethyl ether 6%) was obtained.

The obtained polycarbonate-based urethane resin emulsion A was applied on a slide glass to a film thickness of 10 μm, dried at 100 ° C. for 30 minutes to form a resin film, and a micro surface hardness tester (FISCHERSCOPE HM2000, manufactured by Fischer) The Martens hardness when the Vickers indenter was pushed in with a load of 9.8 mN was 120 N / mm ² .

<Preparation of polycarbonate urethane resin emulsion B>
In the production of polycarbonate urethane resin emulsion A, polycarbonate urethane resin emulsion B (urethane resin component 30%, water 64%, distillate) was used in the same manner except that hexamethylene diisocyanate was used instead of 4,4′-dicyclohexylmethane diisocyanate. Propylene glycol dimethyl ether 6%) was obtained.

With respect to the obtained polycarbonate urethane resin emulsion B, the coating film strength was measured in the same manner. As a result, the Martens hardness was 87 N / mm ² .

Example 1
The following formulation mixture was premixed and then circulated and dispersed in a disk type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mm diameter zirconia ball used) for 7 hours to obtain a pigment dispersion.

Carbon black pigment 15 parts by weight Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 2 parts by weight Deionized water 83 parts by weight

  The pigment dispersion was mixed and stirred with the following formulation, and then filtered through a 0.2 μm polypropylene filter to prepare an ink.

Ion-exchanged water 32.9 parts by weight Propylene glycol (bp 188 ° C) 20.0 parts by weight Diethylene glycol n-butyl ether (bp 230 ° C) 15.0 parts by weight Polycarbonate urethane resin emulsion A 9.0 parts by weight (including dipropylene glycol dimethyl ether ( bp 171 ° C) 0.9 parts by weight included)
Silanol-modified polyvinyl alcohol (R-1130 manufactured by Kuraray Co., Ltd.) 1.0 part by weight The above pigment dispersion 20.0 parts by weight Surfactant CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH 0 parts by weight antiseptic / antifungal agent Proxel LV (Abyssia) 0.1 parts by weight

The following evaluation was performed about the ink produced as mentioned above.
Table 1 shows the composition and evaluation results of the ink.
<Drying evaluation>
The prepared ink was filled in an ink jet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), a solid image was printed on gloss coated paper (OK Topcoat + manufactured by Oji Paper Co., Ltd.), and then dried at 25 ° C. for a predetermined time.
The filter paper was pressed against the solid part after drying, and the determination was made according to the following criteria from the degree of ink transfer to the filter paper.
A: Transfer to filter paper is eliminated under drying conditions at 25 ° C. for 15 minutes.
B: Transfer to filter paper disappears under drying conditions at 25 ° C. for 30 minutes.
C: Transfer to filter paper disappears under drying conditions at 25 ° C. for 60 minutes.
D: Transfer to filter paper does not disappear even under drying conditions at 25 ° C. for 60 minutes.

<Image gloss evaluation>
The prepared ink was filled in an ink jet printer (IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), a solid image was printed on the PVC film, and then heated at 80 ° C. for 1 hour. The 60 ° glossiness of the solid image portion was measured with a gloss meter (manufactured by BYK Gardener, 4501), and judged according to the following criteria.
A: 60 ° gloss is greater than 100%.
B: 60 ° glossiness is 81% to 100%.
C: 60 ° gloss is 60% to 80%.
D: 60 ° gloss is less than 60%

<Abrasion resistance evaluation>
The prepared ink was filled in an ink jet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), a solid image was printed on the PVC film, and then heated at 80 ° C. for 1 hour. The solid part was rubbed with dry cotton (Kanakin No. 3) under a load of 400 g, and the rub resistance was determined according to the following criteria.
A: The image does not change even after rubbing 50 times or more.
B: Some scratches remain after rubbing 50 times, but the image density is not affected, and there is no problem in actual use.
C: The image density decreases during rubbing 21 to 50 times.
D: Image density is lowered by rubbing 20 times or less.

