WO2018066539A1 - Encre non aqueuse pour jet d'encre - Google Patents

Encre non aqueuse pour jet d'encre 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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WIPO (PCT)
Prior art keywords
resin
vinyl chloride
molecular weight
vinyl acetate
inkjet ink
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PCT/JP2017/035925
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English (en)
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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Publication of WO2018066539A1 publication Critical patent/WO2018066539A1/fr

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

Abstract

L'invention fournir une encre non aqueuse pour jet d'encre dont les performances d'impression, telles que la stabilité de décharge en continu, ou similaire, sont excellentes, qui possède une stabilité de conservation satisfaisante, et simultanément permet d'obtenir un objet imprimé d'une brillance et d'une résistance excellentes, et qui est principalement adaptée à une impression sur un matériau de base en chlorure de vinyle. Selon un mode de réalisation de l'invention, l'encre non aqueuse pour jet d'encre comprend un solvant organique, un pigment, et une résine de copolymère chlorure de vinyle – acétate de vinyle. Cette encre non aqueuse pour jet d'encre est caractéristique en ce que la valeur absolue de la masse moléculaire moyenne en poids （｜Ｍｗ｜） de ladite résine de copolymère chlorure de vinyle – acétate de vinyle est comprise entre 20000 et 40000, et le rapport （｜Ｍｗ｜／｜Ｍｎ｜） entre ladite valeur absolue de la masse moléculaire moyenne en poids （｜Ｍｗ｜） et la valeur absolue de la masse moléculaire moyenne en nombre （｜Ｍｎ｜）, est supérieur ou égal à 1,3 et inférieur ou égal à 2,2. Enfin, ladite résine de copolymère chlorure de vinyle – acétate de vinyle consiste en un polymère en émulsion d'un monomère de chlorure de vinyle et d'un monomère d'acétate de vinyle.
PCT/JP2017/035925 2016-10-04 2017-10-03 Encre non aqueuse pour jet d'encre WO2018066539A1 (fr)

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JP2016196584A JP6233485B1 (ja) 2016-10-04 2016-10-04 非水性インクジェットインキ
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