CN117295799A - Nonaqueous ink composition, ink set, recorded matter, recording method, and method for producing recorded matter - Google Patents
Nonaqueous ink composition, ink set, recorded matter, recording method, and method for producing recorded matter Download PDFInfo
- Publication number
- CN117295799A CN117295799A CN202280034830.9A CN202280034830A CN117295799A CN 117295799 A CN117295799 A CN 117295799A CN 202280034830 A CN202280034830 A CN 202280034830A CN 117295799 A CN117295799 A CN 117295799A
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- CN
- China
- Prior art keywords
- ink composition
- composition according
- pigment
- nonaqueous
- aqueous ink
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 487
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000000049 pigment Substances 0.000 claims abstract description 183
- 239000002904 solvent Substances 0.000 claims abstract description 166
- 239000003960 organic solvent Substances 0.000 claims abstract description 133
- 239000000758 substrate Substances 0.000 claims abstract description 96
- 239000012463 white pigment Substances 0.000 claims abstract description 68
- 150000003950 cyclic amides Chemical class 0.000 claims abstract description 46
- 238000005282 brightening Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000004040 coloring Methods 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims description 103
- 239000011347 resin Substances 0.000 claims description 103
- 239000002245 particle Substances 0.000 claims description 79
- 230000001186 cumulative effect Effects 0.000 claims description 57
- -1 siloxane skeleton Chemical group 0.000 claims description 47
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 239000004094 surface-active agent Substances 0.000 claims description 29
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 18
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- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
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- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 4
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- GXOHBWLPQHTYPF-UHFFFAOYSA-N pentyl 2-hydroxypropanoate Chemical compound CCCCCOC(=O)C(C)O GXOHBWLPQHTYPF-UHFFFAOYSA-N 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012165 plant wax Substances 0.000 description 1
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
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- 229960004063 propylene glycol Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- 235000019384 rice bran wax Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000004402 sodium ethyl p-hydroxybenzoate Substances 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a nonaqueous ink composition which can achieve both high cleaning recovery and surface drying on a substrate even when a white pigment or a brightening pigment is contained. The nonaqueous ink composition contains a coloring material and an organic solvent, and is to be discharged by an inkjet method, wherein the coloring material contains a white pigment or a brightening pigment, and the organic solvent contains an organic solvent A described below. Organic solvent a: at least 1 kind selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2).
Description
Technical Field
The present invention relates to a nonaqueous ink composition, an ink set, a recorded matter, a recording method, and a method for producing a recorded matter.
Background
As the ink composition, a nonaqueous ink composition obtained by dissolving or dispersing various coloring materials in a mixed liquid with an organic solvent is widely used. The ink composition is applied directly or via another layer to a substrate such as paper by an inkjet method or the like, and the nonaqueous ink composition is dried, whereby characters and images can be obtained.
Among them, for example, a nonaqueous ink composition containing a white pigment may be ejected onto a transparent substrate or the like by an inkjet method, and then a colored ink may be ejected by an inkjet method. Such a nonaqueous ink composition containing a white pigment is required to have concealing properties in addition to ejection stability.
For example, patent document 1 describes a nonaqueous ink composition containing a white pigment having a predetermined particle diameter and a glycol ether solvent. Patent document 1 describes that the nonaqueous ink composition is excellent in ejection stability, and a recorded matter excellent in hiding property can be obtained.
In addition, there is an ink composition (sometimes referred to as a metallic ink) capable of expressing an image having a metallic texture on a substrate (recording medium) or a coating such as a printed matter in which a coloring layer is laminated on a part or the whole of the surface thereof. For example, patent document 2 describes an ink composition containing a brightening pigment and a predetermined alkoxyamide solvent. Patent document 2 describes that this ink composition can give a recorded matter excellent in abrasion resistance of a metallic luster image.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6617410
Patent document 2: japanese patent application laid-open No. 2012-207119
Disclosure of Invention
Problems to be solved by the invention
The white pigment contains a metal compound such as titanium oxide. The density of the metal compound is higher than that of a general coloring material contained in other ink compositions. Accordingly, clogging may occur in the nozzles of the inkjet head due to solid components such as pigment contained in the nonaqueous ink composition.
An inkjet recording apparatus that ejects a nonaqueous ink composition by inkjet has a cleaning recovery function of removing a nozzle clogging in such an inkjet head, but the nonaqueous ink composition containing a white pigment is likely to cause a clogging in the nozzle in the inkjet head, and the cleaning recovery property of removing such a nozzle clogging may be lowered. In the present specification, the case of removing the nozzle clogging by the cleaning recovery function provided in the inkjet recording apparatus is sometimes referred to as cleaning recovery only.
In particular, as described above, the non-aqueous ink composition containing the white pigment is required to have concealing properties. Therefore, for example, if the discharge amount of the nonaqueous ink composition is increased to provide a recorded matter excellent in concealing properties, the amount of the nonaqueous ink composition on the substrate is also increased, and thus drying takes time.
In order to improve the surface drying property of the nonaqueous ink composition on the substrate, a solvent having high volatility is generally contained. However, since the solvent having high volatility is generally dried in the inkjet head, clogging is likely to occur in the nozzle content in the inkjet head, and the problem of reduction in cleaning recovery becomes remarkable.
The lustrous pigment contains, for example, a metal powder or a metal compound. Therefore, the density is higher than that of the coloring material contained in the other ink composition. Accordingly, clogging may occur in the nozzles of the inkjet head due to solid components such as pigment contained in the nonaqueous ink composition.
An inkjet recording apparatus that ejects a nonaqueous ink composition by inkjet has a cleaning recovery function of eliminating nozzle clogging in such an inkjet head, but the nonaqueous ink composition containing a glittering pigment is likely to cause clogging in the nozzle in the inkjet head, and the cleaning recovery of eliminating such nozzle clogging may be reduced.
In particular, in order to impart excellent glossiness using a nonaqueous ink composition containing a brightening pigment, if the discharge amount of the nonaqueous ink composition is increased, the amount of the nonaqueous ink composition on the substrate also increases, and thus drying takes time.
In order to improve the surface drying property of the nonaqueous ink composition on the substrate, a solvent having high volatility is generally contained. However, since the solvent having high volatility is generally dried in the inkjet head, clogging is likely to occur in the nozzle content in the inkjet head, and the problem of reduction in cleaning recovery becomes remarkable.
The purpose of the present invention is to provide a nonaqueous ink composition which can achieve both high cleaning recovery and surface drying properties on a substrate even when the nonaqueous ink composition contains a white pigment.
The present invention also provides a nonaqueous ink composition which can achieve both high cleaning recovery and surface drying on a substrate even when the nonaqueous ink composition contains a brightening pigment.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by containing a specific organic solvent, and have completed the present invention. Specifically, the following is provided.
(1) A nonaqueous ink composition which contains a coloring material and an organic solvent and is to be discharged by an inkjet method, wherein the coloring material contains a white pigment, and the organic solvent contains an organic solvent A.
Organic solvent a: at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)
(2) The non-aqueous ink composition according to (1), wherein the white pigment contains an inorganic oxide.
(3) The non-aqueous ink composition according to (2), wherein the white pigment contains titanium oxide.
(4) The nonaqueous ink composition according to any one of (1) to (3), wherein the content of the white pigment is 8% by mass or more and 20% by mass or less based on the total amount of the nonaqueous ink composition.
(5) The nonaqueous ink composition according to any one of (1) to (4), further comprising a surfactant, wherein the surfactant comprises a surfactant having a siloxane skeleton, and the content of the surfactant having a siloxane skeleton is 0.01% by mass or more and 1.0% by mass or less.
(6) The non-aqueous ink composition according to any one of (1) to (5), which is used for forming at least 1 or more base layers or top and bottom layers (Japanese: upper ground) selected from the group consisting of a black ink composition, a colored ink composition, a clear ink composition and a clear ink composition)。
(7) A nonaqueous ink composition which contains a brightening pigment and an organic solvent and is to be discharged by an inkjet method, wherein the organic solvent contains the following organic solvent A. Organic solvent a: at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)
(8) The non-aqueous ink composition according to (7), wherein the metallic lustrous pigment is contained in the lustrous pigment.
(9) The non-aqueous ink composition according to (8), wherein the metallic lustrous pigment comprises at least 1 selected from the group consisting of aluminum, aluminum alloy, indium alloy, nickel and nickel alloy.
(10) The non-aqueous ink composition according to (9), wherein the metallic lustrous pigment comprises at least aluminum or an aluminum alloy.
(11) The nonaqueous ink composition according to any one of (8) to (10), wherein the cumulative 50% particle diameter (D50) based on the volume of the metallic lustrous pigment is 0.01 μm or more and 5.0 μm or less, and the cumulative 90% particle diameter (D90) based on the volume of the metallic lustrous pigment is 10.0 μm or less.
(12) The non-aqueous ink composition according to any one of (8) to (11), wherein the metallic luster pigment is a particle having a flat surface.
(13) The non-aqueous ink composition according to (12), wherein the metallic lustrous pigment comprises a plate-like or scale-like metallic lustrous pigment.
(14) The non-aqueous ink composition according to (13), wherein the thickness of the metallic luster pigment in a plate shape or a scale shape is in the range of 5nm to 5.0. Mu.m.
(15) The nonaqueous ink composition according to any one of (7) to (14), wherein the organic solvent further contains an acetate solvent represented by the following formula (2-3).
[ chemical formula 1]
(in the formula (2-3), X 1 Is alkyl, X 2 Is hydrogen or alkyl. n represents an integer of 1 to 4 inclusive. )
(16) The non-aqueous ink composition according to any one of (7) to (15), which is used for forming at least 1 or more base layers or top layers selected from the group consisting of a black ink composition, a colored ink composition, a clear ink composition and a transparent ink composition.
(17) The nonaqueous ink composition according to any one of (1) to (16), wherein the content of the organic solvent A is 1.0% by mass or more and 90.0% by mass or less based on the total amount of the nonaqueous ink composition.
(18) The nonaqueous ink composition according to any one of (1) to (17), wherein the organic solvent A contains the alkylamide-based solvent (a 1).
(19) The nonaqueous ink composition according to (18), wherein the alkylamide solvent is represented by the following general formula (1).
[ chemical formula 2]
(in the formula (1), R 1 Is hydrogen or alkyl with carbon number of 1-4, R 2 、R 3 Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
(20) The nonaqueous ink composition according to (19), wherein the alkylamide-based solvent contains at least 1 selected from the group consisting of N, N-diethylformamide, N-diethylpropionamide and N, N-diethylacetamide.
(21) The nonaqueous ink composition according to any one of (1) to (17), wherein the organic solvent A contains the cyclic amide solvent (a 2).
(22) The nonaqueous ink composition according to (21), wherein the cyclic amide solvent is represented by the following general formula (2).
[ chemical formula 3]
(in the formula (2), R 4 Is an alkylene group having 3 to 5 carbon atoms, R 5 Represents hydrogen or an alkyl group having 1 to 4 carbon atoms or an unsaturated hydrocarbon group. )
(23) The nonaqueous ink composition according to (22), wherein the cyclic amide solvent contains at least 1 selected from epsilon-caprolactam, N-methyl-epsilon-caprolactam and N-vinylcaprolactam.
(24) The non-aqueous ink composition according to any one of (1) to (23), wherein the organic solvent further contains at least 1 selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, dibasic acid esters, lactic acid esters, amides and alcohols.
(25) The non-aqueous ink composition according to any one of (1) to (24), wherein the organic solvent contains a glycol ether solvent.
(26) The non-aqueous ink composition according to (25), wherein the glycol ether solvent contains a glycol dialkyl ether.
(27) The non-aqueous ink composition according to (25) or (26), wherein the glycol ether solvent contains a glycol monoalkyl ether.
(28) The non-aqueous ink composition according to any one of (25) to (27), wherein the glycol ether-based solvent contains at least 2 solvents having different flash points.
(29) The non-aqueous ink composition according to any one of (1) to (28), further comprising a resin.
(30) The nonaqueous ink composition according to (29), wherein the content of the resin is in a range of 0.1% by mass or more and 10.0% by mass or less based on the total amount of the nonaqueous ink composition.
(31) The non-aqueous ink composition according to (29) or (30), wherein the resin contains at least 1 or more selected from the group consisting of an acrylic resin, a vinyl chloride resin, a polyurethane resin, a polyester resin and a cellulose resin.
(32) The nonaqueous ink composition according to any one of (29) to (31), wherein the nonaqueous ink composition is a white ink composition containing a white pigment, and a ratio of a content of the resin to a content of the white pigment is 0.20 to 1.00.
(33) An ink set comprising the nonaqueous ink composition according to any one of (1) to (32).
(34) An ink set comprising the nonaqueous ink composition according to any one of (1) to (32), wherein the nonaqueous ink composition is a white ink composition containing a white pigment,
the nonaqueous ink composition is ejected onto the surface of the substrate by an inkjet method simultaneously with at least 1 or more selected from the group consisting of a black ink composition, a colored ink composition, a clear ink composition and a clear ink composition.
(35) An ink set comprising the non-aqueous ink composition according to any one of (1) to (32), wherein the non-aqueous ink composition is a glitter ink composition containing a glitter pigment, and the non-aqueous ink composition is ejected onto the surface of a substrate by an inkjet method together with at least one selected from the group consisting of a black ink composition, a colored ink composition, a white ink composition, and a clear ink composition.
(36) A recorded matter comprising a recording layer of the nonaqueous ink composition according to any one of (1) to (32) formed on a surface of a substrate.
(37) A recording method comprising ejecting the nonaqueous ink composition according to any one of (1) to (32) onto a surface of a substrate by an inkjet method.
(38) A method for producing a recorded matter, comprising ejecting the nonaqueous ink composition according to any one of (1) to (32) onto a surface of a substrate by an inkjet method.
Effects of the invention
The nonaqueous ink composition of the present invention can achieve both high cleaning recovery and surface drying on a substrate even when it contains a white pigment.
The nonaqueous ink composition of the present invention can achieve both high cleaning recovery and surface drying on a substrate even when it contains a brightening pigment.
Detailed Description
The following describes specific embodiments of the present invention in detail, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. In the present specification, the expressions "to" refer to "above" and "below".
Summary of 1
The nonaqueous ink composition according to 1 embodiment of the present invention is a nonaqueous ink composition containing a pigment, a pigment dispersant, and an organic solvent, and which is to be ejected by an inkjet method. In the present specification, the term "nonaqueous ink composition" means an ink composition containing an organic solvent, which is specially produced without water, unlike an aqueous ink composition containing water as a main component.
