WO2018066539A1 - Nonaqueous inkjet ink - Google Patents

Nonaqueous inkjet ink Download PDF

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Publication number
WO2018066539A1
WO2018066539A1 PCT/JP2017/035925 JP2017035925W WO2018066539A1 WO 2018066539 A1 WO2018066539 A1 WO 2018066539A1 JP 2017035925 W JP2017035925 W JP 2017035925W WO 2018066539 A1 WO2018066539 A1 WO 2018066539A1
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WO
WIPO (PCT)
Prior art keywords
resin
vinyl chloride
molecular weight
vinyl acetate
inkjet ink
Prior art date
Application number
PCT/JP2017/035925
Other languages
French (fr)
Japanese (ja)
Inventor
浅井　太郎
康平 山田
佐々木　寛
Original Assignee
東洋インキＳｃホールディングス株式会社
東洋インキ株式会社
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Application filed by 東洋インキＳｃホールディングス株式会社, 東洋インキ株式会社 filed Critical 東洋インキＳｃホールディングス株式会社
Publication of WO2018066539A1 publication Critical patent/WO2018066539A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention has excellent printing performance such as continuous discharge stability, has good storage stability, and can obtain a printed matter with excellent gloss and durability, and is suitable mainly for printing on a vinyl chloride substrate.
  • the present invention relates to a non-aqueous inkjet ink.
  • the ink jet recording method is a recording method in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle onto a recording member and attaching them. According to this method, there is an advantage that not only the noise of the apparatus to be used is small and the operability is good, but also colorization is easy and plain paper can be used as a recording member. It is widely used as an output machine in offices and homes.
  • non-aqueous (solvent type, UV type) inkjet inks can be printed on plastic substrates such as vinyl chloride (PVC) and PET.
  • PVC vinyl chloride
  • PET PET
  • Solvent-type non-aqueous ink-jet inks are mainly used for printing on PVC substrates, and are mainly used outdoors, so the gloss and durability of printed matter are very important.
  • the gloss and resistance of printed materials mainly depend on the binder resin in the ink.
  • the binder resin acrylic resin and vinyl chloride-vinyl acetate copolymer resin (hereinafter also referred to as “vinyl chloride resin”) are widely used.
  • Patent Documents 1 and 2 discloses an ink-jet ink containing a vinyl acetate resin having a specific molecular weight distribution and a polyalkylene glycol dialkyl ether solvent in order to improve the alcohol resistance and continuous discharge stability of a printed matter.
  • the molecular weight is a major factor related to the physical properties of vinyl chloride resin, but the relative molecular weight in GPC (gel permeation chromatography) in terms of polystyrene has been conventionally used.
  • GPC gel permeation chromatography
  • the present invention has been made in view of the above problems, and is excellent in printing performance such as continuous discharge stability, has good storage stability, and can obtain a printed matter having excellent gloss and durability.
  • a non-aqueous inkjet ink suitable for printing on a vinyl substrate is provided.
  • One embodiment of the present invention is a non-aqueous inkjet ink containing an organic solvent, a pigment, and a vinyl chloride-vinyl acetate copolymer resin
  • the vinyl chloride-vinyl acetate copolymer resin has a weight average absolute molecular weight (
  • ) is 1.3 or more and 2.2 or less
  • a non-aqueous inkjet ink is provided, wherein the vinyl chloride-vinyl acetate copolymer resin is an emulsion polymer of a vinyl chloride monomer and a vinyl acetate monomer.
  • the vinyl chloride-vinyl acetate copolymer resin does not contain a resin having an absolute molecular weight (
  • One embodiment of the present invention is the above non-aqueous inkjet ink, wherein the organic solvent further includes any one or more of the solvents represented by the general formulas (a) to (d). May be: R 1 CO (OR 2 ) Z OR 3 (a) R 4 CO (OR 5 ) Z OCOR 6 (b) R 7 (OR 8 ) Z OR 9 (c) R 10 COOR 11 (d).
  • R 2 , R 5 and R 8 are each independently selected from ethylene group, propylene group and butylene group, and R 1 , R 3 , R 4 and R 6 are each independently selected.
  • An alkyl group having 1 to 4 carbon atoms, R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 10 is a 2-hydroxyethyl group, R 11 Is an alkyl group having 1 to 8 carbon atoms, and Z represents an integer of 1 to 3.
  • One embodiment of the present invention may also be the non-aqueous inkjet ink described above, wherein the organic solvent further contains a nitrogen-containing, sulfur-containing, or lactone-based solvent.
  • One embodiment of the present invention may be the non-aqueous inkjet ink described above, further including a pigment dispersant.
  • the present invention it is excellent in printing performance such as continuous discharge stability, has good storage stability, and can obtain a printed matter having excellent gloss and durability, and is suitable mainly for printing on a vinyl chloride substrate. It has become possible to provide a non-aqueous inkjet ink.
  • non-aqueous means that water is not intentionally added. For example, if it is 5% by weight or less with respect to the total amount of the non-aqueous inkjet ink, There is no problem even if moisture is absorbed.
  • the vinyl chloride-vinyl acetate copolymer resin used in the non-aqueous inkjet ink is an emulsion polymer of a vinyl chloride monomer and a vinyl acetate monomer, and its weight average absolute molecular weight (
  • Suspension polymerization and emulsion polymerization are known as methods for synthesizing these vinyl chloride resins.
  • the suspension polymerization method uses a vinyl chloride, vinyl acetate, and, if necessary, a mixture of monomers copolymerizable (hereinafter referred to as “vinyl chloride monomer”), the vinyl chloride monomer.
  • a polymerization initiator, a dispersant, an emulsifier, a stabilizer, and the like soluble in a polymer are added, dispersed in a dispersion medium by a dispersing machine such as a homogenizer, and homogenized and then polymerized.
  • the suspension polymerization method is a polymerization method generally used in industrial production because water is mainly used as the dispersion medium, the synthesis temperature is easily adjusted, and the polymer can be easily taken out.
  • the dispersant and stabilizer are easily dissolved and remain in the product, and when used in inkjet ink, the insoluble component is clogged or adhered to the inkjet head, so that continuous ejection stability is improved. It will get worse. Further, the molecular weight distribution of the obtained polymer is likely to be widened, which also adversely affects the continuous discharge stability, which is not preferable.
  • a vinyl chloride monomer is emulsified by adding it to a medium (water) together with an emulsifier such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and then a water-soluble polymerization initiator such as ammonium persulfate is added.
  • an emulsifier such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate
  • a water-soluble polymerization initiator such as ammonium persulfate
  • the emulsion polymerization method is preferable in the present invention because the amount of insoluble matter is small compared to the suspension polymerization method, and a polymer having a relatively narrow molecular weight distribution can be obtained by using a chain transfer agent in combination. Selected.
  • the vinyl acetate resin produced by the emulsion polymerization method has a problem that it is easy to obtain a polymer having a high degree of polymerization as a whole.
  • the molecular weight of a binder resin, such as a vinyl acetate resin, contained in an inkjet ink greatly affects the stability of continuous ejection and the gloss and resistance of printed matter. That is, by accurately knowing the molecular weight characteristics of the binder resin, various characteristics of the ink-jet ink using the binder resin can be grasped.
  • the present inventors diligently studied, and even when the polyvinyl chloride resins having the same relative molecular weight characteristics obtained by a general polystyrene conversion GPC (gel permeation chromatography) method are used, continuous discharge is possible. It has been found that there is a large difference in stability. As a result of further investigation, it was found that the superiority or inferiority of the continuous discharge stability is greatly correlated with the absolute molecular weight characteristics of the vinyl chloride resin.
  • ) GPC-MALS method represents a weight average molecular weight, number average molecular weight, and molecular weight.
  • a TSKgel column manufactured by Tosoh Corporation
  • a GPC equipped with a multi-angle light scattering detector manufactured by Wyatt, miniDawn TREOS) (Waters, Alliance GPC)
  • THF is used as a developing solvent.
  • the absolute molecular weight of the resin itself can be obtained.
  • the GPC-MALS method Since the GPC-MALS method is not affected by the resin structure or column adsorption, it can accurately measure the amount of high molecular weight components and gel components in the resin, which greatly affects the continuous discharge stability. It becomes a measurement value that cannot be predicted from the measurement result of the relative molecular weight.
  • the absolute molecular weight which is a value reflecting the state of the resin, is a particularly suitable method for examining the relationship with various physical properties.
  • preferable absolute molecular weight distribution may be applied to commercially available emulsion polymerization products of vinyl chloride resin. These characteristics have been found for the first time in the present invention. Many commercially available vinyl chloride resins have been measured for relative molecular weight and molecular weight distribution by a general polystyrene equivalent GPC method, and the above high molecular weight components and gel components are recognized. It is considered that the product is sold without being removed.
  • of the vinyl chloride-vinyl acetate copolymer resin of the present invention may be 20,000 to 40,000 as described above, preferably 20,000 to 35,000, and 25,000 to 30,000 is particularly preferred. Within this range, an inkjet ink excellent in continuous discharge stability, gloss and resistance of printed matter, and ink storage stability can be obtained.
  • may be 1.3 or more and 2.2 or less, more preferably 1.4 or more and 2.1 or less, and particularly preferably 1.5 or more and 2.0 or less. preferable. If it is in this range, nozzle omission of the ink-jet ink can be suppressed, and the continuous ejection stability can be further enhanced.
  • ) of 200,000 or more is 0 to 10% by weight in the total amount of the vinyl chloride-vinyl acetate copolymer resin. It is preferably 0 to 5% by weight, more preferably 0% by weight. In the above, “0 wt%” means that the target component is not included. Further, among resins having a resin content of
  • or more is calculated by calculating the area from a graph of molecular weight distribution measured by the GPC-MALS method.
  • a vinyl acetate resin obtained by an emulsion polymerization method is used in order to obtain a resin having a suitable absolute molecular weight distribution.
  • emulsion polymerization it is preferable to use a polymerization initiator having an ionic group at the terminal. Further, from the viewpoint of reducing environmental burden, it is preferable that no organic chlorine compound is contained as a raw material for emulsion polymerization.
  • emulsion polymerization as a method for keeping
  • the blending amount of the chain transfer agent is, for example, 1.8 to 2.5% by weight, preferably 2.0 to 2.3% by weight, based on the total amount of the vinyl chloride monomer.
  • the emulsion formed in the medium is reduced, and as a result,
  • the vinyl acetate-vinyl acetate copolymer resin preferably has a vinyl acetate ratio of 10 to 25% by weight in order to obtain a suitable absolute molecular weight distribution by adjusting the ratio of vinyl chloride and vinyl acetate. 12 to 22% by weight is more preferable, and 14 to 20% by weight is still more preferable.
  • are not only within the preferable range, but also an inkjet ink having excellent gloss and solvent resistance of the printed matter is obtained. be able to.
  • Ultrasonic treatment When using an ultrasonic treatment device, after preparing a solution in which an emulsion polymerization product of a commercially available vinyl chloride-vinyl acetate copolymer resin is dissolved in an organic solvent used in a non-aqueous inkjet ink, A method of performing the treatment is preferable.
  • Ultrasonic treatment An ultrasonic homogenizer is preferably used as the apparatus. It should be noted that the ultrasonic frequency is preferably 10 to 30 kHz, and the amplitude range is preferably 20 to 60 ⁇ m in order to keep the above-mentioned preferable absolute molecular weight distribution.
  • the vinyl chloride-vinyl acetate copolymer resin suitable for the present invention is prepared by the above method
  • commercially available products that can be specifically used include VINNOL (registered trademark) E15 / 45, E15 manufactured by Wacker Chemie. / 45M, E15 / 40M, E15 / 48A, E22 / 48A, E15 / 40A TF, E15 / 45M TF, E15 / 45TF, and the like, but are not limited thereto.
  • VINOLL E15 / 45, E15 / 45M, E15 / 40M, E15 / 48A, E15 / 45TF are easy to fit in the above-mentioned absolute molecular weight distribution and can obtain a non-aqueous inkjet ink excellent in continuous discharge stability.
  • VINNOL E15 / 45 and E15 / 45TF are particularly preferable.
  • VINNOL E15 / 45 and E15 / 45TF are both produced by an emulsion polymerization method and contain about 85% by weight of vinyl chloride and about 15% by weight of vinyl acetate based on the total amount of the resin.
  • vinyl chloride-vinyl acetate copolymer resin in both cases of synthesizing vinyl chloride-vinyl acetate copolymer resin and preparing using a commercial product, in addition to vinyl chloride and vinyl acetate as vinyl chloride monomers constituting the resin, for example, it may contain maleic acid or vinyl alcohol.
  • the content of the vinyl chloride-vinyl acetate copolymer contained in the non-aqueous inkjet ink of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the total amount of the non-aqueous inkjet ink. Preferably, 2 to 8% by weight is more preferable. By setting it as the said range, higher continuous discharge stability can be exhibited.
  • binder resin for the purpose of improving substrate adhesion, coating film resistance, and the like.
  • the binder resin used in the present invention is not limited as long as it exhibits functions such as abrasion resistance, solvent resistance, stretchability, glossiness, and general versatility of the ink coating film.
  • the binder resin include acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, rosin resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol.
  • Resin phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, ketone resin, aldehyde
  • resins such as resins can be used. These binder resins may be used alone or in combination of two or more.
  • the acrylic resin refers to a resin obtained by polymerizing (meth) acrylic acid or (meth) acrylic acid ester.
  • the styrene-acrylic resin includes styrene within a range not exceeding 50% by weight in the constituents of the styrene-acrylic resin, and the remainder is (meth) acrylic acid or (meth) acrylic acid ester. And may be modified with maleic acid or the like.
  • suitable components constituting the resin that can be included in the binder resin include (meth) acrylic acid, methyl (meth) acrylate, and (meth) acrylic acid.
  • Ethyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, benzyl (meth) acrylate examples include, but are not limited to, styrene and maleic acid.
  • the binder resin is more preferably a resin containing methyl methacrylate and / or butyl methacrylate as a constituent component, and methyl methacrylate and Particularly preferred is a resin containing butyl methacrylate and further acrylic acid.
  • (meth) acryl means at least one selected from “acryl” and “methacryl”.
  • an acrylic resin and a styrene-acrylic resin are used in combination (hereinafter also referred to as “acrylic resin”)
  • acrylic resin it is preferable to select an acrylic resin having a suitable absolute molecular weight distribution.
  • ) of the acrylic resin preferably used is 4,000 to 50,000, and if it is within this range, a printed matter having high resistance can be obtained without causing mist during printing. Is possible.
  • ) is more preferably 10,000 to 45,000, and still more preferably 15,000 to 40,000. is there.
  • ) is more preferably 4,000 to 20,000, and still more preferably 4,000 to 15,000. is there.
  • the acrylic resin used in combination with the vinyl chloride-vinyl acetate copolymer resin both the acrylic resin and the styrene-acrylic resin can be contained.
  • the content of a resin having an absolute molecular weight of 200,000 or more is preferably 10% or less, more preferably 5% or less, and completely contained in all acrylic resins. It is particularly preferred not to.
  • the acid value of the acrylic resin is preferably 0 to 30 mgKOH / g. Within this range, high alcohol resistance can be exhibited. More preferably, it is 0-20 mgKOH / g, and still more preferably 0-15 mgKOH / g.
  • the acid value of the styrene-acrylic resin is preferably 0 to 250 mgKOH / g. Within this range, the dispersion stability of the ink is good and the continuous ejection stability is excellent. More preferably, it is 50 to 200 mgKOH / g, and still more preferably 75 to 150 mgKOH / g.
  • the “acid value” represents an acid value per gram of acrylic resin, and can be determined by potentiometric titration according to JIS K 0070.
  • the glass transition point of the acrylic resin is preferably 40 to 150 ° C. Within this range, the printed material has good resistance, and even when printed on a flexible print medium, problems such as cracking of the coating film are unlikely to occur. More preferably, the temperature is 50 to 120 ° C, still more preferably 60 to 100 ° C, and still more preferably 70 to 90 ° C.
  • the content with respect to the total amount of the non-aqueous inkjet ink is preferably 0.1 to 10% by weight. This range is preferable because printing can be performed without adversely affecting the continuous ejection stability of the ink and without causing mist. More preferably, it is 1 to 8% by weight, and still more preferably 1.5 to 6% by weight.
  • the content of the acrylic resin when determining the content of the acrylic resin, the content of the vinyl chloride-vinyl acetate copolymer resin used in combination should be taken into consideration.
  • the ratio of the acrylic resin content to the vinyl chloride-vinyl acetate copolymer resin content is preferably 0.01 to 1.25, preferably 0.01 to 1. Is more preferable, 0.03 to 0.8 is even more preferable, and 0.05 to 0.6 is particularly preferable.
  • Dianal registered trademark
  • the organic solvent contained in the non-aqueous inkjet ink of the present invention preferably contains any one or more of the solvents represented by the following general formulas (a) to (d): R 1 CO (OR 2 ) Z OR 3 (a) R 4 CO (OR 5 ) Z OCOR 6 (b) R 7 (OR 8 ) Z OR 9 (c) R 10 COOR 11 (d).
  • R 2 , R 5 and R 8 are each independently selected from an ethylene group, a propylene group and a butylene group, and R 1 , R 3 , R 4 and R 6 are each independently selected.
  • An alkyl group having 1 to 4 carbon atoms, R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 10 is a 2-hydroxyethyl group, and R 11 is a carbon atom.
  • the organic solvent represented by the above (a) and / or (c) is included, and at least (a) from the viewpoint that the storage stability of ink and the reduction of mist during printing are possible. It is particularly preferred that the organic solvent represented is included.
  • organic solvent contained in the non-aqueous inkjet ink of the present invention an organic solvent having a boiling point of 150 to 200 ° C. is selected, and the content thereof is 50 to 98 on the basis of the total weight of the non-aqueous inkjet ink.
