WO2022071477A1 - 非水系インク組成物、それを用いた記録方法及び記録物の製造方法 - Google Patents

非水系インク組成物、それを用いた記録方法及び記録物の製造方法 Download PDF

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Publication number
WO2022071477A1
WO2022071477A1 PCT/JP2021/036069 JP2021036069W WO2022071477A1 WO 2022071477 A1 WO2022071477 A1 WO 2022071477A1 JP 2021036069 W JP2021036069 W JP 2021036069W WO 2022071477 A1 WO2022071477 A1 WO 2022071477A1
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WIPO (PCT)
Prior art keywords
ink composition
aqueous ink
organic solvent
solvent
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/036069
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English (en)
French (fr)
Japanese (ja)
Inventor
圭士郎 吉森
由佳 折笠
貴生 松本
公淳 宇高
充功 田村
満輝 山田
良平 岡
喜哉 前川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DNP Fine Chemicals Co Ltd
Original Assignee
DNP Fine Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DNP Fine Chemicals Co Ltd filed Critical DNP Fine Chemicals Co Ltd
Priority to AU2021355246A priority Critical patent/AU2021355246B2/en
Priority to EP21875773.0A priority patent/EP4223539A4/en
Priority to KR1020237010796A priority patent/KR20230058473A/ko
Priority to EP25215753.2A priority patent/EP4700094A2/en
Priority to US18/246,728 priority patent/US12338356B2/en
Priority to CN202180065779.3A priority patent/CN116323223A/zh
Priority to JP2022554090A priority patent/JPWO2022071477A1/ja
Publication of WO2022071477A1 publication Critical patent/WO2022071477A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/14—Printing inks based on carbohydrates

Definitions

  • the present invention relates to a non-aqueous ink composition, a recording method using the non-aqueous ink composition, and a method for producing a recorded material.
  • an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixed solution of water and an organic solvent, or a non-aqueous ink composition in which a coloring material is dissolved or dispersed in an organic solvent containing no water. Is widely used.
  • Patent Document 1 describes a non-aqueous ink composition containing a coloring material, a predetermined glycol ether, and a 5-membered ring lactone-based solvent. Patent Document 1 describes that this non-aqueous ink composition is suitable for printing on a substrate and is excellent in print quality, recording stability, recording drying property, ink storage stability and the like. ..
  • the non-aqueous ink composition described in Patent Document 1 preferably contains a binder resin, and by containing the binder resin, the viscosity of the non-aqueous ink composition can be adjusted and polyvinyl chloride can be adjusted. It is described to improve the fixability to a vinyl substrate.
  • the 5-membered ring lactone-based solvent is a solvent that easily penetrates into the resin base material, and the non-aqueous ink composition containing the 5-membered ring lactone-based solvent is excellent in record-drying property, but with respect to the resin base material. It is highly permeable.
  • the non-water-based ink composition permeates the resin base material and the amount of permeation increases, the non-water-based ink composition is sufficiently dried even when the non-water-based ink composition on the surface of the resin base material is sufficiently dried. It has been clarified by the present inventors that the solvent in the substance remains on the base material. When the solvent in the non-aqueous ink composition remains on the base material in this way, the solvent remaining in the base material volatilizes later when the film is attached to the recording surface of the recorded material, so that the film floats. May occur. It should be noted that such a problem may be described in the present specification as a decrease in post-workability of the recorded material.
  • An object of the present invention is to provide a non-aqueous ink composition having excellent record-drying property and post-processability of a recorded material.
  • a base material (recording medium) used for the non-aqueous ink composition for example, a resin base material having an adhesive layer on one side can be mentioned. Then, using such a resin base material having an adhesive layer on one side, a non-aqueous ink composition is recorded on the side of the resin base material not provided with the adhesive layer, and the adhesive layer side is adhered to another substrate. May be done.
  • the non-aqueous ink composition containing the 5-membered ring lactone-based solvent permeates from the decorative layer to the adhesive layer on the back side, and the adhesiveness of the adhesive layer ( It has been clarified by the studies of the present inventors that the adhesiveness between the recorded material and the subject is deteriorated.
  • the present invention when a recorded material in which a non-aqueous ink composition is recorded is stretched on a resin base material, the decorative layer of the non-aqueous ink composition is whitened and does not become a decorative layer having a desired color pattern. It became clear by their research.
  • the present invention is a non-aqueous ink composition that can be used for various base materials.
  • a resin base material having an adhesive layer on one side is used, and a base material on the side not provided with the adhesive layer.
  • Even when recording (printing) a non-aqueous ink composition on the surface deterioration of the adhesiveness of the adhesive layer (adhesiveness between the recorded material and the object) is suppressed, and even if the recorded material is stretched, it is decorated. It is an object of the present invention to provide a non-aqueous ink composition capable of effectively suppressing whitening of a layer.
  • the present inventors have obtained a non-aqueous ink composition containing a predetermined organic solvent and a resin having a predetermined weight average absolute molecular weight.
  • a non-aqueous ink composition containing a predetermined organic solvent and a resin having a predetermined weight average absolute molecular weight.
  • a non-aqueous ink composition containing an organic solvent wherein the organic solvent is a non-aqueous ink composition containing the following organic solvent (a) and the following organic solvent (b).
  • R 1 in the formula (1) is a methyl group or an ethyl group
  • R 3 in the formula (1) is an ethyl group, and / or the formula (1).
  • the content of impurities derived from the organic solvent (a) is 0.5% by mass or less in the total amount of the organic solvent (a), and the content of impurities derived from the organic solvent (b) is the organic solvent ( b)
  • the resin contains at least one selected from the group consisting of an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, and a cellulosic resin.
  • the alkylamide-based solvent (b1) is the non-aqueous ink composition according to (10) represented by the following general formula (2).
  • R 4 represents hydrogen or an alkyl group having 1 or more and 4 or less carbon atoms
  • R 5 represents an alkyl group having 2 or more and 4 or less carbon atoms.
  • the alkylamide-based solvent (b1) contains at least one selected from the group consisting of N, N-diethylformamide, N, N-diethylpropaneamide and N, N-diethylacetamide (11).
  • the non-aqueous ink composition according to.
  • the cyclic amide solvent (b2) is the non-aqueous ink composition according to (13) represented by the following general formula (3).
  • R 6 represents an alkylene group having 4 or more and 5 or less carbon atoms
  • R 7 represents hydrogen, an alkyl group having 1 or more and 2 or less carbon atoms, or an unsaturated hydrocarbon group.
  • the lactone-based solvent (b3) having a 6-membered ring or more is the non-aqueous ink composition according to (16) represented by the following general formula (4).
  • R 8 represents an alkylene group having 4 or more and 5 or less carbon atoms
  • R 9 represents hydrogen or an alkyl group having 1 or more and 2 or less carbon atoms.
  • the 6-membered ring or more lactone-based solvent (b3) contains at least one selected from the group consisting of ⁇ -valerolactone, ⁇ -hexanolactone, and ⁇ -caprolactone (17).
  • Non-aqueous ink composition contains at least one selected from the group consisting of ⁇ -valerolactone, ⁇ -hexanolactone, and ⁇ -caprolactone (17).
  • (21) A recording method for ejecting the non-aqueous ink composition according to any one of (1) to (19) onto the surface of a substrate by an inkjet method.
  • (22) A method for producing a recorded material, wherein the non-aqueous ink composition according to any one of (1) to (19) is ejected onto the surface of a base material by an inkjet method.
  • the non-aqueous ink composition of the present invention has excellent record-drying property and post-processability of the recorded material. Therefore, the non-aqueous ink composition of the present invention has various bases including a non-absorbent base material such as a resin base material and a metal plate glass, an absorbent base material such as paper and a cloth, and a base material having a surface coating. It can be used as a material (recording medium).
  • a non-absorbent base material such as a resin base material and a metal plate glass
  • an absorbent base material such as paper and a cloth
  • a base material having a surface coating It can be used as a material (recording medium).
  • the non-aqueous ink composition of the present invention has various bases including a non-absorbent base material such as a resin base material and a metal plate glass, an absorbent base material such as paper and a cloth, and a base material having a surface coating. It can be used for materials (recording media). For example, even when a resin base material having an adhesive layer on one side is used and the non-aqueous ink composition of the present invention is recorded (printed) on the surface of the base material on the side not provided with the adhesive layer, the adhesive layer In addition to suppressing deterioration of adhesiveness (adhesiveness between the recorded material and the object), whitening of the decorative layer can be effectively suppressed even if the recorded material is stretched.
  • the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition containing an organic solvent, and the organic solvents include glycol ether dialkyl (organic solvent (a)), an alkylamide solvent (b1), and the like. It is characterized by containing at least one (organic solvent (b)) selected from the group consisting of a cyclic amide-based solvent (b2) and a lactone-based solvent (b3) having a 6-membered ring or more.
  • organic solvents include glycol ether dialkyl (organic solvent (a)), an alkylamide solvent (b1), and the like. It is characterized by containing at least one (organic solvent (b)) selected from the group consisting of a cyclic amide-based solvent (b2) and a lactone-based solvent (b3) having a 6-membered ring or more.
  • non-aqueous ink composition has excellent record-drying property and post-processability of the recorded material. Therefore, the non-aqueous ink composition according to the present embodiment can be used for various base materials (recording media) including a resin base material.
  • the "non-aqueous ink composition” does not intentionally contain water but contains an organic solvent, except for water in the atmosphere and water that is inevitably contained such as derived from additives. It means that it is an ink composition (oil-based ink composition), and is different from an aqueous ink composition in which a coloring material is dissolved or dispersed in water or a mixed solution of water and an organic solvent. Since it is a "non-water-based ink composition", it dries quickly and can be easily printed (recorded) on a non-absorbent base material such as a resin base material or a metal base material. The same applies to the non-aqueous ink composition of the second embodiment described later.