The ink composition of the present embodiment (including the nonaqueous ink compositions of embodiments 1 and 2 described below) is preferably an ink composition capable of obtaining a recorded matter by drying (volatilizing) an organic solvent. Specifically, such an ink composition is dried (volatilized) by volatile components such as an organic solvent contained in the ink composition, and a residue thereof is deposited on the surface of the substrate to form a recorded matter. The ink composition is different from an active energy ray-curable ink composition which is polymerized and cured on a substrate by irradiation with active energy rays such as ultraviolet rays. The active energy ray-curable ink composition contains a polymerizable compound as an essential component, and the ink composition capable of obtaining a recorded matter by drying (volatilizing) an organic solvent contains the organic solvent, but does not contain the polymerizable compound as an essential component, and may contain the polymerizable compound or may not contain the polymerizable compound.
The organic solvent is characterized by containing the following organic solvent A.
Organic solvent a: at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)
Hereinafter, specific embodiments of the present invention will be described in detail.
1-1. Nonaqueous ink composition of embodiment 1
The nonaqueous ink composition according to embodiment 1 is a nonaqueous ink composition to be discharged by an inkjet method, and includes a coloring material containing a white pigment and an organic solvent.
The organic solvent is characterized by containing the following organic solvent A.
Organic solvent a: at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)
By containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), clogging in the nozzle of the inkjet head can be effectively eliminated and cleaning recovery of the nonaqueous ink composition can be improved even in the nonaqueous ink composition containing the white pigment.
In addition, according to the findings of the present inventors, the organic solvent a has high drying property on the substrate surface, but has low volatility in the plastic supply body (for example, plastic tube). Therefore, the nonaqueous ink composition containing the organic solvent a can provide a recorded matter excellent in surface drying property while maintaining the cleaning recovery property. The reason why the organic solvent a has high drying property on the substrate surface and low volatility in the plastic supply body is that the organic solvent a has low permeability to plastic, and the boiling point of the organic solvent itself does not necessarily correlate with the volatility in the plastic supply body.
The content of the water in the nonaqueous ink composition of the present embodiment is preferably 5.0 mass% or less, more preferably 1.0 mass% or less, and still more preferably 0.5 mass% or less, based on the total amount of the nonaqueous ink composition. If water derived from the raw materials, or water in the atmosphere during the production process, etc., is mixed, the storage stability and ejection stability of the nonaqueous ink composition may be deteriorated, or a solid substance may be generated due to components contained in the nonaqueous ink composition, etc. By reducing the moisture content in the nonaqueous ink composition so as to be as low as possible (intentionally, not containing moisture), the storage stability, the cleaning recovery property, and the like can be more effectively improved.
The components contained in the nonaqueous ink composition of the present embodiment will be described below.
[ organic solvent ]
The organic solvent can disperse or dissolve each component contained in the nonaqueous ink composition of the present embodiment. The organic solvent contains an organic solvent a (at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)).
(1) Alkylamide solvent
The alkylamide solvent is a solvent having an alkyl group (C) n H 2n+1 The compounds of (-) and-C (=O) -N-yl (amide bond) are A solvent containing a compound consisting of hydrogen or an alkyl group and a-C (=o) -N-group. The alkylamide-based solvent may preferably be, for example, an alkylamide-based solvent having the following structure.
[ chemical formula 4]
(in the formula (1), R 1 Is hydrogen or alkyl with carbon number of 1-4, R 2 、R 3 Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms).
R in formula (1) 2 And R is 3 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms.
Specific examples of the alkylamide solvents include N, N-diethylformamide, N-diethylacetamide, N-dipropylcarboxamide, N-dibutylformamide, N-diethylpropionamide, N-dipropylpropionamide, N-ethylformamide, and N-ethylacetamide. Among them, from the viewpoint of particularly exhibiting the effects of the present invention, it is preferable to contain at least 1 selected from the group consisting of N, N-diethylformamide, N-diethylpropionamide and N, N-diethylacetamide.
The content of the alkylamide-based solvent (a 1) is not particularly limited, and the lower limit of the content of the alkylamide-based solvent (a 1) is preferably in the range of 1 mass% or more, more preferably in the range of 5 mass% or more, and still more preferably in the range of 8 mass% or more, based on the total amount of the nonaqueous ink composition.
The upper limit of the content of the alkylamide-based solvent (a 1) is preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less, based on the total amount of the nonaqueous ink composition.
(2) Cyclic amide solvent
The cyclic amide solvent (a 2) is a solvent having a cyclic structure and having a-C (=o) -N-group in the cyclic structure. The cyclic amide solvent may preferably be, for example, a cyclic amide solvent having the following structure.
[ chemical formula 5]
(in the formula (2), R 4 Is an alkylene group having 3 to 5 carbon atoms, R 5 Represents hydrogen or an alkyl group having 1 to 4 carbon atoms or an unsaturated hydrocarbon group. )
Unsaturated hydrocarbon group means hydrocarbon group containing at least 1 or more multiple bonds such as vinyl group.
R is as follows 5 Preferably hydrogen or an alkyl group having 1 to 3 carbon atoms or an unsaturated hydrocarbon group, and preferably hydrogen or an alkyl group having 1 to 2 carbon atoms or an unsaturated hydrocarbon group.
Specific examples of the cyclic amide solvent (a 2) include N-methylcaprolactam, N-acetylcaprolactam, epsilon-caprolactam, N-vinylcaprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-ethyl-epsilon-caprolactam, N-propyl-epsilon-caprolactam, N-methyl-epsilon-caprolactam, and the like. Among them, at least 1 selected from epsilon-caprolactam, N-methyl caprolactam and N-vinyl caprolactam is preferably contained.
The content of the cyclic amide solvent (a 2) is not particularly limited, and the lower limit of the content of the cyclic amide solvent (b 2) is preferably in the range of 1 mass% or more, more preferably in the range of 5 mass% or more, and further preferably in the range of 8 mass% or more, based on the total amount of the nonaqueous ink composition.
The upper limit of the content of the cyclic amide solvent (a 2) is preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass% or less, based on the total amount of the nonaqueous ink composition.
Among the organic solvents a, "solvent containing the alkylamide-based solvent (a 1)" is more preferable. If "the solvent contains the alkylamide-based solvent (a 1)", both the cleaning recovery property and the surface drying property on the substrate are achieved, and the member adaptability of the inkjet recording apparatus becomes good.
The organic solvent a may contain at least 1 of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2) to exhibit the effects of the present invention, and 2 or more solvents may be mixed with the organic solvent a. By mixing 2 or more kinds, the balance of storage stability, member adaptability, surface drying property, and cleaning recovery property can be made arbitrary. When 2 or more solvents of the organic solvent a are mixed, the lower limit of the total content of the organic solvents a is preferably in the range of 1.0 mass% or more, more preferably in the range of 5.0 mass% or more, and even more preferably in the range of 10.0 mass% or more, based on the total amount of the nonaqueous ink composition. The upper limit of the total content of the organic solvents a is preferably 90.0 mass% or less based on the total amount of the nonaqueous ink composition.
(4) Other organic solvents
The nonaqueous ink composition of the present embodiment may contain an organic solvent other than the organic solvent a. Specifically, examples thereof include a dialkyl ether of a diol in which the OH groups at both terminals of the diol are substituted with an alkyl group, a monoalkyl ether of a diol in which one OH group of the diol is substituted with an alkyl group, a carbonate, a cyclic ester, and the like.
Examples of the glycol ether solvent include a glycol dialkyl ether in which the OH groups at both terminals of the glycol are substituted with an alkyl group, and a glycol monoalkyl ether in which one OH group of the glycol is substituted with an alkyl group. The glycol ether solvent includes, for example, at least one of a glycol dialkyl ether and a glycol monoalkyl ether represented by the following formula (5).
R 8 -(-O-R 9 ) n -O-R 10 ···(1-3)
(in the formula (1-3), R 8 、R 10 Each independently is hydrogen or an alkyl group having 1 to 8 carbon atoms which may have a branch, R 9 An alkylene group having 1 to 4 carbon atoms which may have a branched chain. n represents an integer of 1 to 6 inclusive. )
Examples of such glycol ether solvents include alkylene glycol monoalkyl ethers such as ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, triethylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tetraethylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether, tripropylene glycol monomethyl (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl) ether, tetrapropylene glycol monomethyl ether (or ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl) ether; and dialkyl ethers of polyhydric alcohols such as 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 methyl propyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl butyl ether, diethylene glycol ethyl butyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl 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, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol dipropyl ether, dipropylene glycol methyl butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, and tripropylene glycol methyl ethyl ether.
Among them, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol methyl propyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl butyl ether, diethylene glycol ethyl butyl ether, diethylene glycol methyl-2-ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl 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, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol dipropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol methyl ethyl ether, and the like are preferable examples.
In addition, it is preferable to combine 2 or more glycol ether solvents having different flash points among these glycol ether solvents. The nonaqueous ink composition having high cleaning recovery is obtained by containing a glycol ether solvent having a high flash point (for example, a flash point of 70 ℃ or higher). The non-aqueous ink composition having a high surface drying property on a substrate is obtained by containing a glycol ether solvent having a low flash point (for example, a flash point of less than 70 ℃). The nonaqueous ink composition which contains a glycol ether solvent having a flash point of 70 ℃ or higher and a glycol ether solvent having a flash point of less than 70 ℃ can achieve both high cleaning recovery and surface drying on a substrate, and thus can particularly effectively exhibit the effects of the present invention.
Further, a solvent other than the glycol ether solvent may be contained. Specifically, examples thereof include cyclic esters such as gamma-butyrolactone, delta-valerolactone, delta-caprolactone, epsilon-caprolactone, gamma-valerolactone, gamma-caprolactone, gamma-enantholactone, gamma-octanolactone, gamma-nonanolactone, gamma-decanolactone, gamma-undecalactone, delta-heptanolactone, delta-octanolactone, delta-nonanolactone, delta-decanolactone, and delta-undecalactone; carbonates such as propylene carbonate and ethylene carbonate; oxazolidone solvents such as 3-methyl-2-oxazolidone, 3-ethyl-2-oxazolidone, and N-vinylmethyl oxazolidone; an acetate solvent such as 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 glycol methyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, or cyclohexyl acetate; amide solvents different from the alkylamide solvents (a 1) and the cyclic amide solvents (a 2), such as 3-methoxypropionamide, 3-butoxypropionamide, N-dimethyl-3-methoxypropionamide, N-dibutyl-3-butoxypropionamide, and N, N-dimethyl-3-butoxypropionamide; alkyl alcohols having 1 to 5 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, and n-pentanol; 1-membered alcohol solvents such as 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, and 3-methoxy-n-butanol; ketones or ketoalcohols such as acetone, diacetone alcohol, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl hexyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, isophorone, and acetyl ketone; ethers such as tetrahydrofuran and dioxane; ethylene oxide or propylene oxide copolymers such as polyethylene glycol and polypropylene glycol; diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 3-propanediol, isobutylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, 1, 3-propanediol, 2-methyl-1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, 3-methyl-1, 3-butanediol, 3-methyl-1, 5-pentanediol, and 2-methyl-2, 4-pentanediol; triols such as glycerin, trimethylolethane, trimethylolpropane, and 1,2, 6-hexanetriol: alkanolamines such as 4-membered alcohols (e.g., meso-erythritol, pentaerythritol, etc.), monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, etc.; acetic esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, and octyl acetate; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethylhexyl lactate, pentyl lactate, and isopentyl lactate; saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, and isododecane, and unsaturated hydrocarbons such as 1-hexene, 1-heptene, and 1-octene; cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,3,5, 7-cyclooctatetraene, cyclododecene, aromatic hydrocarbons such as benzene, toluene, and xylene, morpholines such as N-methylmorpholine, N-ethylmorpholine, and N-formylmorpholine, and terpene solvents; dibasic acid esters such as dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate and diethyl glutarate, etc. Among them, at least 1 selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, dibasic acid esters, lactic acid esters, amides and alcohols is preferably contained. The solvent having an appropriate HLB value is preferably selected according to the resin, dispersant, etc. to be combined.
The content of the other organic solvent is not particularly limited, but the lower limit of the content of the other organic solvent is preferably in the range of 10 mass% or more, more preferably in the range of 20 mass% or more, and still more preferably in the range of 30 mass% or more. The upper limit of the content of the other organic solvent is preferably in the range of 85 mass% or less, more preferably in the range of 80 mass% or less, and still more preferably in the range of 75 mass% or less.
[ colorant ]
The nonaqueous ink composition of the present embodiment contains a coloring material. The colorant contains a white pigment. The white pigment will be described below.
(white pigment)
The white pigment is not particularly limited, and examples thereof include c.i. pigment white 6, 18, 21, titanium oxide, zinc oxide, silica, calcium carbonate, magnesium carbonate, zinc sulfide, metallic compounds such as precipitated barium sulfate, antimony oxide and zirconium oxide, clay, and white inorganic pigments including pearlescent pigments.
Among them, the white pigment preferably contains an inorganic oxide, more preferably contains a titanium oxide. In the case of a nonaqueous ink composition containing an inorganic oxide (more preferably, a nonaqueous ink composition containing a titanium oxide), a recorded matter having more excellent concealing properties can be obtained. In particular, if the content of the white pigment is large, a recorded matter having more excellent concealing properties can be obtained, but the nozzle content in the inkjet head tends to be clogged, and the cleaning recovery properties tend to be further lowered. However, by containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), clogging in the nozzle of the inkjet head can be effectively eliminated and the cleaning recovery of the nonaqueous ink composition can be improved even in the nonaqueous ink composition containing the titanium oxide.
As titanium oxide, commercially available products can be used, and examples thereof include STR-100N (trade name, manufactured by Sakai chemical Co., ltd., rutile type), TTO-51A, TTO-55A, TTO-55A, TTO-80A, MPT-140, MPT-141 (trade name, shichen Co., ltd., rutile type), MKR-1 (trade name, chemical Co., ltd., rutile type), KA-10 (trade name, titanium Co., ltd., anatase type), RDI-S, RODI, RDO, RDE2, EDDI (trade name, manufactured by SACHTLEBEN, rutile type), JR-301, JR-403, JR-405, JR-600A, JR-605, JR-600E, JR-603, JR-805, JR-800, JR-806, JR-701, JRNC, JR (trade name, manufactured by TAYCA type, rutile type), JA-1, C, JA-3 (trade name, manufactured by JAYCA type), and the like.
The average particle diameter of the white pigment is not particularly limited, and the upper limit of the cumulative 50% particle diameter (D50) on a volume basis is preferably 500nm or less, more preferably 450nm or less, and still more preferably 400nm. This effectively suppresses aggregation of the white pigment in the nonaqueous ink composition, and improves the cleaning recovery and ejection stability. The lower limit of the cumulative 50% particle diameter (D50) on a volume basis is preferably 50nm or more, and more preferably 100nm or more. When the cumulative 50% particle diameter (D50) based on the volume of the white pigment is in such a range, the storage stability of the nonaqueous ink composition can be improved.