<Ethanol resistance evaluation>
The prepared ink was filled in an ink jet printer (IPSiO GXe5500 manufactured by Ricoh Co., Ltd.), a solid image was printed on the PVC film, and then heated at 80 ° C. for 1 hour. A cotton swab was impregnated with a 50% aqueous solution of ethanol, the solid part of the image was rubbed 20 times, and the degree of peeling of the coating film on the solid part was determined according to the following criteria.
A: There is no peeling at all on the solid part, and no dirt is seen on the cotton swab.
B: Peeling is not found on the solid part, but the dirt is slightly adhered to the cotton swab.
C: Ink melted out in the solid portion.
D: The solid part of the ink is peeled off, and a part or more of the PVC film is exposed.

(Example 2)
A pigment dispersion was obtained in the same manner as in the preparation of the pigment dispersion in Example 1, except that Pigment Blue 15: 3 was used as the pigment.
The obtained dispersion was used, mixed and stirred with the following formulation, and then filtered through a 0.2 μm polypropylene filter to prepare an ink.

Ion-exchanged water 32.9 parts by weight 2,3-butanediol (bp 183 ° C.) 20.0 parts by weight Ethylene glycol n-hexyl ether (bp 208 ° C.) 15.0 parts by weight Polycarbonate urethane resin emulsion A 9.0 parts by weight (inside Dipropylene glycol dimethyl ether (bp 171 ° C.)
Silanol-modified polyvinyl alcohol (R-1130 manufactured by Kuraray Co., Ltd.) 1.0 part by weight The above pigment dispersion 20.0 parts by weight Surfactant CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH 0 part by weight antiseptic / antifungal agent Proxel LV (manufactured by Avicia) 0.1 part by weight The ink produced as described above was evaluated in the same manner as in Example 1.

(Example 3)
A pigment dispersion was obtained in the same manner as in the preparation of the pigment dispersion in Example 1, except that Pigment Red 122 was used as the pigment. The obtained dispersion was used, mixed and stirred with the following formulation, and then filtered through a 0.2 μm polypropylene filter to prepare an ink.

Ion-exchanged water 37.9 parts by weight Propylene glycol (bp 188 ° C) 15.0 parts by weight 1,2-butanediol (bp 194 ° C) 10.0 parts by weight Diethylene glycol n-butyl ether (bp 230 ° C) 15.0 parts by weight Polycarbonate urethane resin Emulsion A 4.5 parts by weight (including 0.6 parts by weight of dipropylene glycol dimethyl ether (bp 171 ° C.))
Silanol-modified polyvinyl alcohol (R-1130 manufactured by Kuraray Co., Ltd.) 0.5 parts by weight The above pigment dispersion 15.0 parts by weight Surfactant CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH 0 part by weight antiseptic / antifungal agent Proxel LV (manufactured by Avicia) 0.1 part by weight The ink produced as described above was evaluated in the same manner as in Example 1.

Example 4
A pigment dispersion was obtained in the same manner as in the preparation of the pigment dispersion in Example 1, except that Pigment Yellow 74 was used as the pigment. The obtained dispersion was used, mixed and stirred with the following formulation, and then filtered through a 0.2 μm polypropylene filter to prepare an ink.

Deionized water 32.9 parts by weight 2,3-butanediol (bp 183 ° C) 25.0 parts by weight Diethylene glycol n-butyl ether (bp 230 ° C) 15.0 parts by weight Polycarbonate urethane resin emulsion A 7.5 parts by weight Propylene glycol dimethyl ether (bp 171 ° C)
Acrylic resin emulsion (DIC Co., Ltd. Boncoat R-3380-E) 2.0 parts by weight Silanol-modified polyvinyl alcohol (Kuraray Co., Ltd. R-1130) 0.5 part by weight The above pigment dispersion 15.0 parts by weight Surfactant CH ₃ (CH ₂ ) ₁₂ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH 2.0 parts by weight Antiseptic / antifungal agent Proxel LV (manufactured by Abyssia) 0.1 part by weight Inks prepared as described above are examples Evaluation similar to 1 was performed.