  • the water content is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and further preferably 1.0% by mass or less in the total amount of the non-aqueous ink composition. , 0.5 mass or less is even more preferable.
  • the non-aqueous ink composition is a non-aqueous inkjet ink composition that is ejected onto the surface of a base material by an inkjet method, problems such as clogging of the ink composition in the nozzle are eliminated, and ejection stability and storage stability are eliminated. It is possible to improve the sex and the like.
  • Organic solvent contains an organic solvent (a) and an organic solvent (b).
  • organic solvent (a) and the organic solvent (b) will be described more specifically.
  • the organic solvent (a) is glycol ether dialkyl.
  • Glycol ether dialkyl is a compound in which the OH groups at both ends of glycol are alkyl-substituted. Since the glycol ether dialkyl has an appropriate volatility, the non-aqueous ink composition dries before the image is blurred, and the image quality is improved. Further, since the glycol ether dialkyl does not have high permeability to the resin, the post-processability of the recorded material can be improved.
  • non-aqueous ink composition is a non-aqueous inkjet ink composition that is ejected onto the surface of a substrate by an inkjet method, The suitability of the member for an inkjet head or the like is also good.
  • glycol ether dialkyl examples include glycol ether dialkyl represented by the following formula (1).
  • R 1 R 3 is an alkyl group
  • R 2 represents an ethylene group or a propylene group
  • n represents an integer of 2 to 4.
  • glycol ether dialkyl examples include ethylene glycol dibutyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol isopropyl methyl ether, and diethylene glycol.
  • Dibutyl ether diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, Tetraethylene glycol ethyl methyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di Examples thereof include propylene glycol ethyl methyl ether, dipropylene glycol methyl propyl
  • glycol ether dialkyls the glycol ether dialkyl having a total number of carbon atoms contained in R 1 and R 3 in the formula (1) of 2 or more and 8 or less is preferable, and the glycol ether dialkyl having a total of 2 or more and 6 or less is more preferable.
  • Glycol ether dialkyl having a total carbon number of 2 or more and 6 or less contained in R 1 and R 3 is volatile as compared with, for example, diethylene glycol dibutyl ether (total carbon number contained in R 1 and R 3 is 8). Since it has high properties, it is a non-aqueous ink composition having excellent recording drying properties.
  • glycol ether dialkyl in which the total number of carbon atoms contained in R 1 and R 3 is 2 or more and 6 or less include diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
  • examples thereof include diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether.
  • R 1 in the formula (1) is a methyl group or an ethyl group and R 3 is a glycol ether dialkyl which is an ethyl group, and / or R 1 and R 3 in the formula (1) are methyl groups.
  • Glycol ether dialkyl in which R 2 is a propylene group has even lower permeability than, for example, diethylene glycol dimethyl ether (R 1 and R 3 are methyl groups and R 2 is an ethylene group). Therefore, the post-workability of the recorded material can be further effectively improved.
  • glycol ether dialkyl in which R 1 is a methyl group or an ethyl group and R 3 is an ethyl group in the formula (1) include diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and triethylene glycol. Examples thereof include diethyl ether and tetraethylene glycol diethyl ether. Examples of the glycol ether dialkyl in which R 1 and R 3 in the formula (1) are methyl groups and R 2 is a propylene group include dipropylene glycol dimethyl ether.
  • the lower limit of the content of the organic solvent (a) is not particularly limited, but is preferably 30.0% by mass or more in the total amount of the non-aqueous ink composition, and 40.0% by mass or more is contained. It is more preferable that the ink is contained in an amount of 50.0% by mass or more.
  • the upper limit of the content of the organic solvent (a) is not particularly limited, but it is preferably contained in an amount of 90.0% by mass or less, and 80.0% by mass or less in the total amount of the non-aqueous ink composition. Is more preferable.
  • the glycol ether dialkyl may absorb water vapor or the like contained in the atmosphere, for example, it is preferable to dry the glycol ether dialkyl in advance before mixing with other constituents.
  • the water content in the non-aqueous ink composition can be adjusted to an appropriate amount (for example, 1.0% by mass or less in the total amount of the non-aqueous ink composition).
  • Examples of the method for drying the glycol ether dialkyl include a method of spraying an inert gas (for example, nitrogen gas) dried under an atmosphere of an inert gas such as nitrogen for a predetermined time.
  • the organic solvent (a) (glycol ether dialkyl) tends to generate impurities such as multimers, side reactants and decomposition products in the manufacturing process.
  • the content of impurities contained in the commercially available glycol ether dialkyl is high. It may be about 10% by mass in the total amount of glycol ether dialkyl. Therefore, before mixing the organic solvent (a) with other constituent components, the content of impurities derived from the organic solvent (a) should be 0.5% by mass or less in the total amount of the organic solvent (a). Is preferable.
  • Post-processability of recorded materials deteriorates due to low boiling point impurities contained in the organic solvent (a), and defects such as dissolution and swelling in plastics and adhesives used for printer members such as inkjet heads. May occur. Further, when the impurities contained in the glycol ether dialkyl have a high boiling point, bleeding of printing may occur due to the deterioration of the recording dryness of the non-aqueous ink composition.
  • the organic solvent (a) is prepared so that the content of impurities derived from the organic solvent (a) is 0.5% by mass or less in the total amount of the organic solvent (a). The record-drying property, member suitability, and post-processability of the recorded material are further improved.
  • the impurities contained in the organic solvent (a) include triethylene glycol (boiling point 285 ° C.), tetraethylene glycol (boiling point 327 ° C.), polyethylene glycol (boiling point of 330 ° C. or higher), ethylene glycol monoethyl ether (boiling point of 135 ° C.), and the like.
  • Ethylene glycol monomethyl ether (boiling point 124 ° C), ethylene glycol diethyl ether (boiling point 121 ° C), ethylene glycol dimethyl ether (boiling point 98 ° C), diethyl ether (boiling point 35 ° C), ethyl methyl ether (boiling point 12 ° C), diethyl ketone (boiling point) 101 ° C.), dimethyl ketone (boiling point 57 ° C.), ethyl methyl ketone (boiling point 80 ° C.), ethoxyethanol (boiling point 135 ° C.), ethanol (boiling point 78 ° C.), etc., but are limited thereto. is not.
  • the organic solvent (a) may be repeatedly distilled, the step size of the distillation temperature may be reduced so as not to contain impurities as much as possible, the extraction may be repeated, or the like.
  • the industrial manufacturing process in addition to the above-mentioned process, it can be realized by further taking measures to suppress the contamination and the like.
  • Organic solvent (b) is at least one selected from the group consisting of an alkylamide-based solvent (b1), a cyclic amide-based solvent (b2), and a lactone-based solvent (b3) having a 6-membered ring or more.
  • the organic solvent (b) has a lower permeability to the substrate than the non-aqueous ink composition containing the 5-membered ring lactone-based solvent. Therefore, the non-aqueous ink composition has good post-processability of the recorded material.
  • this organic solvent (b) is a solvent that penetrates into the base material to some extent, and has a quick drying property on the base material surface. Therefore, the ink composition containing the organic solvent (b) has high record-drying property like the non-aqueous ink composition containing the 5-membered ring lactone-based solvent, and can be printed (recorded). Since there is little blurring of the print, the print becomes clear. Such an effect of less bleeding of printing cannot be achieved by simply selecting a solvent having a low boiling point in order to improve the drying property.
  • the non-aqueous ink composition is a non-aqueous inkjet ink composition that is ejected onto the surface of a substrate by an inkjet method. Also improves the suitability of the member for an inkjet head or the like.
  • alkylamide-based solvent (b1) the alkylamide-based solvent (b2), and the lactone-based solvent (b3) having a 6-membered ring or more contained in the organic solvent (b) will be described.
  • the alkylamide-based solvent for example, one having the following structure can be preferably used.
  • R 4 represents hydrogen or an alkyl group having 1 or more and 4 or less carbon atoms
  • R 5 represents an alkyl group having 2 or more and 4 or less carbon atoms.
  • alkylamide solvent examples include N, N-diethylformamide, N, N-diethylacetamide, N, N-dipropylformamide, N, N-dibutylformamide, N, N-diethylpropanamide, and N. , N-dipropylpropaneamide and the like.
  • at least one selected from the group consisting of N, N-diethylformamide, N, N-diethylpropaneamide and N, N-diethylacetamide may be contained from the viewpoint of particularly exerting the effect of the present invention. preferable.
  • N, N-dimethylformamide and N, N-dimethylacetamide may be contained, it is preferable not to contain them from the viewpoint of particularly exerting the effect of the present invention.
  • the cyclic amide solvent for example, one having the following structure can be preferably used.
  • R 6 represents an alkylene group having 4 or more and 5 or less carbon atoms
  • R 7 represents hydrogen, an alkyl group having 1 or more and 2 or less carbon atoms, or an unsaturated hydrocarbon group.
  • R 7 is hydrogen or an alkyl group having 1 or more and 2 or less carbon atoms.
  • the cyclic amide solvent examples include N-methylcaprolactam, N-acetylcaprolactam, ⁇ -caprolactam, N-vinylcaprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and the like.
  • Examples thereof include N-propyl-2-pyrrolidone, N-ethyl- ⁇ -caprolactam, N-propyl- ⁇ -caprolactam, N-methyl- ⁇ -caprolactam and the like.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-methyloxazolidinone may be contained, the effect of the present invention is particularly exhibited. From the viewpoint, it is preferable not to contain it.
  • Lactone-based solvent having a 6-membered ring or more is a solvent having a cyclic ester structure of 6-membered rings or more.
  • the lactone-based solvent having a 6-membered ring or more for example, one having the following structure can be preferably used.
  • R 8 represents an alkylene group having 4 or more and 5 or less carbon atoms
  • R 9 represents hydrogen or an alkyl group having 1 or more and 2 or less carbon atoms.