  • the weight percent is preferable from the viewpoint of improving the printing speed.
  • 3-methoxybutanol (boiling point 158 ° C.), diethylene glycol dimethyl ether (boiling point) 162 ° C), 3-methylmethoxybutanol (boiling point 174 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol methyl isopropyl ether (boiling point 179 ° C), dipropylene glycol dimethyl ether (boiling point) 171 ° C.), ethylene glycol monobutyl ether acetate (boiling point 192 ° C.), 3-methoxybutyl acetate (boiling point 171 ° C.), 3-methyl-3-
  • diethylene glycol diethyl ether dipropylene glycol dimethyl ether, or ethylene glycol monobutyl ether acetate
  • the organic solvent contained in the non-aqueous inkjet ink of the present invention is preferably contained in an amount of 50 to 98% by weight, more preferably 60 to 95% by weight, still more preferably 65 to 90% based on the total weight of the non-aqueous inkjet ink. % By weight, still more preferably 70-85% by weight.
  • a nitrogen-containing, sulfur-containing or lactone solvent in addition to the organic solvents represented by the above formulas (a) to (d), can be used in combination.
  • These nitrogen-containing, sulfur-containing or lactone solvents are all solvents having a cyclic structure containing an element other than carbon, and the use of the ink increases the permeability of the ink to the substrate, and the drying property during printing.
  • the printed material is preferable because the abrasion resistance and alcohol resistance of the printed matter are increased.
  • nitrogen-containing, sulfur-containing, or lactone solvents examples include: A solvent having an oxazolidinone structure such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone; 2-pyrrolidone ( ⁇ -butyrolactam), 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, ⁇ -valerolactam, ⁇ -hexalactam, ⁇ -heptalactam, ⁇ -octalactam, ⁇ -nonalactam, ⁇ -Lactams such as decaractam, ⁇ -undecalactam, ⁇ -valerolactam, ⁇ -hexalactam, ⁇ -heptalactam, ⁇ -octalactam, ⁇ -nonalactam, ⁇ -decalactam, ⁇ -undecalactam, and ⁇ -caprolactam
  • a solvent having a structure such as 3-methyl-2-oxazolidinone, 3-eth
  • 3-methyl-2-oxazolidinone (boiling point 266 ° C.) is used as a nitrogen-containing, sulfur-containing or lactone solvent used in the present invention from the viewpoint of ink permeability to the substrate and drying property at the time of printing.
  • 2-pyrrolidone ( ⁇ -butyrolactam) (boiling point 245 ° C.), 1-methyl-2-pyrrolidone (boiling point 202 ° C.), ⁇ -caprolactam (boiling point 267 ° C.), ⁇ -butyrolactone (boiling point 204 ° C.), ⁇ -valerolactone (Boiling point 230 ° C.), and ⁇ -caprolactone (boiling point 237 ° C.), propylene carbonate (boiling point 240 ° C.), etc.
  • 3-methyl-2-oxazolidinone (boiling point 266 ° C.), ⁇ -butyrolactone (boiling point 204 ° C.), and ⁇ -caprolactone (boiling point 237 ° C.) is more preferably selected.
  • the boiling point is preferably 200 ° C to 300 ° C.
  • the boiling point of the nitrogen-containing, sulfur-containing, or lactone solvent is the highest among the constituent components of the ink.
  • the blending amount of the nitrogen-containing, sulfur-containing or lactone solvent is preferably 1 to 25% by weight based on the total weight of the inkjet ink. If the blending amount of the nitrogen-containing, sulfur-containing or lactone solvent is within this range, it is preferable because good drying properties can be exhibited and resistance of printed matter can be improved.
  • the blending amount of the nitrogen-containing, sulfur-containing or lactone solvent is more preferably 2 to 20% by weight, still more preferably 4 to 15% by weight, and still more preferably 5 to 13% by weight.
  • solvents other than those described above can be used in combination for the purpose of adjusting the viscosity and dischargeability of the ink.
  • methyl lactate (boiling point 144 ° C.), propyl lactate (boiling point 170 ° C.), butyl lactate (boiling point 189 ° C.), N, N-dimethyl- ⁇ -butoxypropionamide (boiling point 216 ° C.), N, N—
  • Examples thereof include, but are not limited to, dibutyl- ⁇ -butoxypropionamide (boiling point 252 ° C.).
  • the pigment used in the non-aqueous inkjet ink of the present invention should be appropriately selected from those generally used for printing and paint applications according to desired applications such as color development and light resistance. Can do. Moreover, a pigment may be used individually by 1 type and may be used in mixture of 2 or more types.
  • achromatic pigments such as carbon black, titanium oxide, calcium carbonate, and / or chromatic organic pigments can be used.
  • An example of an organic pigment preferably used in the present invention is a color index (CI) number.
  • CI color index
  • the content of these pigments in the ink is preferably 1 to 15% by weight, and more preferably 1 to 8% by weight from the viewpoint of coloring power, storage stability, and ink jet viscosity suitability.
  • the pigment content is preferably 1/10 to 1/2 that of dark ink.
  • the average particle diameter (D50) of the pigment in the non-aqueous inkjet ink is preferably 50 to 300 nm. If D50 is 50 nm or more, light resistance and coloring power can be obtained, and if it is 300 nm or less, ink storage stability and continuous ejection stability are stable.
  • the D50 can be measured, for example, by diluting a non-aqueous inkjet ink 200 to 1000 times with ethyl acetate and using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. D50 indicates the median diameter.
  • Pigment dispersant In the present invention, it is preferable to use a pigment dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink.
  • Conventionally known compounds can be used as the pigment dispersant. From the viewpoint of continuous discharge stability and ink storage stability, a resin-type dispersant having a basic functional group is preferred.
  • pigment dispersants examples include Solsperse 32000, 76400, 76500, J200, and J180 manufactured by Lubrizol; Disperbyk-161, 162, 163, 164, 165, 166, 167, and 168 manufactured by Big Chemie; Ajinomoto Fine Techno Co., Ltd. Ajisper PB821, PB822 etc. are mentioned, but it is not limited to these.
  • the weight average molecular weight (hereinafter referred to as Mw) of the pigment dispersant is preferably 5,000 to 20,000, more preferably 10,000 to 20,000.
  • Mw weight average molecular weight
  • Mw is 5,000 or more, the stability of the pigment dispersion is improved because the stability of the pigment dispersant itself in the organic solvent used in the ink is good. If Mw is 20,000 or less, the compatibility with the binder resin is good, the whitening phenomenon of the ink coating is suppressed, and the color developability is good.
  • the pigment dispersant preferably has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (hereinafter referred to as Mn) determined by GPC of 1 to 2.5, and the Mw / Mn is 1 to 2.5. 2 is more preferable, and 1 to 1.8 is particularly preferable.
  • the above Mw and Mn can be determined as styrene equivalent molecular weight by general gel permeation chromatography (GPC).
  • GPC general gel permeation chromatography
  • the molecular weight can be expressed in terms of polystyrene when using TSKgel column (manufactured by Tosoh Corporation) and GPC (HLC-8320 GPC, manufactured by Tosoh Corporation) equipped with an RI detector and using DMF as a developing solvent.
  • the acid value (mgKOH / g) of the pigment dispersant suitably used in the present invention is preferably from 5 to 20, and more preferably from 5 to 15.
  • the amine value (mgKOH / g) is preferably 5 to 50, more preferably 20 to 45, more preferably 20 to 40, and particularly preferably 25 to 40.
  • the acid value and amine value of the pigment dispersant are within the above ranges, in the pigment dispersion step, the time until the viscosity of the pigment dispersion becomes low enough to be suitable for an inkjet ink is shortened. It is preferable because storage stability is improved.
  • the said acid value can be calculated
  • the “amine value” represents an amine value per 1 g of the solid content of the dispersant, and is a value converted to an equivalent of potassium hydroxide after being determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution.
  • a pigment derivative can also be used in the ink of the present invention.
  • the pigment derivative is used for the purpose of enhancing the adsorptivity between the dispersant and the pigment and improving the storage stability.
  • a compound having an acidic group such as a sulfonic acid group or a carboxyl group in the organic pigment residue is preferably used.
  • the content of the pigment derivative is preferably from 0.1% by weight to 20% by weight, particularly preferably from 1% by weight to 15% by weight, based on the pigment. If the content of the pigment derivative is 0.1% by weight or more, the stability and color developability will be good, and if it is 20% by weight or less, the viscosity of the ink will be finished in a suitable range, and the storage stability will be good. Therefore, it is preferable.
  • the ink of the present invention has various surface modifiers, slip agents, plasticizers, UV inhibitors, light stabilizers, antioxidants, hydrolysis inhibitors, rust inhibitors, etc., in order to enhance printability and printed matter resistance. Additives can be used.
  • Examples of the surface conditioner include silicon-based, fluorine-based, acrylic-based, and acetylene glycol-based, among which silicon-based is preferable.
  • silicon-based surface conditioners a modified polysiloxane compound in which an organic group is introduced into part of the methyl group of dimethylpolysiloxane is preferable.
  • modification include polyether modification, methylstyrene modification, alcohol modification, alkyl modification, aralkyl modification, fatty acid ester modification, epoxy modification, amine modification, amino modification, mercapto modification, etc., and are polyether modification and aralkyl modification. It is preferable in terms of continuous discharge stability and the like, and aralkyl modification is particularly preferable in terms of continuous discharge stability and ink drying properties.
  • polyether-modified polysiloxane compounds include, for example, KF-353A, KF-354L, KF6017, X-22-6551, AW-3 manufactured by Shin-Etsu Chemical Co., Ltd., SAG001, SAG002 manufactured by Nissin Chemical Industry Co., Ltd.
  • aralkyl-modified polysiloxane compounds examples include BYK-322 and 323 manufactured by Big Chemie Japan Co., Ltd., KF-410 manufactured by Shin-Etsu Chemical Co., Ltd., SM 7001EX and SM manufactured by Toray Dow Corning Co., Ltd. 7002EX etc. are mentioned, but it is not limited to these.
  • BYK-322 and 323 which are aralkyl-modified polysiloxane compounds are particularly preferably used.
  • the content of the surface conditioning agent is preferably 0 to 2% by weight, preferably 0.001 to 1% by weight, based on the total weight of the non-aqueous inkjet ink, and 0.01 to 0.5% by weight. % Is more preferable.
  • the recording medium used in the present invention is not particularly limited, and a plastic substrate such as soft PVC, hard PVC, polystyrene, polystyrene foam, PMMA, polypropylene, polyethylene, PET, polycarbonate, or a mixed or modified product thereof, fine paper
  • a plastic substrate such as soft PVC, hard PVC, polystyrene, polystyrene foam, PMMA, polypropylene, polyethylene, PET, polycarbonate, or a mixed or modified product thereof, fine paper
  • paper substrates such as art paper, coated paper, and cast coated paper, and metal substrates such as glass and stainless steel.
  • soft PVC and hard PVC which are non-absorbent substrates are preferably used.
  • the ink of the present invention can be produced by a known method. Specifically, first, after mixing a single organic solvent or a mixed organic solvent, a pigment, and a binder resin, a dispersant, etc. when blended, a paint shaker, a sand mill, a roll mill, a medialess dispersion A pigment dispersion is prepared by dispersing the pigment by a machine or the like. To the obtained pigment dispersion, the remainder of the organic solvent, the remainder of the binder resin, and other additives (for example, a surface conditioner) are added so as to have desired ink properties, and after the binder resin is dissolved, It can be obtained by removing coarse particles with a filter or the like.
  • the non-aqueous inkjet ink of the present invention preferably has a surface tension at 25 ° C. of 20 mN / m or more and 50 mN / m or less from the viewpoint of the balance between the ejectability from the inkjet head and the reliability of dot formation after landing. 25 mN / m or more and 40 mN / m or less is more preferable. From the same viewpoint, the viscosity at 25 ° C. is preferably 2 mPa ⁇ s or more and 20 mPa ⁇ s or less, and more preferably 5 mPa ⁇ s or more and 15 mPa ⁇ s or less.
  • the surface tension can be measured by using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. and confirming the surface tension when the platinum plate is wetted with ink in an environment of 25 ° C. it can.
  • the viscosity can be measured by reading the viscosity at 50 rpm in a 25 ° C. environment using a TVE25L viscometer manufactured by Toki Sangyo Co., Ltd.
  • a solution prepared by dissolving 5 parts of ammonium persulfate in 100 parts of deionized water as a polymerization initiator is dropped, and the reaction is carried out for 20 hours while maintaining the temperature inside the container at 60 to 70 ° C, and then cooled to 30 ° C. The polymerization was terminated.
  • 1800 parts of a 1M sodium chloride aqueous solution was added little by little, and the resulting precipitate was filtered off, and then washed with deionized water three times to give a vinyl chloride-vinyl acetate copolymer resin A.
  • Vinyl chloride-acetic acid is the same as vinyl chloride-vinyl acetate copolymer resin A except that the amount of chain transfer agent, the amount of vinyl chloride, and the amount of vinyl acetate are changed to those shown in Table 1 below. Vinyl copolymer resins B to M were produced.
  • pigment dispersion 20 parts of Pigment Blue 15: 4 as a pigment, 7 parts of Solsperse J200 (weight average molecular weight 15,000, acid value 12 mgKOH / g, amine value 22 mgKOH / g) as a pigment dispersion resin, and 73 parts of ethylene glycol butyl ether acetate are mixed. After preliminary dispersion with a disper, this dispersion was performed for 2 hours using a 0.6 L capacity dyno mill filled with 1800 g of zirconia beads having a diameter of 0.5 mm to obtain a pigment dispersion.
  • Example 1 20 parts of the pigment dispersion, 5.4 parts of vinyl chloride-vinyl acetate copolymer resin, JONCRYL586 (styrene-acrylic copolymer resin manufactured by BASF, weight average absolute molecular weight of 4000, 1.4 parts of glass transition point 60 ° C., acid value 108 mgKOH / g), Dianal BR-113 (Mitsubishi Rayon acrylic resin, weight average absolute molecular weight 35000, glass transition point 75 ° C., acid value 3.5 mg KOH / g) ), 80.0 parts of ethylene glycol monobutyl ether acetate, and 7.5 parts of ⁇ -butyrolactone were sequentially added while stirring with a disper, and stirred until sufficiently uniform. Thereafter, filtration was carried out with a membrane filter having an opening of 1.0 ⁇ m to remove coarse particles that cause clogging of the head, and the ink-jet ink of the present invention was prepared.
  • Example 2 to 18 Nonaqueous inkjet inks of Examples 2 to 18 were produced in the same manner as Example 1 except that the materials shown in Table 2 below were used.
  • the organic solvents used in Table 2 and Table 3 are as follows: ⁇ BGAc (ethylene glycol monobutyl ether acetate, boiling point 192 ° C.) ⁇ DEDG (diethylene glycol diethyl ether, boiling point 189 ° C) ⁇ Ethyl lactate (boiling point 154 °C) ⁇ PGDA (propylene glycol diacetate, boiling point 190 ° C) GBL ( ⁇ -butyrolactone, boiling point 204 ° C.) ECL ( ⁇ -caprolactone, boiling point 237 ° C.).
  • the obtained ink-jet ink was filled into a wide format ink-jet printer (ColorPainter 64S manufactured by Seiko I Infotech Co., Ltd.), and printing evaluation was performed using a polyvinyl chloride sheet (MD-5 manufactured by Metamark Co., Ltd.) as a printing medium.
  • a wide format ink-jet printer ColorPainter 64S manufactured by Seiko I Infotech Co., Ltd.
  • printing evaluation was performed using a polyvinyl chloride sheet (MD-5 manufactured by Metamark Co., Ltd.) as a printing medium.
  • a 10 m 2 solid was printed on the print medium at a speed of 30 m 2 / h, a nozzle check pattern was printed, and the number of missing nozzles was confirmed.
  • the evaluation criteria are as follows, and B or better was considered good: A: No nozzle missing after printing B: Nozzle missing from 1 to 3 after printing C: Nozzle missing from 4 to 7 after printing D: Nozzle missing from 8 to 20 after printing E: Nozzle missing from 8 to 20 after printing E: More than 20 nozzles are missing after printing.
  • Alcohol resistance was evaluated by rubbing a printed matter on which a single-color solid was printed on a printing medium at a speed of 4 m 2 / h with a cotton swab dipped in an aqueous ethanol solution. The concentration of the aqueous alcohol solution was changed, the color transfer of the ink coating to the cotton swab was confirmed, the evaluation was made according to the following criteria, and B or better was considered good: A: No color transfer to cotton swabs with 80% ethanol solution B: No color transfer to cotton swabs with 60% ethanol solution C: Color transfer to cotton swabs with 60% ethanol solution.
  • Viscosity change rate after storage for 6 weeks is less than ⁇ 10%
  • B Viscosity change rate after storage for 6 weeks is ⁇ 10% to less than 20%
  • C Viscosity change rate after storage for 6 weeks is ⁇ 20% or more.
  • the binder resin has a weight average absolute molecular weight (
  • ) of 1.3 or more and 2.2 or less continuous discharge stability, deflection, etc.

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Abstract

The present invention provides a nonaqueous inkjet ink which has excellent printing properties such as continuous ejection stability, while having good storage stability, and which is mainly suitable for printing on vinyl chloride substrates and enables the achievement of a printed material that has excellent gloss and endurance. One embodiment of the present invention provides a nonaqueous inkjet ink which contains an organic solvent, a pigment and a vinyl chloride-vinyl acetate copolymer resin, and which is characterized in that: the weight average absolute molecular weight (|Mw|) of the vinyl chloride-vinyl acetate copolymer resin is 20,000 to 40,000; the ratio of the weight average absolute molecular weight (|Mw|) to the number average absolute molecular weight (|Mn|), namely (|Mw|/|Mn|) is from 1.3 to 2.2 (inclusive); and the vinyl chloride-vinyl acetate copolymer resin is an emulsion polymerization product of a vinyl chloride monomer and a vinyl acetate monomer.