In the present specification, the term "volume-based cumulative 50% particle diameter (D50)" means a particle diameter at which the cumulative volume calculated from the small particle diameter side becomes 50%. The "volume-based cumulative 50% particle diameter (D50)" is sometimes also referred to as "volume average particle diameter D50" or "median (median) particle diameter". The "volume-based cumulative 50% particle diameter (D50)" can be measured, for example, using "FPIA-3000S" manufactured by Sysmex corporation, or "SALD 7500nano" manufactured by Shimadzu corporation.
The content of the white pigment is not particularly limited, but the lower limit of the content of the white pigment is preferably 8 mass% or more, more preferably 9 mass% or more, and still more preferably 10 mass% or more, based on the total amount of the nonaqueous ink composition. When the content of the white pigment is 8 mass% or more, a nonaqueous ink composition which can give a recorded matter having more excellent concealing properties can be obtained.
In particular, if the content of the white pigment is large, a recorded matter having more excellent concealing properties can be obtained, but the nozzle content in the inkjet head tends to be clogged, and the cleaning recovery property tends to be further lowered. However, by containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), even in the nonaqueous ink composition containing a large amount of the white pigment, clogging in the nozzle of the inkjet head can be effectively eliminated, and the cleaning recovery of the nonaqueous ink composition can be improved.
The upper limit of the content of the white pigment is preferably 20 mass% or less, more preferably 18 mass% or less, and still more preferably 16 mass% or less. This can more effectively improve the cleaning recovery of the nonaqueous ink composition.
The nonaqueous ink composition of the present embodiment may contain a coloring material other than a white pigment. Examples of the coloring material other than the white pigment include metallic pigments containing elemental metals or alloys of aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, copper, and the like.
[ pigment dispersant ]
In the nonaqueous ink composition of the present embodiment, a pigment dispersant may be used as needed. As the dispersant, any pigment dispersant that can be used in a nonaqueous ink composition can be used. As the pigment dispersant, a polymer dispersant can be used. As such a dispersant, a main chain is composed of a polyester system, a polyacrylic system, a polyurethane system, a polyamine system, a polycaprolactone system, or the like, and has a polar group such as an amino group, a carboxyl group, a sulfo group, or a hydroxyl group as a side chain. Examples of the polyacrylic acid-based dispersant include Disperbyk-2000, 2001, 2008, 2009, 2010, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131, 9132, 9133, 9151 (manufactured by BYK-Chemie Co., ltd.), efkaPX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF Co., ltd.), TREPLUSD-1200, D-1410, D-1420, MD-1000 (manufactured by Dai Kagaku chemical Co., ltd.), flowlen DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Zoor Co., ltd.), and the like. Examples of polycaprolactone-based dispersants that can be used include AJISPER PB821, PB822, PB881 (manufactured by Ajinomoto Fine-Techno Co., ltd.), hinoact KF-1000, T-6000, T-7000, T-8000E, T-9050 (manufactured by Kawaken Fine Chemicals Co., ltd.), solsperse20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J180, J200 (manufactured by Lubrizol Co., ltd.), TEGO Dispers652, 655, 685, 688, 690 (manufactured by Evonik Japan Co., ltd.). As preferred dispersants, BYKJET-9130, 9131, 9132, 9133, 9151, efkaPX4310, PX4320, PX4330, PX4700, PX4701, solsperse20000, 24000, 32000, 33000, 33500, 34000, 35200, 39000, 71000, 76500, 86000, 88000, J180, J200, TEGO Dispers655, 685, 688, 690, and the like can be used. They may be used alone or as a mixture thereof.
The content of the pigment dispersant is not particularly limited, but the lower limit of the content of the pigment dispersant is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the pigment in the nonaqueous ink composition. The upper limit of the content of the pigment dispersant is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and further preferably 100 parts by mass or less, relative to 100 parts by mass of the pigment in the nonaqueous ink composition.
[ resin ]
The nonaqueous ink composition of the present embodiment may contain no resin or may contain a resin. By containing the resin, the fixability, water resistance, and stretchability of the recording layer formed of the nonaqueous ink composition can be improved. Further, the glossiness of the obtained recorded matter can be improved.
The resin is not particularly limited, and for example, an acrylic resin, a polystyrene resin, a polyester resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, a polyethylene resin, a polyurethane resin, a rosin-modified resin, a phenol resin, a terpene resin, a polyamide resin, a vinyltoluene- α -methylstyrene copolymer, an ethylene-vinyl acetate copolymer, cellulose acetate butyrate, cellulose acetate propionate, a silicone (silicon) resin, an acrylamide resin, an epoxy resin, or a copolymer resin or a mixture thereof may be used. Among them, acrylic resins, vinyl chloride resins, cellulose resins, polyester resins, and polyurethane resins are preferably contained.
The acrylic resin is not particularly limited as long as it is contained as a main component of a monomer constituting the (meth) acrylate monomer. The acrylic resin may be a homopolymer of 1 radical polymerizable monomer or a copolymer of 2 or more radical polymerizable monomers, and particularly, the acrylic resin preferable as the nonaqueous ink composition of the present embodiment is a methyl methacrylate homopolymer or a copolymer of methyl methacrylate and at least 1 or more compounds selected from butyl methacrylate, ethoxyethyl methacrylate and benzyl methacrylate. Examples of commercially available (meth) acrylic resins include "Paraloid B99N", "Paraloid B60", "Paraloid B66", and "Paraloid B82" from Rohm and Haas.
The vinyl chloride resin may be a homopolymer formed of a vinyl chloride monomer, or may be any copolymer selected from among 2 or more kinds of polymerizable monomers. 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 vinyl chloride monomer and vinyl acetate monomer. Examples of the vinyl chloride-vinyl acetate copolymer resin include a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinyl acetate-maleic acid copolymer, a vinyl chloride-vinyl acetate-vinyl alcohol copolymer, a vinyl chloride-vinyl acetate-hydroxyalkyl acrylate copolymer, and the like, and mixtures thereof. The vinyl chloride-vinyl acetate copolymer resin may be used as obtained from the Kagaku corporation under the trade names of "SOLBIN C", "SOLBIN CL", "SOLBIN CNL", "SOLBIN CLL2", "SOLBINC5R", "SOLBIN TA2", "SOLBIN TA3", "SOLBIN A", "SOLBINAL", "SOLBIN TA5R", "SOLBIN M5", etc.
The vinyl chloride-vinyl acetate copolymer resin may be obtained by polymerization of vinyl chloride monomer and vinyl acetate monomer. The polymerization method may be any conventionally known polymerization method. The polymerization method is preferably emulsion polymerization or suspension polymerization, more preferably suspension polymerization.
The cellulose-based resin is a resin having a cellulose skeleton obtained by biologically or chemically introducing a functional group into cellulose as a raw material. For example, examples of the cellulose-based resin include cellulose acetate alkylation resins such as cellulose acetate butyrate resins, cellulose acetate propionate resins, and cellulose acetate propionate butyrate resins, cellulose acetate resins, nitrocellulose resins, and mixtures thereof. The cellulose resins are available under the trade names of EASTMAN company, such as "CAB551-0.01", "CAB551-0.2", "CAB 553-0.4", "CAB531-1", "CAB381-0.1", "CAB381-0.5", "CAB381-2", "CAB381-20", "CAP504", "CAP 482-0.5".
The polyester resin is a resin containing at least a structural unit obtained by polycondensing an alcohol component and a carboxylic acid component. The polyester-based resin may include a modified polyester-based resin. The polyester resin may be used as obtained under trade names such as "VYLON226", "VYLON270", "VYLON560", "VYLON600", "VYLON630", "VYLON660", "VYLON885", "VYLONGK250", "VYLONGK810", "VYLONGK890" and the like of united ka company "elitleUE-3200", "elitleUE-3285", "elitleUE-3320", "elitleUE-9800" and the like.
The polyurethane resin is a resin containing at least a structural unit obtained by copolymerizing an alcohol component and an isocyanate component. The polyurethane resin may include polyurethane resins modified with polyester, polyether, and caprolactone. The polyurethane resin may be used as obtained under trade names such as "UREANO KL-424", "UREANO KL-564", "UREANO KL-593", "UREANO 3262", etc. of the Sichuan chemical industry, and "Pandex 372E", "Pandex 390E", "Pandex 394E", "Pandex 304", "Pandex 305E", "Pandex P-870", "Pandex P-910", "Pandex P-895", "Pandex 4030" and "Pandex 4110" of the DIC company.
The acrylic resin, vinyl chloride resin, cellulose resin, polyester resin, and urethane resin may be used alone, but 2 kinds of the resins are preferably used in combination, and more preferably a resin obtained by mixing an acrylic resin with a vinyl chloride resin is used. The content ratio of the acrylic resin to the vinyl chloride resin can be controlled so as to satisfy the requirements of color development, drying property, coating film physical properties, printing suitability, and the like required for the nonaqueous ink composition. In the case of mixing the acrylic resin and the vinyl chloride resin, the mixing ratio is not particularly limited, and may be appropriately changed.
The resin contained in the nonaqueous ink composition is not particularly limited, but is preferably contained in a range of 0.05 mass% or more, more preferably 0.1 mass% or more, and still more preferably 0.5 mass% or more, based on the total amount of the nonaqueous ink composition. This can further improve the surface drying property of the recorded matter obtained. The resin contained in the nonaqueous ink composition is preferably contained in a range of 20.0 mass% or less, more preferably 15.0 mass% or less, and still more preferably 10.0 mass% or less of the total amount of the nonaqueous ink composition. This can effectively eliminate clogging in the nozzles of the inkjet head, further improve the cleaning recovery property, and improve the storage stability of the nonaqueous ink composition.
The content ratio of the resin to the content of the white pigment (content of the resin contained in the nonaqueous ink composition/content of the white pigment contained in the nonaqueous ink composition) is preferably controlled. Specifically, the lower limit of the ratio of the content of the resin to the content of the white pigment is preferably 0.20 or more, more preferably 0.23 or more, and still more preferably 0.25 or more. This can improve the concealment of the recorded matter obtained. The upper limit of the ratio of the content of the resin to the content of the white pigment is preferably 1.00 or less, more preferably 0.90 or less, and still more preferably 0.80 or less. This can improve the discharge stability of the nonaqueous ink composition.
[ surfactant ]
In the nonaqueous ink composition of the present embodiment, a surfactant may be added for the purpose of suppressing volatilization of the nonaqueous ink composition in a nozzle portion, a tube, or the like, preventing curing, or resolubility at the time of curing, or for the purpose of improving wettability with a recording medium (substrate) by lowering surface tension, or for the purpose of suppressing bleeding of the ink composition on the substrate, or for the purpose of improving abrasion resistance of a coating film, or for the purpose of improving glossiness of a recorded matter.
As the surfactant, for example, nonionic substances such as polyoxyalkylene alkyl ethers P-208, P-210, P-213, E-202S, E-205S, E-215, K-204, K-220, S-207, S-215, A-10R, A-13P, NC-203, NC-207 (manufactured by Japanese fat and oil Co., ltd.), EMULGEN 106, 108, 707, 709, A-90, A-60 (manufactured by Kagaku Co., ltd.), flowlen G-70, D-90, TG-740W (manufactured by Kagrong chemical Co., ltd.), POEM J-0081 (manufactured by RIKEN VITAMIN Co., ltd.), aliphatic phosphoric acid esters such as Adekatol NP-620, NP-650, NP-660, NP-675, NP-683, NP-686, adekal CS-141E, TS-230E (manufactured by Ind., ltd.), SORGV, 40, TW-20, TW-80, CX-100, etc. are preferably used, as the fluorine-based surfactant, fluorine-modified polymers are preferably used, and as specific examples, BYK-340 (manufactured by BYK-Chemie Japan Co., ltd.) and the like are preferably used, and as the silicon-based surfactant having a siloxane skeleton, polyester-modified silicon and polyether-modified silicon are preferably used, and as specific examples, BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by BYK-Chemie Japan Co., ltd.) and the like are exemplified, and as specific examples, SURFYNOL (registered trademark) 82, 104. 465, 485, TG (all manufactured by Air Products Japan Co., ltd.), OLFINE (registered trademark) STG, E1010 (all manufactured by Nissan chemical Co., ltd.), etc. The surfactant is not limited to the above-described surfactants, and any of anionic, cationic, amphoteric or nonionic surfactants may be used.
Among them, the surfactant preferably contains a surfactant having a siloxane skeleton. In the case of a nonaqueous ink containing a surfactant having a siloxane skeleton, bleeding of printing is reduced, and a recorded matter having improved abrasion resistance can be obtained.
As the surfactant having a siloxane skeleton, polyester-modified silicon and polyether-modified silicon are preferably used, and as specific examples, BYK-313, 315N, 322, 326, 331, 347, 348, BYK-UV3500, 3510, 3530, 3570 (all manufactured by BYK-ChemieJapan corporation) and the like can be used.
The nonaqueous ink composition of the present embodiment may contain a surfactant having a siloxane skeleton, and a surfactant different from the surfactant having a siloxane skeleton.
In the nonaqueous ink composition of the present embodiment, the content of the surfactant is not particularly limited, but the lower limit of the content of the surfactant is preferably in the range of 0.01 mass% or more, more preferably in the range of 0.05 mass% or more, and still more preferably in the range of 0.1 mass% or more. The lower limit of the content of the surfactant is preferably 1.0 mass% or less, more preferably 0.9 mass% or less, and still more preferably 0.8 mass% or less.
[ other Components ]
The nonaqueous ink composition of the present embodiment may contain, as optional components, known additives such as antioxidants, light stabilizers such as ultraviolet absorbers, epoxides and the like, polycarboxylic acids, surface regulators, slip agents, leveling agents (acrylic, silicon and the like), defoamers, pH regulators, bactericides, preservatives, deodorants, charge regulators, wetting agents and the like. Specific examples of the antioxidant include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. Specifically, BHA (2, 3-butyl-4-hydroxyanisole), BHT (2, 6-di-tert-butyl-p-cresol), and the like can be exemplified. Further, as the ultraviolet absorber, a benzophenone compound or a benzotriazole compound can be used. Specific examples of the epoxide include epoxyglyceride, epoxyfatty acid monoester, epoxyhexahydrophthalate, and the like, and specifically, ADEKA CIZER O-130P, ADEKA CIZER O-180A (manufactured by ADEKA Co.) and the like. Specific examples of the polycarboxylic acid include citric acid and maleic acid.