  • 6-membered ring or more lactone-based solvent examples include ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, and ⁇ -undecalactone ⁇ -caprolactone. Can be mentioned.
  • a non-aqueous ink composition containing an organic solvent (b) is a non-aqueous ink composition that exhibits the effects of the present invention.
  • the organic solvent (b) contains at least one of an alkylamide-based solvent (b1) and a cyclic amide-based solvent (b2), and the organic solvent (b) contains an alkylamide-based solvent (b1). It is particularly preferable to do so.
  • Upper limit of the content of the organic solvent (b) (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more).
  • the organic solvent (b) is not particularly limited, but is preferably contained in an amount of 60.0% by mass or less, more preferably 45.0% by mass or less, and 35.0 in the total amount of the non-aqueous ink composition. It is more preferably contained in an amount of 17.0% by mass or less, and even more preferably it is contained in an amount of 17.0% by mass or less.
  • the lower limit of the content of the organic solvent (b) is not particularly limited, but is preferably 3.0% by mass or more, and preferably 5.0% by mass or more in the total amount of the ink composition. Is more preferable.
  • the upper and lower limits of the content of the organic solvent (b) are common to all of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3) having a 6-membered ring or more. do.
  • the organic solvent (b) when it is a lactone-based solvent (b3) having a 6-membered ring or more, it may be contained in an amount of 5.0% by mass or more and 15.0% by mass or less in the total amount of the non-aqueous ink composition. Most preferred.
  • Organic solvent (b) (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more) and other components.
  • an alkylamide solvent (b1) at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more
  • the content of the impurities derived from the organic solvent (b) it is preferable to adjust the content of the impurities derived from the organic solvent (b) to 0.5% by mass or less in the total amount of the organic solvent (b) in advance. Impurities with a low boiling point contained in the organic solvent (b) deteriorate the post-processability of the recorded material, and cause problems such as dissolution and swelling in the plastics and adhesives used for printer members such as inkjet heads. It may occur.
  • the organic solvent (b) may be repeatedly distilled, the step size of the distillation temperature may be reduced so as not to contain impurities as much as possible, the extraction may be repeated, or the like.
  • the industrial manufacturing process in addition to the above-mentioned process, it can be realized by further taking measures to suppress the contamination and the like.
  • the organic solvent may contain an organic solvent other than the above-mentioned organic solvent (a) and organic solvent (b).
  • organic solvent include glycol ether monoalkyl and carbonic acid esters in which one OH group of glycol is alkyl-substituted.
  • Glycol ether monoalkyl includes ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, and diethylene glycol monomethyl (or ethyl, propyl, isopropyl, n).
  • Examples of the carbonic acid ester include ethylene carbonate and propylene carbonate.
  • cyclic esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, and ⁇ -undecalactone; 3-methyl.
  • Oxazolidinone-based solvents such as -2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-vinylmethyloxazolidinone; triethylene glycol butyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, propylene.
  • Acetate-based solvents such as glycolmethyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, cyclohexyl acetate; 3-methoxypropaneamide, 3 -Butoxypropanamide, N, N-dimethyl-3-methoxypropanamide, N, N-dibutyl-3-methoxypropaneamide, N, N-dibutyl-3-butoxypropaneamide, N, N-dimethyl-3-butoxy Amido-based solvents different from alkylamide-based solvents (b1) such as propaneamide and cyclic amide-based solvents (b2); methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, Alcohols having 1 to 5 carbon atoms such as tert-
  • Acetate esters such as methyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethyl hexyl lactate, amyl lactate, isoamyl lactate and the like; saturation of n-hexane, isohexane, n-nonan, isononan, dodecane, isododecane and the like.
  • Unsaturated hydrocarbons such as charcoal hydrogens, 1-hexene, 1-heptene, 1-octene; cyclic non-cyclics such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc.
  • Saturated hydrocarbons aromatic hydrocarbons such as benzene, toluene, xylene, morpholins such as N-methylmorpholin, N-ethylmorpholin, N-formylmorpholin, terpene solvents; dimethyl oxalate, diethyl oxalate, malon Dimethyl acid, malo Examples thereof include dibasic acid esters such as diethyl acid acid, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, and diethyl glutarate. It is preferable to select a solvent having an appropriate HLB value according to the resin to be combined, the dispersant, and the like.
  • the 5-membered ring lactone-based solvent may be contained, it is preferable not to contain the 5-membered ring lactone-based solvent.
  • the content of the 5-membered ring lactone-based solvent is preferably 5.0% by mass or less, and preferably 3.0% by mass or less in the total amount of the non-aqueous ink composition. Is more preferable, 1.0% by mass or less is further preferable, and it is even more preferable that the content is not contained.
  • Examples of the 5-membered ring lactone-based solvent include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone and the like.
  • the coloring material contained in the non-aqueous ink composition according to the present embodiment is not particularly limited, and may be dye-based or pigment-based, but the water resistance of the recorded material may be used. It is preferable to use a pigment (pigment-based coloring material) from the viewpoint of good resistance such as light resistance and light resistance.
  • the pigments that can be used in the non-aqueous ink composition according to the present embodiment are not particularly limited, and examples thereof include organic pigments and inorganic pigments used in conventional ink compositions. These may be used alone or in combination of two or more.
  • organic pigments include, for example, insoluble azo pigments, soluble azo pigments, derivatives from dyes, phthalocyanine-based organic pigments, quinacridone-based organic pigments, perylene-based organic pigments, perinone-based organic pigments, azomethine-based organic pigments, and anthraquinone-based.
  • Organic pigments include lake pigments and carbon black. Be done.
  • Dyes, merocyanine dyes, stilben dyes, diarylmethane dyes, triarylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes such as indigoids, flugide dyes, nickel complex dyes, and Azulene dyes can be mentioned.
  • the average dispersed particle size of the pigment that can be contained is not particularly limited as long as it can develop a desired color.
  • the volume average particle size is preferably in the range of 5 nm or more, preferably 20 nm or more, from the viewpoint of good dispersibility and dispersion stability of the pigment and sufficient coloring power. More preferably, it is more preferably 30 nm or more.
  • the volume average particle diameter is preferably in the range of 300 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less.
  • the volume average particle size of the pigment is measured under the condition of 25 ° C. using a particle size distribution measuring device (particle size analyzer NANOTRACWAVE manufactured by Microtrac Bell Co., Ltd.) (D50). ).
  • the volume average particle diameters of the pigments contained in the respective non-aqueous ink compositions may be the same or have different relationships. May be.
  • the pigment content is not particularly limited as long as a desired image can be formed, and is appropriately adjusted. Specifically, although it varies depending on the type of pigment, it is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more in the total amount of the non-aqueous ink composition. It is preferably 20% by mass or less, and more preferably 10% by mass or less in the total amount of the non-aqueous ink composition. When the content of the pigment is in the range of 0.05% by mass or more or 20% by mass or less, the balance between the dispersion stability and the coloring power of the pigment can be excellent.
  • the non-aqueous ink composition according to the present embodiment is not particularly limited in the color to be recorded (printed), and a coloring material may be selected according to the purpose and used in combination.
  • the color can be used for inks of various colors such as yellow, magenta, cyan, and black, and also for light magenta, light cyan, light black, orange, green, red, and white.
  • the non-aqueous ink composition according to the present embodiment may contain a resin for the purpose of improving the fixability, water resistance and stretchability of the decorative layer formed by the non-aqueous ink composition.
  • the resin is not particularly limited, and for example, acrylic resin, polystyrene resin, polyester resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl acetate copolymer resin, polyethylene resin, polyurethane resin, rosin modification.
  • Resin phenol resin, terpene resin, polyamide resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, cellulose acetate propionate, silicone (silicon)
  • a resin, an acrylamide resin, an epoxy resin, or a copolymer resin or a mixture thereof can be used.
  • those containing an acrylic resin, a vinyl chloride resin, a cellulosic resin, a polyester resin, and a polyurethane resin are preferable.
  • these copolymer resins or mixtures can be used.
  • the non-aqueous ink composition in the non-aqueous ink composition according to the present embodiment, at least an acrylic resin and a copolymer resin (salt) of vinyl chloride and vinyl acetate can be improved because water resistance, solvent resistance and stretchability can be improved. It is preferable that it contains one or more kinds of vinyl acetate). Further, if the ink composition contains at least one acrylic resin or a copolymer resin (vinyl chloride) of vinyl chloride and vinyl acetate, the non-aqueous ink composition is ejected onto the surface of the base material by an inkjet method. In the case of an inkjet ink composition, it is possible to improve the ejection responsiveness and ejection stability at the time of high-speed recording.
  • the acrylic resin is not particularly limited as long as it is contained as the main component of the monomer constituting the (meth) acrylic acid ester monomer, and may be a homopolymer of one kind of radically polymerizable monomer.
  • any of the copolymers in which two or more radically polymerizable monomers are selected and used may be used, and in particular, the acrylic resin preferable as the non-aqueous ink composition according to the present embodiment is methyl methacrylate alone.
  • Examples of commercially available (meth) acrylic resins include "Paraloid B99N", "Paraloid B60", “Paraloid B66", and "Paraloid B82" manufactured by Rohm and Haas.
  • the vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer in which two or more kinds of polymerizable monomers are selected and used.
  • Examples of the copolymer of the vinyl chloride resin include a vinyl chloride-vinyl acetate copolymer resin.
  • the vinyl chloride-vinyl acetate copolymer resin is a polymer of a vinyl chloride monomer and a vinyl acetate monomer.
  • vinyl chloride vinyl acetate-based copolymer resin examples include vinyl chloride vinyl acetate copolymer, vinyl chloride / vinyl acetate / maleic acid copolymer, vinyl chloride / vinyl acetate / vinyl alcohol copolymer, and vinyl chloride / vinyl acetate. / Hydroxyalkyl acrylate copolymers and the like, and mixtures thereof.