Description

非水性インクジェットインキNon-aqueous inkjet ink
　本発明は、連続吐出安定性等の印刷性能に優れ、良好な保存安定性を有するとともに、光沢や耐性に優れた印刷物を得ることが可能な、主に塩化ビニル基材への印刷に適した非水性インクジェットインキに関する。 The present invention has excellent printing performance such as continuous discharge stability, has good storage stability, and can obtain a printed matter with excellent gloss and durability, and is suitable mainly for printing on a vinyl chloride substrate. The present invention relates to a non-aqueous inkjet ink.
　インクジェット記録方式は、非常に微細なノズルからインク液滴を記録部材に直接吐出し、付着させて文字や画像を得る記録方式である。この方式によれば、使用する装置の騒音が小さく、操作性がよいという利点を有するのみならず、カラー化が容易であり、かつ記録部材として普通紙を使用することができるという利点があるため、オフィスや家庭での出力機として広く用いられている。 The ink jet recording method is a recording method in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle onto a recording member and attaching them. According to this method, there is an advantage that not only the noise of the apparatus to be used is small and the operability is good, but also colorization is easy and plain paper can be used as a recording member. It is widely used as an output machine in offices and homes.
　一方、産業用途においても、インクジェット技術の向上によりデジタル印刷の出力機として利用され、非水性（溶剤型、ＵＶ型）インクジェットインキが塩化ビニル（ＰＶＣ）、ＰＥＴなどのプラスチック基材に対して印刷可能な印刷機が実際に市販されている。 On the other hand, in industrial applications, it is used as an output device for digital printing by improving inkjet technology, and non-aqueous (solvent type, UV type) inkjet inks can be printed on plastic substrates such as vinyl chloride (PVC) and PET. Printing presses are actually commercially available.
　溶剤型の非水性インクジェットインキは主にＰＶＣ基材への印刷用途が多く、屋外での使用がメインとなるため印刷物の光沢や耐性が非常に重視される。印刷物の光沢や耐性は主にインキ中のバインダー樹脂に依存し、バインダー樹脂としてはアクリル樹脂や塩化ビニル－酢酸ビニル共重合体樹脂（以下、「塩酢ビ樹脂」とも言う）が広く使用されている（特許文献１，２）。特許文献３では、印刷物の耐アルコール性と連続吐出安定性を向上させるために、特定の分子量分布を持つ塩酢ビ樹脂とポリアルキレングリコールジアルキルエーテル溶剤とを含むインクジェットインキが開示されている。 Solvent-type non-aqueous ink-jet inks are mainly used for printing on PVC substrates, and are mainly used outdoors, so the gloss and durability of printed matter are very important. The gloss and resistance of printed materials mainly depend on the binder resin in the ink. As the binder resin, acrylic resin and vinyl chloride-vinyl acetate copolymer resin (hereinafter also referred to as “vinyl chloride resin”) are widely used. (Patent Documents 1 and 2). Patent Document 3 discloses an ink-jet ink containing a vinyl acetate resin having a specific molecular weight distribution and a polyalkylene glycol dialkyl ether solvent in order to improve the alcohol resistance and continuous discharge stability of a printed matter.
特開２００５－１０５１２６号公報JP 2005-105126 A 特開２０１４－０６２１６３号公報JP 2014-062163 A 特開２０１５－０６７７６３号公報Japanese Patent Laying-Open No. 2015-067673
　しかしながら、印刷物の光沢や耐性を維持したまま、連続吐出安定性やミスト（主たる液滴以外の微小液滴が基材に付着する現象）等の性能、更にはインキの保存安定性を両立させるのは困難だった。なお、連続吐出安定性に係る具体的な現象として、長時間にわたって印刷する際、ノズル詰まりを起こすことで画像にヌケが生じる「ノズル抜け」や、インクジェットインキの液滴が所望の位置に着弾しない「偏向」がある。例えば上記特許文献３では、印刷を続けることで偏向が発生し、連続的に良質な画像を得ることが困難であった。 However, while maintaining the gloss and durability of the printed material, it is possible to achieve both continuous discharge stability, performance such as mist (a phenomenon in which fine droplets other than the main droplets adhere to the substrate), and ink storage stability. Was difficult. In addition, as a specific phenomenon related to continuous ejection stability, when printing for a long time, “nozzle missing” in which an image is missing due to nozzle clogging, or ink-jet ink droplets do not land at a desired position. There is “deflection”. For example, in Patent Document 3 described above, deflection is generated by continuing printing, and it has been difficult to continuously obtain high-quality images.
　塩酢ビ樹脂の物性に関与する大きな要因に分子量があるが、従来はポリスチレン換算のＧＰＣ（ゲルパーミエーションクロマトグラフィー）での相対分子量が用いられている。しかしながら、このような相対分子量の場合、標準物質であるポリスチレンの樹脂構造と塩酢ビ樹脂の樹脂構造との間に差があることや、カラム吸着の影響により樹脂中の高分子量成分やゲル成分の量を正確に測定できないことのため、実際の樹脂の状態を反映した値とは言えず、分子量と樹脂物性との関連をみるには不十分であった。 The molecular weight is a major factor related to the physical properties of vinyl chloride resin, but the relative molecular weight in GPC (gel permeation chromatography) in terms of polystyrene has been conventionally used. However, in the case of such relative molecular weight, there is a difference between the resin structure of polystyrene, which is a standard substance, and the resin structure of vinyl acetate resin, and the high molecular weight component and gel component in the resin due to the effect of column adsorption. Since the amount of water cannot be measured accurately, it cannot be said to reflect the actual state of the resin, and is insufficient to see the relationship between the molecular weight and the physical properties of the resin.
　本発明は、前記課題に鑑みたものであり、連続吐出安定性等の印刷性能に優れ、良好な保存安定性を有するとともに、光沢や耐性に優れた印刷物を得ることが可能な、主に塩化ビニル基材への印刷に適した非水性インクジェットインキを提供する。 The present invention has been made in view of the above problems, and is excellent in printing performance such as continuous discharge stability, has good storage stability, and can obtain a printed matter having excellent gloss and durability. A non-aqueous inkjet ink suitable for printing on a vinyl substrate is provided.
　本発明の一実施形態は、有機溶剤、顔料、及び塩化ビニル－酢酸ビニル共重合体樹脂を含有する非水性インクジェットインキであって、
　前記塩化ビニル－酢酸ビニル共重合体樹脂の重量平均絶対分子量（｜Ｍｗ｜）が２０，０００～４０，０００であり、かつ、前記重量平均絶対分子量（｜Ｍｗ｜）と数平均絶対分子量（｜Ｍｎ｜）の比（｜Ｍｗ｜／｜Ｍｎ｜）が１．３以上２．２以下であり、
　前記塩化ビニル－酢酸ビニル共重合体樹脂が、塩化ビニル単量体及び酢酸ビニル単量体の乳化重合物であることを特徴とする、非水性インクジェットインキを提供する。 One embodiment of the present invention is a non-aqueous inkjet ink containing an organic solvent, a pigment, and a vinyl chloride-vinyl acetate copolymer resin,
The vinyl chloride-vinyl acetate copolymer resin has a weight average absolute molecular weight (| Mw |) of 20,000 to 40,000, and the weight average absolute molecular weight (| Mw |) and the number average absolute molecular weight (| Mn |) ratio (| Mw | / | Mn |) is 1.3 or more and 2.2 or less,
A non-aqueous inkjet ink is provided, wherein the vinyl chloride-vinyl acetate copolymer resin is an emulsion polymer of a vinyl chloride monomer and a vinyl acetate monomer.
　本発明の一実施形態はまた、前記塩化ビニル－酢酸ビニル共重合体樹脂が、絶対分子量（｜Ｍ｜）２００，０００以上の樹脂を含まないか、前記塩化ビニル－酢酸ビニル共重合体樹脂全量中１０重量％以下含有することを特徴とする、上記非水性インクジェットインキであってよい。 In one embodiment of the present invention, the vinyl chloride-vinyl acetate copolymer resin does not contain a resin having an absolute molecular weight (| M |) of 200,000 or more, or the total amount of the vinyl chloride-vinyl acetate copolymer resin. The non-aqueous inkjet ink described above, characterized by containing 10% by weight or less.
　本発明の一実施形態はさらに、有機溶剤が、一般式（ａ）～一般式（ｄ）で表される溶剤のいずれか１つ以上を含むことを特徴とする、上記非水性インクジェットインキであってよい：
　　　　Ｒ１ＣＯ（ＯＲ２）ＺＯＲ３　　　（ａ）
　　　　Ｒ４ＣＯ（ＯＲ５）ＺＯＣＯＲ６　（ｂ）
　　　　Ｒ７（ＯＲ８）ＺＯＲ９　　　　　（ｃ）
　　　　Ｒ１０ＣＯＯＲ１１　　　　　　　（ｄ）。 One embodiment of the present invention is the above non-aqueous inkjet ink, wherein the organic solvent further includes any one or more of the solvents represented by the general formulas (a) to (d). May be:
R 1 CO (OR 2 ) Z OR 3 (a)
R 4 CO (OR 5 ) Z OCOR 6 (b)
R 7 (OR 8 ) Z OR 9 (c)
R 10 COOR 11 (d).
　なお上式中、Ｒ２、Ｒ５、Ｒ８はそれぞれ独立して、エチレン基、プロピレン基、ブチレン基から選択されるいずれかであり、Ｒ１、Ｒ３、Ｒ４、Ｒ６はそれぞれ独立して炭素数１～４のアルキル基であり、Ｒ７、Ｒ９はそれぞれ独立して水素原子又は炭素数１～４のアルキル基であり、Ｒ１０は２－ヒドロキシエチル基であり、Ｒ１１は炭素数１～８のアルキル基であり、Ｚは１～３の整数を表す。 In the above formula, R 2 , R 5 and R 8 are each independently selected from ethylene group, propylene group and butylene group, and R 1 , R 3 , R 4 and R 6 are each independently selected. An alkyl group having 1 to 4 carbon atoms, R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 10 is a 2-hydroxyethyl group, R 11 Is an alkyl group having 1 to 8 carbon atoms, and Z represents an integer of 1 to 3.
　本発明の一実施形態はまた、有機溶剤が、含窒素系または含硫黄系またはラクトン系溶剤を更に含有することを特徴とする上記非水性インクジェットインキであってよい。 One embodiment of the present invention may also be the non-aqueous inkjet ink described above, wherein the organic solvent further contains a nitrogen-containing, sulfur-containing, or lactone-based solvent.
　本発明の一実施形態は、顔料分散剤を更に含むことを特徴とする、上記非水性インクジェットインキであってよい。 One embodiment of the present invention may be the non-aqueous inkjet ink described above, further including a pigment dispersant.
　本発明により、連続吐出安定性等の印刷性能に優れ、良好な保存安定性を有するとともに、光沢や耐性に優れた印刷物を得ることが可能な、主に塩化ビニル基材への印刷に適した非水性インクジェットインキを提供することが可能となった。 According to the present invention, it is excellent in printing performance such as continuous discharge stability, has good storage stability, and can obtain a printed matter having excellent gloss and durability, and is suitable mainly for printing on a vinyl chloride substrate. It has become possible to provide a non-aqueous inkjet ink.
　以下に、好ましい実施の形態を挙げて、本発明について説明する。なお本発明において「非水性」とは、意図的に水を添加しないことを意味するものであり、例えば非水性インクジェットインキ全量に対し５重量％以下であれば、原料に含まれる水分や外気の吸湿による水分が含まれても差し支えない。 Hereinafter, the present invention will be described with reference to preferred embodiments. In the present invention, “non-aqueous” means that water is not intentionally added. For example, if it is 5% by weight or less with respect to the total amount of the non-aqueous inkjet ink, There is no problem even if moisture is absorbed.
　本発明は、非水性インクジェットインキに用いる塩化ビニル－酢酸ビニル共重合体樹脂が塩化ビニル単量体及び酢酸ビニル単量体の乳化重合物であり、その重量平均絶対分子量（｜Ｍｗ｜）が２０，０００～４０，０００であり、かつ、前記重量平均絶対分子量（｜Ｍｗ｜）と数平均絶対分子量（｜Ｍｎ｜）の比（｜Ｍｗ｜／｜Ｍｎ｜）が１．３以上２．２以下であることを特徴とする。 In the present invention, the vinyl chloride-vinyl acetate copolymer resin used in the non-aqueous inkjet ink is an emulsion polymer of a vinyl chloride monomer and a vinyl acetate monomer, and its weight average absolute molecular weight (| Mw |) is 20 And a ratio (| Mw | / | Mn |) of the weight average absolute molecular weight (| Mw |) to the number average absolute molecular weight (| Mn |) is 1.3 or more and 2.2. It is characterized by the following.
　従来技術にて説明した通り、溶剤型の非水性インクジェットインキの主な対象基材であるＰＶＣ基材に対応するためには、印刷物の光沢や耐性、更にはＰＶＣ基材に対する密着性に優れる、塩化ビニル－酢酸ビニル共重合体樹脂の使用が好ましい。 As explained in the prior art, in order to correspond to the PVC base material which is the main target base material of the solvent-type non-aqueous inkjet ink, it is excellent in gloss and resistance of the printed matter, and further, the adhesion to the PVC base material. The use of vinyl chloride-vinyl acetate copolymer resin is preferred.
　これら塩酢ビ樹脂を合成する方法として、懸濁重合法や乳化重合法が知られている。 Suspension polymerization and emulsion polymerization are known as methods for synthesizing these vinyl chloride resins.
　このうち懸濁重合法は、塩化ビニル、酢酸ビニル、及び必要に応じて共重合可能な単量体の混合物（以下、「塩化ビニル系単量体」と記す）に対し、前記塩化ビニル系単量体に可溶な重合開始剤、分散剤、乳化剤、安定化剤等を加え、ホモジナイザー等の分散機によって分散媒中に分散させ、均質化処理した上で重合させる方法である。懸濁重合法は、前記分散媒として主に水を用いること、合成温度を調整しやすいこと、重合体の取出しが容易であることから、工業生産で一般的に使われる重合方法である。しかしながら、分散剤や安定化剤が不溶解分となって生成物に残留しやすく、インクジェットインキに用いた場合、前記不溶解分がインクジェットヘッドに詰まる、あるいは付着することで、連続吐出安定性が悪化してしまう。また得られる重合体の分子量分布が広くなりやすく、やはり連続吐出安定性に悪影響を与えることから、好ましいものではない。 Among these, the suspension polymerization method uses a vinyl chloride, vinyl acetate, and, if necessary, a mixture of monomers copolymerizable (hereinafter referred to as “vinyl chloride monomer”), the vinyl chloride monomer. In this method, a polymerization initiator, a dispersant, an emulsifier, a stabilizer, and the like soluble in a polymer are added, dispersed in a dispersion medium by a dispersing machine such as a homogenizer, and homogenized and then polymerized. The suspension polymerization method is a polymerization method generally used in industrial production because water is mainly used as the dispersion medium, the synthesis temperature is easily adjusted, and the polymer can be easily taken out. However, the dispersant and stabilizer are easily dissolved and remain in the product, and when used in inkjet ink, the insoluble component is clogged or adhered to the inkjet head, so that continuous ejection stability is improved. It will get worse. Further, the molecular weight distribution of the obtained polymer is likely to be widened, which also adversely affects the continuous discharge stability, which is not preferable.
　一方で乳化重合法は、塩化ビニル系単量体を、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等の乳化剤とともに媒体（水）に加えて乳化させたのち、過硫酸アンモニウム等の水溶性重合開始剤を加えて重合させる方法である。乳化重合法は、重合反応が高速で進行すること、主な媒体として水を用いること、合成温度を調整しやすいことから、乳化重合法もまた工業生産に向いた合成方法といえる。更に乳化重合法では、懸濁重合法に比べて不溶解分の量が少なく、また連鎖移動剤を併用することで、分子量分布が比較的狭い重合体を得ることができることから、本発明において好適に選択される。 On the other hand, in the emulsion polymerization method, a vinyl chloride monomer is emulsified by adding it to a medium (water) together with an emulsifier such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and then a water-soluble polymerization initiator such as ammonium persulfate is added. In addition, it is a method of polymerizing. The emulsion polymerization method is a synthesis method suitable for industrial production because the polymerization reaction proceeds at high speed, water is used as a main medium, and the synthesis temperature is easy to adjust. Further, the emulsion polymerization method is preferable in the present invention because the amount of insoluble matter is small compared to the suspension polymerization method, and a polymer having a relatively narrow molecular weight distribution can be obtained by using a chain transfer agent in combination. Selected.
　しかしながら、乳化重合法で製造した塩酢ビ樹脂には、全体的に重合度の高いポリマーが得られやすい、といった問題点が存在する。従来から周知の通り、インクジェットインキに含まれる、塩酢ビ樹脂を始めとしたバインダー樹脂の分子量は、連続吐出安定性や、印刷物の光沢や耐性に大きく影響する。すなわちバインダー樹脂の分子量特性を正確に知ることにより、前記バインダー樹脂を用いたインクジェットインキの諸特性を把握することができる。 However, the vinyl acetate resin produced by the emulsion polymerization method has a problem that it is easy to obtain a polymer having a high degree of polymerization as a whole. As is well known in the art, the molecular weight of a binder resin, such as a vinyl acetate resin, contained in an inkjet ink greatly affects the stability of continuous ejection and the gloss and resistance of printed matter. That is, by accurately knowing the molecular weight characteristics of the binder resin, various characteristics of the ink-jet ink using the binder resin can be grasped.