(viscosity and surface tension of ink composition)
The viscosity of the nonaqueous ink composition of the present embodiment is preferably 30mpa·s or less, more preferably 20mpa·s or less, and even more preferably 15mpa·s or less at 25 ℃ in terms of inkjet ejectability and ejection stability. The viscosity of the nonaqueous ink composition of the present embodiment is preferably 2.0mpa·s or more, more preferably 3.0mpa·s or more, and still more preferably 3.5mpa·s or more.
In addition, regarding the surface tension of the nonaqueous ink composition of the present embodiment, the surface tension at 25 ℃ is preferably 20mN/m or more, more preferably 22mN/m or more, and still more preferably 24mN/m or more from the viewpoints of ejection property of an ink jet, ejection stability, and leveling property to a substrate. The nonaqueous ink composition of the present embodiment preferably has a surface tension of 40mN/m or less, more preferably 37mN/m or less, and still more preferably 35mN/m or less.
1-2. Nonaqueous ink composition of embodiment 2
The nonaqueous ink composition of the present embodiment contains a brightening pigment and an organic solvent, and is a nonaqueous ink composition discharged by an inkjet method.
The organic solvent is characterized by containing the following organic solvent A.
Organic solvent a: at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)
By containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), clogging in the nozzle of the inkjet head can be effectively eliminated and cleaning recovery of the nonaqueous ink composition can be improved even in the nonaqueous ink composition containing the glittering pigment.
In addition, according to the findings of the present inventors, the organic solvent a has high drying property on the substrate surface, but has low volatility in the plastic supply body (for example, plastic tube). Therefore, the nonaqueous ink composition containing the organic solvent a can provide a recorded matter excellent in surface drying property while maintaining the cleaning recovery property. The reason why the organic solvent a has high drying property on the substrate surface and low volatility in the plastic supply body is that the organic solvent a has low permeability to plastic, and the boiling point of the organic solvent itself does not necessarily correlate with the volatility in the plastic supply body.
In addition, when the glossy layer is formed from the nonaqueous ink composition of the present embodiment containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), the glossiness of the glossy layer can be improved, and the gloss of the metallic texture can be suitably imparted.
The content of the water in the nonaqueous ink composition of the present embodiment is preferably 5.0 mass% or less, more preferably 1.0 mass% or less, and still more preferably 0.5 mass% or less, based on the total amount of the nonaqueous ink composition. If water derived from the raw materials, or water in the atmosphere during the production process, etc., is mixed, the storage stability and ejection stability of the nonaqueous ink composition may be deteriorated, or a solid substance may be generated due to components contained in the nonaqueous ink composition, etc. By reducing the moisture content in the nonaqueous ink composition so as to be as low as possible (intentionally) as possible, the storage stability, the cleaning recovery property, and the like can be more effectively improved.
The components contained in the nonaqueous ink composition of the present embodiment will be described below.
[ organic solvent ]
The organic solvent can disperse or dissolve each component contained in the nonaqueous ink composition of the present embodiment. The organic solvent contains an organic solvent a (at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)).
The preferable types and preferable content ranges of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2) are the same as those of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2) in the nonaqueous ink composition of embodiment 1.
Among the organic solvents a, "solvent containing the alkylamide-based solvent (a 1)" is more preferable. If "the solvent contains the alkylamide-based solvent (a 1)", both the cleaning recovery property and the surface drying property on the substrate are achieved, and the member adaptability of the inkjet recording apparatus becomes good. The organic solvent a may contain at least 1 of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2) to exhibit the effects of the present invention, and 2 or more solvents may be mixed with the organic solvent a. By mixing 2 or more kinds, the balance of storage stability, member adaptability, surface drying property, and cleaning recovery property can be made arbitrary. When 2 or more organic solvents a are mixed, the preferable range of the total content of the organic solvents a contained in the nonaqueous ink composition is the same as that of the nonaqueous ink composition of embodiment 1.
(4) Other organic solvents
The nonaqueous ink composition of the present embodiment may contain an organic solvent other than the organic solvent a. Specifically, examples thereof include a dialkyl ether of a diol in which the OH groups at both terminals of the diol are substituted with an alkyl group, a monoalkyl ether of a diol in which one OH group of the diol is substituted with an alkyl group, a carbonate, an acetate solvent, a cyclic ester, and the like.
The type of the glycol ether solvent is preferably the same as that of the non-aqueous ink composition of embodiment 1.
In addition, as in the case of the nonaqueous ink composition of embodiment 1, it is preferable to combine 2 or more kinds of glycol ether solvents having different flash points among the glycol ether solvents. As in the case of the nonaqueous ink composition of embodiment 1, the nonaqueous ink composition can achieve both high cleaning recovery and surface drying on a substrate, and can particularly effectively exhibit the effects of the present invention.
Examples of the other solvents than the glycol ether solvents include acetate solvents represented by the formula (2-3). By containing the acetate-based solvent, the glitter pigment can be dispersed efficiently, and the storage stability of the non-aqueous ink composition containing the glitter pigment can be improved.
[ chemical formula 6]
(in the formula (2-3), X 1 Is alkyl, X 2 Is hydrogen or alkyl. n represents an integer of 1 to 4 inclusive. )
Examples of such an acetate solvent include an acetate solvent such as 3-methoxybutyl acetate, 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 glycol methyl ether acetate, dipropylene glycol methyl ether acetate, 1-methoxy-2-propyl acetate, 2-methylbutyl acetate, 3-methoxybutyl ether acetate, and cyclohexyl acetate.
The content of the acetate-based solvent is not particularly limited, but the lower limit of the content of the acetate-based solvent is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1.0 mass% or more. This can further improve the storage stability of the non-aqueous ink composition containing the luminescent pigment. The upper limit of the content of the acetate-based solvent is preferably 10.0 mass% or less, more preferably 7.0 mass% or less, and still more preferably 5.0 mass% or less. Accordingly, the content of other components such as the organic solvent a can be relatively increased, and thus a nonaqueous ink composition which can achieve both high cleaning recovery and surface drying on a substrate can be obtained.
Further, a glycol ether solvent or a solvent other than an acetate solvent may be contained. Specifically, examples of the "solvents other than glycol ether solvents" described in the nonaqueous ink composition of embodiment 1 above are given. Among them, at least 1 selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, dibasic acid esters, lactic acid esters, amides and alcohols is preferably contained. The preferable range of the total content of the other organic solvents contained in the nonaqueous ink composition is the same as that of the nonaqueous ink composition of embodiment 1.
[ brightening pigment ]
The nonaqueous ink composition of the present embodiment contains a brightening pigment. The luster pigment has a function of imparting metallic luster to the coating body. Examples of the lustrous pigment include pearlescent pigments and metallic lustrous pigments. Among them, the luminescent pigment preferably contains a metal-containing luminescent pigment. The coating body can be provided with a preferable metallic luster.
When the luminescent pigment contains a metal-containing luminescent pigment, the content of the metal-containing luminescent pigment is more preferably 30 mass% or more, still more preferably 50 mass% or more, and still more preferably 70 mass% or more, based on the total amount of the luminescent pigment.
Examples of the pearlescent pigment include pigments having a pearl luster or an interference luster such as mica, titanium dioxide coated mica, fish scale foil, bismuth oxychloride, silica, metal oxide, and a laminate thereof.
Examples of the metallic lustrous pigment include elemental metals such as aluminum, silver, gold, nickel, chromium, tin, zinc, indium, titanium, and copper; a metal compound; at least 1 of an alloy and mixtures thereof. As the metallic lustrous pigment, a pigment containing at least 1 selected from aluminum, an aluminum alloy, indium, an indium alloy, nickel, and a nickel alloy is preferably used, and a pigment containing at least aluminum or an aluminum alloy is particularly preferably used. By using a pigment containing at least 1 kind selected from aluminum, aluminum alloy, indium alloy, nickel, and nickel alloy as the metallic luster pigment, it is possible to impart more preferable metallic luster to the coating body.
The lower limit of the content of the brightening pigment is not particularly limited, but is preferably 0.5 mass% or more, more preferably 0.8 mass% or more, still more preferably 1.0 mass% or more, and still more preferably 1.2 mass% or more, based on the total amount of the nonaqueous ink composition. This can impart a preferable metallic luster to the coating body. In particular, if the content of the brightening pigment is large, a recorded matter having more excellent glossiness can be obtained, but clogging tends to occur in the nozzle of the inkjet head, and the cleaning recovery property tends to be further lowered. However, by containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), even in the nonaqueous ink composition containing a large amount of the brightening pigment, clogging in the nozzle of the inkjet head can be effectively eliminated, and the cleaning recovery of the nonaqueous ink composition can be improved.
The upper limit of the content of the brightening pigment is not particularly limited, but is preferably 10.0 mass% or less, more preferably 8.0 mass% or less, and still more preferably 6.0 mass% or less, based on the total amount of the nonaqueous ink composition. This can improve the cleaning recovery of the nonaqueous ink composition.
The lower limit of the cumulative 50% particle diameter (D50) based on the volume of the metallic lustrous pigment is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.10 μm or more, and still more preferably 0.50 μm or more. When the metallic lustrous pigment has a cumulative 50% particle diameter (D50) of 0.01 μm or more based on the volume of the metallic lustrous pigment, the lustrous layer can be improved in glossiness and appropriate metallic lustrousness can be imparted to the metallic lustrous layer in the case of forming the lustrous layer from the nonaqueous ink composition of the present embodiment.
The upper limit of the cumulative 50% particle diameter (D50) of the bright pigment on a volume basis is not particularly limited, but is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 2.5 μm or less. By setting the cumulative 50% particle diameter (D50) of the metal-containing brightening pigment to 5.0 μm or less based on the volume, clogging in the nozzle of the inkjet head can be effectively eliminated, and ejection stability and cleaning recovery of the nonaqueous ink composition can be improved.
In particular, the nonaqueous ink composition of the present embodiment can effectively eliminate clogging in the nozzle of the inkjet head and improve the cleaning recovery of the nonaqueous ink composition by containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)). Therefore, even if the volume-based cumulative 50% particle diameter (D50) of the glittering pigment is increased, the decrease in ejection stability and cleaning recovery of the nonaqueous ink composition can be suppressed, and when the volume-based cumulative 50% particle diameter (D50) of the glittering pigment is increased, the glossiness of the glittering layer can be improved and the glossiness of the metallic texture can be given to the nonaqueous ink composition.
In the present specification, the term "volume-based cumulative 50% particle diameter (D50)" means a particle diameter at which the cumulative volume calculated from the small particle diameter side becomes 50%. The "volume-based cumulative 50% particle diameter (D50)" is sometimes also referred to as "volume average particle diameter D50" or "median (median) particle diameter".
The upper limit of the cumulative 90% particle diameter (D90) based on the volume of the metallic lustrous pigment is not particularly limited, but is preferably 10.0 μm or less, more preferably 7.0 μm or less, and still more preferably 5.0 μm or less.
In the present specification, the "volume-based cumulative 90% particle diameter (D90)" means a particle diameter at which the cumulative volume calculated from the small particle diameter side becomes 90%.
The metallic lustrous pigment is preferably particles having a flat face. By having a flat surface, a shiny layer having high glossiness can be obtained. Examples of the particles having a flat surface include particles having a rectangular parallelepiped shape including a cube, and particles having a flat plate shape or a scale shape. This can impart a preferable metallic luster to the coating body. Further, the particles having a flat surface are more preferably plate-like or scale-like particles.
In this case, the lower limit of the thickness of the metallic lustrous pigment is preferably 5nm or more, more preferably 10nm or more, and still more preferably 15nm or more. The upper limit of the thickness of the metallic lustrous pigment is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 1.0 μm or less.
The volume-based cumulative 50% particle diameter (D50), the volume-based cumulative 90% particle diameter (D90), and the thickness of the luminescent pigment can be measured using, for example, "FPIA-3000S" manufactured by Sysmex corporation, laser diffraction particle size distribution analyzer "SALD 7500nano" manufactured by shimadzu corporation.
The lustrous pigment can be obtained by mechanically shaping metal-containing particles, for example by grinding in a ball mill or attritor. The metal-containing particles can also be obtained by a known atomization method.
In addition, as another method for producing the luminescent pigment, the metal-containing thin film formed on the substrate may be finely pulverized. Examples of such a method include the following: a metal-containing film of 5.0nm to 5.0 μm is formed on a flat substrate coated with a resin layer for peeling by vacuum vapor deposition, ion plating, sputtering, or the like, and the metal-containing film is peeled from the substrate and finely pulverized. The term metal-containing film is used in the concept of a film that also includes a metal compound such as a metal oxide. The lower limit of the thickness of the metal-containing film is preferably 5nm or more, more preferably 10nm or more, and still more preferably 15nm or more. The upper limit of the thickness of the metal-containing film is preferably 5.0 μm or less, more preferably 3.0 μm or less, and still more preferably 1.0 μm or less.
Specific examples of the substrate used for producing the lustrous pigment are polytetrafluoroethylene films; a polyethylene film; a polypropylene film; polyester films such as polyethylene terephthalate; polyamide films such as nylon 66 and nylon 6; a polycarbonate film; a triacetate film; polyimide film. The preferred substrate is a film of polyethylene terephthalate or a copolymer thereof.
The lower limit of the thickness of the base material used in the production of the luminescent pigment is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more. When the thickness of the base material is 10 μm or more, the handling property becomes good. The upper limit of the thickness of the sheet-like base material is not particularly limited, but is preferably 150 μm or less, more preferably 145 μm or less, and further preferably 140 μm or less. By setting the thickness of the base material to 150 μm or less, the flexibility of the obtained laminate is improved, and rolling and peeling are facilitated.
Specific examples of the resin used for the release resin layer coated on the substrate include polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, cellulose derivatives, polyvinyl acetal, acrylic acid copolymers, and modified nylon resins. In order to form a resin layer from a resin used for the release resin layer, a resin solution is coated on a sheet-like substrate by gravure coating, roll coating, doctor blade coating, extrusion coating, dip coating, spin coating, or the like to form the release resin layer.
The lower limit of the thickness of the release resin layer is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more. When the thickness is 0.1 μm or more, the metal-containing film can be easily peeled from the substrate. The upper limit of the thickness of the release resin layer is not particularly limited, but is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 10 μm or less. When the thickness is 50 μm or less, the metal-containing film can be easily peeled from the substrate.