  • vinyl chloride vinyl acetate-based copolymer resin "Solvine C", “Solvine CL”, “Solvine CNL”, “Solvine CLL”, “Solvine CLL2”, “Solvine C5R” from Nissin Chemical Industry Co., Ltd. , "Solvine TA2", “Solvine TA3", “Solvine A”, “Solvine AL”, “Solvine TA5R", “Solvine M5" and the like.
  • Cellulose-based resin is a resin having a cellulosic skeleton obtained by biologically or chemically introducing a functional group from cellulose as a raw material.
  • a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin, a cellulose acetate resin, a nitrocellulose resin and a mixture thereof can be used.
  • a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin, a cellulose acetate resin, a nitrocellulose resin and a mixture thereof.
  • Examples of the cellulose resin include “CAB551-0.01”, “CAB551-0.2”, “CAB553-0.4", “CAB531-1”, “CAB381-0.1”, and “CAB381-0.” It can be obtained and used under trade names such as “5", “CAB381-2”, “CAB381-20”, “CAP504", and "CAP482-0.5".
  • the polyester resin contains at least a structural unit obtained by polycondensing an alcohol component and a carboxylic acid component.
  • the polyester-based resin may contain a modified polyester-based resin.
  • polyester resins Toyobo's "VYLON226", “VYLON270", “VYLON560”, “VYLON600”, “VYLON630,” VYLON660 “,” VYLON885 “,” VYLONGK250 “,” VYLONGK810 “,” VYLONGK810 “,” VYLONGK810 “,” VYLONGK810 “,” VYLONGK810 “,” It can be obtained and used under product names such as "elittleUE-3200”, “elittleUE-3285", “elittleUE-3320”, “elittleUE-9800", and "elittleUE-9885” manufactured by Unitika Ltd.
  • the polyurethane resin contains at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component.
  • the polyurethane-based resin may contain a polyurethane-based resin modified with polyester, a polyether, or caprolactone. Examples of the above polyurethane resin include "Juliano KL-424", “Juliano KL-564", “Juliano KL-593", “Juliano 3262”, etc. of Arakawa Chemical Industry Co., Ltd., and "Pandex 372E”, “Pandex 372E” of DIC Co., Ltd.
  • acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins may be used alone, but it is preferable to use a mixture of the two, and the acrylic resin. It is more preferable to use a resin in which a resin and a vinyl chloride resin are mixed. Depending on the content ratio of the acrylic resin and the vinyl chloride resin, it is possible to control so as to satisfy the requirements such as color development, drying property, coating film physical properties, printability and the like required for the non-aqueous ink composition. When the acrylic resin and the vinyl chloride resin are mixed, the mixing ratio is not particularly limited and can be appropriately changed.
  • the mass% of the resin contained in the total amount of the non-aqueous ink composition according to the present embodiment is not particularly limited, but is, for example, 0.05% by mass or more in the total amount of the non-aqueous ink composition. Of the above, 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is more preferable.
  • the mass% of the resin contained in the total amount of the non-aqueous ink composition is not particularly limited, but is preferably 20% by mass or less in the non-aqueous ink composition, and more preferably 15% by mass or less. Is more preferable.
  • a dispersant may be used as necessary in the non-aqueous ink composition contained in the ink set according to the present embodiment.
  • any dispersant used in the non-aqueous ink composition can be used.
  • a polymer dispersant may be used.
  • the main chain is composed of polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaprolactone-based, etc., and the side chain has a polar group such as an amino group, a carboxyl group, a sulfone group, and a hydroxyl group. Is.
  • polyacrylic dispersants examples include Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131.
  • polycaprolactone-based dispersant examples include Azispar PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, T-6000, T-7000, T-8000, T-8000E, T-9050 ( Kawaken Fine Chemicals Co., Ltd., Solspace 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J180, J200 (Llust) Zol), TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan) and the like are used.
  • Preferred dispersants include BYKJET-9130, 9131, 9132, 9133, 9151, EfkaPX4310, PX4320, PX4330, PX4700, PX4701, Solspace 20000, 24000, 32000, 33000, 33500, 34000, 35200, 39000, 71000, 76500, 86000. 88000, J180, J200, TEGO Dispers 655, 685, 688, 690 and the like are used. These alone or a mixture thereof can be used.
  • a dispersion aid may be used in the non-aqueous ink composition contained in the ink set according to the present embodiment.
  • the dispersion aid is adsorbed on the surface of the coloring material (pigment), and the functional group enhances the affinity with the organic solvent and the dispersant in the non-aqueous ink composition, and improves the dispersion stability.
  • a known pigment derivative having a functional group such as an acidic group, a basic group, or a neutral group in the organic pigment residue can be used.
  • a surfactant may be added for the purpose of lowering the surface tension and improving the wettability with the recording medium (base material).
  • polyether-modified silicon It is preferable to use polyether-modified silicon, and specific examples thereof include BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by Big Chemie Japan) and the like.
  • Specific examples of the acetylene glycol-based surfactant include Surfinol (registered trademark) 82, 104, 465, 485, TG (all manufactured by Air Products Japan Co., Ltd.), Orfin (registered trademark) STG, and E1010 (all). (Manufactured by Nissin Chemical Co., Ltd.), etc. are exemplified.
  • the surfactant is not limited to the above, and any anionic, cationic, amphoteric or nonionic surfactant may be used, and may be appropriately selected according to the purpose of addition.
  • the non-aqueous ink composition according to the present embodiment includes stabilizers such as antioxidants and ultraviolet absorbers, epoxidized products, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicon, etc.), and defoamers.
  • stabilizers such as antioxidants and ultraviolet absorbers, epoxidized products, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicon, etc.), and defoamers.
  • Known additives such as foaming agents, pH adjusting agents, bactericidal agents, preservatives, deodorants, charge adjusting agents, and wetting agents may be contained as optional components.
  • Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like.
  • Specific examples thereof include BHA (2,3-butyl-4-oxyanisole) and BHT (2,6-di-t-butyl-p-cresol).
  • the ultraviolet absorber a benzophenone-based compound or a benzotriazole-based compound can be used.
  • Specific examples of the epoxidized product include epoxy glyceride, epoxy fatty acid monoester, and epoxy hexahydrophthalate, and specific examples thereof include ADEKA Sizer O-130P and ADEKA SIZER O-180A (manufactured by ADEKA).
  • Specific examples of the polyvalent carboxylic acid include citric acid and maleic acid.
  • the base material (recording medium) that can be used for the non-aqueous ink composition according to the present embodiment is not particularly limited, and even if it is a non-absorbable base material such as a resin base material or a metal plate glass, paper or cloth is used. It may be an absorbent base material such as, or a base material having a surface coating such as a base material having a receiving layer, and various base materials can be used. Among them, since the non-water-based ink composition according to the present embodiment is a non-water-based ink composition containing no water, a resin base material is preferably used.
  • a polyvinyl chloride polymer acrylic, PET, polycarbonate, PE, PP and the like are used.
  • a base material (recording medium) having a hard or soft polyvinyl chloride-based polymer on the surface is preferable.
  • the base material (recording medium) whose surface is made of a polyvinyl chloride polymer include a polyvinyl chloride base material (film or sheet).
  • the non-aqueous ink composition according to the present embodiment has excellent record-drying property and post-processability of the recorded material. Therefore, it is more preferable to use it as a resin base material (so-called resin base material for laminating) that is premised on laminating a film on the recording surface of a recorded material, and a polyvinyl chloride-based polymer for laminating. It is particularly preferable to use it as a base material.
  • the non-aqueous ink composition according to the present embodiment is a non-aqueous ink composition containing an organic solvent, and the organic solvent includes an alkylamide solvent (b1), a cyclic amide solvent (b2), and a 6-membered ring. It is characterized by containing at least one (organic solvent (b)) selected from the group consisting of the above lactone-based solvent (b3) and a resin having a weight average absolute molecular weight of 15,000 or more and 80,000 or less.
  • Such a non-aqueous ink composition can be used for various substrates.
  • a resin base material having an adhesive layer on one side is used and the non-aqueous ink composition of the present invention is recorded (printed) on the surface of the base material on the side not provided with the adhesive layer, the adhesive layer
  • the adhesive layer In addition to suppressing deterioration of adhesiveness (adhesiveness between the recorded material and the object), whitening of the decorative layer can be effectively suppressed even if the recorded material is stretched.
  • a resin having a weight average absolute molecular weight of 15,000 or more and 80,000 or less has a high weight average absolute molecular weight and low solubility in an organic solvent, and it is difficult to dissolve the resin in a non-aqueous ink composition. However, it is easy to precipitate. For this reason, for example, when the non-aqueous ink composition is a non-aqueous inkjet ink composition that is ejected onto the surface of the base material by an inkjet method, resin precipitates adhere to the inside of the inkjet nozzle and the nozzle is chipped or bent. May reduce the ejection stability and prevent normal printing.
  • This embodiment contains at least one organic solvent (b) selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more.
  • organic solvent selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more.
  • the water content is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and further preferably 1.0% by mass or less in the total amount of the non-aqueous ink composition. , 0.5 mass or less is even more preferable.
  • the non-aqueous ink composition according to the present embodiment contains a resin having a large weight average absolute molecular weight that can reduce the ejection stability and storage stability of the non-aqueous ink composition.
  • (b) is contained and the water content is 5.0% by mass or less in the total amount of the non-aqueous ink composition, it is possible to maintain ejection stability and storage stability.
  • Organic solvent contains the organic solvent (b).
  • Organic solvent (b) At least one organic solvent (b) selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more. ) And other organic solvents contained in the organic solvent will be described more specifically.