　上記観点のもと本発明者らが鋭意検討したところ、一般的なポリスチレン換算のＧＰＣ（ゲルパーミエーションクロマトグラフィー）法により得られる相対分子量特性が同じ塩酢ビ樹脂同士であっても、連続吐出安定性の優劣に大きな差が生じることが判明した。更なる調査の結果、連続吐出安定性の優劣が塩酢ビ樹脂の絶対分子量特性に大きく相関していることを突き止めた。 Based on the above viewpoints, the present inventors diligently studied, and even when the polyvinyl chloride resins having the same relative molecular weight characteristics obtained by a general polystyrene conversion GPC (gel permeation chromatography) method are used, continuous discharge is possible. It has been found that there is a large difference in stability. As a result of further investigation, it was found that the superiority or inferiority of the continuous discharge stability is greatly correlated with the absolute molecular weight characteristics of the vinyl chloride resin.
　具体的には、塩化ビニル－酢酸ビニル共重合体樹脂の｜Ｍｗ｜が２０，０００～４０，０００であり、かつ、｜Ｍｗ｜／｜Ｍｎ｜が１．３以上２．２以下であることで、連続吐出安定性が極めて優れるだけでなく、印刷物の光沢や耐性、更にはインキの保存安定性が良好なインクジェットインキが得られることが判明した。 Specifically, | Mw | of the vinyl chloride-vinyl acetate copolymer resin is 20,000 to 40,000, and | Mw | / | Mn | is 1.3 or more and 2.2 or less. Thus, it has been found that not only the continuous discharge stability is extremely excellent, but also an ink-jet ink having good gloss and resistance of the printed matter and further excellent ink storage stability can be obtained.
　本明細書において、重量平均絶対分子量（｜Ｍｗ｜）、数平均絶対分子量（｜Ｍｎ｜）、及び絶対分子量（｜Ｍ｜）は、ゲルパーミエーションクロマトグラフィー・マルチアングルライトスカッターリング法（以下ＧＰＣ－ＭＡＬＳ法）で求められる重量平均分子量、数平均分子量、及び分子量を表す。具体的には、ＴＳＫｇｅｌカラム（東ソー社製）、及び多角度光散乱検出器（Ｗｙａｔｔ社製、ｍｉｎｉＤａｗｎ　ＴＲＥＯＳ）を装備したＧＰＣ（Ｗａｔｅｒｓ社製、Ａｌｌｉａｎｃｅ　ＧＰＣ）を使用し、展開溶媒にＴＨＦを用いることで測定できる値であり、従来のＧＰＣ法で得られるポリスチレン換算値（相対値）とは異なり、樹脂自身の絶対分子量を求めることができる。 In the present specification, the weight average absolute molecular weight (| Mw |), the number average absolute molecular weight (| Mn |), and the absolute molecular weight (| M |) GPC-MALS method) represents a weight average molecular weight, number average molecular weight, and molecular weight. Specifically, a TSKgel column (manufactured by Tosoh Corporation) and a GPC equipped with a multi-angle light scattering detector (manufactured by Wyatt, miniDawn TREOS) (Waters, Alliance GPC) are used, and THF is used as a developing solvent. Unlike the polystyrene conversion value (relative value) obtained by the conventional GPC method, the absolute molecular weight of the resin itself can be obtained.
　ＧＰＣ－ＭＡＬＳ法では、樹脂構造やカラム吸着の影響を受けることがないため、連続吐出安定性に大きく影響を与える、樹脂中の高分子量成分やゲル成分の量を正確に測定できるものであり、相対分子量の測定結果からは予測できない測定値となる。このように、樹脂の状態を反映した値である絶対分子量は、各種物性との関係について検討するのに特に適した方法である。 Since the GPC-MALS method is not affected by the resin structure or column adsorption, it can accurately measure the amount of high molecular weight components and gel components in the resin, which greatly affects the continuous discharge stability. It becomes a measurement value that cannot be predicted from the measurement result of the relative molecular weight. Thus, the absolute molecular weight, which is a value reflecting the state of the resin, is a particularly suitable method for examining the relationship with various physical properties.
　なお、本発明者らが調査した限り、市販されている塩酢ビ樹脂の乳化重合品に、上記好適な｜Ｍｗ｜や｜Ｍｗ｜／｜Ｍｎ｜（以下総称して「好適な絶対分子量分布」ともいう）を満たしているものはなく、これらの特性は、本発明において初めて見出されたものである。従来市販されている塩酢ビ樹脂は、一般的なポリスチレン換算のＧＰＣ法により相対値である分子量や分子量分布が測定されているものが多く、上記の高分子量成分やゲル成分については認識されておらず、当該成分が除去されないまま販売されているものと考えられる。 In addition, as long as the present inventors investigated, the above-mentioned suitable | Mw | and | Mw | / | Mn | (hereinafter collectively referred to as “preferable absolute molecular weight distribution”) may be applied to commercially available emulsion polymerization products of vinyl chloride resin. These characteristics have been found for the first time in the present invention. Many commercially available vinyl chloride resins have been measured for relative molecular weight and molecular weight distribution by a general polystyrene equivalent GPC method, and the above high molecular weight components and gel components are recognized. It is considered that the product is sold without being removed.
　続いて以下に、本実施形態の主要となる各成分について述べる。 Subsequently, each main component of this embodiment will be described below.
　〔バインダー樹脂〕
　本発明の塩化ビニル－酢酸ビニル共重合体樹脂の｜Ｍｗ｜は、上記の通り２０，０００～４０，０００であってよく、２０，０００～３５，０００であることが好ましく、２５，０００～３０，０００であることが特に好ましい。この範囲内であれば連続吐出安定性や印刷物の光沢や耐性、及びインキの保存安定性に優れたインクジェットインキを得ることができる。また｜Ｍｗ｜／｜Ｍｎ｜は１．３以上２．２以下であってよく、１．４以上２．１以下であることがより好ましく、１．５以上２．０以下であることが特に好ましい。この範囲内であればインクジェットインキのノズル抜けを抑制でき、連続吐出安定性を更に高めることができる。 [Binder resin]
| Mw | of the vinyl chloride-vinyl acetate copolymer resin of the present invention may be 20,000 to 40,000 as described above, preferably 20,000 to 35,000, and 25,000 to 30,000 is particularly preferred. Within this range, an inkjet ink excellent in continuous discharge stability, gloss and resistance of printed matter, and ink storage stability can be obtained. | Mw | / | Mn | may be 1.3 or more and 2.2 or less, more preferably 1.4 or more and 2.1 or less, and particularly preferably 1.5 or more and 2.0 or less. preferable. If it is in this range, nozzle omission of the ink-jet ink can be suppressed, and the continuous ejection stability can be further enhanced.
　更に、塩化ビニル－酢酸ビニル共重合体樹脂において、絶対分子量（｜Ｍ｜）２００，０００以上の樹脂の含有率が、前記塩化ビニル－酢酸ビニル共重合体樹脂全量中０～１０重量％であることが好ましく、０～５重量％であることがより好ましく、０重量％であることが特に好ましい。なお上記において「０重量％」とは、対象となる成分を含まないことを意味する。また、｜Ｍ｜が２００，０００以上の樹脂の含有率が０重量％であるもののうち、｜Ｍ｜が１５０，０００以上の樹脂を含まないか、あるいは前記共重合体樹脂全量中の含有量が１０重量％以下であることが更により好ましい。高絶対分子量成分の配合量を上記範囲まで減らすことで、連続吐出安定性に極めて優れたインクジェットインキを得ることができる。なお、ある｜Ｍ｜以上の樹脂の含有率は、ＧＰＣ－ＭＡＬＳ法で測定される分子量分布のグラフから面積を計算することで算出される。 Further, in the vinyl chloride-vinyl acetate copolymer resin, the content of the resin having an absolute molecular weight (| M |) of 200,000 or more is 0 to 10% by weight in the total amount of the vinyl chloride-vinyl acetate copolymer resin. It is preferably 0 to 5% by weight, more preferably 0% by weight. In the above, “0 wt%” means that the target component is not included. Further, among resins having a resin content of | M | of 200,000 or more of 0% by weight, | M | does not contain a resin of 150,000 or more, or the content in the total amount of the copolymer resin. Is more preferably 10% by weight or less. By reducing the blending amount of the high absolute molecular weight component to the above range, it is possible to obtain an ink-jet ink having extremely excellent continuous ejection stability. Note that the content of a resin having a certain | M | or more is calculated by calculating the area from a graph of molecular weight distribution measured by the GPC-MALS method.
　本発明では、上記の通り、好適な絶対分子量分布を有する樹脂を得るために、乳化重合法により得られる塩酢ビ樹脂を使用する。なお乳化重合においては、末端にイオン性基を有する重合開始剤を用いることが好ましい。また環境負荷低減の観点から、乳化重合の原料として、有機塩素化合物が含まれないことが好ましい。 In the present invention, as described above, a vinyl acetate resin obtained by an emulsion polymerization method is used in order to obtain a resin having a suitable absolute molecular weight distribution. In emulsion polymerization, it is preferable to use a polymerization initiator having an ionic group at the terminal. Further, from the viewpoint of reducing environmental burden, it is preferable that no organic chlorine compound is contained as a raw material for emulsion polymerization.
　乳化重合において、塩化ビニル－酢酸ビニル共重合体樹脂の｜Ｍｗ｜や｜Ｍｗ｜／｜Ｍｎ｜を上記の好適な範囲に収める方法として、例えば連鎖移動剤及び乳化剤の種類及び量を調整すること、塩化ビニル及び酢酸ビニルの量及び比率を調整すること、並びに前記の組合せが挙げられる。 In emulsion polymerization, as a method for keeping | Mw | and | Mw | / | Mn | of a vinyl chloride-vinyl acetate copolymer resin within the above-mentioned preferable range, for example, adjusting the types and amounts of chain transfer agents and emulsifiers. Adjusting the amount and ratio of vinyl chloride and vinyl acetate, and combinations of the foregoing.
　具体的には、連鎖移動剤の配合量を、塩化ビニル系単量体全量に対し、例えば１．８～２．５重量％、好ましくは２．０～２．３重量％とすることにより、媒体中で形成される乳化物が小さくなり、結果として塩化ビニル－酢酸ビニル共重合体樹脂の｜Ｍｗ｜や｜Ｍｗ｜／｜Ｍｎ｜が好適なものとなる。 Specifically, the blending amount of the chain transfer agent is, for example, 1.8 to 2.5% by weight, preferably 2.0 to 2.3% by weight, based on the total amount of the vinyl chloride monomer. The emulsion formed in the medium is reduced, and as a result, | Mw | and | Mw | / | Mn | of the vinyl chloride-vinyl acetate copolymer resin are suitable.
　また、塩化ビニル及び酢酸ビニルの比率を調整することにより好適な絶対分子量分布に収めるべく、塩化ビニル－酢酸ビニル共重合体樹脂中における酢酸ビニルの割合は、１０～２５重量％とすることが好ましく、１２～２２重量％とすることがより好ましく、１４～２０重量％とすることが更に好ましい。酢酸ビニルの割合を上記範囲内とすることで、｜Ｍｗ｜や｜Ｍｗ｜／｜Ｍｎ｜を好適な範囲内に収められるだけでなく、印刷物の光沢性や耐溶剤性に優れるインクジェットインキを得ることができる。 Further, the vinyl acetate-vinyl acetate copolymer resin preferably has a vinyl acetate ratio of 10 to 25% by weight in order to obtain a suitable absolute molecular weight distribution by adjusting the ratio of vinyl chloride and vinyl acetate. 12 to 22% by weight is more preferable, and 14 to 20% by weight is still more preferable. By setting the ratio of vinyl acetate within the above range, | Mw | and | Mw | / | Mn | are not only within the preferable range, but also an inkjet ink having excellent gloss and solvent resistance of the printed matter is obtained. be able to.
　なお上記の通り、市販の塩化ビニル－酢酸ビニル共重合体樹脂の乳化重合品には、本発明において好適な絶対分子量分布を有するものはないが、例えば超音波処理装置やメディア分散機等を利用することによって、塩化ビニル－酢酸ビニル共重合体鎖を切断することにより、市販品を原料として好適な絶対分子量分布を有する塩酢ビ樹脂を得ることができる。 As described above, there is no commercially available emulsion polymerized vinyl chloride-vinyl acetate copolymer resin having an absolute molecular weight distribution suitable for the present invention. However, for example, an ultrasonic treatment device or a media disperser is used. Thus, by cutting the vinyl chloride-vinyl acetate copolymer chain, a vinyl chloride resin having a suitable absolute molecular weight distribution can be obtained using a commercially available product as a raw material.
　超音波処理装置を利用する場合、市販の塩化ビニル－酢酸ビニル共重合体樹脂の乳化重合品を、非水性インクジェットインキに用いる有機溶剤に溶解させた溶液を作製したのち、前記溶液に対し超音波処理を施す方法が好適である。超音波処理前記装置としては、超音波ホモジナイザーが好適に利用される。なお、上記の好適な絶対分子量分布に収めるため、超音波の周波数は１０～３０ｋＨｚであることが好ましく、また振幅範囲としては２０～６０μｍであることが好ましい。 When using an ultrasonic treatment device, after preparing a solution in which an emulsion polymerization product of a commercially available vinyl chloride-vinyl acetate copolymer resin is dissolved in an organic solvent used in a non-aqueous inkjet ink, A method of performing the treatment is preferable. Ultrasonic treatment An ultrasonic homogenizer is preferably used as the apparatus. It should be noted that the ultrasonic frequency is preferably 10 to 30 kHz, and the amplitude range is preferably 20 to 60 μm in order to keep the above-mentioned preferable absolute molecular weight distribution.
　上記方法により、本発明に好適な塩化ビニル－酢酸ビニル共重合体樹脂を調製する場合、具体的に用いることができる市販品としては、ワッカーケミー社製のＶＩＮＮＯＬ（登録商標）Ｅ１５／４５、Ｅ１５／４５Ｍ、Ｅ１５／４０Ｍ、Ｅ１５／４８Ａ、Ｅ２２／４８Ａ、Ｅ１５／４０Ａ　ＴＦ、Ｅ１５／４５Ｍ　ＴＦ、Ｅ１５／４５ＴＦ等が挙げられるが、これらに限定されない。中でも前記絶対分子量分布を好適なものに収めやすく、連続吐出安定性に優れた非水性インクジェットインキを得られる点から、ＶＩＮＮＯＬ　Ｅ１５／４５、Ｅ１５／４５Ｍ、Ｅ１５／４０Ｍ、Ｅ１５／４８Ａ、Ｅ１５／４５ＴＦが好ましく、印刷物の耐性の面も考慮すると、ＶＩＮＮＯＬ　Ｅ１５／４５、Ｅ１５／４５ＴＦが特に好ましい。なお、ＶＩＮＮＯＬ　Ｅ１５／４５、Ｅ１５／４５ＴＦはともに、乳化重合法で製造され、樹脂全量に対し塩化ビニルを約８５重量％、酢酸ビニルを約１５重量％含むものである。 When the vinyl chloride-vinyl acetate copolymer resin suitable for the present invention is prepared by the above method, commercially available products that can be specifically used include VINNOL (registered trademark) E15 / 45, E15 manufactured by Wacker Chemie. / 45M, E15 / 40M, E15 / 48A, E22 / 48A, E15 / 40A TF, E15 / 45M TF, E15 / 45TF, and the like, but are not limited thereto. Among them, VINOLL E15 / 45, E15 / 45M, E15 / 40M, E15 / 48A, E15 / 45TF are easy to fit in the above-mentioned absolute molecular weight distribution and can obtain a non-aqueous inkjet ink excellent in continuous discharge stability. In view of the durability of printed matter, VINNOL E15 / 45 and E15 / 45TF are particularly preferable. VINNOL E15 / 45 and E15 / 45TF are both produced by an emulsion polymerization method and contain about 85% by weight of vinyl chloride and about 15% by weight of vinyl acetate based on the total amount of the resin.
　塩化ビニル－酢酸ビニル共重合体樹脂を合成する場合、及び市販品を用いて調製する場合のどちらにおいても、前記樹脂を構成する塩化ビニル系単量体として、塩化ビニル、及び酢酸ビニルの他に、例えばマレイン酸やビニルアルコールを含んでいてもよい。 In both cases of synthesizing vinyl chloride-vinyl acetate copolymer resin and preparing using a commercial product, in addition to vinyl chloride and vinyl acetate as vinyl chloride monomers constituting the resin, For example, it may contain maleic acid or vinyl alcohol.
　また本発明の非水性インクジェットインキに含まれる、塩化ビニル－酢酸ビニル共重合体の含有量としては、非水性インクジェットインキ全量に対し０．５～２０重量％が好ましく、１～１０重量％がより好ましく、２～８重量％が更に好ましい。上記範囲とすることでより高い連続吐出安定性を発揮することができる。 Further, the content of the vinyl chloride-vinyl acetate copolymer contained in the non-aqueous inkjet ink of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the total amount of the non-aqueous inkjet ink. Preferably, 2 to 8% by weight is more preferable. By setting it as the said range, higher continuous discharge stability can be exhibited.