The nonaqueous ink composition and the dispersion used for producing the nonaqueous ink composition may be produced from a substrate on which a metal-containing film is formed. The resin may be immersed in a solvent which is capable of dissolving the release resin and which does not react with the luminescent pigment, or may be subjected to ultrasonic treatment simultaneously with the immersion. Examples of such solvents include organic solvents constituting the nonaqueous ink composition. The release resin functions as a dispersant for dispersing the lustrous pigment, and the dispersibility of the lustrous pigment is improved. In this case, the particle diameter and film thickness of the lustrous pigment are adjusted by the conditions and the ultrasonic dispersion time at the time of forming the metal-containing thin film. The brightening pigment may be recovered by settling the brightening pigment from the stripping resin solution by centrifugation, and the brightening pigment may be dispersed in an organic solvent constituting the nonaqueous ink composition. The lustrous pigment may be surface-treated with a silane compound, a fluorine-containing compound, phosphoric acid, a phosphoric acid ester, a fatty acid ester, or the like.
The nonaqueous ink composition of the present embodiment may contain a coloring material other than a brightening pigment.
[ pigment dispersant ]
In the nonaqueous ink composition of the present embodiment, a dispersant may be used as needed. The pigment dispersant is preferably the same as the pigment dispersant in the non-aqueous ink composition according to embodiment 1. The preferable range of the content of the pigment dispersant contained in the nonaqueous ink composition is the same as that of the nonaqueous ink composition of embodiment 1.
[ resin ]
The nonaqueous ink composition of the present embodiment may contain no resin or may contain a resin. By containing the resin, the fixability, water resistance, and stretchability of the recording layer formed of the nonaqueous ink composition can be improved. Further, the glossiness of the obtained recorded matter can be improved. The type of the resin is preferably the same as that of the non-aqueous ink composition according to embodiment 1. The preferable range of the content of the resin contained in the nonaqueous ink composition is the same as that of the nonaqueous ink composition of embodiment 1.
[ surfactant ]
The nonaqueous ink composition of the present embodiment may contain a surfactant. The type of the surfactant is preferably the same as that in the nonaqueous ink composition of embodiment 1. The preferable range of the content of the surfactant contained in the nonaqueous ink composition is the same as that of the nonaqueous ink composition of embodiment 1.
[ wax ]
To the nonaqueous ink composition of the present embodiment, wax may be added. This can improve scratch resistance of a printed matter obtained by imparting slidability to the surface of the glossy layer formed from the nonaqueous ink composition of the present embodiment.
The wax herein refers to an organic substance or an organosilicon compound which is solid at normal temperature or below and which liquefies when heated. Specifically, examples thereof include low molecular weight polyolefin waxes such as polyethylene, polypropylene, polybutene, polyethylene blend wax, polypropylene blend wax, and mineral waxes such as silicone (silicon) having a softening point, silicone (silicon) -acrylic waxes, oleamides, erucamides, fatty acid amides such as ricinoleamides and stearamides, ester waxes, carnauba wax, rice bran waxes, candelilla waxes, plant waxes such as Japanese wax (Japanese: mukou), jojoba oils, animal waxes such as beeswax, lanolin, spermaceti, mineral waxes such as montan wax, ozokerite, ceresin, and Fischer-Tropsch wax, petroleum waxes such as paraffin, microcrystalline waxes, vaseline, and paraffin blend waxes, and modified products thereof. These waxes are readily available in the form of commercial products. In the nonaqueous ink composition of the present embodiment, 1 kind of wax may be used alone, or 2 or more kinds may be used in combination.
The wax contained in the nonaqueous ink composition of the present embodiment may be liquid at ordinary temperature, and the melting point is not particularly limited, but the lower limit of the melting point is preferably 20 ℃ or higher, more preferably 25 ℃ or higher, and still more preferably 30 ℃ or higher. By setting the melting point of the wax to 20 ℃ or higher, it is possible to suppress adhesion of printed matters to each other due to surface tackiness caused by melting of the wax of the obtained printed matter. The upper limit of the melting point is preferably 130℃or lower, more preferably 125℃or lower, and still more preferably 120℃or lower. When the melting point of the wax is 130 ℃ or lower, whitening of the obtained printed matter can be suppressed or a suitable metallic luster can be imparted to the coating.
In the nonaqueous ink composition of the present embodiment, the lower limit of the content of the wax is not particularly limited, but is preferably 0.05 mass% or more, more preferably 0.07 mass% or more, and still more preferably 0.1 mass% or more, based on the total amount of the nonaqueous ink composition. This can impart more preferable slidability to the surface of the coating body, and can provide a printed matter having good scratch resistance. The upper limit of the content of the wax is preferably 1.0 mass% or less, more preferably 0.8 mass% or less, and still more preferably 0.5 mass% or less, based on the total amount of the nonaqueous ink composition. This can impart a preferable metallic luster to the coating body.
[ other Components ]
The nonaqueous ink composition of the present embodiment may contain other components as optional components. The types of other components contained in the nonaqueous ink composition are the same as those in the nonaqueous ink composition of embodiment 1.
(viscosity and surface tension of non-aqueous ink composition)
The preferable viscosity and preferable surface tension range of the nonaqueous ink composition of the present embodiment are the same as those of the nonaqueous ink composition of embodiment 1.
Method for producing ink composition 2
The method for producing the ink composition of the present embodiment can be produced by mixing an organic solvent a (at least 1 selected from the group consisting of an alkylamide-based solvent (a 1) and a cyclic amide-based solvent (a 2)), a white pigment or a luminescent pigment, and other components (e.g., a resin, etc.) as needed, using a paint shaker. In this case, the components may be dispersed by zirconia beads. The nonaqueous ink composition thus obtained may be subjected to degassing treatment or the like as needed to adjust the amount of dissolved oxygen and the amount of dissolved nitrogen to desired amounts.
In this case, the organic solvent is preferably dried in advance. By drying the organic solvent in advance, the amount of water contained in the nonaqueous ink composition can be reduced. Examples of the method of drying the organic solvent include a method of blowing the dried inert gas (for example, nitrogen gas) under an inert gas atmosphere such as nitrogen for a predetermined period of time, a method of purifying the organic solvent by distillation, a method of allowing the organic solvent to permeate through a semipermeable membrane which selectively permeates water, and a method of allowing water mixed in the organic solvent to be selectively adsorbed to a water adsorbent which adsorbs water.
Ink set 3
The ink set of the present embodiment is formed of a plurality of ink compositions including the above-described nonaqueous ink composition. The nonaqueous ink compositions of embodiment 1 and embodiment 2 can achieve both high cleaning recovery and surface drying on a substrate, and can also provide recorded matter excellent in surface drying of recorded matter in the ink set of this embodiment.
Examples of the ink composition other than the white pigment-containing nonaqueous ink composition of embodiment 1 include black ink compositions containing black pigments, colored ink compositions such as yellow, magenta, cyan, pale magenta, pale cyan, pale black, orange, green, and red, glittering ink compositions containing glittering pigments, and transparent ink compositions containing no coloring material.
For example, by using the non-aqueous ink composition containing a white pigment according to embodiment 1 as a non-aqueous ink composition for forming a base layer or an upper base layer, the concealment of the recorded matter obtained can be improved. Further, for example, a desired image can be formed by using a colored ink composition as an ink composition other than the non-aqueous ink composition containing a white pigment of embodiment 1.
The non-aqueous ink composition containing a white pigment according to embodiment 1 may be ejected onto the surface of the substrate by an inkjet method simultaneously with at least one selected from the group consisting of a black ink composition, a colored ink composition, a clear ink composition, and a transparent ink composition.
Examples of the ink composition other than the non-aqueous ink composition containing a luminescent pigment according to embodiment 2 include black ink compositions containing a black pigment, colored ink compositions such as yellow, magenta, cyan, pale magenta, pale cyan, pale black, white, orange, green, and red, and transparent ink compositions containing no coloring material.
For example, by using the non-aqueous ink composition containing a luminescent pigment according to embodiment 2 as a non-aqueous ink composition for forming a base layer or an upper base layer, the glossiness of the obtained recorded matter can be improved. Further, for example, a desired image can be formed by using a colored ink composition as an ink composition other than the non-aqueous ink composition containing a luminescent pigment.
The non-aqueous ink composition containing a luminescent pigment according to embodiment 2 may be ejected onto the surface of the substrate by an inkjet method simultaneously with at least one selected from the group consisting of a black ink composition, a colored ink composition, a white ink composition, and a transparent ink composition.
Recording method Using ink composition
The recording method according to the present embodiment is a recording method in which the nonaqueous ink composition according to the above 1 st or 2 nd embodiment is discharged onto the surface of a substrate by an inkjet method. The nonaqueous ink compositions of embodiment 1 and embodiment 2 can achieve both high cleaning recovery and surface drying on a substrate, and can also provide a recorded matter excellent in surface drying of the recorded matter in the recording method of the present embodiment.
In particular, the nonaqueous ink compositions of embodiment 1 and embodiment 2 are extremely excellent in surface drying property, and can be ejected onto the surface of a substrate (recording medium) by an inkjet method by transporting the substrate at high speed, thereby improving the production speed of printed matter. The same applies to a method for producing a printed matter described later.
Specifically, the recording speed (transport speed of the substrate) in the recording method of the present embodiment is preferably 10m depending on the type of the substrate 2 Preferably at least/h, more preferably at least 20m 2 Preferably at least/h, more preferably 30m 2 And/or more.
The inkjet recording apparatus for ejecting the nonaqueous ink composition of embodiments 1 and 2 described above by the inkjet method can be any conventionally known apparatus. For example, an inkjet printer manufactured by Versaart RE-640 or Roland DG, etc. may be used.
As an example of the configuration of the inkjet recording apparatus, a carriage type (japanese) serial printer type inkjet recording apparatus will be described, but the inkjet recording apparatus capable of implementing the recording method of the present embodiment may be a carriage type inkjet recording apparatus in which an ink cartridge is fixed to the outside, or a line printer type inkjet recording apparatus in which an inkjet head ejects an ink composition onto a recording medium (substrate) without moving.
The ink jet recording apparatus preferably includes a heating mechanism and a fixing mechanism for fixing the substrate. The organic solvent contained in the nonaqueous ink composition can be volatilized by controlling the surface temperature of the substrate by a heating means provided in the inkjet recording apparatus and drying the nonaqueous ink composition landed on the substrate (recording medium).
Further, by the fixing mechanism for fixing the substrate, the nonaqueous ink composition can be dried in a state where the substrate (recording medium) is fixed, and it is possible to suppress the substrate from being bent by heating and thus the heat application from becoming uneven. Thus, the nonaqueous ink composition landed on the substrate (recording medium) can be effectively dried. Such a drying mechanism and fixing mechanism are particularly effective in conveying a substrate (recording medium) at a high speed to thereby increase the manufacturing speed of a recorded matter.
The heating means provided in the ink jet recording apparatus may be a preheater, a plate heater, a post heater, or the like, or may be a means for blowing warm air to the recorded matter. In addition, a plurality of these heating means may be combined.
The surface temperature of the substrate heated by the heating means is not particularly limited as long as the organic solvent contained in the nonaqueous ink composition can be volatilized, and the lower limit of the surface temperature of the substrate is preferably 20 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 40 ℃ or higher. The upper limit of the surface temperature of the substrate is preferably 70 ℃ or less, more preferably 60 ℃ or less, and still more preferably 50 ℃ or less.
The method of ejection by the inkjet method is not particularly limited, and may be a piezoelectric method using a piezoelectric element or a thermal method using a heating element.
Since the nonaqueous ink compositions of embodiment 1 and embodiment 2 have high drying properties, such a mechanism is not necessarily required in the inkjet recording apparatus of the present embodiment. For example, the ink jet recording apparatus may be configured to be miniaturized without providing a heating mechanism, and the entire conveyance section may be shortened, thereby increasing the manufacturing speed of the printed matter.
The inkjet recording apparatus may be configured as follows: the ink jet recording apparatus includes a plastic tube for connecting a container (ink cartridge, bottle, etc.) for storing the nonaqueous ink composition of the 1 st and 2 nd embodiments to an ink jet head for ejecting the nonaqueous ink composition of the 1 st and 2 nd embodiments, and the nonaqueous ink composition of the 1 st and 2 nd embodiments is supplied to the ink jet head through the plastic tube and ejected by an ink jet method.
The organic solvent a (at least 1 selected from the alkylamide-based solvents (a 1) and the cyclic amide-based solvents (a 2)) contained in the nonaqueous ink compositions of the above-mentioned embodiments 1 and 2 is relatively less volatile than other organic solvents even if a plastic tube is present, and thus can be inkjet-discharged while maintaining the component amount of the organic solvent contained in the nonaqueous ink composition. This effectively eliminates clogging in the nozzles of the inkjet head, and improves the cleaning recovery of the nonaqueous ink composition.
The material of the plastic pipe is not particularly limited, and examples thereof include polyolefin resins such as polyethylene resins, ethylene propylene diene monomer rubber, nylon, polyurethane, PTFE, and the like. Among them, polyethylene resins and ethylene propylene diene monomer rubber are preferable.
The inkjet recording apparatus according to the present embodiment may use the white pigment-containing non-aqueous ink composition according to embodiment 1 and the glitter pigment-containing non-aqueous ink composition according to embodiment 2 together with inks of respective colors such as yellow, magenta, cyan, black, pale magenta, pale cyan, pale black, orange, green, red, and the like, and the order of the colors to be printed, the positions and the configurations of the inkjet heads are not particularly limited. The ink jet recording apparatus according to the present embodiment may or may not include a winding mechanism for a recording medium (substrate), a drying mechanism for drying the surface of the substrate, and a circulation mechanism for ink.
Method for producing recorded matter (5)
The recording method using the nonaqueous ink composition according to embodiment 1 and embodiment 2 may be defined as a method for producing a recorded matter. The nonaqueous ink compositions of embodiment 1 and embodiment 2 can achieve both high cleaning recovery and surface drying on a substrate, and can also provide a recorded matter excellent in surface drying of the recorded matter in the method for producing a recorded matter of the present embodiment.
6 record
Each layer constituting the recorded matter manufactured by the method for manufacturing a recorded matter of the above-described embodiment will be described. The recorded matter in the embodiment is a recorded matter in which the white layer of the non-aqueous ink composition of the 1 st embodiment and/or the glossy layer of the non-aqueous ink composition of the 2 nd embodiment are formed on the surface of the substrate, but the non-aqueous ink composition of the 1 st embodiment is not limited to the non-aqueous ink composition for forming a white layer, and the non-aqueous ink composition of the 2 nd embodiment is not limited to the non-aqueous ink composition for forming a glossy layer, and for example, a recorded layer for forming a desired image may be formed by simultaneously ejecting the non-aqueous ink composition containing a white pigment of the 1 st embodiment and a colored ink composition such as yellow, magenta, cyan, black, light magenta, light cyan, light black, orange, green, red, or the like. The desired image may be formed by simultaneously ejecting the nonaqueous ink composition containing the glittering pigment according to embodiment 2 and the colored ink composition of yellow, magenta, cyan, black, pale magenta, pale cyan, pale black, orange, green, red, white, or the like. The term "simultaneously ejecting the above-described non-aqueous ink composition containing a white pigment and the colored ink composition" does not mean that a plurality of ink compositions are ejected onto the surface of the substrate at exactly the same timing by an inkjet method, but means that a plurality of ink compositions are ejected at substantially the same timing to form a desired image as in a usual inkjet method (including any of a serial head method, a line head method, and the like). Similarly, "simultaneously ejecting the above-described non-aqueous ink composition containing a luminescent pigment and the colored ink composition" does not mean that a plurality of ink compositions are ejected onto the surface of the substrate at exactly the same timing by an inkjet method, but means that a plurality of ink compositions are ejected at substantially the same timing to form a desired image as in a usual inkjet method (including any of a serial head method, a line head method, and the like).