  • the organic solvent (b) is at least one selected from the group consisting of an alkylamide-based solvent (b1), a cyclic amide-based solvent (b2), and a lactone-based solvent (b3) having a 6-membered ring or more.
  • the organic solvent (b) has a lower permeability to the substrate than the non-aqueous ink composition containing the 5-membered ring lactone-based solvent. Therefore, deterioration of the adhesiveness of the adhesive layer (adhesiveness between the recorded material and the object) due to the permeation of the non-aqueous ink composition from the resin base material to the adhesive layer can be effectively suppressed.
  • this organic solvent (b) is a solvent that penetrates into the base material to some extent, and has a quick drying property on the base material surface. Therefore, the ink composition containing the organic solvent (b) has high record-drying property like the non-aqueous ink composition containing the 5-membered ring lactone-based solvent, and can be printed (recorded). Since there is little blurring of the print, the print becomes clear. Such an effect of less bleeding of printing cannot be achieved by simply selecting a solvent having a low boiling point in order to improve the drying property.
  • the high molecular weight resin can be effectively dissolved in the non-aqueous ink composition.
  • the alkylamide-based solvent (b1), the cyclic amide-based solvent (b2), and the lactone-based solvent (b3) having a 6-membered ring or more are the organic solvent (b) contained in the non-aqueous ink composition of the first embodiment described above. Is similar to.
  • the preferred alkylamide-based solvent (b1), cyclic amide-based solvent (b2), and lactone-based solvent (b3) having a 6-membered ring or more are also included in the non-aqueous ink composition of the first embodiment described above (b). ).
  • the above-mentioned organic solvent (b) contains at least one selected from the group consisting of an alkylamide-based solvent (b1), a cyclic amide-based solvent (b2), and a lactone-based solvent (b3) having a 6-membered ring or more. If it is a water-based ink composition, it is a non-water-based ink composition that exhibits the effect of the present invention. Among them, from the viewpoint of particularly exerting the effect of the present invention, it is preferable to contain at least one of an alkylamide-based solvent (b1) and a cyclic amide-based solvent (b2) as the organic solvent (b), and the organic solvent (b) is preferable. ), It is particularly preferable to contain an alkylamide-based solvent (b1).
  • Upper limit of the content of the organic solvent (b) (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more).
  • the organic solvent (b) is not particularly limited, but is preferably contained in an amount of 30.0% by mass or less, more preferably 25.0% by mass or less, and 20.0 in the total amount of the non-aqueous ink composition. It is more preferably contained in an amount of 15.0% by mass or less, and even more preferably contained in an amount of 15.0% by mass or less.
  • the lower limit of the content of the organic solvent (b) (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more). Is not particularly limited, but is preferably contained in an amount of 3.0% by mass or more, more preferably 5.0% by mass or more, in the total amount of the ink composition.
  • the upper and lower limits of the content of the organic solvent (b) are common to all of the alkylamide solvent (b1), the cyclic amide solvent (b2), and the lactone solvent (b3) having a 6-membered ring or more. do.
  • the organic solvent (b) when it is a lactone-based solvent (b3) having a 6-membered ring or more, it may be contained in an amount of 5.0% by mass or more and 15.0% by mass or less in the total amount of the non-aqueous ink composition. Most preferred.
  • the organic solvent (b) (at least one selected from the group consisting of an alkylamide solvent (b1), a cyclic amide solvent (b2), and a lactone solvent (b3) having a 6-membered ring or more) and other configurations. It is preferable that the content of the impurity derived from the organic solvent (b) is 0.5% by mass or less in the total amount of the organic solvent (b) before mixing with the components. For example, when a non-aqueous ink composition is recorded on a resin substrate having an adhesive layer on one side, low boiling point impurities contained in the organic solvent (b) permeate from the decorative layer to the adhesive layer on the back side to adhere.
  • the adhesiveness of the layer may deteriorate.
  • low boiling point impurities contained in the organic solvent (b) may cause problems such as dissolution and swelling of plastics and adhesives used in printer members such as inkjet heads.
  • the non-aqueous ink composition further exerts the effect of the present invention.
  • the organic solvent (b) may be repeatedly distilled, the step size of the distillation temperature may be reduced so as not to contain impurities as much as possible, the extraction may be repeated, or the like.
  • the industrial manufacturing process in addition to the above-mentioned process, it can be realized by further taking measures to suppress the contamination and the like.
  • the organic solvent may contain an organic solvent other than the above-mentioned organic solvent (b).
  • organic solvent include glycol ether dialkyl in which the OH groups at both ends of the glycol are alkyl-substituted, glycol ether monoalkyl in which one OH group of the glycol is alkyl-substituted, and a carbonic acid ester.
  • glycol ether dialkyl examples include glycol ether dialkyl represented by the following formula (1).
  • R 1 R 3 is an alkyl group
  • R 2 represents an ethylene group or a propylene group
  • n represents an integer of 2 to 4.
  • glycol ether dialkyl examples include ethylene glycol dibutyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol propyl methyl ether, diethylene glycol isopropyl methyl ether, and diethylene glycol.
  • Dibutyl ether diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, Tetraethylene glycol ethyl methyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl-2-ethylhexyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, di Examples thereof include propylene glycol ethyl methyl ether, dipropylene glycol methyl propyl
  • glycol ether dialkyls the glycol ether dialkyl having a total number of carbon atoms contained in R 1 and R 3 in the formula (1) of 2 or more and 8 or less is preferable, and the glycol ether dialkyl having a total of 2 or more and 6 or less is more preferable.
  • Glycol ether dialkyl having a total carbon number of 2 or more and 6 or less contained in R 1 and R 3 is volatile as compared with, for example, diethylene glycol dibutyl ether (total carbon number contained in R 1 and R 3 is 8). Since it has high properties, it is a non-aqueous ink composition having excellent recording drying properties.
  • glycol ether dialkyl in which the total number of carbon atoms contained in R 1 and R 3 is 2 or more and 6 or less include diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
  • examples thereof include diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether.
  • R 1 in the formula (1) is a methyl group or an ethyl group and R 3 is a glycol ether dialkyl which is an ethyl group, and / or R 1 and R 3 in the formula (1) are methyl groups.
  • Glycol ether dialkyl in which R 2 is a propylene group has even lower permeability than, for example, diethylene glycol dimethyl ether (R 1 and R 3 are methyl groups and R 2 is an ethylene group). Therefore, for example, even when a resin base material having an adhesive layer on one side is used and a non-aqueous ink composition is recorded (printed) on the surface of the base material on the side not provided with the adhesive layer, the adhesive layer is used. It is possible to more effectively suppress the deterioration of the adhesiveness (adhesiveness between the recorded object and the object).
  • glycol ether dialkyl in which R 1 is a methyl group or an ethyl group and R 3 is an ethyl group in the formula (1) include diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and triethylene glycol. Examples thereof include diethyl ether and tetraethylene glycol diethyl ether. Examples of the glycol ether dialkyl in which R 1 and R 3 in the formula (1) are methyl groups and R 2 is a propylene group include dipropylene glycol dimethyl ether.
  • Glycol ether dialkyl is prone to generate impurities such as multimers, side reactants, and decomposition products in the manufacturing process.
  • the content of impurities contained in commercially available glycol ether dialkyl is 10% by mass in the total amount of glycol ether dialkyl. It may be about%. Therefore, it is preferable that the content of impurities derived from glycol ether dialkyl is 0.5% by mass or less in the total amount of glycol ether dialkyl before mixing with other constituents.
  • the low boiling point impurities contained in glycol ether dialkyl may exacerbate the odor.
  • low boiling point impurities contained in glycol ether dialkyl permeate from the decorative layer to the adhesive layer on the back side to adhere.
  • the adhesiveness of the layer may deteriorate.
  • low boiling point impurities contained in glycol ether dialkyl may cause problems such as dissolution and swelling in plastics and adhesives used for printer members such as inkjet heads.
  • the impurities contained in the glycol ether dialkyl have a high boiling point, bleeding of printing may occur due to the deterioration of the recording dryness of the non-aqueous ink composition.
  • the above problem can be solved by setting the content of the impurity derived from the glycol ether dialkyl to 0.5% by mass or less in the total amount of the glycol ether dialkyl before mixing the glycol ether dialkyl with other constituents. Therefore, the non-aqueous ink composition further exerts the effect of the present invention.
  • the impurities contained in the glycol ether dialkyl are the same as the impurities contained in the organic solvent (a) contained in the non-aqueous ink composition of the first embodiment described above.
  • the purification method is the same.
  • the lower limit of the content of the glycol ether dialkyl is not particularly limited, but it is preferably 30.0% by mass or more in the total amount of the non-aqueous ink composition. It is more preferably contained in an amount of 0% by mass or more, and further preferably contained in an amount of 50.0% by mass or more.
  • the upper limit of the content of glycol ether dialkyl is not particularly limited, but is preferably 90.0% by mass or less, and is preferably 80.0% by mass or less in the total amount of the non-aqueous ink composition. Is more preferable.
  • Glycol ether monoalkyl includes ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, and diethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-).
  • Examples of the carbonic acid ester include ethylene carbonate and propylene carbonate.
  • cyclic esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, and ⁇ -undecalactone; 3-methyl.
  • Oxazolidinone-based solvents such as -2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-vinylmethyloxazolidinone; triethylene glycol butyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, propylene.
  • Acetate-based solvents such as glycolmethyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, cyclohexyl acetate; 3-methoxypropaneamide, 3 -Butoxypropanamide, N, N-dimethyl-3-methoxypropanamide, N, N-dibutyl-3-methoxypropaneamide, N, N-dibutyl-3-butoxypropaneamide, N, N-dimethyl-3-butoxy Amido-based solvents different from alkylamide-based solvents (b1) such as propaneamide and cyclic amide-based solvents (b2); methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, Alcohols having 1 to 5 carbon atoms such as tert-
  • Acetate esters such as methyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethyl hexyl lactate, amyl lactate, isoamyl lactate and the like; saturation of n-hexane, isohexane, n-nonan, isononan, dodecane, isododecane and the like.