　本発明において、基材密着性や塗膜耐性等を向上させる目的で、バインダー樹脂としてその他の樹脂を更に併用することができる。本発明において使用されるバインダー樹脂としては、インキ塗膜の耐擦性、耐溶剤性、延伸性、光沢性、基材汎用性などの機能を発揮するものであれば制限されるものでない。バインダー樹脂としては、例えば、アクリル樹脂、スチレン－アクリル系樹脂、スチレン－マレイン酸系樹脂、ロジン系樹脂、ロジンエステル系樹脂、エチレン－酢ビ系樹脂、石油樹脂、クマロンインデン系樹脂、テルペンフェノール系樹脂、フェノール樹脂、ウレタン樹脂、メラミン樹脂、尿素樹脂、エポキシ系樹脂、セルロース系樹脂、キシレン樹脂、アルキッド樹脂、脂肪族炭化水素樹脂、ブチラール樹脂、マレイン酸樹脂、フマル酸樹脂、ケトン樹脂、アルデヒド樹脂等、一般的に使用される樹脂が使用できる。これらバインダー樹脂は、単独で使用しても、２種類以上を併用しても良い。 In the present invention, other resins can be used in combination as a binder resin for the purpose of improving substrate adhesion, coating film resistance, and the like. The binder resin used in the present invention is not limited as long as it exhibits functions such as abrasion resistance, solvent resistance, stretchability, glossiness, and general versatility of the ink coating film. Examples of the binder resin include acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, rosin resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol. Resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, ketone resin, aldehyde Commonly used resins such as resins can be used. These binder resins may be used alone or in combination of two or more.
　本発明では、バインダー樹脂として、塩化ビニル－酢酸ビニル共重合体樹脂の他に、アクリル樹脂、スチレン－アクリル系樹脂、及びスチレン－マレイン酸系樹脂から選択される少なくとも１種を使用することが好ましい。本明細書において、アクリル樹脂とは、（メタ）アクリル酸や（メタ）アクリル酸エステルを重合した樹脂を指す。また本明細書において、スチレン－アクリル系樹脂とは、前記スチレン－アクリル系樹脂の構成成分中５０重量％を超えない範囲でスチレンを含み、残りが（メタ）アクリル酸や（メタ）アクリル酸エステルにより構成される樹脂であり、マレイン酸等で変性されていても良い。塩化ビニル－酢酸ビニル共重合体樹脂の他にバインダー樹脂に含まれ得る上記樹脂を構成する成分として好適なものを例示すると、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸－２－エチルヘキシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ベンジル、スチレン、マレイン酸などが挙げられるが、これらに限定されない。本発明ではインキ中への樹脂の溶解性や印刷物の耐性の面から、バインダー樹脂としては、メタクリル酸メチル及び／又はメタクリル酸ブチルを構成成分とした樹脂であることがより好ましく、メタクリル酸メチル及び／又はメタクリル酸ブチルと更にアクリル酸とを含む樹脂であることが特に好ましい。本明細書において「（メタ）アクリル」とは、「アクリル」及び「メタクリル」から選ばれる少なくとも１種であることを意味する。 In the present invention, it is preferable to use at least one selected from an acrylic resin, a styrene-acrylic resin, and a styrene-maleic acid resin in addition to the vinyl chloride-vinyl acetate copolymer resin as the binder resin. . In this specification, the acrylic resin refers to a resin obtained by polymerizing (meth) acrylic acid or (meth) acrylic acid ester. In the present specification, the styrene-acrylic resin includes styrene within a range not exceeding 50% by weight in the constituents of the styrene-acrylic resin, and the remainder is (meth) acrylic acid or (meth) acrylic acid ester. And may be modified with maleic acid or the like. In addition to the vinyl chloride-vinyl acetate copolymer resin, examples of suitable components constituting the resin that can be included in the binder resin include (meth) acrylic acid, methyl (meth) acrylate, and (meth) acrylic acid. Ethyl, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, Examples include, but are not limited to, styrene and maleic acid. In the present invention, from the viewpoint of the solubility of the resin in the ink and the resistance of the printed matter, the binder resin is more preferably a resin containing methyl methacrylate and / or butyl methacrylate as a constituent component, and methyl methacrylate and Particularly preferred is a resin containing butyl methacrylate and further acrylic acid. In this specification, “(meth) acryl” means at least one selected from “acryl” and “methacryl”.
　本発明においてアクリル樹脂、スチレン－アクリル系樹脂を併用する場合（以下、「アクリル系樹脂」とも言う）、適した絶対分子量分布を有するアクリル系樹脂を選択することが好ましい。好適に用いられるアクリル系樹脂の重量平均絶対分子量（｜Ｍｗ｜）は４，０００～５０，０００であり、この範囲であれば印刷時にミストを生じることなく、また高い耐性を有する印刷物を得ることが可能となる。ここで、併用する樹脂がアクリル樹脂の場合には、重量平均絶対分子量（｜Ｍｗ｜）は、より好ましくは１０，０００～４５，０００であり、更により好ましくは１５，０００～４０，０００である。併用する樹脂がスチレン－アクリル系樹脂の場合には、重量平均絶対分子量（｜Ｍｗ｜）は、より好ましくは４，０００～２０，０００であり、更により好ましくは４，０００～１５，０００である。塩化ビニル－酢酸ビニル共重合体樹脂と併用するアクリル系樹脂として、上記アクリル樹脂と上記スチレン－アクリル系樹脂とをともに含有することもできる。 In the present invention, when an acrylic resin and a styrene-acrylic resin are used in combination (hereinafter also referred to as “acrylic resin”), it is preferable to select an acrylic resin having a suitable absolute molecular weight distribution. The weight average absolute molecular weight (| Mw |) of the acrylic resin preferably used is 4,000 to 50,000, and if it is within this range, a printed matter having high resistance can be obtained without causing mist during printing. Is possible. Here, when the resin used in combination is an acrylic resin, the weight average absolute molecular weight (| Mw |) is more preferably 10,000 to 45,000, and still more preferably 15,000 to 40,000. is there. When the resin used in combination is a styrene-acrylic resin, the weight average absolute molecular weight (| Mw |) is more preferably 4,000 to 20,000, and still more preferably 4,000 to 15,000. is there. As the acrylic resin used in combination with the vinyl chloride-vinyl acetate copolymer resin, both the acrylic resin and the styrene-acrylic resin can be contained.
　また、好適に用いられるアクリル系樹脂として、絶対分子量２００，０００以上の樹脂の含有量が、全アクリル系樹脂中１０％以下であることが好ましく、５％以下であることがより好ましく、全く含まないことが特に好ましい。 Further, as the acrylic resin suitably used, the content of a resin having an absolute molecular weight of 200,000 or more is preferably 10% or less, more preferably 5% or less, and completely contained in all acrylic resins. It is particularly preferred not to.
　更に、併用する樹脂がアクリル樹脂である場合には、そのアクリル樹脂の酸価は０～３０ｍｇＫＯＨ／ｇであることが好ましい。この範囲であれば高い耐アルコール性を発揮することが可能である。より好ましくは０～２０ｍｇＫＯＨ／ｇ、更に好ましくは０～１５ｍｇＫＯＨ／ｇである。また、併用する樹脂がスチレン－アクリル系樹脂の場合には、スチレン－アクリル系樹脂の酸価は０～２５０ｍｇＫＯＨ／ｇであることが好ましい。この範囲であればインキの分散安定性が良好であり、連続吐出安定性に優れる。より好ましくは５０～２００ｍｇＫＯＨ／ｇ、更に好ましくは７５～１５０ｍｇＫＯＨ／ｇである。ここで「酸価」とは、アクリル樹脂１ｇあたりの酸価を表し、ＪＩＳ　Ｋ　００７０に準じ、電位差滴定法によって求めることができる。 Furthermore, when the resin used in combination is an acrylic resin, the acid value of the acrylic resin is preferably 0 to 30 mgKOH / g. Within this range, high alcohol resistance can be exhibited. More preferably, it is 0-20 mgKOH / g, and still more preferably 0-15 mgKOH / g. When the resin used in combination is a styrene-acrylic resin, the acid value of the styrene-acrylic resin is preferably 0 to 250 mgKOH / g. Within this range, the dispersion stability of the ink is good and the continuous ejection stability is excellent. More preferably, it is 50 to 200 mgKOH / g, and still more preferably 75 to 150 mgKOH / g. Here, the “acid value” represents an acid value per gram of acrylic resin, and can be determined by potentiometric titration according to JIS K 0070.
　アクリル系樹脂のガラス転移点は４０～１５０℃であることが好ましい。この範囲であれば印刷物の耐性が良好であり、フレキシブルな印刷媒体へ印刷した場合にも塗膜のワレなどの不具合が生じにくい。より好ましくは５０～１２０℃であり、更に好ましくは６０～１００℃であり、更により好ましくは７０～９０℃である。 The glass transition point of the acrylic resin is preferably 40 to 150 ° C. Within this range, the printed material has good resistance, and even when printed on a flexible print medium, problems such as cracking of the coating film are unlikely to occur. More preferably, the temperature is 50 to 120 ° C, still more preferably 60 to 100 ° C, and still more preferably 70 to 90 ° C.
　アクリル系樹脂を併用する場合、非水性インクジェットインキ全量に対する含有量として０．１～１０重量％であることが好ましい。この範囲であればインキの連続吐出安定性に悪影響を与えず、また、ミストも生じることなく印刷が可能であるため好ましい。より好ましくは１～８重量％、更に好ましくは１．５～６重量％である。 When an acrylic resin is used in combination, the content with respect to the total amount of the non-aqueous inkjet ink is preferably 0.1 to 10% by weight. This range is preferable because printing can be performed without adversely affecting the continuous ejection stability of the ink and without causing mist. More preferably, it is 1 to 8% by weight, and still more preferably 1.5 to 6% by weight.
　またアクリル系樹脂の含有量を決定する際は、併用する塩化ビニル－酢酸ビニル共重合体樹脂の含有量も考慮するのが良い。両者を併用する場合、塩化ビニル－酢酸ビニル共重合体樹脂の含有量に対するアクリル系樹脂の含有量の比は、０．０１～１．２５であることが好ましく、０．０１～１であることがより好ましく、０．０３～０．８であることが更により好ましく、０．０５～０．６であることが特に好ましい。上記範囲に収めることで、連続吐出安定性、印刷物の耐擦性、光沢を高いレベルで満足することが可能となる。 Also, when determining the content of the acrylic resin, the content of the vinyl chloride-vinyl acetate copolymer resin used in combination should be taken into consideration. When both are used in combination, the ratio of the acrylic resin content to the vinyl chloride-vinyl acetate copolymer resin content is preferably 0.01 to 1.25, preferably 0.01 to 1. Is more preferable, 0.03 to 0.8 is even more preferable, and 0.05 to 0.6 is particularly preferable. By being in the above range, it becomes possible to satisfy the continuous discharge stability, the abrasion resistance of the printed matter, and the gloss at a high level.
　好適に用いられるアクリル系樹脂の具体例としては、
　三菱レイヨン社製のダイヤナール（登録商標）ＢＲ－５０、ＢＲ－５２、ＭＢ－２５３９、ＢＲ－６０、ＢＲ－６４、ＢＲ－７３、ＢＲ－７５、ＭＢ－２３８９、ＢＲ－８０、ＢＲ－８２、ＢＲ－８３、ＢＲ－８４、ＢＲ－８５、ＢＲ－８７、ＢＲ－８８、ＢＲ－９０、ＢＲ－９５、ＢＲ－９６、ＢＲ－１００、ＢＲ－１０１、ＢＲ－１０２、ＢＲ－１０５、ＢＲ－１０６、ＢＲ－１０７、ＢＲ－１０８、ＢＲ－１１０、ＢＲ－１１３、ＭＢ－２６６０、ＭＢ－２９５２、ＭＢ－３０１２、ＭＢ－３０１５、ＭＢ－７０３３、ＢＲ－１１５、ＭＢ－２４７８、ＢＲ－１１６、ＢＲ－１１７、ＢＲ－１１８、ＢＲ－１２２、ＥＲ－５０２；
　ダウ・ケミカル社製のパラロイド（登録商標）Ａ－１１、Ａ－１２、Ａ－１４、Ａ－２１、Ｂ－３８、Ｂ－６０、Ｂ－６４、Ｂ－６６、Ｂ－７２、Ｂ－８２、Ｂ－４４、Ｂ－４８Ｎ、Ｂ－６７、Ｂ－９９Ｎ、ＤＭ－５５；
　ＢＡＳＦ社製のＪＯＮＣＲＹＬ（登録商標）６７、６７８、５８６、６１１、６８０、６８２、６８３、６９０、８１９、ＪＤＸ－Ｃ３０００、ＪＤＸＣ３０８０などが挙げられるが、これらに限定されない。 As a specific example of the acrylic resin suitably used,
Mitsubishi Rayon Co., Ltd. Dianal (registered trademark) BR-50, BR-52, MB-2539, BR-60, BR-64, BR-73, BR-75, MB-2389, BR-80, BR-82 , BR-83, BR-84, BR-85, BR-87, BR-88, BR-90, BR-95, BR-96, BR-100, BR-101, BR-102, BR-105, BR -106, BR-107, BR-108, BR-110, BR-113, MB-2660, MB-2952, MB-3012, MB-3015, MB-7033, BR-115, MB-2478, BR-116 , BR-117, BR-118, BR-122, ER-502;
Paraloid (registered trademark) A-11, A-12, A-14, A-21, B-38, B-60, B-64, B-66, B-72, B-82 manufactured by Dow Chemical , B-44, B-48N, B-67, B-99N, DM-55;
Examples include, but are not limited to, JONCRYL (registered trademark) 67, 678, 586, 611, 680, 682, 683, 690, 819, JDX-C3000, and JDXC3080 manufactured by BASF.
　〔有機溶剤〕
　本発明の非水性インクジェットインキに含まれる有機溶剤は、下記一般式（ａ）～一般式（ｄ）で表される溶剤のいずれか１つ以上を含むことが好ましい：
　　　　Ｒ１ＣＯ（ＯＲ２）ＺＯＲ３　　　（ａ）
　　　　Ｒ４ＣＯ（ＯＲ５）ＺＯＣＯＲ６　（ｂ）
　　　　Ｒ７（ＯＲ８）ＺＯＲ９　　　　　（ｃ）
　　　　Ｒ１０ＣＯＯＲ１１　　　　　　　（ｄ）。 〔Organic solvent〕
The organic solvent contained in the non-aqueous inkjet ink of the present invention preferably contains any one or more of the solvents represented by the following general formulas (a) to (d):
R 1 CO (OR 2 ) Z OR 3 (a)
R 4 CO (OR 5 ) Z OCOR 6 (b)
R 7 (OR 8 ) Z OR 9 (c)
R 10 COOR 11 (d).
　上記式中、Ｒ２、Ｒ５、Ｒ８はそれぞれ独立してエチレン基、プロピレン基、ブチレン基から選択されるいずれかであり、Ｒ１、Ｒ３、Ｒ４、Ｒ６はそれぞれ独立して炭素数１～４のアルキル基であり、Ｒ７、Ｒ９はそれぞれ独立して水素原子又は炭素数１～４のアルキル基であり、Ｒ１０は２－ヒドロキシエチル基であり、Ｒ１１は炭素数１～８のアルキル基であり、Ｚは１～３の整数を表す。 In the above formula, R 2 , R 5 and R 8 are each independently selected from an ethylene group, a propylene group and a butylene group, and R 1 , R 3 , R 4 and R 6 are each independently selected. An alkyl group having 1 to 4 carbon atoms, R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 10 is a 2-hydroxyethyl group, and R 11 is a carbon atom. An alkyl group of 1 to 8; Z represents an integer of 1 to 3;
　上記の中でも、インキの保存安定性、印刷時のミストの低減が可能である点から、上記（ａ）及び／または（ｃ）で表される有機溶剤を含むことが好ましく、少なくとも（ａ）で表される有機溶剤を含むことが特に好ましい。 Among the above, it is preferable that the organic solvent represented by the above (a) and / or (c) is included, and at least (a) from the viewpoint that the storage stability of ink and the reduction of mist during printing are possible. It is particularly preferred that the organic solvent represented is included.
　また、本発明の非水性インクジェットインキに含まれる有機溶剤としては、沸点が１５０～２００℃である有機溶媒を選択し、かつ、その含有量を、非水性インクジェットインキ全重量を基準として５０～９８重量％とすることが、印刷速度向上の観点から好ましい。 Further, as the organic solvent contained in the non-aqueous inkjet ink of the present invention, an organic solvent having a boiling point of 150 to 200 ° C. is selected, and the content thereof is 50 to 98 on the basis of the total weight of the non-aqueous inkjet ink. The weight percent is preferable from the viewpoint of improving the printing speed.
　本発明において好適に用いられ得る、沸点が１５０～２００℃であり上記式（ａ）及び／または（ｃ）で表される有機溶剤として、３－メトキシブタノール（沸点１５８℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、３－メチルメトキシブタノール（沸点１７４℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、ジエチレングリコールジエチルエーテル（沸点１８９℃）、ジエチレングリコールメチルイソプロピルエーテル（沸点１７９℃）、ジプロピレングリコールジメチルエーテル（沸点１７１℃）、エチレングリコールモノブチルエーテルアセテート（沸点１９２℃）、３－メトキシブチルアセテート（沸点１７１℃）、３－メチル－３－メトキシブチルアセテート（沸点１８８℃）等が挙げられるが、これらに限定されない。中でもインキの保存安定性の観点から、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジメチルエーテル、エチレングリコールモノブチルエーテルアセテートを使用することが好ましく、エチレングリコールモノブチルエーテルアセテートを使用することがより好ましい。 As an organic solvent having a boiling point of 150 to 200 ° C. and having the above formula (a) and / or (c) that can be suitably used in the present invention, 3-methoxybutanol (boiling point 158 ° C.), diethylene glycol dimethyl ether (boiling point) 162 ° C), 3-methylmethoxybutanol (boiling point 174 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol methyl isopropyl ether (boiling point 179 ° C), dipropylene glycol dimethyl ether (boiling point) 171 ° C.), ethylene glycol monobutyl ether acetate (boiling point 192 ° C.), 3-methoxybutyl acetate (boiling point 171 ° C.), 3-methyl-3-methoxybutyl acetate (boiling point 188 ° C.), etc. It is, but is not limited thereto. Among these, from the viewpoint of storage stability of the ink, it is preferable to use diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, or ethylene glycol monobutyl ether acetate, and it is more preferable to use ethylene glycol monobutyl ether acetate.