[ Medium (recording Medium) ]
The substrate (recording medium) that can be used in the recording method of the present embodiment is not particularly limited, and may be a non-absorbent substrate such as a resin substrate, a metal plate, or glass, an absorbent substrate such as paper or cloth, a surface-coated substrate such as a substrate having a receiving layer, or various substrates may be used.
Among these, the nonaqueous ink compositions of embodiment 1 and embodiment 2 are nonaqueous ink compositions containing no water, and therefore, it is preferable that the surface is mainly formed of a resin. In particular, since the nonaqueous ink composition of embodiment 1 and embodiment 2 contains the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)) which exhibits permeability to the resin base material, bleeding of the print in the medium (recording medium) whose surface is formed of the resin is small. Examples of the resin include polyvinyl chloride polymers, acrylic acid, PET, polycarbonate, PE, PP, and the like. The present invention can also be used for a resin substrate (so-called a resin substrate for lamination) on the premise of attaching a film to a recording surface of a recorded matter. Particularly preferred is a substrate (recording medium) having a surface formed of a hard or soft polyvinyl chloride polymer. As a substrate (recording medium) whose surface is formed of a polyvinyl chloride polymer, a polyvinyl chloride substrate (film or sheet) and the like can be exemplified.
[ white layer ]
The white layer is a layer formed by volatilizing a solvent contained in the non-aqueous ink composition containing a white pigment according to embodiment 1. The non-aqueous ink composition containing a white pigment according to embodiment 1 can effectively eliminate clogging in the nozzle of the inkjet head and improve the cleaning recovery of the non-aqueous ink composition even when a large amount of white pigment is contained, for example. In addition, the non-aqueous ink composition containing a white pigment according to embodiment 1 has high surface drying property on a substrate, and the drying time does not take a lot of time even if the discharge amount of the non-aqueous ink composition is increased to provide a recorded matter excellent in hiding property. Therefore, the non-aqueous ink composition containing the white pigment according to embodiment 1 can be used to easily control the content of the white pigment and the discharge amount of the non-aqueous ink composition, for example, and can easily form a white layer having high hiding property. The white layer may be a base layer of a recording layer described later, an upper layer, or the same as the recording layer described later.
[ Brightness layer ]
The glitter layer is a layer formed by volatilizing a solvent contained in the non-aqueous ink composition containing a glitter pigment according to embodiment 2. The non-aqueous ink composition containing a glitter pigment according to embodiment 2 can effectively eliminate clogging in the nozzle of the inkjet head and improve cleaning recovery of the non-aqueous ink composition, for example, even when a large amount of glitter pigment is contained. In addition, the non-aqueous ink composition containing the lustrous pigment according to embodiment 2 has high surface drying property on the substrate, and the drying time does not take a lot of time even if the discharge amount of the non-aqueous ink composition is increased to give a recorded matter excellent in concealing property. Therefore, when the non-aqueous ink composition containing the lustrous pigment according to embodiment 2 is used, for example, the content of the lustrous pigment and the discharge amount of the non-aqueous ink composition can be easily controlled, and a lustrous layer having high lustrousness can be easily formed. The glitter layer may be a base layer of a recording layer described later, an upper layer, or the same as the recording layer described later.
[ recording layer ]
The recording layer is a layer for forming a desired image or the like formed of an ink composition of yellow, magenta, cyan, black, pale magenta, pale cyan, pale black, orange, green, red or the like. The nonaqueous ink composition of embodiment 1 containing a white pigment forming a white layer and the nonaqueous ink composition of embodiment 2 containing a luminescent pigment forming a luminescent layer have high surface drying properties on a substrate, and therefore can increase the production speed of printed matter.
[ other layers ]
The recorded matter of the present embodiment may further include a layer having a desired function on the medium (recording medium) and on the upper surface of the entire recorded matter. For example, in order to improve adhesion between a medium (recording medium) and a glitter layer or a recording layer, a primer layer may be formed, or a glitter layer containing a glitter pigment, a white layer containing a white pigment, or the like may be formed as a base layer. The brightening layer and the white layer may be formed of the non-aqueous ink compositions of embodiment 1 and embodiment 2, or may not be formed of the non-aqueous ink compositions of embodiment 1 and embodiment 2. In addition, for the purpose of further imparting abrasion resistance and glossiness to the recorded matter, an overcoat layer containing at least 1 kind of resin or wax may be formed on the upper surface of the entire recorded matter. Further, by containing a filler, changing the film thickness in pixel units, or the like, a layer exhibiting a rough feel (matte surface) can be formed on the upper surface of the entire recorded matter. In order to impart weather resistance to the recorded matter, a weather resistant layer containing an ultraviolet absorber, a light stabilizer, or the like, a luminescent layer containing a luminescent pigment, a white layer containing a white pigment, or the like may be formed on the upper surface of the entire recorded matter. The brightening layer and the white layer may be formed of the non-aqueous ink compositions of embodiment 1 and embodiment 2, or may not be formed of the non-aqueous ink compositions of embodiment 1 and embodiment 2.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these descriptions.
(embodiment 1)
1. Preparation of resin
(1) Acrylic resin
To 300g of diethylene glycol diethyl ether maintained at 100℃were added dropwise a mixture of 150g of methyl methacrylate and 50g of butyl methacrylate with a prescribed amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) over 1.5 hours. After completion of the dropwise addition, the mixture was allowed to react at 100℃for 2 hours and then cooled to obtain a colorless transparent polymer solution of methyl methacrylate. Then, the solvent was distilled off sufficiently from the polymer solution to obtain a polymer of methyl methacrylate. In this case, the amount of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was changed, and the polymerization average molecular weight of methyl methacrylate (acrylic resin) was controlled so as to be 10000 to 105000 (the mass of the polymerization initiator used in this case is shown in table 1 below, and the "initiator amount" is shown in table 1).
(2) Vinyl chloride-vinyl acetate copolymer resin
After nitrogen substitution, 100 parts by mass of deionized water, 40 parts by mass of methanol, 32 parts by mass of vinyl chloride, 5 parts by mass of vinyl acetate, 0.2 parts by mass of glycidyl methacrylate, 3.55 parts by mass of hydroxypropyl acrylate, 0.1 parts by mass of hydroxypropyl methylcellulose (suspension), 0.026 parts by mass of di-2-ethylhexyl peroxydicarbonate (polymerization initiator), and a predetermined amount of di-3, 5-trimethylhexanol peroxide (polymerization initiator) were charged into an autoclave equipped with a stirring device, and the mixture of 48 parts by mass of vinyl chloride, 0.6 parts by mass of glycidyl methacrylate, and 10.65 parts by mass of hydroxypropyl acrylate was continuously pressed in for 5.4 hours while stirring in a nitrogen atmosphere to raise the temperature to 63 ℃. At the time when the internal pressure of the autoclave reached 0.3MPa, the residual pressure was removed, the resin slurry was taken out after cooling, and the resin slurry was filtered and dried to obtain a vinyl chloride-based copolymer resin. At this time, the amount of di-3, 5-trimethylhexanol peroxide as a polymerization initiator was changed, and the polymerization average molecular weight of the vinyl chloride-vinyl acetate copolymer resin was controlled to 40000 to 90000 (the mass of the polymerization initiator used at this time is described in the following table 1. The mass is described as "initiator amount" in table 1).
TABLE 1
(3) Polyester resin
104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were charged into a round-bottomed flask, and the temperature was slowly raised to 240℃over 4 hours, and the esterification reaction was carried out while removing the distillate from the system. After the completion of the esterification reaction, the pressure was reduced to 10mmHg over 30 minutes, and the temperature was raised to 250℃to conduct the initial polymerization. Then, the polymerization was carried out for 1 hour or less at 1mmHg to obtain a polyester resin.
(4) Polyurethane resin
192.5 parts by mass of polycarbonate diol (PLACCEL CD-220: manufactured by Daicel), 41.6 parts by mass of isophorone diisocyanate (IPDI: manufactured by Evonik) and 100 parts by mass of N, N-Diethylformamide (DEF) were added to a round-bottomed flask, and after mixing uniformly, a mixed solution of 0.01 part by mass of T100BHJ (catalyst) and 0.09 part by mass of N, N-Diethylformamide (DEF) was added, and reacted at 75℃for 3 hours to obtain a prepolymer having an isocyanate group at the end. To this solution, 250 parts by mass of N, N-Diethylformamide (DEF) was added, and after the solution was uniformly dissolved, a chain extender solution obtained by dissolving 12 parts by mass of 3-aminomethyl-3, 5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by mass of N, N-Diethylformamide (DEF) was added, and the mixture was further stirred at 60℃for 40 minutes. Then, a reaction terminator prepared by dissolving 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) in 50 parts by mass of N, N-diethylformamide was added, and finally 250 parts by mass of N, N-Diethylformamide (DEF) was added to obtain a polyurethane solution having a solid content of 25.0%.
2. Production of nonaqueous ink composition
The nonaqueous ink compositions of examples and comparative examples were prepared so that the respective organic solvents, resins, dispersants, and pigments were in the proportions shown in the following table. Specifically, a nonaqueous ink composition was prepared by dispersing each component using a paint shaker with zirconia beads. The unit is mass%.
3. Evaluation
(bleeding Property)
The nonaqueous ink compositions of examples and comparative examples were evaluated for bleeding property. Specifically, the nonaqueous ink compositions of examples and comparative examples were printed on a recording medium (polyvinyl chloride film with paste (IMAGIN JT5829R: manufactured by MACTac Co.) in a high-quality printing mode (1440×720 dpi) at a substrate surface temperature of 40 ℃ C.) by an inkjet method using an inkjet printer (using a trade name of Versaart RE-640, manufactured by Roland DG Co., ltd.), and the obtained printed matter was dried in an oven at 60 ℃ C. For 5 minutes, and then the bleeding of the printed matter was observed by visual observation and a magnifying glass (x 10) (in the table, referred to as "bleeding property").
Evaluation criterion
Evaluation 5: no bleeding of the ink was observed when observed with a magnifying glass.
Evaluation 4: no bleeding of the ink was observed visually, and the 6pt text was clear.
Evaluation 3: bleeding of the ink was slightly observed by visual observation, but the design was not impaired.
Evaluation 2: the bleeding of the ink was visually observed, but a 6pt character was recognized.
Evaluation 1: the bleeding of the ink was visually observed remarkably, and 6pt characters could not be visually recognized.
(surface drying Property)
The nonaqueous ink compositions of examples and comparative examples were evaluated for surface drying properties. Specifically, as in the evaluation of bleeding property, solid images were printed in a high-quality printing mode (1440×720 dpi) on a recording medium (a polyvinyl chloride film with paste (IMAGin JT5829R: manufactured by MACtac)), and the time until drying at 40 ℃ was measured (in the table, the time was referred to as "surface drying property").
Evaluation criterion
Evaluation 5: drying in less than 2 minutes.
Evaluation 4: drying in more than 2 minutes and less than 4 minutes.
Evaluation 3: drying in more than 4 minutes and less than 6 minutes.
Evaluation 2: drying in more than 6 minutes and less than 8 minutes.
Evaluation 1: drying for 8 min or more.
(storage stability)
The nonaqueous ink compositions of examples, comparative examples and reference examples were evaluated for storage stability. Specifically, the nonaqueous ink composition was stored at 60℃for 1 month, and the change in the cumulative 50% particle diameter (D50) of the viscosity before and after the test and the volume basis of the pigment was observed, and the storage stability was evaluated according to the following criteria. The viscosity of the ink was measured at 20℃using a falling ball viscometer (AMVn, manufactured by Anton Paar Co., ltd.), and the volume-based cumulative 50% particle diameter (D50) of the pigment was measured at 25℃using a particle diameter distribution measuring apparatus (NANOTACAVE, manufactured by Microtrac BEL Co., ltd.). In the following evaluation, the one having the larger rate of change of the "viscosity" and the "volume-based cumulative 50% particle diameter (D50)" of the pigment was used as the evaluation (in the table, referred to as "storage stability") of the nonaqueous ink composition.
Evaluation criterion
Evaluation 5: the rate of change of the cumulative 50% particle size (D50) based on the volume of the viscosity and pigment is less than 3%.
Evaluation 4: any one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 3% or more and less than 5%.
Evaluation 3: any one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 5% or more and less than 8%.
Evaluation 2: any one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 8% or more and less than 10%.
Evaluation 1: either one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 10% or more.
(concealment)
The non-aqueous ink compositions of examples, comparative examples and reference examples were evaluated for concealing properties. Specifically, solid printing was performed in a high-quality printing mode (1440×720 dpi) on a recording medium (transparent polyvinyl chloride film with paste (SCP-AS: manufactured by 3M company)) in the same manner AS in the evaluation of the bleeding property, and the solid printing was performed at a substrate surface temperature of 40 ℃ and dried at room temperature for 1 day. Then, the visible light transmittance was measured in the range of 380nm to 780nm by a spectrophotometer (UV-1800: shimadzu corporation) on the scale of 1nm, and the average value obtained by dividing the cumulative value by the number of measurements was recorded as the visible light transmittance.
Evaluation criterion
Evaluation 5: the visible light transmittance is less than 10%.
Evaluation 4: the visible light transmittance is less than 20% and more than 10%.
Evaluation 3: the visible light transmittance is less than 30% and more than 20%.
Evaluation 2: the visible light transmittance is less than 40% and more than 30%.
Evaluation 1: the visible light transmittance is 40% or more.
(ejection stability)
The nonaqueous ink compositions of examples, comparative examples and reference examples were evaluated for ejection stability. Specifically, as in the evaluation of the bleeding property, a solid (japanese: tare) and a thin line were printed by continuous printing at a substrate surface temperature of 40 ℃ in a high-quality printing mode (1440×720 dpi) on a recording medium (a polyvinyl chloride film with paste (IMAGin JT5829R: manufactured by MACtac corporation)), and the presence or absence of drop of ink dots, flying deflection, and scattering of ink were visually observed, and the number of times of generation (in the table, referred to as "ejection stability") was measured.