  • Unsaturated hydrocarbons such as charcoal hydrogens, 1-hexene, 1-heptene, 1-octene; cyclic non-cyclics such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc.
  • Saturated hydrocarbons aromatic hydrocarbons such as benzene, toluene, xylene, morpholins such as N-methylmorpholin, N-ethylmorpholin, N-formylmorpholin, terpene solvents; dimethyl oxalate, diethyl oxalate, malon Dimethyl acid, malo Examples thereof include dibasic acid esters such as diethyl acid acid, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, and diethyl glutarate. It is preferable to select a solvent having an appropriate HLB value according to the resin to be combined, the dispersant, and the like.
  • the 5-membered ring lactone-based solvent may be contained, it is preferable not to contain the 5-membered ring lactone-based solvent.
  • the content of the 5-membered ring lactone-based solvent is preferably 5.0% by mass or less, and preferably 3.0% by mass or less in the total amount of the non-aqueous ink composition. Is more preferable, 1.0% by mass or less is further preferable, and it is even more preferable that the content is not contained.
  • Examples of the 5-membered ring lactone-based solvent include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone and the like.
  • the coloring material is the same as the coloring material contained in the non-aqueous ink composition of the first embodiment described above. The same applies to the content of preferable pigments.
  • the non-aqueous ink composition according to the present embodiment is characterized by containing a resin having a weight average absolute molecular weight of 15,000 or more and 80,000 or less. As a result, whitening of the decorative layer can be effectively suppressed even if the recorded material is stretched.
  • a resin having a high weight average absolute molecular weight has low solubility in an organic solvent, but an alkylamide-based solvent (b1), a cyclic amide-based solvent (b2), and a lactone-based solvent having a 6-membered ring or more (6-membered ring or more).
  • the non-aqueous ink composition according to the present embodiment containing at least one organic solvent (b) selected from the group consisting of b3) can dissolve a resin having a high weight average absolute molecular weight. It is possible to enjoy the effect of effectively suppressing the whitening of the decorative layer while maintaining the storage stability and the ejection stability.
  • the weight average absolute molecular weight means the weight average absolute molecular weight obtained by the gel permission chromatography / multi-angle light scatter ring (hereinafter GPC-MALS) method.
  • the weight average absolute molecular weight was measured using a TSKgel column (manufactured by Tosoh) and a GPC (Waters, Alliance GPC) equipped with a multi-angle light scattering detector (Wyatt, miniDawn TREOS) as the developing solvent. It can be measured by using THF.
  • This weight average absolute molecular weight is different from the weight average relative molecular weight obtained by the polystyrene conversion value (relative value) obtained by the conventional GPC method.
  • the weight average relative molecular weight obtained by the polystyrene conversion value is the measurement target due to the difference in molecular structure between the resin to be measured and polystyrene, which is the standard substance, and the influence of column adsorption. It is not always possible to accurately measure the molecular weight and the amount of gel components in a certain resin. Therefore, a weight average absolute molecular weight measured by a GPC equipped with a predetermined column and a multi-angle light scattering detector can serve as a guideline for the original weight average molecular weight of the resin.
  • the weight average absolute molecular weight of the resin is not particularly limited as long as it is in the range of 15,000 or more and 80,000 or less, but the lower limit of the weight average absolute molecular weight of the resin is preferably 25,000 or more, more preferably 32,500 or more. As a result, the stretchability of the decorative layer can be further improved, and whitening of the decorative layer can be effectively suppressed.
  • the upper limit of the weight average absolute molecular weight of the resin is preferably 70,000 or less, and more preferably 50,000 or less. Since the ejection stability of the non-aqueous ink composition is improved, for example, when the non-aqueous ink composition is a non-aqueous inkjet ink composition ejected to the surface of the base material by an inkjet method, the print quality is more excellent. Can be.
  • the resin is not particularly limited, and for example, acrylic resin, polystyrene resin, polyester resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride acetic acid resin, polyethylene resin, polyurethane resin, rosin-modified resin. , Phenolic resin, terpene resin, polyamide resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, cellulose acetate propionate, silicone (silicon) resin , Acrylamide-based resin, epoxy-based resin, or copolymer resins or mixtures thereof can be used.
  • the non-aqueous ink composition according to the present embodiment is selected from the group consisting of an acrylic resin, a vinyl chloride resin, and a cellulosic resin because it can improve water resistance, solvent resistance, and stretchability. It is preferable that it contains at least one of the above-mentioned types. Further, when used as an ink for inkjet, it is possible to improve the ejection responsiveness and ejection stability at the time of high-speed recording.
  • the acrylic resin is not particularly limited as long as it is contained as the main component of the monomer constituting the (meth) acrylic acid ester monomer, and examples thereof are the same as those of the above-mentioned non-aqueous ink composition. ..
  • the acrylic resin may be a homopolymer of one kind of radically polymerizable monomer, or may be any of a copolymers in which two or more kinds of radically polymerizable monomers are selected and used, and in particular, the present invention.
  • the acrylic resin preferable as the non-aqueous ink composition of the embodiment is a polymer of methyl methacrylate alone, or at least selected from the group consisting of methyl methacrylate, butyl methacrylate, ethoxyethyl methacrylate, and benzyl methacrylate. It is a copolymer with one or more compounds.
  • the vinyl chloride resin may be either a homopolymer composed of a vinyl chloride monomer or a copolymer in which two or more kinds of polymerizable monomers are selected and used.
  • Examples of the copolymer of the vinyl chloride resin include a vinyl chloride-vinyl acetate copolymer resin.
  • the vinyl chloride-vinyl acetate copolymer resin is a polymer of a vinyl chloride monomer and a vinyl acetate monomer.
  • vinyl chloride vinyl acetate-based copolymer resin examples include vinyl chloride vinyl acetate copolymer, vinyl chloride / vinyl acetate / maleic acid copolymer, vinyl chloride / vinyl acetate / vinyl alcohol copolymer, and vinyl chloride / vinyl acetate. / Hydroxyalkyl acrylate copolymers and the like, and mixtures thereof.
  • Cellulose-based resin is a resin having a cellulosic skeleton obtained by biologically or chemically introducing a functional group from cellulose as a raw material.
  • a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin, a cellulose acetate resin, a nitrocellulose resin and a mixture thereof can be used.
  • a cellulose acetate alkylate resin such as a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a cellulose acetate propionate butyrate resin, a cellulose acetate resin, a nitrocellulose resin and a mixture thereof.
  • the content of the resin contained in the total amount of the non-aqueous ink composition according to the present embodiment is not particularly limited, but is, for example, 0.05% by mass or more in the total amount of the non-aqueous ink composition. Of the above, 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is more preferable.
  • the mass% of the resin contained in the total amount of the non-aqueous ink composition is not particularly limited, but is preferably 20% by mass or less in the non-aqueous ink composition, and more preferably 15% by mass or less. Is more preferable.
  • the dispersant is the same as the dispersant contained in the non-aqueous ink composition of the first embodiment described above.
  • Dispersion aid is the same as the dispersion aid contained in the non-aqueous ink composition of the first embodiment described above.
  • the surfactant is the same as the surfactant contained in the non-aqueous ink composition of the first embodiment described above.
  • the non-aqueous ink composition according to the present embodiment includes stabilizers such as antioxidants and ultraviolet absorbers, epoxidized products, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicon, etc.), and defoamers.
  • stabilizers such as antioxidants and ultraviolet absorbers, epoxidized products, polyvalent carboxylic acids, surface conditioners, leveling agents (acrylic, silicon, etc.), and defoamers.
  • Known additives such as foaming agents, pH adjusting agents, bactericidal agents, preservatives, deodorants, charge adjusting agents, and wetting agents may be contained as optional components.
  • the other components are the same as those of the dispersant contained in the non-aqueous ink composition of the first embodiment described above.
  • base material As the base material (recording medium) that can be used for the non-aqueous ink composition according to the present embodiment, the same base material (recording medium) that can be used for the non-aqueous ink composition of the first embodiment described above is used. can do.
  • the non-aqueous ink composition according to the present embodiment is used for a resin base material (resin base material for laminating) having an adhesive layer on one side, the film can be peeled off and the adhesive layer can be adhered (adhesiveness of the adhesive layer). Deterioration of the adhesiveness between the recorded material and the object) can be suppressed more effectively. Therefore, the base material (recording medium) used for the non-aqueous ink composition according to the present embodiment is not particularly limited, but it is preferably used for a resin base material having an adhesive layer on one side, and one side is preferable. It is particularly preferable to use it for a polyvinyl chloride base material provided with an adhesive layer.
  • Recording is performed on the surface of the base material (recording medium) using the non-aqueous ink composition according to the present embodiment (the non-aqueous ink composition of the first embodiment or the non-aqueous ink composition of the second embodiment described above).
  • the recording method is not particularly limited. For example, a spray method, a coater method, an inkjet method, a gravure method, a flexographic method and the like can be mentioned.
  • the non-aqueous ink composition according to the present embodiment has little dissolution or swelling in a plastic member or an adhesive, the suitability of the non-aqueous ink composition for inkjet as a member for an inkjet head or the like, which may be a problem, is also good. .. Further, since the non-aqueous ink composition of the first embodiment described above has good drying property, it is possible to efficiently produce a recorded material having good post-processability by an inkjet method.
  • the inkjet printer used in the inkjet method can be a conventionally known one.
  • an inkjet printer such as VersaArt RE-640 or Roland DG Co., Ltd. can be used.
  • the non-aqueous ink composition according to the present embodiment shall be used for inks of various colors such as yellow, magenta, cyan, and black, as well as light magenta, light cyan, light black, orange, green, red, and white.