　また、上記沸点が１５０～２００℃であり上記式（ａ）及び／または（ｃ）で表される有機溶剤以外の、上記式（ａ）～（ｄ）で表される有機溶剤を例示すると、ジエチレングリコールメチルブチルエーテル（沸点２１２℃）、ジエチルグリコールジブチルエーテル（沸点２５６℃）、トリエチレングリコールメチルブチルエーテル（沸点２６１℃）、テトラエチレングリコールジメチルエーテル（沸点２７５℃）、ジエチレングリコールエチルエーテルアセテート（沸点２１７℃）、ジエチレングリコールブチルエーテルアセテート（沸点２４５℃）、プロピレングリコールメチルエーテルアセテート（沸点１４６℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、ジエチレングリコールモノブチルエーテル（沸点２３０℃）、ジプロピレングリコールモノメチルエーテル（沸点１９０℃）、ジプロピレングリコールモノブチルエーテル（沸点２３０℃）、乳酸エチル（沸点１５４℃）、プロピレングリコールジアセテート（沸点１９０℃）等が挙げられる。 Examples of organic solvents represented by the above formulas (a) to (d) other than the organic solvent represented by the above formulas (a) and / or (c) having a boiling point of 150 to 200 ° C. Diethylene glycol methyl butyl ether (bp 212 ° C.), diethyl glycol dibutyl ether (bp 256 ° C.), triethylene glycol methyl butyl ether (bp 261 ° C.), tetraethylene glycol dimethyl ether (bp 275 ° C.), diethylene glycol ethyl ether acetate (bp 217 ° C.), Diethylene glycol butyl ether acetate (boiling point 245 ° C), propylene glycol methyl ether acetate (boiling point 146 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), diethylene glycol monobutyl ether ( Point 230 ° C.), dipropylene glycol monomethyl ether (boiling point 190 ° C.), dipropylene glycol monobutyl ether (boiling point 230 ° C.), ethyl lactate (boiling point 154 ° C.), propylene glycol diacetate (boiling point 190 ° C.), and the like.
　上記本発明の非水性インクジェットインキに含まれる有機溶剤は、非水性インクジェットインキ全重量を基準として５０～９８重量％含有することが好ましく、より好ましくは６０～９５重量％、更に好ましくは６５～９０重量％、更により好ましくは７０～８５重量％である。 The organic solvent contained in the non-aqueous inkjet ink of the present invention is preferably contained in an amount of 50 to 98% by weight, more preferably 60 to 95% by weight, still more preferably 65 to 90% based on the total weight of the non-aqueous inkjet ink. % By weight, still more preferably 70-85% by weight.
　本発明では、上記式（ａ）～（ｄ）で表される有機溶剤に加えて、更に含窒素系または含硫黄系またはラクトン系溶剤を併用することができる。これらの含窒素系または含硫黄系またはラクトン系溶剤はいずれも、炭素以外の元素を含む環状構造を有する溶剤であり、使用することで基材に対するインキの浸透性が増し、印刷時の乾燥性や印刷物の耐擦性、耐アルコール性が高まるため好ましい。本発明で使用できる含窒素系または含硫黄系またはラクトン系溶剤として、例えば、
　３－メチル－２－オキサゾリジノン、３－エチル－２－オキサゾリジノン等のオキサゾリジノン構造を有する溶剤；
　２－ピロリドン（γ－ブチロラクタム）、１－メチル－２－ピロリドン、１－エチル－２－ピロリドン、γ－バレロラクタム、γ－ヘキサラクタム、γ－ヘプタラクタム、γ－オクタラクタム、γ－ノナラクタム、γ－デカラクタム、γ－ウンデカラクタム、δ－バレロラクタム、δ－ヘキサラクタム、δ－ヘプタラクタム、δ－オクタラクタム、δ－ノナラクタム、δ－デカラクタム、δ－ウンデカラクタム、及びε－カプロラクタム等のラクタム構造を有する溶剤；
　γ－ブチロラクトン、γ－バレロラクトン、γ－カプロラクトン、γ－カプリロラクトン、γ－ラウロラクトン、γ－ラクトン、γ－ヘキサラクトン、γ－ヘプタラクトン、γ－オクタラクトン、γ－ノナラクトン、γ－デカラクトン、γ－ウンデカラクトン、δ－バレロラクトン、δ－ヘキサラクトン、δ－ヘプタラクトン、δ－オクタラクトン、δ－ノナラクトン、δ－デカラクトン、δ－ウンデカラクトン、ε－カプロラクトン、及びε－ラクトン等のラクトン構造を有する溶剤；
　エチレンカーボネート、プロピレンカーボネート、及び１，２－ブチレンカーボネート等の含酸素系溶剤等が挙げられるが、これらに限定されない。 In the present invention, in addition to the organic solvents represented by the above formulas (a) to (d), a nitrogen-containing, sulfur-containing or lactone solvent can be used in combination. These nitrogen-containing, sulfur-containing or lactone solvents are all solvents having a cyclic structure containing an element other than carbon, and the use of the ink increases the permeability of the ink to the substrate, and the drying property during printing. And the printed material is preferable because the abrasion resistance and alcohol resistance of the printed matter are increased. Examples of nitrogen-containing, sulfur-containing, or lactone solvents that can be used in the present invention include:
A solvent having an oxazolidinone structure such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone;
2-pyrrolidone (γ-butyrolactam), 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, γ-valerolactam, γ-hexalactam, γ-heptalactam, γ-octalactam, γ-nonalactam, γ -Lactams such as decaractam, γ-undecalactam, δ-valerolactam, δ-hexalactam, δ-heptalactam, δ-octalactam, δ-nonalactam, δ-decalactam, δ-undecalactam, and ε-caprolactam A solvent having a structure;
γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone, γ-laurolactone, γ-lactone, γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone , Γ-undecalactone, δ-valerolactone, δ-hexalactone, δ-heptalactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, ε-caprolactone, ε-lactone, etc. A solvent having the following lactone structure:
Examples include, but are not limited to, oxygen-containing solvents such as ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate.
　中でも、基材へのインキの浸透性や印刷時の乾燥性の点から、本発明に用いられる含窒素系または含硫黄系またはラクトン系溶剤として、３－メチル－２－オキサゾリジノン（沸点２６６℃）、２－ピロリドン（γ－ブチロラクタム）（沸点２４５℃）、１－メチル－２－ピロリドン（沸点２０２℃）、ε－カプロラクタム（沸点２６７℃）、γ－ブチロラクトン（沸点２０４℃）、γ－バレロラクトン（沸点２３０℃）、及びε－カプロラクトン（沸点２３７℃）、プロピレンカーボネート（沸点２４０℃）等が好ましく、３－メチル－２－オキサゾリジノン（沸点２６６℃）、γ－ブチロラクトン（沸点２０４℃）、及びε－カプロラクトン（沸点２３７℃）がより好ましく選択される。 Among them, 3-methyl-2-oxazolidinone (boiling point 266 ° C.) is used as a nitrogen-containing, sulfur-containing or lactone solvent used in the present invention from the viewpoint of ink permeability to the substrate and drying property at the time of printing. 2-pyrrolidone (γ-butyrolactam) (boiling point 245 ° C.), 1-methyl-2-pyrrolidone (boiling point 202 ° C.), ε-caprolactam (boiling point 267 ° C.), γ-butyrolactone (boiling point 204 ° C.), γ-valerolactone (Boiling point 230 ° C.), and ε-caprolactone (boiling point 237 ° C.), propylene carbonate (boiling point 240 ° C.), etc. are preferred, 3-methyl-2-oxazolidinone (boiling point 266 ° C.), γ-butyrolactone (boiling point 204 ° C.), and ε-caprolactone (boiling point 237 ° C.) is more preferably selected.
　含窒素系または含硫黄系またはラクトン系溶剤を使用する場合、その沸点は２００℃～３００℃であることが好ましい。含窒素系または含硫黄系またはラクトン系溶剤の沸点を前記範囲とすることで、基材への浸透性と、溶剤の揮発性のバランスを取ることができ、印刷時の乾燥性が高く、印刷物の耐性に優れた非水性インクジェットインキを得ることができる。また、含窒素系または含硫黄系またはラクトン系溶剤の沸点をインキの構成成分中最も高くすることが好ましい。インキ乾燥時、溶解性の高い含窒素系または含硫黄系またはラクトン系溶剤が最後まで残留し、インクジェットヘッドにおいて非水性インクジェットインキ中の不揮発成分の固化を防ぐことで、ノズル抜けを防止することができる。 When a nitrogen-containing, sulfur-containing or lactone solvent is used, the boiling point is preferably 200 ° C to 300 ° C. By setting the boiling point of the nitrogen-containing, sulfur-containing, or lactone solvent in the above range, it is possible to balance the permeability to the substrate and the volatility of the solvent, and the drying property at the time of printing is high. It is possible to obtain a non-aqueous inkjet ink having excellent resistance to water. In addition, it is preferable that the boiling point of the nitrogen-containing, sulfur-containing, or lactone solvent is the highest among the constituent components of the ink. When the ink is dried, highly soluble nitrogen-containing, sulfur-containing or lactone solvents remain until the end, preventing non-volatile components in the non-aqueous inkjet ink from solidifying in the inkjet head, thereby preventing nozzle omission. it can.
　含窒素系または含硫黄系またはラクトン系溶剤の配合量は、インクジェットインキ全重量を基準として１～２５重量％であることが好ましい。含窒素系または含硫黄系またはラクトン系溶剤の配合量がこの範囲であれば良好な乾燥性を示し、印刷物の耐性向上が見込めるため好ましい。含窒素系または含硫黄系またはラクトン系溶剤の配合量は、より好ましくは２～２０重量％、更に好ましくは４～１５重量％、更により好ましくは５～１３重量％である。 The blending amount of the nitrogen-containing, sulfur-containing or lactone solvent is preferably 1 to 25% by weight based on the total weight of the inkjet ink. If the blending amount of the nitrogen-containing, sulfur-containing or lactone solvent is within this range, it is preferable because good drying properties can be exhibited and resistance of printed matter can be improved. The blending amount of the nitrogen-containing, sulfur-containing or lactone solvent is more preferably 2 to 20% by weight, still more preferably 4 to 15% by weight, and still more preferably 5 to 13% by weight.
　本発明ではインキの粘度や吐出性の調整を目的として、上記に記載した以外の溶剤も併用することができる。具体的には、乳酸メチル（沸点１４４℃）、乳酸プロピル（沸点１７０℃）、乳酸ブチル（沸点１８９℃）、Ｎ，Ｎ－ジメチル－β－ブトキシプロピオンアミド（沸点２１６℃）、Ｎ，Ｎ－ジブチル－β－ブトキシプロピオンアミド（沸点２５２℃）等が挙げられるが、これらに限定されない。 In the present invention, solvents other than those described above can be used in combination for the purpose of adjusting the viscosity and dischargeability of the ink. Specifically, methyl lactate (boiling point 144 ° C.), propyl lactate (boiling point 170 ° C.), butyl lactate (boiling point 189 ° C.), N, N-dimethyl-β-butoxypropionamide (boiling point 216 ° C.), N, N— Examples thereof include, but are not limited to, dibutyl-β-butoxypropionamide (boiling point 252 ° C.).
　〔顔料〕
　本発明の非水性インクジェットインキに使用される顔料は、印刷用途及び塗料用途のインキに一般的に使用されるものの中から、発色性及び耐光性等の所望の用途に応じて適切に選択することができる。また、顔料は１種単独で用いてもよいし、２種以上混合して用いても良い。 [Pigment]
The pigment used in the non-aqueous inkjet ink of the present invention should be appropriately selected from those generally used for printing and paint applications according to desired applications such as color development and light resistance. Can do. Moreover, a pigment may be used individually by 1 type and may be used in mixture of 2 or more types.
　顔料としては、カーボンブラック、酸化チタン、炭酸カルシウム等の無彩色の顔料、及び／または有彩色の有機顔料が使用できる。 As the pigment, achromatic pigments such as carbon black, titanium oxide, calcium carbonate, and / or chromatic organic pigments can be used.
　本発明に好ましく用いられる有機顔料をカラーインデックス（Ｃ．Ｉ．）ナンバーで例示すると、Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１５、１６、１７、２０、２４、５５、７４、８３、８６、８７、９３、１０９、１１０、１１７、１２０、１２５、１２４、１２８、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１６６、１６８、１７０、１７１、１７２、１７４、１７６、１８０、１８５、１８８、Ｃ．Ｉ．ピグメントオレンジ１６、３６、４３、５１、５５、５９、６１、６４、Ｃ．Ｉ．ピグメントレッド９、４８、４９、５２、５３、５７、９７、１２２、１２３、１４６、１４７、１４９、１５０、１６８、１７７、１８０、１８５、１９２、２０２、２０６、２０７、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２３８、２４０、２４５、２６９、Ｃ．Ｉ．ピグメントバイオレット１９、２３、２９、３０、３７、４０、５０、Ｃ．Ｉ．ピグメントブルー１５、１５：１、１５：３、１５：４、１５：６、２２、６０、６４、Ｃ．Ｉ．ピグメントグリーン７、３６、Ｃ．Ｉ．ピグメントブラウン２３、２５、２６、Ｃ．Ｉ．ピグメントブラック１、６、７等が挙げられるが、これらに限定されない。 An example of an organic pigment preferably used in the present invention is a color index (CI) number. I. Pigment Yellow 12, 13, 14, 15, 16, 17, 20, 24, 55, 74, 83, 86, 87, 93, 109, 110, 117, 120, 125, 124, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 170, 171, 172, 174, 176, 180, 185, 188, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, 64, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 146, 147, 149, 150, 168, 177, 180, 185, 192, 202, 206, 207, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 245, 269, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, C.I. I. Examples thereof include, but are not limited to, pigment blacks 1, 6, and 7.
　これらの顔料のインキ中の含有量は、着色力、保存安定性、インクジェット粘度適性の点から、１～１５重量％が好ましく、１～８重量％がより好ましい。画像粒状感を低減するために淡色インクを用いる場合は、顔料の含有量を濃色インクの場合の１／１０～１／２とすることが好ましい。 The content of these pigments in the ink is preferably 1 to 15% by weight, and more preferably 1 to 8% by weight from the viewpoint of coloring power, storage stability, and ink jet viscosity suitability. When light color ink is used to reduce the image graininess, the pigment content is preferably 1/10 to 1/2 that of dark ink.
　非水性インクジェットインキ中の顔料の平均粒径（Ｄ５０）は、５０～３００ｎｍであることが好ましい。Ｄ５０が５０ｎｍ以上であれば、耐光性と着色力が得られ、３００ｎｍ以下であれば、インキ保存安定性や連続吐出安定性が安定になる。なお前記Ｄ５０は、例えば、非水性インクジェットインキを酢酸エチルで２００～１０００倍に希釈し、日機装社製　ＭＩＣＲＯＴＲＡＣ　ＵＰＡ１５０により測定することができる。またＤ５０は、メジアン径を指す。 The average particle diameter (D50) of the pigment in the non-aqueous inkjet ink is preferably 50 to 300 nm. If D50 is 50 nm or more, light resistance and coloring power can be obtained, and if it is 300 nm or less, ink storage stability and continuous ejection stability are stable. The D50 can be measured, for example, by diluting a non-aqueous inkjet ink 200 to 1000 times with ethyl acetate and using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd. D50 indicates the median diameter.
　〔顔料分散剤〕
　本発明では、顔料の分散性及びインキの保存安定性を向上させるために、顔料分散剤を使用することが好ましい。顔料分散剤としては、従来既知の化合物を使用することできる。連続吐出安定性やインキの保存安定性の点から、塩基性官能基を有する樹脂型分散剤が好ましい。 (Pigment dispersant)
In the present invention, it is preferable to use a pigment dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink. Conventionally known compounds can be used as the pigment dispersant. From the viewpoint of continuous discharge stability and ink storage stability, a resin-type dispersant having a basic functional group is preferred.
　顔料分散剤の市販例として、ルーブリゾール社製のソルスパース３２０００、７６４００、７６５００、Ｊ２００、及びＪ１８０等；
　ビックケミー社製のＤｉｓｐｅｒｂｙｋ－１６１、１６２、１６３、１６４、１６５、１６６、１６７、及び１６８等；
　味の素ファインテクノ社製のアジスパーＰＢ８２１、ＰＢ８２２等が挙げられるが、これらに限定されない。 Examples of commercially available pigment dispersants include Solsperse 32000, 76400, 76500, J200, and J180 manufactured by Lubrizol;
Disperbyk-161, 162, 163, 164, 165, 166, 167, and 168 manufactured by Big Chemie;
Ajinomoto Fine Techno Co., Ltd. Ajisper PB821, PB822 etc. are mentioned, but it is not limited to these.
　顔料分散剤の重量平均分子量（以下Ｍｗ）は、５，０００～２０，０００が好ましく、１０，０００～２０，０００がより好ましい。Ｍｗが５，０００以上であれば、インキに使用される有機溶剤中での顔料分散剤自体の安定性が良好のため顔料分散体の安定性が向上する。Ｍｗが２０，０００以下であれば、バインダー樹脂との相溶性が良好となりインキ塗膜の白化現象が抑制され、発色性が良好になる。 The weight average molecular weight (hereinafter referred to as Mw) of the pigment dispersant is preferably 5,000 to 20,000, more preferably 10,000 to 20,000. When Mw is 5,000 or more, the stability of the pigment dispersion is improved because the stability of the pigment dispersant itself in the organic solvent used in the ink is good. If Mw is 20,000 or less, the compatibility with the binder resin is good, the whitening phenomenon of the ink coating is suppressed, and the color developability is good.