(Example 5)
An ink was prepared in the same manner as in Example 2, except that 2,3-butanediol (bp 183 ° C.) was replaced with 1,3-propanediol (bp 214 ° C.) in Example 2.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Example 6)
An ink was prepared in the same manner as in Example 2, except that 2,3-butanediol (bp 183 ° C.) was replaced with 1,2-propanediol (bp 187 ° C.) in Example 2.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Example 7)
An ink was prepared in the same manner as in Example 2, except that 2,3-butanediol (bp 183 ° C.) was replaced with 1,3-butane diol (bp 203 ° C.) in Example 2.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Example 8)
An ink was prepared in the same manner as in Example 2 except that the polycarbonate-based urethane resin emulsion A in Example 2 was replaced with the polycarbonate-based urethane resin emulsion B.
The ink produced as described above was evaluated in the same manner as in Example 1.

Example 9
An ink was prepared in the same manner as in Example 2 except that silanol-modified polyvinyl alcohol was replaced with carboxyl-modified polyvinyl alcohol (Goseinal T330H manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) in Example 2.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Comparative Example 1)
Ink was prepared in the same manner as in Example 2 except that polycarbonate urethane resin emulsion A was not added, silanol-modified polyvinyl alcohol (R1130) was replaced with 3 parts by weight, and ion-exchanged water was replaced with 39.9 parts by weight. Was made.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Comparative Example 2)
An ink was prepared in the same manner as in Example 2 except that the silanol-modified polyvinyl alcohol (R1130) was not added and the polycarbonate urethane resin emulsion A was changed to 10 parts by weight.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Comparative Example 3)
When the ink of Example 2 was evaluated for scratch resistance and ethanol resistance, it was evaluated by allowing it to stand at 25 ° C. overnight and drying at a temperature of 80 ° C. for 1 hour. Both sexes were D rank.

(Comparative Example 4)
Ink was prepared in the same manner as in Example 2 except that 9 parts by weight of polyether urethane resin emulsion (WBR-016U) was added without adding polycarbonate urethane resin emulsion A in Example 2.
The ink produced as described above was evaluated in the same manner as in Example 1.

(Comparative Example 5)
In Example 2, 9 parts by weight of the polycarbonate-based urethane resin emulsion A was replaced with 9.5 parts by weight, and 1 part by weight of the silanol-modified polyvinyl alcohol (R1130) was replaced with 0.5 parts by weight of a styrene acrylic resin monomer (Joncry 586). Prepared an ink in the same manner as in Example 2.
The ink produced as described above was evaluated in the same manner as in Example 1.

  According to the present invention, it is possible to obtain an ink that exhibits good drying properties even when printed on a non-porous substrate and has high gloss, scratch resistance, and ethanol resistance in the printed portion.

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 105 Operation part 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Non-porous base material loading part (pressure plate)
142 Non-porous substrate 143 Feed roller 144 Separation pad 145 Guide 151 Transport belt 152 Counter roller 153 Transport guide 154 Press member 155 Tip pressure roller 156 Charging roller 157 Transport roller 158 Tension roller 161 Guide member 171 Separation claw 172 Paper discharge Roller 173 Paper discharge roller 174 Fan heater 181 Double-sided paper feed unit 182 Manual paper feed unit 200 Ink cartridge

JP 2005-220352 A JP 2011-94082 A JP-A-10-292141 JP 2010-270190 A JP 2011-741 A

Claims (6)

An aqueous inkjet ink used for an inkjet recording method including a heating step, comprising water, a water-soluble organic solvent, a pigment, polycarbonate-based urethane resin fine particles, and modified polyvinyl alcohol,
An aqueous inkjet ink characterized in that the modified polyvinyl alcohol is one or two selected from silanol-modified polyvinyl alcohol and carboxyl-modified polyvinyl alcohol.   The aqueous inkjet ink according to claim 1, wherein the modified polyvinyl alcohol is silanol-modified polyvinyl alcohol.   The water-soluble organic solvent is at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol. The water-based ink for ink jet according to claim 1 or 2, wherein the ink contains a seed.   An ink jet recorded product formed using the ink jet water-based ink according to claim 1.   An inkjet recording method comprising: a printing step of printing on a recording medium using the inkjet water-based ink according to claim 1; and a heating step of heating a printed matter.   An inkjet recording apparatus, comprising: a printing unit that prints on a recording medium using the inkjet water-based ink according to claim 1; and a heating unit that heats a printed matter.

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