  • the order of printing colors and the position and configuration of heads are not particularly limited.
  • the inkjet printer may or may not have a winding mechanism of a recording medium (base material), a drying mechanism for drying the surface of the base material, and an ink circulation mechanism.
  • a recorded material can also be produced by using the non-aqueous ink composition according to the present embodiment (the non-aqueous ink composition of the first embodiment or the non-aqueous ink composition of the second embodiment described above).
  • the method for producing the recorded material is not particularly limited, and the recorded material can be produced by the method exemplified by the recording method using the ink composition described above. Above all, it is preferable to eject it to the surface of the base material by an inkjet method.
  • the non-aqueous ink composition of the first embodiment described above has high drying property on the surface of the substrate and good post-processability of the obtained recorded material, it is adhered by using a resin substrate for laminating.
  • a laminated body (a laminated body in which the non-aqueous ink composition according to the present embodiment is applied (discharged) to the surface of the resin base material on the opposite side of the layer to form a decorative layer, and a laminated film is provided on the surface of the decorative layer.
  • the bonded film can be effectively suppressed from floating, the post-processability of the recorded material is good.
  • the non-aqueous ink composition of the second embodiment described above does not have high permeability to the resin base material, for example, a resin base material having an adhesive layer on one side is used, and the side not provided with the adhesive layer. Even when the non-aqueous ink composition according to the present embodiment is recorded (printed) on the surface of the base material, the deterioration of the adhesiveness of the adhesive layer (adhesiveness between the recorded material and the object) is suppressed. Can be done.
  • organic solvent (b) selected from the group consisting of an alkylamide-based solvent (b1), a cyclic amide-based solvent (b2), and a lactone-based solvent (b3) having a 6-membered ring or more.
  • Non-water-based ink composition of the first embodiment 1.
  • Preparation of Resin (1) Acrylic Resin In 300 g of diethylene glycol diethyl ether kept at 100 ° C., 150 g of methyl methacrylate and 50 g of butyl methacrylate and a predetermined amount of t-butylperoxy-2-ethylhexanoate (polymerization started). The mixture with 1.2 g of the agent) was added dropwise over 1.5 hours. After completion of the dropping, the mixture was reacted at 100 ° C. for 2 hours and then cooled to obtain a colorless and transparent polymer solution of methyl methacrylate (solid content: 39.5%). Then, the solvent was sufficiently distilled off from this polymer solution. At this time, the polymerization average molecular weight (polystyrene conversion value) of methyl methacrylate (acrylic resin) was 30,000 (denoted as "acrylic resin" in the table).
  • Example A The non-water-based ink compositions of Example A and Comparative Example A were prepared according to the proportions shown in the table below. Specifically, a non-aqueous ink composition was prepared by dispersing each component with zirconia beads using a paint shaker. The unit is parts by mass. For the organic solvent (a) and the organic solvent (b) used in Examples 1 to 69, impurities were determined by gas chromatography before mixing.
  • Evaluation Criteria Evaluation 5 Dry in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: Dry in 8 minutes or more.
  • the member suitability (member suitability of the inkjet head) was evaluated for the non-aqueous ink compositions of Example A and Comparative Example A. Specifically, 0.2 g of a cured product obtained by drying an epoxy adhesive (two-component curable epoxy adhesive "1500", manufactured by Cemedine Co., Ltd.) used for a member of an inkjet head at 60 ° C. for one day is used. The ink composition of Example A and Comparative Example A was immersed in the ink composition and left at 60 ° C. for 1 week to perform an immersion test, and the weight change of the cured product was measured (indicated as "member suitability" in the table).
  • Evaluation Criteria Evaluation 5 The rate of change in weight is less than 3%, and there is no deterioration of the material of the epoxy adhesive.
  • Evaluation 4 The rate of change in weight is 3% or more and less than 5%, and there is no deterioration of the material of the epoxy adhesive.
  • Evaluation 3 The rate of change in weight is 5% or more and less than 10%, and there is no deterioration of the material of the epoxy adhesive.
  • Evaluation 2 The rate of change in weight is 10% or more and less than 15%, and there is no deterioration of the material of the epoxy adhesive.
  • Evaluation 1 The weight change rate is 15% or more and / or the material of the epoxy adhesive is deteriorated.
  • Example A The post-processability of the non-aqueous ink compositions of Example A and Comparative Example A was evaluated. Similar to the above recording dryness evaluation, a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)) is used in a high quality printing mode (1440 x 720 dpi), and the substrate surface temperature is 40 ° C. and a magenta 100% concentration of 30 cm x 30 cm. Immediately after printing, a laminated film (LL glossy Lami S: manufactured by Sakurai Co., Ltd.) was attached to the entire recording surface of the recorded material and left for a day, and the peeled area of the film was confirmed.
  • a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
  • IMAGin JT5829R manufactured by MACtac
  • Evaluation Criteria Evaluation 5 Film peeling is 0%.
  • Evaluation 4 Film peeling is more than 0% and less than 3%.
  • Evaluation 3 The peeling of the film is 3% or more and less than 5%.
  • Evaluation 2 The peeling of the film is 5% or more and less than 10%.
  • Evaluation 1 The peeling of the film is 10% or more.
  • the storage stability of the non-aqueous ink compositions of Example A and Comparative Example A was evaluated. Specifically, the non-aqueous ink composition is stored at 60 ° C. for 1 month, the changes in the viscosity and the volume average particle size (D50) of the pigment before and after the test are observed, and the storage stability is evaluated according to the following criteria. bottom.
  • the viscosity of the ink was measured under the condition of 20 ° C. using a falling ball viscometer (AMVn manufactured by Anton Pearl Co., Ltd.), and the volume average particle size of the pigment was measured by a particle size distribution measuring device (Microtrac Bell Co., Ltd.).
  • the volume average particle size (D50) was measured under the condition of 25 ° C.
  • evaluation Criteria Evaluation 5 The rate of change in viscosity and volume average particle size of the pigment is less than 3%.
  • Evaluation 4 The rate of change in viscosity and volume average particle size of the pigment is 3% or more and less than 5%.
  • Evaluation 3 The rate of change in viscosity and volume average particle size of the pigment is 5% or more and less than 8%.
  • Evaluation 2 The rate of change in viscosity and volume average particle size of the pigment is 8% or more and less than 10%.
  • Evaluation 1 The rate of change in viscosity and volume average particle size of the pigment is 10% or more.
  • a recording medium polyvinyl chloride film with glue (IMAGin JT5829R: manufactured by MACtac)
  • IMAGin JT5829R manufactured by MACtac
  • the substrate surface temperature is 40 ° C.
  • An image having 6 pt characters having a color different from that of the part was printed, and the obtained recorded material was dried in an oven at 60 ° C. for 5 minutes, and then the bleeding of the recorded material was visually observed.
  • Evaluation Criteria Evaluation 4 No ink bleeding is observed, and 6pt characters are clear.
  • Evaluation 3 Slight ink bleeding was observed, but the design was not impaired.
  • Evaluation 2 Ink bleeding was observed, but 6pt characters are identifiable.
  • Evaluation 1 Ink bleeding was noticeably observed, and 6pt characters could not be visually recognized.
  • the non-aqueous ink composition of Example A containing the organic solvent (a) and the organic solvent (b) has high record-drying property on the surface of the substrate, and the obtained recorded matter is obtained. It can be seen that the post-workability is also good. Further, the non-aqueous ink composition of Example A containing the organic solvent (a) and the organic solvent (b) was also good in terms of member suitability, storage stability, and bleeding property. And, as shown in Examples 55 to 69, the result was the same as that of Example 20 containing carbon black even if it contained coloring materials of various colors.
  • Example 20 (containing an alkylamide-based solvent (b1)) containing 15.0% by mass of the organic solvent (b) in the total amount of the non-aqueous ink composition and Example 24 (alkylamide-based solvent (b1)).
  • Example 30 (contains cyclic amide solvent (b2)), Example 32 (contains cyclic amide solvent (b2)), Example 33 (contains cyclic amide solvent (b2)), and examples.
  • 34 containing 6-membered ring or more lactone-based solvent (b3)
  • Example 35 (containing 6-membered ring or more lactone-based solvent (b3))
  • Example 39 (containing 6-membered ring or more lactone-based solvent (b3)).
  • the alkylamide-based solvent (b1) or the cyclic amide-based solvent (b2) was used as the organic solvent (b) as compared with Example 34, Example 35, and Example 39.
  • Examples 20, 24, 30, 32, and 33 containing the solvent were more excellent in recording dryness.
  • Examples 20 and 21 contained in proportion were particularly good in member suitability and post-workability.
  • the non-aqueous ink composition of Example 30 had a lower water content, higher record-drying property on the surface of the substrate, and better storage stability than Example 51 having the same composition ratio. .. Further, the non-aqueous ink composition of Example 30 has a lower concentration of impurities derived from the organic solvent (a) and the organic solvent (b) than that of Example 52 having the same composition ratio, and is dried on the surface of the substrate. The properties were high, and the post-processability of the obtained recorded material was also good.
  • Example 20 containing diethylene glycol methyl ethyl ether as the organic solvent (a) and an example containing diethylene glycol diethyl ether as the organic solvent (a).
  • Example 46 containing dipropylene glycol dimethyl ether as the organic solvent (a) had particularly good record-drying properties.
  • the non-aqueous ink composition of Example 70 which does not contain the organic solvent (b) or the 5-membered ring lactone-based solvent, had low record-drying property and bleeding occurred. Further, the non-aqueous ink compositions of Examples 71 to 75 containing a 5-membered ring lactone-based solvent or 3-methoxy-N, N-dimethylpropanamide instead of the organic solvent (b) had less bleeding. Post-workability had deteriorated. Further, the non-aqueous ink compositions of Examples 76 to 81 containing no organic solvent (a) had deteriorated record-drying property and member suitability.