Evaluation criterion
Evaluation 5: the thin line can be accurately reproduced.
Evaluation 4: the thin line can be reproduced substantially accurately.
Evaluation 3: the thin line slightly observes a bend.
Evaluation 2: the landing position was shifted, and bending was observed.
Evaluation 1: the landing position is severely deviated, and a thin line cannot be reproduced.
(cleaning recovery)
It is evaluated whether or not the nozzle clogging of the ink jet head can be eliminated by the cleaning operation of the printer when the nozzle clogging occurs. Specifically, the ink compositions of examples and comparative examples were filled using an ink jet printer (trade name Versaart RE-640, manufactured by Roland DG Co., ltd.) equipped with a cleaning system, and 1.80m was printed in a high-quality printing mode (1440X 720 dpi) 2 After leaving the solid image of (2) at room temperature of 25℃for 1 week, the pattern was inspected by printing a nozzle, and cleaning was performed until the falling off disappeared (in the table, referred to as "cleaning recovery").
Evaluation criterion
Evaluation 5: and the product is not fallen off.
Evaluation 4: cleaning 1 time eliminates nozzle clogging.
Evaluation 3: cleaning for 2-3 times eliminates nozzle blockage.
Evaluation 2: cleaning for 4-5 times eliminates nozzle blockage.
Evaluation 1: the cleaning was also not done 6 times to eliminate nozzle clogging.
TABLE 2
TABLE 3
TABLE 4
TABLE 5
From the above table, it is clear that the nonaqueous ink composition of the example containing the organic solvent a (at least 1 selected from the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)) can achieve both high cleaning recovery and surface drying on the substrate even with the nonaqueous ink composition containing the white pigment.
In particular, in the nonaqueous ink compositions of examples 1-8 to 1-13 in which the content of the organic solvent a (alkylamide-based solvent) was changed, the recorded matter having particularly high cleaning recovery and excellent surface drying properties was obtained in examples 1-9 to 1-13 in which the content of the organic solvent a (alkylamide-based solvent) (a 1) was in the range of 1 mass% or more and 90 mass% or less than in examples 1-8.
In addition, in the nonaqueous ink compositions of examples 1-1 and 1-23 to 1-26 in which the volume-based cumulative 50% particle diameter (D50) of the white pigment contained was changed, the nonaqueous ink compositions of examples 1-1 and 1-23 to 1-25 in which the volume-based cumulative 50% particle diameter (D50) of the white pigment was in the range of 50nm to 400nm were also capable of providing recorded matter having particularly high cleaning recovery and excellent surface drying properties, as compared with examples 1-26.
The nonaqueous ink compositions of examples 1-1 and 1-16 to 1-22, in which the types of the organic solvent A were changed to the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2), exhibited the effects of the present invention.
The nonaqueous ink compositions of examples 1-1 and 1-29 to 1-31, in which the types of the resins contained therein were changed, exhibited the effects of the present invention.
The nonaqueous ink compositions of examples 1-1, 1-30 to 1-31 and 1-33 to 1-35, in which the ratio of the content of the resin to the content of the white pigment was 0.20 to 1.00, were excellent in hiding performance as compared with examples 1-32 and in ejection stability as compared with example 36.
The nonaqueous ink compositions of examples 1-38 to 1-46, in which the types of other organic solvents were changed, all exhibited the effects of the present invention.
On the other hand, the nonaqueous ink compositions of comparative examples 1-1 to 1-5, which did not contain the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), were inferior in surface drying property, and failed to exhibit the effects of the present invention.
(embodiment 2)
1. Preparation of resin
(1) Acrylic resin
To 300g of diethylene glycol diethyl ether maintained at 100℃were added dropwise a mixture of 150g of methyl methacrylate and 50g of butyl methacrylate with a prescribed amount of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) over 1.5 hours. After completion of the dropwise addition, the mixture was allowed to react at 100℃for 2 hours and then cooled to obtain a colorless transparent polymer solution of methyl methacrylate. Then, the solvent was distilled off sufficiently from the polymer solution to obtain a polymer of methyl methacrylate. In this case, the amount of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was changed, and the polymerization average molecular weight of methyl methacrylate (acrylic resin) was controlled so as to be 10000 to 105000 (the mass of the polymerization initiator used in this case is shown in the following table 6. The "initiator amount" is shown in table 6).
(2) Vinyl chloride-vinyl acetate copolymer resin
After nitrogen substitution, 100 parts by mass of deionized water, 40 parts by mass of methanol, 32 parts by mass of vinyl chloride, 5 parts by mass of vinyl acetate, 0.2 parts by mass of glycidyl methacrylate, 3.55 parts by mass of hydroxypropyl acrylate, 0.1 parts by mass of hydroxypropyl methylcellulose (suspension), 0.026 parts by mass of di-2-ethylhexyl peroxydicarbonate (polymerization initiator), and a predetermined amount of di-3, 5-trimethylhexanol peroxide (polymerization initiator) were charged into an autoclave equipped with a stirring device, and the mixture of 48 parts by mass of vinyl chloride, 0.6 parts by mass of glycidyl methacrylate, and 10.65 parts by mass of hydroxypropyl acrylate was continuously pressed in for 5.4 hours while stirring in a nitrogen atmosphere to raise the temperature to 63 ℃. At the time when the internal pressure of the autoclave reached 0.3MPa, the residual pressure was removed, the resin slurry was taken out after cooling, and the resin slurry was filtered and dried to obtain a vinyl chloride-based copolymer resin. At this time, the amount of di-3, 5-trimethylhexanol peroxide as a polymerization initiator was changed, and the polymerization average molecular weight of the vinyl chloride-vinyl acetate copolymer resin was controlled to 40000 to 90000 (the mass of the polymerization initiator used at this time is described in the following table 6. The mass is described as "initiator amount" in table 6).
TABLE 6
(3) Polyester resin
104 parts by mass of terephthalic acid, 104 parts by mass of isophthalic acid, 79 parts by mass of ethylene glycol, 89 parts by mass of neopentyl glycol, and 0.1 part by mass of tetrabutyl titanate were charged into a round-bottomed flask, and the temperature was slowly raised to 240℃over 4 hours, and the esterification reaction was carried out while removing the distillate from the system. After the completion of the esterification reaction, the pressure was reduced to 10mmHg over 30 minutes, and the temperature was raised to 250℃to conduct the initial polymerization. Then, the polymerization was carried out for 1 hour or less at 1mmHg to obtain a polyester resin.
(4) Polyurethane resin
192.5 parts by mass of polycarbonate diol (PLACCEL CD-220: manufactured by Daicel), 41.6 parts by mass of isophorone diisocyanate (IPDI: manufactured by Evonik) and 100 parts by mass of N, N-Diethylformamide (DEF) were added to a round-bottomed flask, and after mixing uniformly, a mixed solution of 0.01 part by mass of T100 BHJ (catalyst) and 0.09 part by mass of N, N-Diethylformamide (DEF) was added, and reacted at 75℃for 3 hours to obtain a prepolymer having an isocyanate group at the end. To this solution, 250 parts by mass of N, N-Diethylformamide (DEF) was added, and after the solution was uniformly dissolved, a chain extender solution obtained by dissolving 12 parts by mass of 3-aminomethyl-3, 5-trimethylcyclohexylamine (IPD: manufactured by Evonik) in 100 parts by mass of N, N-Diethylformamide (DEF) was added, and the mixture was further stirred at 60℃for 40 minutes. Then, a reaction terminator prepared by dissolving 3.8 parts by mass of monoisopropanolamine (MIPA: manufactured by Daicel) in 50 parts by mass of N, N-diethylformamide was added, and finally 250 parts by mass of N, N-Diethylformamide (DEF) was added to obtain a polyurethane solution having a solid content of 25.0%.
2. Preparation of lustrous pigment
(1) Brightness pigment 1
The coating liquid 1 having the following composition was uniformly applied to a PET film having a thickness of 100 μm by a bar coating method, and dried at 60℃for 10 minutes to form a release resin layer.
Coating liquid 1
Cellulose acetate butyrate (butyl rate 35-39%, manufactured by Kanto chemical Co., ltd.) 3%
Isopropyl alcohol 97%
Next, a metal-containing thin film having a film thickness of 20nm was formed on the release resin layer by using a "VE-1010 side VACUUM vapor deposition apparatus" manufactured by VACUUM DEVICE, inc., to prepare a laminate. The obtained laminate was immersed in an organic solvent, and subjected to peeling, pulverization, and micro-pulverization treatment for 12 hours using a "VS-150 ultrasonic disperser" manufactured by AS ONE, co., ltd.) to obtain a bright pigment dispersion containing the organic solvent and a bright pigment (a metallic bright pigment containing aluminum). The "organic solvent" used herein is the solvent having the largest content among the solvents contained in the nonaqueous ink compositions of examples and comparative examples described later.
The obtained bright pigment dispersion was filtered through a SUS mesh filter having a mesh size of 5 μm to remove coarse particles. Then, the concentration of the lustrous pigment was adjusted to prepare a lustrous pigment dispersion liquid 1 containing 5 mass% of the lustrous pigment 1. The lustrous pigment 1 had a volume-based cumulative 50% particle diameter (D50) of 1.5. Mu.m, a volume-based cumulative 90% particle diameter (D90) of 3.5. Mu.m, and a thickness of 20nm.
(2) Lustrous pigment 2
A lustrous pigment dispersion was produced in the same manner as described above, and a solution obtained by dissolving 5g of stearic acid in 100g of acetone was added to 200g of the lustrous pigment dispersion, and after stirring for 1 hour, the above-described centrifugal separation and washing were performed, and the acetone was replaced with an organic solvent (the solvent having the largest content in the solvents contained in the nonaqueous ink compositions of examples and comparative examples described later), to prepare a lustrous pigment dispersion 2 containing 5 mass% of the lustrous pigment 2. The lustrous pigment 2 had a volume-based cumulative 50% particle diameter (D50) of 1.5. Mu.m, a volume-based cumulative 90% particle diameter (D90) of 3.2. Mu.m, and a thickness of 20nm.
(3) Lustrous pigment 3
In addition to the production of the lustrous pigment 1, the thickness of the metal-containing thin film, the fine-sizing treatment, and the mesh of the mesh filter were changed to prepare a lustrous pigment dispersion 3 containing 5 mass% of the lustrous pigment 3. The lustrous pigment 3 had a volume-based cumulative 50% particle diameter (D50) of 4.8. Mu.m, a volume-based cumulative 90% particle diameter (D90) of 8.2. Mu.m, and a thickness of 100nm.
(4) Lustrous pigment 4
The lustrous pigment dispersion 4 containing the lustrous pigment 4 was prepared by changing the film thickness of the metal-containing thin film, the fine-sizing treatment, and the mesh of the mesh filter in addition to the production of the lustrous pigment 1. The lustrous pigment 4 had a volume-based cumulative 50% particle diameter (D50) of 3.0. Mu.m, a volume-based cumulative 90% particle diameter (D90) of 5.0. Mu.m, and a thickness of 1000nm.
(5) Lustrous pigment 5
In addition to the production of the lustrous pigment 1, the thickness of the metal-containing thin film, the fine-size treatment, and the mesh of the mesh filter were changed by changing aluminum to indium, to prepare a lustrous pigment dispersion 5 containing the lustrous pigment 5. The bright pigment 5 had a volume-based cumulative 50% particle diameter (D50) of 0.05 μm, a volume-based cumulative 90% particle diameter (D90) of 1.0 μm and a thickness of 5nm.
(6) Brightness pigment 6
The bright pigment dispersion 6 containing the bright pigment 6 was prepared by changing aluminum to nickel, changing the thickness of the metal-containing thin film, and changing the mesh of the mesh filter and the fine treatment, in addition to the production of the bright pigment 1. The bright pigment 5 had a volume-based cumulative 50% particle diameter (D50) of 3.8 μm, a volume-based cumulative 90% particle diameter (D90) of 5.0 μm and a thickness of 5nm.
3. Production of nonaqueous ink composition
The nonaqueous ink compositions of examples and comparative examples were prepared so that the proportions of the organic solvent, resin, dispersant and brightening pigment were as shown in the following table. Specifically, the nonaqueous ink compositions of examples and comparative examples were adjusted so that the proportions of the pigment dispersion, the organic solvent, the resin, the dispersant and the additive were as shown in the following table. The unit is mass%.
4. Evaluation
(bleeding Property)
The nonaqueous ink compositions of examples and comparative examples were evaluated for bleeding property. Specifically, the nonaqueous ink compositions of examples and comparative examples were printed on a recording medium (polyvinyl chloride film with paste (IMAGIN JT5829R: manufactured by MACTac Co.) in a high-quality printing mode (1440×720 dpi) at a substrate surface temperature of 40 ℃ C. With a letter 6pt in the solid portion of each color, and the obtained printed matter was dried in an oven at 60 ℃ C. For 5 minutes by using an ink jet system of a trade name Versaart RE-640, manufactured by RolandDG Co., ltd.), and then the bleeding of the printed matter was observed by a visual observation and a magnifying glass (x 10) (in the table, referred to as "bleeding property").
Evaluation criterion
Evaluation 5: no bleeding of the ink was observed when observed with a magnifying glass.
Evaluation 4: no bleeding of the ink was observed visually, and the 6pt text was clear.
Evaluation 3: bleeding of the ink was slightly observed by visual observation, but the design was not impaired.
Evaluation 2: the bleeding of the ink was visually observed, but a 6pt character was recognized.
Evaluation 1: the bleeding of the ink was visually observed remarkably, and 6pt characters could not be visually recognized.
(surface drying Property)
The nonaqueous ink compositions of examples and comparative examples were evaluated for surface drying properties. Specifically, as in the evaluation of bleeding property, solid images were printed in a high-quality printing mode (1440×720 dpi) on a recording medium (a polyvinyl chloride film with paste (IMAGin JT5829R: manufactured by MACtac)), and the time until drying at 40 ℃ was measured (in the table, the time was referred to as "surface drying property").
Evaluation criterion
Evaluation 5: drying in less than 2 minutes.
Evaluation 4: drying in more than 2 minutes and less than 4 minutes.
Evaluation 3: drying in more than 4 minutes and less than 6 minutes.
Evaluation 2: drying in more than 6 minutes and less than 8 minutes.
Evaluation 1: drying for 8 min or more.