　更に、顔料分散剤は、ＧＰＣにより求めた数平均分子量（以下Ｍｎ）に対する重量平均分子量（Ｍｗ）の比（Ｍｗ／Ｍｎ）が１～２．５であることが好ましく、Ｍｗ／Ｍｎが１～２であることがより好ましく、１～１．８が特に好ましい。Ｍｗ／Ｍｎを２．５以下とすることにより、顔料の粒径のばらつきの少ない顔料分散体を得ることができ、顔料分散体の低粘度化と保存安定性の両立が可能となる。 Further, the pigment dispersant preferably has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (hereinafter referred to as Mn) determined by GPC of 1 to 2.5, and the Mw / Mn is 1 to 2.5. 2 is more preferable, and 1 to 1.8 is particularly preferable. By setting Mw / Mn to 2.5 or less, it is possible to obtain a pigment dispersion with little variation in the particle size of the pigment, and it is possible to achieve both low viscosity and storage stability of the pigment dispersion.
　なお上記ＭｗやＭｎは、一般的なゲルパーミエーションクロマトグラフィー（ＧＰＣ）によりスチレン換算分子量として求めることができる。例えば、ＴＳＫｇｅｌカラム（東ソー社製）を用い、ＲＩ検出器を装備したＧＰＣ（東ソー社製、ＨＬＣ－８３２０ＧＰＣ）で、展開溶媒にＤＭＦを用いたときのポリスチレン換算分子量で示すことができる。 The above Mw and Mn can be determined as styrene equivalent molecular weight by general gel permeation chromatography (GPC). For example, the molecular weight can be expressed in terms of polystyrene when using TSKgel column (manufactured by Tosoh Corporation) and GPC (HLC-8320 GPC, manufactured by Tosoh Corporation) equipped with an RI detector and using DMF as a developing solvent.
　本発明で好適に用いられる顔料分散剤の酸価（ｍｇＫＯＨ／ｇ）は５～２０が好ましく、５～１５がより好ましい。またアミン価（ｍｇＫＯＨ／ｇ）は５～５０が好ましく、２０～４５がより好ましく、２０～４０がより好ましく、２５～４０が特に好ましい。顔料分散剤の酸価、アミン価が上記の範囲内である場合、顔料分散工程において、顔料分散体の粘度がインクジェットインキに相応しい程度の低粘度になるまでの時間が短くなり、更に、インキの保存安定性が良好になるため好ましい。なお上記酸価は、アクリル樹脂の場合と同様にして求めることができる。また「アミン価」は、分散剤固形分１ｇあたりのアミン価を表し、０．１Ｎの塩酸水溶液を用い、電位差滴定法によって求めた後、水酸化カリウムの当量に換算した値をいう。 The acid value (mgKOH / g) of the pigment dispersant suitably used in the present invention is preferably from 5 to 20, and more preferably from 5 to 15. The amine value (mgKOH / g) is preferably 5 to 50, more preferably 20 to 45, more preferably 20 to 40, and particularly preferably 25 to 40. When the acid value and amine value of the pigment dispersant are within the above ranges, in the pigment dispersion step, the time until the viscosity of the pigment dispersion becomes low enough to be suitable for an inkjet ink is shortened. It is preferable because storage stability is improved. In addition, the said acid value can be calculated | required similarly to the case of an acrylic resin. The “amine value” represents an amine value per 1 g of the solid content of the dispersant, and is a value converted to an equivalent of potassium hydroxide after being determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution.
　〔顔料誘導体〕
　本発明のインキには、顔料誘導体も使用することができる。顔料誘導体は、分散剤と顔料との吸着性を強固にし、保存安定性を良化させる目的で使用される。顔料誘導体としては、有機顔料残基に、スルホン酸基やカルボキシル基等の酸性基を有する化合物が好ましく使用される。 [Pigment derivative]
A pigment derivative can also be used in the ink of the present invention. The pigment derivative is used for the purpose of enhancing the adsorptivity between the dispersant and the pigment and improving the storage stability. As the pigment derivative, a compound having an acidic group such as a sulfonic acid group or a carboxyl group in the organic pigment residue is preferably used.
　顔料誘導体の含有量は、顔料に対して０．１重量％以上２０重量％以下が好ましく、１重量％以上１５重量％以下が特に好ましい。顔料誘導体の含有量が０．１重量％以上であれば、安定性、発色性が良好になり、２０％重量以下であれば、インキの粘度が好適な範囲で仕上がり、保存安定性が良好となるため、好ましい。 The content of the pigment derivative is preferably from 0.1% by weight to 20% by weight, particularly preferably from 1% by weight to 15% by weight, based on the pigment. If the content of the pigment derivative is 0.1% by weight or more, the stability and color developability will be good, and if it is 20% by weight or less, the viscosity of the ink will be finished in a suitable range, and the storage stability will be good. Therefore, it is preferable.
　〔添加剤〕
　本発明のインキは、印刷適性や印刷物耐性を高めるため、表面調整剤、スリップ剤、可塑剤、紫外線防止剤、光安定化剤、酸化防止剤、加水分解防止剤、防錆剤等の種々の添加剤を使用することができる。 〔Additive〕
The ink of the present invention has various surface modifiers, slip agents, plasticizers, UV inhibitors, light stabilizers, antioxidants, hydrolysis inhibitors, rust inhibitors, etc., in order to enhance printability and printed matter resistance. Additives can be used.
　表面調整剤としては、シリコン系、フッ素系、アクリル系、アセチレングリコール系が挙げられ、中でもシリコン系が好ましい。またシリコン系の表面調整剤の中でも、ジメチルポリシロキサンのメチル基の一部に有機基を導入した変性ポリシロキサン化合物であることが好ましい。変性の例として、ポリエーテル変性、メチルスチレン変性、アルコール変性、アルキル変性、アラルキル変性、脂肪酸エステル変性、エポキシ変性、アミン変性、アミノ変性、メルカプト変性などが挙げられ、ポリエーテル変性、アラルキル変性であることが、連続吐出安定性等の点で好ましく、アラルキル変性であることが、連続吐出安定性や、インキの乾燥性の点で特に好ましい。 Examples of the surface conditioner include silicon-based, fluorine-based, acrylic-based, and acetylene glycol-based, among which silicon-based is preferable. Among silicon-based surface conditioners, a modified polysiloxane compound in which an organic group is introduced into part of the methyl group of dimethylpolysiloxane is preferable. Examples of modification include polyether modification, methylstyrene modification, alcohol modification, alkyl modification, aralkyl modification, fatty acid ester modification, epoxy modification, amine modification, amino modification, mercapto modification, etc., and are polyether modification and aralkyl modification. It is preferable in terms of continuous discharge stability and the like, and aralkyl modification is particularly preferable in terms of continuous discharge stability and ink drying properties.
　ポリエーテル変性ポリシロキサン化合物の例として、例えば、信越化学工業株式会社製のＫＦ－３５３Ａ、ＫＦ－３５４Ｌ、ＫＦ６０１７、Ｘ－２２－６５５１、ＡＷ－３、日信化学工業株式会社製のＳＡＧ００１、ＳＡＧ００２、ＳＡＧ００３、ＳＡＧ００５、ＳＡＧ５０３Ａ、ＳＡＧ００８、ＳＡＧ０１０、東レ・ダウコーニング株式会社製の８０１９ＡＤＤＩＴＩＶＥ、８０２９ＡＤＤＩＴＩＶＥ、８０３２ＡＤＤＩＴＩＶＥ、８０５４ＡＤＤＩＴＩＶＥ、８５２６ＡＤＤＩＴＩＶＥ、８６１６ＡＤＤＩＴＩＶＥ、５７ＡＤＤＩＴＩＶＥ、６７ＡＤＤＩＴＩＶＥ、Ｌ７００１、Ｌ７００２、Ｌ７６０４、ＦＺ２１０５、ＦＺ２１１０、ＦＺ２１２３、ＦＺ２１９１、ビックケミー・ジャパン株式会社製のＢＹＫ－３００、３０２、３０６、３０７、３３０、３７７、エボニックデグサ社製のＴＥＧＯ　Ｇｌｉｄｅ　１００，１１０、１３０、４０６、４１０、４１５、４２０、４３２、４３５、４４０、４５０；
が挙げられるが、これらに限定されない。 Examples of polyether-modified polysiloxane compounds include, for example, KF-353A, KF-354L, KF6017, X-22-6551, AW-3 manufactured by Shin-Etsu Chemical Co., Ltd., SAG001, SAG002 manufactured by Nissin Chemical Industry Co., Ltd. , SAG003, SAG005, SAG503A, SAG008, SAG010, 8019ADDITIVE, 8029ADDITIVE, 8054ADDITIVE, 8526ADDIZIVE, 8616DIDIVITE, 57ADDITL, FAD -BYK-300, 302, 30 manufactured by Japan , 307,330,377, TEGO made of Evonik Degussa Glide 100,110,130,406,410,415,420,432,435,440,450;
However, it is not limited to these.
　またアラルキル変性ポリシロキサン化合物の例として、例えば、ビックケミー・ジャパン株式会社製のＢＹＫ－３２２、３２３、信越化学工業（株）社製のＫＦ－４１０、東レダウコーニング（株）製のＳＭ　７００１ＥＸ、ＳＭ　７００２ＥＸ等が挙げられるが、これらに限定されない。 Examples of aralkyl-modified polysiloxane compounds include BYK-322 and 323 manufactured by Big Chemie Japan Co., Ltd., KF-410 manufactured by Shin-Etsu Chemical Co., Ltd., SM 7001EX and SM manufactured by Toray Dow Corning Co., Ltd. 7002EX etc. are mentioned, but it is not limited to these.
　上記のとおり、これらの材料の中でも、アラルキル変性ポリシロキサン化合物であるＢＹＫ－３２２、３２３が特に好ましく用いられる。 As described above, among these materials, BYK-322 and 323 which are aralkyl-modified polysiloxane compounds are particularly preferably used.
　表面調整剤の含有量は、非水性インクジェットインキ全重量を基準として、０～２重量％であることが好ましく、０．００１～１質量％であることが好ましく、０．０１～０．５重量％であることが更に好ましい。 The content of the surface conditioning agent is preferably 0 to 2% by weight, preferably 0.001 to 1% by weight, based on the total weight of the non-aqueous inkjet ink, and 0.01 to 0.5% by weight. % Is more preferable.
　〔記録媒体〕
　本発明で用いられる記録媒体については特に限定はなく、軟質ＰＶＣ、硬質ＰＶＣ、ポリスチレン、発泡スチロール、ＰＭＭＡ、ポリプロピレン、ポリエチレン、ＰＥＴ、ポリカーボネート等のプラスチック基材やこれらの混合品または変性品、上質紙、アート紙、コート紙、キャストコート紙等の紙基材、ガラス、ステンレス等の金属基材等が挙げられるが、これらに限定されない。中でも、価格や加工性の点から、上記の通り、非吸収性基材である軟質ＰＶＣや硬質ＰＶＣが好ましく用いられる。 〔recoding media〕
The recording medium used in the present invention is not particularly limited, and a plastic substrate such as soft PVC, hard PVC, polystyrene, polystyrene foam, PMMA, polypropylene, polyethylene, PET, polycarbonate, or a mixed or modified product thereof, fine paper, Examples include, but are not limited to, paper substrates such as art paper, coated paper, and cast coated paper, and metal substrates such as glass and stainless steel. Among these, from the viewpoint of price and workability, as described above, soft PVC and hard PVC which are non-absorbent substrates are preferably used.
　〔インキの製造方法〕
　本発明のインキは既知の方法によって製造することができる。具体的に例示すると、まず初めに、単一有機溶剤もしくは混合した有機溶剤、顔料、及び、配合する場合にはバインダー樹脂、分散剤等を混合した後、ペイントシェーカー、サンドミル、ロールミル、メディアレス分散機等によって顔料を分散することで顔料分散体を調製する。得られた顔料分散体に対し、所望のインキ特性を有するように、有機溶剤の残部、バインダー樹脂の残部、その他添加剤（たとえば表面調整剤）を添加し、前記バインダー樹脂を溶解させたのち、フィルター等により粗大粒子を除去することで得ることができる。 [Ink production method]
The ink of the present invention can be produced by a known method. Specifically, first, after mixing a single organic solvent or a mixed organic solvent, a pigment, and a binder resin, a dispersant, etc. when blended, a paint shaker, a sand mill, a roll mill, a medialess dispersion A pigment dispersion is prepared by dispersing the pigment by a machine or the like. To the obtained pigment dispersion, the remainder of the organic solvent, the remainder of the binder resin, and other additives (for example, a surface conditioner) are added so as to have desired ink properties, and after the binder resin is dissolved, It can be obtained by removing coarse particles with a filter or the like.
　〔インクジェットインキの物性〕
　本発明の非水性インクジェットインキは、インクジェットヘッドからの吐出性、着弾後のドット形成の信頼性とのバランスの観点から、２５℃における表面張力が２０ｍＮ／ｍ以上５０ｍＮ／ｍ以下であることが好ましく、２５ｍＮ／ｍ以上４０ｍＮ／ｍ以下であることがより好ましい。同様の観点から、２５℃における粘度は、２ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下が好ましく、５ｍＰａ・ｓ以上１５ｍＰａ・ｓ以下がより好ましい。 [Physical properties of inkjet ink]
The non-aqueous inkjet ink of the present invention preferably has a surface tension at 25 ° C. of 20 mN / m or more and 50 mN / m or less from the viewpoint of the balance between the ejectability from the inkjet head and the reliability of dot formation after landing. 25 mN / m or more and 40 mN / m or less is more preferable. From the same viewpoint, the viscosity at 25 ° C. is preferably 2 mPa · s or more and 20 mPa · s or less, and more preferably 5 mPa · s or more and 15 mPa · s or less.
　なお、表面張力の測定は、協和界面科学社製　自動表面張力計ＣＢＶＰ－Ｚを用いて、２５℃の環境下で白金プレートをインキで濡らしたときの表面張力を確認することにより測定することができる。粘度の測定は、東機産業社製　ＴＶＥ２５Ｌ型粘度計を用いて、２５℃環境下で、５０ｒｐｍ時の粘度を読み取ることにより測定することができる。 The surface tension can be measured by using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. and confirming the surface tension when the platinum plate is wetted with ink in an environment of 25 ° C. it can. The viscosity can be measured by reading the viscosity at 50 rpm in a 25 ° C. environment using a TVE25L viscometer manufactured by Toki Sangyo Co., Ltd.
　以下、実施例及び比較例により本発明を具体的に説明するが、本発明は実施例に特に限定されるものではない。なお、以下の記載において、「部」及び「％」とあるものは特に断らない限りそれぞれ「重量部」、「重量％」を表す。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not particularly limited to the examples. In the following description, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
　〔塩化ビニル－酢酸ビニル共重合体樹脂Ａの製造〕
　撹拌機、温度計、窒素ガス導入口を備えた耐圧容器内を窒素置換したのち、脱イオン水７５０部、酢酸ビニル２９０部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム２０部、連鎖移動剤としてポリオキシエチレンノニルフェニルエーテル２０部を添加した。続いて容器内部を減圧にして塩化ビニル７００部を添加したのち、撹拌しながら６０℃に昇温させた。重合開始剤として過硫酸アンモニウム５部を脱イオン水１００部に溶解させた溶液を滴下し、容器内部の温度を６０～７０℃に保持しながら２０時間反応を行ったのち、３０℃まで冷却することで重合を終了させた。前記反応溶液に、１Ｍ塩化ナトリウム水溶液１８００部を少しずつ添加し、得られた沈殿物を濾別した後、脱イオン水による洗浄を３回繰返すことで、塩化ビニル－酢酸ビニル共重合体樹脂Ａを得た。 [Production of vinyl chloride-vinyl acetate copolymer resin A]
After replacing the inside of the pressure vessel equipped with a stirrer, thermometer and nitrogen gas inlet with nitrogen, 750 parts of deionized water, 290 parts of vinyl acetate, 20 parts of sodium dodecylbenzenesulfonate as an emulsifier, polyoxyethylene as a chain transfer agent 20 parts of nonylphenyl ether was added. Subsequently, after the inside of the container was depressurized and 700 parts of vinyl chloride was added, the temperature was raised to 60 ° C. while stirring. A solution prepared by dissolving 5 parts of ammonium persulfate in 100 parts of deionized water as a polymerization initiator is dropped, and the reaction is carried out for 20 hours while maintaining the temperature inside the container at 60 to 70 ° C, and then cooled to 30 ° C. The polymerization was terminated. To the reaction solution, 1800 parts of a 1M sodium chloride aqueous solution was added little by little, and the resulting precipitate was filtered off, and then washed with deionized water three times to give a vinyl chloride-vinyl acetate copolymer resin A. Got.