  • Non-water-based ink composition of the second embodiment 1.
  • Preparation of Resin (1) Acrylic Resin In 300 g of diethylene glycol diethyl ether kept at 100 ° C., 150 g of methyl methacrylate and 50 g of butyl methacrylate and a predetermined amount of t-butylperoxy-2-ethylhexanoate (polymerization started). The mixture with the agent) was added dropwise over 1.5 hours. After completion of the dropping, the mixture was reacted at 100 ° C. for 2 hours and then cooled to obtain a colorless and transparent polymer solution of methyl methacrylate (solid content: 39.5%). Then, the solvent was sufficiently distilled off from this polymer solution.
  • the amount of t-butylperoxy-2-ethylhexanoate which is a polymerization initiator, was changed to control the polymerization average absolute molecular weight of methyl methacrylate (acrylic resin) (the polymerization initiator used at this time).
  • the mass of the above is shown in Table 1 below. In Table 1, it is referred to as "initiator amount").
  • the weight average absolute molecular weight was measured by a GPC equipped with a TSKgel column (manufactured by Tosoh Corporation) and a multi-angle light scattering detector (manufactured by Wyatt, miniDawn TREOS). THF was used as the developing solvent.
  • the amount of the polymerization initiator di-3,5,5-trimethylhexanol peroxide was changed to control the polymerization average absolute molecular weight of the vinyl chloride-vinyl acetate copolymer resin (the polymerization initiation used at this time).
  • the mass of the agent is shown in Table 1 below. In Table 1, it is referred to as "initiator amount").
  • the weight average absolute molecular weight was measured by a GPC equipped with a TSKgel column (manufactured by Tosoh Corporation) and a multi-angle light scattering detector (manufactured by Wyatt, miniDawn TREOS). THF was used as the developing solvent.
  • Cellulose-based resin A commercially available cellulosic resin (CAP-482-0.5, CAB553-0.4, CAB551-0.01 of EASTMAN CHEMICAL) was used.
  • Table 5 shows the weight average absolute molecular weight of each resin (acrylic resin, vinyl chloride-vinyl acetate copolymer resin, cellulosic resin).
  • non-water-based ink composition The non-water-based ink composition of Example B and Comparative Example B was prepared according to each component so as to have the ratio shown in Table 6 below. Specifically, a non-aqueous ink composition was prepared by dispersing each component with zirconia beads using a paint shaker. The unit is parts by mass. For the organic solvent (b) and glycol ether dialkyl used in Examples 1 to 69, the impurity concentration was determined by gas chromatography before mixing.
  • Evaluation Criteria Evaluation 5 Dry in less than 2 minutes. Evaluation 4: Dry in 2 minutes or more and less than 4 minutes. Evaluation 3: Dry in 4 minutes or more and less than 6 minutes. Evaluation 2: Dry in 6 minutes or more and less than 8 minutes. Evaluation 1: Dry in 8 minutes or more.
  • Example B (Original anti-glue adhesive strength) The body adhesiveness of the non-aqueous ink compositions of Example B and Comparative Example B was evaluated. Specifically, as in the above recording dryness evaluation, a recording medium (polyvinyl chloride film with glue (3M control tack graphic film IJ180: manufactured by 3M)), a high quality printing mode (1440x720dpi), and a substrate surface temperature of 40 ° C. The solid image printed in 1 was attached to an aluminum plate (body), left for 1 hour, and then subjected to a peel strength test using a tensile tester TSNSILON RTG1250 manufactured by A & D Co., Ltd. The test was carried out at a speed of 5 mm / s using a 50 N load cell.
  • a recording medium polyvinyl chloride film with glue (3M control tack graphic film IJ180: manufactured by 3M)
  • a high quality printing mode (1440x720dpi
  • substrate surface temperature 40 ° C.
  • Evaluation 5 5N / 20mm or more
  • Evaluation 4 4N / 20mm or more and less than 5N / 20mm
  • Evaluation 3 3N / 20mm or more and less than 4N / 20mm
  • Evaluation 2 2N / 20mm or more and less than 3N / 20mm
  • Evaluation 1 2N / 20mm or less
  • the storage stability of the non-aqueous ink compositions of Example B and Comparative Example B was evaluated. Specifically, the non-aqueous ink compositions of Example B and Comparative Example B were stored at 60 ° C. for 1 month, and changes in the viscosity and the average particle size (D50) of the pigment before and after the test were observed, and the following criteria were observed.
  • the storage stability was evaluated. The viscosity of the ink is measured under the condition of 20 ° C. using a falling ball viscometer (AMVn manufactured by Anton Pearl Co., Ltd.), and the volume average particle size of the pigment is measured by a particle size distribution measuring device (microtrack bell). The volume average particle size (D50) was measured under the condition of 25 ° C.
  • Evaluation Criteria Evaluation 5 The rate of change in viscosity and volume average particle size of the pigment is less than 3%.
  • Evaluation 4 The rate of change in viscosity and volume average particle size of the pigment is 3% or more and less than 5%.
  • Evaluation 3 The rate of change in viscosity and volume average particle size of the pigment is 5% or more and less than 8%.
  • Evaluation 2 The rate of change in viscosity and volume average particle size of the pigment is 8% or more and less than 10%.
  • Evaluation 1 The rate of change in viscosity and volume average particle size of the pigment is 10% or more.
  • Example B The storage stability of the non-aqueous ink compositions of Example B and Comparative Example B was evaluated. Specifically, a printed matter is created by printing (recording) on a polyvinyl chloride base material with an inkjet printer, and a recording medium (polyvinyl chloride film with glue (IMAGin JT5829R:: For recorded materials immediately after printing in a high-quality printing mode (1440x720 dpi) in MACtac) at a substrate surface temperature of 40 ° C., the magenta 100% density solid printing (recording) portion of the recorded material is reduced to 200% at room temperature.
  • a recording medium polyvinyl chloride film with glue
  • a resin base material having an adhesive layer on one side is used. Even when the non-aqueous ink composition is recorded (printed) on the surface of the base material on the side not provided with the adhesive layer, the adhesiveness of the adhesive layer (adhesiveness between the recorded material and the object) is maintained. It can be seen that the deterioration can be suppressed and the whitening of the decorative layer can be effectively suppressed even if the recorded material is stretched.
  • a non-aqueous ink composition containing an organic solvent (b) and a resin having a weight average absolute molecular weight of 15,000 or more and 80,000 or less is excellent in record-drying property, odor, storage stability, ejection stability, and bleeding property. It was. And, as shown in Examples 42 to 56, the result was the same as that of Example 3 containing carbon black even if it contained coloring materials of various colors.
  • Examples 3, 5 and 6 containing an alkylamide-based solvent (b1)) containing 10.0% by mass of the organic solvent (b) in the total amount of the non-aqueous ink composition
  • Examples 7, 10 and 11 containing the alkylamide-based solvent (b1)
  • the cyclic amide-based solvent (b2) is contained
  • Examples 12, 13, 16 containing the lactone-based solvent (b3) having a 6-membered ring or more
  • Examples 12, 13, 16 Examples 3, 5, 6, 7, 10 and 11 containing an alkylamide-based solvent (b1) or a cyclic amide-based solvent (b2) as the organic solvent (b) were excellent in the adhesive strength of the raw fabric paste.
  • Examples 3, 17 to 19 which are common except that they contain resins having different weight average absolute molecular weights
  • Examples 3, 17, and 18 in which the weight average absolute molecular weights of the resins are 25,000 or more are stretched.
  • the properties were excellent, and among them, Examples 3 and 17 in which the weight average absolute molecular weight of the resin was 32500 or more were particularly excellent in stretchability.
  • the non-aqueous ink composition of Example 3 had a low water content, and had good storage stability and record-drying property, even when compared with Example 37 having the same composition ratio. Further, the non-aqueous ink composition of Example 3 has a lower concentration of impurities derived from the organic solvent (b) and the glycol ether dialkyl, and is excellent in the adhesive strength of the raw fabric adhesive, even when compared with Example 38 having the same composition ratio. The dryness and odor were also good.
  • Examples 61, 62, and 64 containing a resin having a weight average absolute molecular weight of more than 80,000 did not have excellent discharge stability. Further, in Examples 63 and 65 containing a resin having a weight average absolute molecular weight of less than 15,000, the stretchability was lowered. Further, the non-aqueous ink compositions of Examples 66 to 70 containing a 5-membered ring lactone-based solvent or 3-methoxy-N, N-dimethylpropanamide instead of the organic solvent (b) have the adhesive strength of the original anti-glue. Was getting worse.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
PCT/JP2021/036069 2020-09-30 2021-09-30 非水系インク組成物、それを用いた記録方法及び記録物の製造方法 Ceased WO2022071477A1 (ja)

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AU2021355246A AU2021355246B2 (en) 2020-09-30 2021-09-30 Nonaqueous ink composition, and recording method and recorded matter manufacturing method using same
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KR1020237010796A KR20230058473A (ko) 2020-09-30 2021-09-30 비수계 잉크 조성물, 그것을 이용한 기록 방법 및 기록물의 제조 방법
EP25215753.2A EP4700094A2 (en) 2020-09-30 2021-09-30 Nonaqueous ink composition, and recording method and recorded matter manufacturing method using same
US18/246,728 US12338356B2 (en) 2020-09-30 2021-09-30 Nonaqueous ink composition, and recording method and recorded matter manufacturing method using same
CN202180065779.3A CN116323223A (zh) 2020-09-30 2021-09-30 非水系油墨组合物、使用其的记录方法和记录物的制造方法
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EP4700094A2 (en) 2026-02-25
AU2021355246B2 (en) 2024-07-11
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US20230365826A1 (en) 2023-11-16
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