(storage stability)
The nonaqueous ink compositions of examples and comparative examples were evaluated for storage stability. Specifically, the nonaqueous ink composition was stored at 60℃for 1 month, and the change in the cumulative 50% particle diameter (D50) of the viscosity before and after the test and the volume basis of the pigment was observed, and the storage stability was evaluated according to the following criteria. The viscosity of the ink was measured at 20℃using a falling ball viscometer (AMVn, manufactured by Anton Paar Co., ltd.), and the volume-based cumulative 50% particle diameter (D50) of the pigment was measured at 25℃using a particle diameter distribution measuring apparatus (NANOTACAVE, manufactured by Microtrac BEL Co., ltd.). In the following evaluation, the one having the larger rate of change of the "viscosity" and the "volume-based cumulative 50% particle diameter (D50)" of the pigment was used as the evaluation (in the table, referred to as "storage stability") of the nonaqueous ink composition.
Evaluation criterion
Evaluation 5: the rate of change of the cumulative 50% particle size (D50) based on the volume of the viscosity and pigment is less than 3%.
Evaluation 4: any one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is less than 3% or more and less than 5%.
Evaluation 3: any one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 5% or more and less than 8%.
Evaluation 2: any one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 8% or more and less than 10%.
Evaluation 1: either one of the viscosity and the rate of change of the cumulative 50% particle diameter (D50) based on the volume of the pigment is 10% or more.
(ejection stability)
The nonaqueous ink compositions of examples and comparative examples were evaluated for ejection stability. Specifically, as in the evaluation of the bleeding property, solid and thin lines were printed on a recording medium (a polyvinyl chloride film with paste (IMAGin JT5829R: manufactured by MACtac corporation)) in a high-quality printing mode (1440×720 dpi) at a substrate surface temperature of 40 ℃ by continuous printing, and the presence or absence of drop of ink dots, flying deflection, and scattering of ink was visually observed, and the number of times of generation (in the table, referred to as "ejection stability") was measured.
Evaluation criterion
Evaluation 5: the thin line can be correctly reproduced.
Evaluation 4: the thin line can be reproduced substantially accurately.
Evaluation 3: the thin line slightly observes a bend.
Evaluation 2: the landing position was shifted, and bending was observed.
Evaluation 1: the landing position is severely deviated, and a thin line cannot be reproduced.
(evaluation of nozzle clogging)
The nonaqueous ink compositions of examples, comparative examples and reference examples were evaluated for clogging of the ink jet printer. Specifically, the ink compositions of examples and comparative examples were filled in an inkjet printer (trade name: versaart RE-640, manufactured by Roland DG Co., ltd.), and the nozzle check pattern was printed to confirm that the ink was discharged from all the nozzles. Then, after the inkjet head was reciprocated for 30 minutes without discharging ink, the nozzle check pattern was printed again, and the number of nozzles which were not discharged was counted. The operating environment of the printer was set at 40℃at room temperature and 60% relative humidity. (the table is described as "evaluation of nozzle clogging")
Evaluation criterion
Evaluation 5: no ejection of less than 5
Evaluation 4: 6-10 non-spraying materials
Evaluation 3: no ejection of 11-15
Evaluation 2: the number of the non-ejected materials is 16 to 20
Evaluation 1: not ejecting more than 21
(glossiness)
The glossiness of the printed matter obtained using the nonaqueous ink compositions of examples and comparative examples was evaluated. Specifically, the printed matter was produced by ejecting the ink onto the surface of a recording medium (a pasted polyvinyl chloride film (IMAGIN JT5829R: manufactured by MACTac Co.) in the same manner as the evaluation of the bleeding property described above, and drying the ink. The resultant printed matter was measured for L at a measurement angle by using a multi-angle color measuring system CM-M6 manufactured by Konikoku Megawa Co., ltd.) in which incident light was made incident on the shining layer at an incident angle of 45 DEG from the printed surface, and an angle obtained by changing the angle from the reflection angle with respect to the incident angle to the normal direction by 15 DEG was used as the measurement angle * a * b * L in the color system * The value was evaluated for gloss (referred to as "gloss" in the table) according to the following evaluation criteria.
Evaluation criterion
Evaluation 5: the brightness index is 120 or more.
Evaluation 4: the brightness index is 110 or more and less than 120.
Evaluation 3: the brightness index is 100 or more and less than 110.
Evaluation 2: the brightness index is 90 or more and less than 100.
Evaluation 1: the brightness index is less than 90.
(cleaning recovery)
With respect to the nonaqueous ink compositions of examples and comparative examples, when nozzle clogging in the inkjet head occurred, it was evaluated whether or not nozzle clogging could be eliminated by the cleaning operation of the printer. Specifically, the ink compositions of examples and comparative examples were filled using an ink jet printer (trade name Versaart RE-640, manufactured by Roland DG Co., ltd.) equipped with a cleaning system, and 1.80m was printed in a high-quality printing mode (1440X 720 dpi) 2 After leaving at room temperature for 1 day at 25 ℃, the pattern was inspected by printing a nozzle, and cleaning was performed until the fall-off disappeared (in the table, referred to as "cleaning recovery").
Evaluation criterion
Evaluation 5: cleaning for 0-4 times to eliminate nozzle blockage.
Evaluation 4: cleaning for 5-6 times to eliminate nozzle blockage.
Evaluation 3: cleaning for 7-8 times to eliminate nozzle blockage.
Evaluation 2: cleaning for 9-10 times to eliminate nozzle blockage.
Evaluation 1: nozzle clogging was not eliminated even with 10 cleans.
TABLE 7
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TABLE 8
TABLE 9
TABLE 10
From the above table, it is clear that the nonaqueous ink composition of the example containing the organic solvent a (at least 1 selected from the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)) can achieve both high cleaning recovery and surface drying on the substrate even with the nonaqueous ink composition containing the brightening pigment.
It is also clear that even when the glossy layer is formed from the nonaqueous ink composition of the example containing the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)), the glossy layer can have an improved glossiness, and can impart a preferable metallic luster.
In particular, in the nonaqueous ink compositions of examples 2-8 to 2-13 in which the content of the organic solvent a (alkylamide-based solvent) was changed, the recorded matter having particularly high cleaning recovery and excellent surface drying properties was obtained in examples 2-9 to 2-13 in which the content of the organic solvent a (alkylamide-based solvent) (a 1) was in the range of 1 mass% or more and 90 mass% or less, as compared with examples 2-8.
The nonaqueous ink compositions of examples 2-1 and 2-16 to 2-22, in which the types of the organic solvent A were changed to the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2), each exhibited the effects of the present invention.
The nonaqueous ink compositions of examples 2-1 and 2-23 to 2-27, in which the volume-based cumulative 50% particle diameter (D50) of the luminance pigment contained was changed, also gave recorded matter having particularly high cleaning recovery and excellent surface drying properties, as compared with examples 2-28.
The nonaqueous ink compositions of examples 2-30 to 2-34, in which the types of the resins contained therein were changed, and the nonaqueous ink compositions of examples 2-35 to 2-37, in which the resins contained therein were not contained, all exhibited the effects of the present invention.
The nonaqueous ink compositions of examples 2-45 to 2-50 and 2-53 to 2-58, in which the types of the other organic solvents were changed, all exhibited the effects of the present invention. In addition, since the storage stability of the nonaqueous ink compositions of examples 2-53 to 2-58, which did not contain an acetate solvent, was slightly lowered, it was confirmed that the storage stability of the nonaqueous ink composition containing a brightening pigment could be improved if the nonaqueous ink composition contained an acetate solvent.
On the other hand, the non-aqueous ink compositions of comparative examples 2-1 to 2-6 which did not contain the organic solvent a (at least 1 selected from the group consisting of the alkylamide-based solvent (a 1) and the cyclic amide-based solvent (a 2)) were inferior in surface drying property, and the effect of the present invention could not be exhibited.
Claims (38)
1. A nonaqueous ink composition which contains a coloring material and an organic solvent and is to be discharged by an inkjet method,
the colorant comprises a white pigment and is,
the organic solvent contains an organic solvent A,
organic solvent a: at least 1 selected from the group consisting of an alkylamide solvent a1 and a cyclic amide solvent a 2.
2. The non-aqueous ink composition according to claim 1, wherein the white pigment contains an inorganic oxide.
3. The non-aqueous ink composition according to claim 2, wherein the white pigment contains titanium oxide.
4. The non-aqueous ink composition according to any one of claims 1 to 3, wherein the content of the white pigment is 8 mass% or more and 20 mass% or less in the total amount of the non-aqueous ink composition.
5. The non-aqueous ink composition according to any one of claims 1 to 4, further comprising a surfactant,
The surfactant contains a surfactant having a siloxane skeleton,
the content of the surfactant having a siloxane skeleton is 0.01 mass% or more and 1.0 mass% or less.
6. The non-aqueous ink composition according to any one of claims 1 to 5, which is used for forming at least 1 or more base layers or upper base layers selected from a black ink composition, a colored ink composition, a clear ink composition and a clear ink composition.
7. A nonaqueous ink composition which contains a brightening pigment and an organic solvent and is to be ejected by an inkjet method,
the organic solvent contains an organic solvent A,
organic solvent a: at least 1 selected from the group consisting of an alkylamide solvent a1 and a cyclic amide solvent a 2.
8. The non-aqueous ink composition according to claim 7, wherein the glitter pigment contains a metallic glitter pigment.
9. The non-aqueous ink composition according to claim 8, wherein the metallic lustrous pigment comprises at least 1 selected from the group consisting of aluminum, aluminum alloy, indium alloy, nickel, and nickel alloy.
10. The non-aqueous ink composition according to claim 9, wherein the metallic lustrous pigment comprises at least aluminum or an aluminum alloy.
11. The non-aqueous ink composition according to any one of claims 8 to 10, wherein the cumulative 50% particle diameter D50 on a volume basis of the metallic lustrous pigment is 0.01 μm or more and 5.0 μm or less,
the cumulative 90% particle diameter D90 based on the volume of the metallic lustrous pigment is 10.0 μm or less.
12. The non-aqueous ink composition according to any one of claims 8 to 11, wherein the metallic lustrous pigment is a particle having a flat face.
13. The non-aqueous ink composition according to claim 12, wherein the metallic lustrous pigment comprises a plate-like or scale-like metallic lustrous pigment.
14. The non-aqueous ink composition according to claim 13, wherein the thickness of the plate-like or scale-like metallic lustrous pigment is in a range of 5nm or more and 5.0 μm or less.
15. The non-aqueous ink composition according to any one of claims 7 to 14, wherein the organic solvent further comprises an acetate-based solvent represented by the following formula (2-3),
in the formula (2-3), X 1 Is alkyl, X 2 Is hydrogen or alkyl, and n represents an integer of 1 to 4 inclusive.
16. The non-aqueous ink composition according to any one of claims 7 to 15, which is used for forming at least 1 or more base layers or upper base layers selected from a black ink composition, a colored ink composition, a clear ink composition, and a clear ink composition.
17. The nonaqueous ink composition according to any one of claims 1 to 16, wherein a content of the organic solvent a is 1.0 mass% or more and 90.0 mass% or less in a total amount of the nonaqueous ink composition.
18. The non-aqueous ink composition according to any one of claims 1 to 17, wherein the organic solvent a contains the alkylamide-based solvent a1.
19. The non-aqueous ink composition according to claim 18, wherein the alkylamide-based solvent is represented by the following general formula (1),
in the formula (1), R 1 Is hydrogen or alkyl with carbon number of 1-4, R 2 、R 3 Each independently represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
20. The non-aqueous ink composition according to claim 19, wherein the alkylamide-based solvent contains at least 1 selected from the group consisting of N, N-diethylformamide, N-diethylpropionamide and N, N-diethylacetamide.
21. The non-aqueous ink composition according to any one of claims 1 to 17, wherein the organic solvent a contains the cyclic amide-based solvent a2.
22. The non-aqueous ink composition according to claim 21, wherein the cyclic amide-based solvent is represented by the following general formula (2),
In the formula (2), R 4 Is an alkylene group having 3 to 5 carbon atoms, R 5 Represents hydrogen or an alkyl group having 1 to 4 carbon atoms or an unsaturated hydrocarbon group.
23. The non-aqueous ink composition according to claim 22, wherein the cyclic amide-based solvent contains at least 1 selected from epsilon-caprolactam, N-methyl-epsilon-caprolactam, and N-vinyl caprolactam.
24. The non-aqueous ink composition according to any one of claims 1 to 23, wherein the organic solvent further contains at least 1 selected from the group consisting of glycol ether solvents, acetate solvents, cyclic esters, carbonates, dibasic acid esters, lactic acid esters, amides, and alcohols.
25. The non-aqueous ink composition according to any one of claims 1 to 24, wherein the organic solvent contains a glycol ether-based solvent.
26. The non-aqueous ink composition according to claim 25, wherein the glycol ether-based solvent contains a glycol dialkyl ether.
27. The non-aqueous ink composition according to claim 25 or 26, wherein the glycol ether-based solvent contains a glycol monoalkyl ether.
28. The non-aqueous ink composition according to any one of claims 25 to 27, wherein the glycol ether-based solvent contains at least 2 solvents having different flash points.
29. The non-aqueous ink composition according to any one of claims 1 to 28, further comprising a resin.
30. The nonaqueous ink composition according to claim 29, wherein a content of the resin is in a range of 0.1 mass% or more and 10.0 mass% or less in a total amount of the nonaqueous ink composition.
31. The non-aqueous ink composition according to claim 29 or 30, wherein the resin contains at least 1 or more selected from an acrylic resin, a vinyl chloride resin, a polyurethane resin, a polyester resin and a cellulose resin.
32. The non-aqueous ink composition according to any one of claims 29 to 31, wherein the non-aqueous ink composition is a white ink composition containing a white pigment,
the ratio of the content of the resin to the content of the white pigment is 0.20 to 1.00.
33. An ink set comprising the non-aqueous ink composition of any one of claims 1 to 32.
34. An ink set comprising the non-aqueous ink composition according to any one of claim 1 to 32,
the non-aqueous ink composition is a white ink composition containing a white pigment,
The nonaqueous ink composition is ejected onto the surface of a substrate by an inkjet method simultaneously with at least 1 or more selected from the group consisting of a black ink composition, a colored ink composition, a clear ink composition, and a clear ink composition.
35. An ink set comprising the non-aqueous ink composition according to any one of claim 1 to 32,
the non-aqueous ink composition is a brightening ink composition containing a brightening pigment,
the nonaqueous ink composition is ejected simultaneously with at least 1 or more selected from the group consisting of a black ink composition, a colored ink composition, a white ink composition, and a transparent ink composition onto the surface of a substrate by an ink jet method.
36. A recorded matter comprising a substrate and, formed on a surface thereof, a recording layer of the nonaqueous ink composition according to any one of claims 1 to 32.
37. A recording method of ejecting the nonaqueous ink composition according to any one of claims 1 to 32 onto a surface of a substrate by an inkjet method.
38. A method for producing a recorded matter by ejecting the nonaqueous ink composition according to any one of claims 1 to 32 onto a surface of a substrate by an inkjet method.
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