　〔塩化ビニル－酢酸ビニル共重合体樹脂Ｂ～Ｍの製造〕
　連鎖移動剤の量、塩化ビニルの量、及び酢酸ビニルの量を、下記表１に示したものに変える以外は、上記塩化ビニル－酢酸ビニル共重合体樹脂Ａと同様にして、塩化ビニル－酢酸ビニル共重合体樹脂Ｂ～Ｍを製造した。 [Production of vinyl chloride-vinyl acetate copolymer resins B to M]
Vinyl chloride-acetic acid is the same as vinyl chloride-vinyl acetate copolymer resin A except that the amount of chain transfer agent, the amount of vinyl chloride, and the amount of vinyl acetate are changed to those shown in Table 1 below. Vinyl copolymer resins B to M were produced.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお表１には、後述する実施例に用いた、ＶＩＮＮＯＬ　Ｅ１５／４５ＴＦ（ワッカーケミー社製乳化重合品）、及びソルバインＣＬ（日信化学工業製懸濁重合品）についても、そのスペックを記載した。表１において｜Ｍ｜は絶対分子量、｜Ｍｗ｜は重量平均絶対分子量、｜Ｍｎ｜は数平均絶対分子量である。 In Table 1, the specifications of VINNOL E15 / 45TF (emulsion polymerization product manufactured by Wacker Chemie) and Solvine CL (suspension polymerization product manufactured by Nissin Chemical Industry) used in Examples described later are also described. . In Table 1, | M | is the absolute molecular weight, | Mw | is the weight average absolute molecular weight, and | Mn | is the number average absolute molecular weight.
　〔顔料分散液の製造例〕
　顔料としてピグメントブルー１５：４を２０部、顔料分散樹脂としてソルスパースJ２００（重量平均分子量１５，０００、酸価１２ｍｇＫＯＨ／ｇ、アミン価２２ｍｇＫＯＨ／ｇ）を７部、エチレングリコールブチルエーテルアセテート７３部を混合し、ディスパーで予備分散した後、直径０．５ｍｍのジルコニアビーズ１８００ｇを充填した容積０．６Ｌのダイノーミルを用いて２時間本分散を行い、顔料分散液を得た。 [Production example of pigment dispersion]
20 parts of Pigment Blue 15: 4 as a pigment, 7 parts of Solsperse J200 (weight average molecular weight 15,000, acid value 12 mgKOH / g, amine value 22 mgKOH / g) as a pigment dispersion resin, and 73 parts of ethylene glycol butyl ether acetate are mixed. After preliminary dispersion with a disper, this dispersion was performed for 2 hours using a 0.6 L capacity dyno mill filled with 1800 g of zirconia beads having a diameter of 0.5 mm to obtain a pigment dispersion.
　〔実施例１〕
　表２の配合比になるように、顔料分散液を２０部、塩化ビニル－酢酸ビニル共重合体樹脂を５．４部、ＪＯＮＣＲＹＬ５８６（ＢＡＳＦ社製スチレン－アクリル共重合樹脂、重量平均絶対分子量４０００、ガラス転移点６０℃、酸価１０８ｍｇＫＯＨ／ｇ）を１．４部、ダイヤナールＢＲ－１１３（三菱レイヨン社製アクリル樹脂、重量平均絶対分子量３５０００、ガラス転移点７５℃、酸価３．５ｍｇＫＯＨ／ｇ）を０．３部、エチレングリコールモノブチルエーテルアセテート８０．０部、γ－ブチロラクトン７．５部をディスパーで撹拌を行いながら順次投入し、十分に均一になるまで攪拌した。その後、目開き１．０μｍのメンブランフィルターで濾過を行い、ヘッドつまりの原因となる粗大粒子を除去し本発明のインクジェットインキを作成した。 [Example 1]
20 parts of the pigment dispersion, 5.4 parts of vinyl chloride-vinyl acetate copolymer resin, JONCRYL586 (styrene-acrylic copolymer resin manufactured by BASF, weight average absolute molecular weight of 4000, 1.4 parts of glass transition point 60 ° C., acid value 108 mgKOH / g), Dianal BR-113 (Mitsubishi Rayon acrylic resin, weight average absolute molecular weight 35000, glass transition point 75 ° C., acid value 3.5 mg KOH / g) ), 80.0 parts of ethylene glycol monobutyl ether acetate, and 7.5 parts of γ-butyrolactone were sequentially added while stirring with a disper, and stirred until sufficiently uniform. Thereafter, filtration was carried out with a membrane filter having an opening of 1.0 μm to remove coarse particles that cause clogging of the head, and the ink-jet ink of the present invention was prepared.
　〔実施例２～１８〕
　下記表２の材料を用いる以外は、実施例１と同様にして、実施例２～１８の非水性インクジェットインキを作製した。 [Examples 2 to 18]
Nonaqueous inkjet inks of Examples 2 to 18 were produced in the same manner as Example 1 except that the materials shown in Table 2 below were used.
　〔比較例１～７〕
　下記表３の材料を用いる以外は、実施例１と同様にして、比較例１～７の非水性インクジェットインキを作製した。 [Comparative Examples 1 to 7]
Nonaqueous inkjet inks of Comparative Examples 1 to 7 were prepared in the same manner as in Example 1 except that the materials shown in Table 3 below were used.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　なお、表２中および表３中で使用した有機溶剤は以下の通りである：
・ＢＧＡｃ（エチレングリコールモノブチルエーテルアセテート、沸点１９２℃）
・ＤＥＤＧ（ジエチレングリコールジエチルエーテル、沸点１８９℃）
・乳酸エチル（沸点１５４℃）
・ＰＧＤＡ（プロピレングリコールジアセテート、沸点１９０℃）
・ＧＢＬ（γ－ブチロラクトン、沸点２０４℃）
・ＥＣＬ（ε－カプロラクトン、沸点２３７℃）。 The organic solvents used in Table 2 and Table 3 are as follows:
・ BGAc (ethylene glycol monobutyl ether acetate, boiling point 192 ° C.)
・ DEDG (diethylene glycol diethyl ether, boiling point 189 ° C)
・ Ethyl lactate (boiling point 154 ℃)
・ PGDA (propylene glycol diacetate, boiling point 190 ° C)
GBL (γ-butyrolactone, boiling point 204 ° C.)
ECL (ε-caprolactone, boiling point 237 ° C.).
　〔印刷評価〕
　得られたインクジェットインキを、ワイドフォーマットインクジェットプリンタ（セイコーアイ・インフォテック社製ＣｏｌｏｒＰａｉｎｔｅｒ６４Ｓ）に充填し、ポリ塩化ビニルシート（メタマーク社製ＭＤ－５）を印刷媒体として印刷評価を行った。 [Printing evaluation]
The obtained ink-jet ink was filled into a wide format ink-jet printer (ColorPainter 64S manufactured by Seiko I Infotech Co., Ltd.), and printing evaluation was performed using a polyvinyl chloride sheet (MD-5 manufactured by Metamark Co., Ltd.) as a printing medium.
　〔連続吐出安定性評価〕
　印刷媒体へ３０ｍ２／ｈの速度で、１０ｍ２ベタ印刷し、ノズルチェックパターンを印刷しノズル抜けの本数を確認した。評価基準は以下のとおりとし、Ｂ以上を良好とした：
Ａ：印刷後に０本のノズル抜け
Ｂ：印刷後に１本以上３本以下のノズル抜け
Ｃ：印刷後に４本以上７本以下のノズル抜け
Ｄ：印刷後に８本以上２０本以下のノズル抜け
Ｅ：印刷後に２０本超のノズル抜け。 [Continuous discharge stability evaluation]
A 10 m 2 solid was printed on the print medium at a speed of 30 m 2 / h, a nozzle check pattern was printed, and the number of missing nozzles was confirmed. The evaluation criteria are as follows, and B or better was considered good:
A: No nozzle missing after printing B: Nozzle missing from 1 to 3 after printing C: Nozzle missing from 4 to 7 after printing D: Nozzle missing from 8 to 20 after printing E: Nozzle missing from 8 to 20 after printing E: More than 20 nozzles are missing after printing.
　〔偏向評価〕
　印刷媒体へ３０ｍ２／ｈの速度で、１０ｍ２ベタ印刷し、ノズルチェックパターンを印刷し、インクジェットインキの液滴が所望の位置に着弾しているかを確認した。評価は、光学顕微鏡（キーエンス社製デジタルマイクロスコープＶＨＸ－５００、観察倍率：１００倍）または目視による観察により行った。評価基準は以下のとおりとし、Ｂ以上を良好とした：
Ａ：光学顕微鏡観察でもインクジェットインキの液滴のズレが見られない
Ｂ：目視ではインクジェットインキの液滴のズレが見られない
Ｃ：目視でもインクジェットインキの液滴のズレが見られる。 [Bias evaluation]
A 10 m 2 solid was printed on the print medium at a speed of 30 m 2 / h, a nozzle check pattern was printed, and it was confirmed whether the droplets of the inkjet ink had landed at a desired position. The evaluation was performed by optical microscope (Digital microscope VHX-500 manufactured by Keyence Corporation, observation magnification: 100 times) or visual observation. The evaluation criteria are as follows, and B or better was considered good:
A: No deviation of inkjet ink droplets is observed even by observation with an optical microscope. B: No deviation of inkjet ink droplets is observed visually. C: Inkjet ink droplet deviation is observed visually.
　〔耐アルコール性評価〕
　印刷媒体へ４ｍ２／ｈの速度で単色ベタ印刷を行った印刷物を、エタノール水溶液を浸した綿棒で擦ることにより、耐アルコール性の評価を行った。アルコール水溶液の濃度を変え、綿棒へのインキ塗膜の色移りを確認し、以下の基準にて評価を行い、Ｂ以上を良好とした：
Ａ：８０％エタノール溶液にて綿棒への色移りが生じない
Ｂ：６０％エタノール溶液にて綿棒への色移りが生じない
Ｃ：６０％エタノール溶液で綿棒への色移りが生じる。 [Evaluation of alcohol resistance]
Alcohol resistance was evaluated by rubbing a printed matter on which a single-color solid was printed on a printing medium at a speed of 4 m 2 / h with a cotton swab dipped in an aqueous ethanol solution. The concentration of the aqueous alcohol solution was changed, the color transfer of the ink coating to the cotton swab was confirmed, the evaluation was made according to the following criteria, and B or better was considered good:
A: No color transfer to cotton swabs with 80% ethanol solution B: No color transfer to cotton swabs with 60% ethanol solution C: Color transfer to cotton swabs with 60% ethanol solution.
　〔光沢評価〕
　印刷媒体へ４ｍ２／ｈの速度で印刷を行ったベタ印刷物について、光沢度計（ＢＹＫ社製マイクロトリグロス）を用いて６０°光沢度を測定した。評価基準は以下のとおりとし、Ｂ以上を良好とした：
Ａ：光沢度７０以上
Ｂ：光沢度５０以上～７０未満
Ｃ：光沢度３０以上～５０未満
Ｄ：光沢度３０未満。 [Gloss evaluation]
About the solid printed matter which printed on the printing medium at a speed | rate of 4 m < 2 > / h, 60 degree glossiness was measured using the glossiness meter (BYK Co., Ltd. micro trigloss). The evaluation criteria are as follows, and B or better was considered good:
A: Glossiness of 70 or more B: Glossiness of 50 or more and less than 70 C: Glossiness of 30 or more and less than 50 D: Glossiness of less than 30
　〔保存安定性評価〕
　作成したインキの粘度を、Ｅ型粘度計（東機産業社製ＴＶＥ－２０Ｌ）を用いて、２５℃において回転数５０ｒｐｍという条件で測定した。このインキを７０℃の恒温機に保存し、経時促進させた後、経時前後でのインキの粘度変化を評価した。評価基準は下記のとおりとし、Ｂ以上を良好とした：
Ａ：６週間保存後の粘度変化率が±１０％未満
Ｂ：６週間保存後の粘度変化率が±１０以上～２０％未満
Ｃ：６週間保存後の粘度変化率が±２０％以上。 [Evaluation of storage stability]
The viscosity of the prepared ink was measured using an E-type viscometer (TVE-20L, manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and a rotation speed of 50 rpm. This ink was stored in a thermostat at 70 ° C. and accelerated with time, and the change in the viscosity of the ink before and after aging was evaluated. The evaluation criteria are as follows, and B or better was considered good:
A: Viscosity change rate after storage for 6 weeks is less than ± 10% B: Viscosity change rate after storage for 6 weeks is ± 10% to less than 20% C: Viscosity change rate after storage for 6 weeks is ± 20% or more.
　〔評価結果〕
　以上の評価試験の結果について、上記表２および表３に記載した。 〔Evaluation results〕
The results of the above evaluation tests are shown in Table 2 and Table 3 above.
　表２および表３に記載の通り、バインダー樹脂として、重量平均絶対分子量（｜Ｍｗ｜）が２０，０００～４０，０００であり、かつ、前記重量平均絶対分子量（｜Ｍｗ｜）と数平均絶対分子量（｜Ｍｎ｜）の比（｜Ｍｗ｜／｜Ｍｎ｜）が１．３以上２．２以下である塩化ビニル－酢酸ビニル共重合体樹脂を用いたことにより、連続吐出安定性、偏向といった印刷適性に関する評価が良好であり、高い品質の印刷物を得ることができた。一方、比較例では印刷適性、印刷物の品質を満足するインキは得られなかった。 As shown in Tables 2 and 3, the binder resin has a weight average absolute molecular weight (| Mw |) of 20,000 to 40,000, and the weight average absolute molecular weight (| Mw |) and the number average absolute By using a vinyl chloride-vinyl acetate copolymer resin having a molecular weight (| Mn |) ratio (| Mw | / | Mn |) of 1.3 or more and 2.2 or less, continuous discharge stability, deflection, etc. The evaluation regarding printability was good, and high-quality printed matter could be obtained. On the other hand, in the comparative example, an ink satisfying printability and print quality could not be obtained.

Claims (5)

  1. 　有機溶剤、顔料、及び塩化ビニル－酢酸ビニル共重合体樹脂を含有する非水性インクジェットインキであって、
    　前記塩化ビニル－酢酸ビニル共重合体樹脂の重量平均絶対分子量（｜Ｍｗ｜）が２０，０００～４０，０００であり、かつ、前記重量平均絶対分子量（｜Ｍｗ｜）と数平均絶対分子量（｜Ｍｎ｜）との比（｜Ｍｗ｜／｜Ｍｎ｜）が１．３以上２．２以下であり、
    　前記塩化ビニル－酢酸ビニル共重合体樹脂が、塩化ビニル単量体及び酢酸ビニル単量体の乳化重合物であることを特徴とする、非水性インクジェットインキ。     A non-aqueous inkjet ink containing an organic solvent, a pigment, and a vinyl chloride-vinyl acetate copolymer resin,
    The vinyl chloride-vinyl acetate copolymer resin has a weight average absolute molecular weight (| Mw |) of 20,000 to 40,000, and the weight average absolute molecular weight (| Mw |) and the number average absolute molecular weight (| Mn |) ratio (| Mw | / | Mn |) is 1.3 or more and 2.2 or less,
    A non-aqueous inkjet ink, wherein the vinyl chloride-vinyl acetate copolymer resin is an emulsion polymer of a vinyl chloride monomer and a vinyl acetate monomer.
  2. 　前記塩化ビニル－酢酸ビニル共重合体樹脂が、絶対分子量（｜Ｍ｜）２００，０００以上の樹脂を含まないか、または前記塩化ビニル－酢酸ビニル共重合体樹脂全量中１０重量％以下で含有することを特徴とする、請求項１に記載の非水性インクジェットインキ。 The vinyl chloride-vinyl acetate copolymer resin does not contain a resin having an absolute molecular weight (| M |) of 200,000 or more, or is contained at 10% by weight or less in the total amount of the vinyl chloride-vinyl acetate copolymer resin. The non-aqueous inkjet ink according to claim 1, wherein
  3. 　前記有機溶剤が、一般式（ａ）～一般式（ｄ）で表される溶剤のいずれか１つ以上を含むことを特徴とする、請求項１または２に記載の非水性インクジェットインキ。
    　　　　Ｒ１ＣＯ（ＯＲ２）ＺＯＲ３　　　（ａ）
    　　　　Ｒ４ＣＯ（ＯＲ５）ＺＯＣＯＲ６　（ｂ）
    　　　　Ｒ７（ＯＲ８）ＺＯＲ９　　　　　（ｃ）
    　　　　Ｒ１０ＣＯＯＲ１１　　　　　　　（ｄ）
    　（式中、Ｒ２、Ｒ５、Ｒ８はそれぞれ独立して、エチレン基、プロピレン基、及び、ブチレン基から選択されるいずれかであり、
    　Ｒ１、Ｒ３、Ｒ４、Ｒ６はそれぞれ独立して炭素数１～４のアルキル基であり、
    　Ｒ７、Ｒ９はそれぞれ独立して水素原子又は炭素数１～４のアルキル基であり、
    　Ｒ１０は２－ヒドロキシエチル基であり、
    　Ｒ１１は炭素数１～８のアルキル基であり、
    　Ｚは１～３の整数を表す。）     The non-aqueous inkjet ink according to claim 1 or 2, wherein the organic solvent contains any one or more of the solvents represented by the general formulas (a) to (d).
    R 1 CO (OR 2 ) Z OR 3 (a)
    R 4 CO (OR 5 ) Z OCOR 6 (b)
    R 7 (OR 8 ) Z OR 9 (c)
    R 10 COOR 11 (d)
    (Wherein R 2 , R 5 , and R 8 are each independently selected from an ethylene group, a propylene group, and a butylene group,
    R 1 , R 3 , R 4 , and R 6 are each independently an alkyl group having 1 to 4 carbon atoms,
    R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
    R 10 is a 2-hydroxyethyl group,
    R 11 is an alkyl group having 1 to 8 carbon atoms,
    Z represents an integer of 1 to 3. )
  4. 　前記有機溶剤が、含窒素系または含硫黄系またはラクトン系溶剤を更に含有することを特徴とする、請求項１～３いずれかに記載の非水性インクジェットインキ。 The non-aqueous inkjet ink according to any one of claims 1 to 3, wherein the organic solvent further contains a nitrogen-containing, sulfur-containing, or lactone solvent.
  5. 　顔料分散剤を更に含むことを特徴とする、請求項１～４いずれかに記載の非水性インクジェットインキ。 The non-aqueous inkjet ink according to any one of claims 1 to 4, further comprising a pigment dispersant.
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