WO2007072804A1 - Nonaqueous inkjet ink composition and printed matter obtained by using same - Google Patents

Abstract

Disclosed is a nonaqueous inkjet ink composition having good wettability and fixability to a base whose printing surface is mainly composed of a vinyl chloride polymer or an ethylene-vinyl acetate copolymer, while having excellent ejection stability. Specifically disclosed is a nonaqueous inkjet ink composition containing at least one vinyl polymer as a binder resin which is selected from the group consisting of vinyl chloride polymers, vinyl chloride-vinyl acetate copolymers and ethylene-vinyl acetate copolymers, a coloring agent and an organic solvent. This nonaqueous inkjet ink composition is characterized in that the organic solvent contains a polyalkylene glycol dialkyl ether represented by the general formula (I) below in an amount of 15-30% by mass relative to the total mass of the organic solvent. R1-O-(-CH2-CHX-O-)n-R2 (I)

Description

 Specification

 Non-aqueous inkjet ink composition and printed matter obtained using the same

 [0001] The present invention has good wettability and fixability to a base sheet whose printing surface is mainly a vinyl chloride polymer or an ethylene vinyl acetate copolymer, and has high ejection stability. The present invention relates to a non-aqueous ink jet ink composition suitable for producing large-sized billboard advertisements that can be maintained for a long time, and a printed matter obtained by using the ink composition. Background art

 [0002] In recent billboard advertisements, in addition to logos and patterns with vivid and sophisticated designs, there are an increasing number of photographic styles such as the appearance of products and the faces of people. In addition, the size of the signboard has become so large that it can be seen more and more so that the viewer has a stronger impact.

 [0003] Conventionally, as a method of producing a signboard advertisement, it has been common to cut and paste a colored sheet into a character shape in the case of a logo, or to use various printing machines in the case of a photographic tone. For this reason, there were a number of problems such as requiring a lot of time and labor for production, and requiring large-scale equipment such as a printing machine. Therefore, in order to more easily produce a clear image signboard, an attempt has been made to use an ink jet method capable of directly printing a design created on a personal computer (hereinafter referred to as a PC) on a base material.

 [0004] The ink jet method has a feature that it can be easily printed on sheets of paper, polymers, metals, and other hard and soft materials that can be used as a substrate for printing. In particular, billboard advertisements installed outdoors are required to be lightweight, excellent in strength and durability, resistant to rain, and inexpensive, so it is easy to print on polymer sheets with these characteristics. It will be a very big advantage. In addition, an ultra-wide format inkjet printer with a printing width of 2, OOOmm or more has recently appeared, making it easier to print large-format prints that have been supported by pasting together. You can now make signboards!

[0005] On the other hand, water-based tie has been the main development of inkjet inks so far. This type of ink is repelled on the surface of the polymer sheet and cannot be printed (insufficient wettability). Therefore, a new non-aqueous ink for polymer sheets based on organic solvents has been developed. For example, a technique of using a (poly) alkylene glycol derivative and a nitrogen-containing heterocyclic compound as an organic solvent (JP 2005/2005) — No. 23298), and a technique for mixing organic solvents having different vapor pressures at a specific ratio (Japanese Patent Laid-Open No. 2005-36199) has been proposed. However, in order to obtain a good printed matter, in addition to the above-mentioned wettability to the surface, various ink performances such as dryness and adhesion to the substrate (usually referred to as fixability) are necessary. The physical properties of these often affect their performance directly or indirectly.

 [0006] Since the surface of the polymer sheet is impermeable, drying mainly depends on the evaporation rate of the solvent, but an organic solvent having an excessive evaporation rate decreases the ejection stability in the ink jet system. Therefore, it is an important issue to efficiently obtain a printed material with good power on how to achieve the balance. Also, if the fixability of the ink film on the printing substrate is not good, the ink film immediately peels off the printing substrate force, making it impossible to maintain a clear printed product for a long period of time. The fixability of the ink depends mainly on the performance of the fixative resin (binder resin). However, the organic solvent must dissolve the fixative resin, and in this case, the fixability depends on the organic solvent used. It depends indirectly on the physical properties. In addition, when using an organic solvent that slightly dissolves the surface of the polymer sheet, which is the base material, during the drying process, the fixability is improved, so the fixability is directly related to the physical properties of the organic solvent used. It can be said that it depends on the situation. Since there are a wide variety of polymer sheets, it is necessary to design them individually according to the type of polymer used as a printing substrate in order to satisfy the above conditions and obtain a good ink composition. .

[0007] Generally, a polymer sheet called turbolin is often used for billboard advertisements. Tarpaulin is a composite sheet in which polyester or polyamide is used as a core material, and vinyl polymers such as polysalt polybutyl and ethylene acetate butyl copolymer are laminated on both sides. For this reason, as described above, the ink for printing with tarpaulin is made of a material having good wettability, drying property, fixing property, etc. with respect to the above-mentioned bull polymer as a material of the sheet surface. It is necessary to use it. [0008] The ink described in the above Japanese Patent Application Laid-Open No. 2005-23298 is intended for a polysilicic resin sheet as a printing substrate, but is exemplified as a suitable binder resin. There is a limit to improving the fixability of system resin, polyester resin, polyurethane resin, nitrocellulose and the like. On the other hand, the salt-vinyl resin similar to the base material has a good fixing property, but for the solvent specifically exemplified in JP-A-2005-23298, There is a problem that the ink does not exhibit sufficient solubility and becomes the most important ink with low ejection stability when used in an ink jet system.

 [0009] In addition, the invention described in the above Japanese Patent Application Laid-Open No. 2005-36199 is also directed to a vinyl chloride polymer sheet, but for that purpose, it depends only on the evaporation rate of the organic solvent. In addition, it cannot be said that there is some effect on the ink performance that becomes satisfactory only when the conditions of specific mathematical formulas (1) to (3) are satisfied. However, performance such as wettability and fixability that changes in any way due to factors that have nothing to do with the evaporation rate of organic solvents (the water resistance and light resistance described as effective in this invention also change) As for the technology for obtaining a high level of performance, it is completely disclosed.

 Disclosure of the invention

 Accordingly, the problem to be solved by the present invention is that the wettability and the fixability are good for a substrate whose printing surface is mainly a vinyl chloride polymer or an ethylene acetate butyl copolymer, It is an object of the present invention to provide a non-aqueous inkjet ink composition having excellent ejection stability during inkjet printing and after a long rest period.

[0011] As a result of diligent studies to solve the above problems, the present inventors have found that, in a non-aqueous inkjet ink composition containing a colorant, a binder resin, and an organic solvent, Use at least one vinyl polymer selected from the group consisting of a salt vinyl polymer, a vinyl chloride-vinyl acetate copolymer and an ethylene vinyl acetate copolymer, and an organic solvent. As a result, it has been found that the above-mentioned problems can be realized by containing a specific amount of a specific polyalkylene glycol dialkyl ether in an organic solvent, and the present invention has been completed.

That is, the present invention provides the following non-aqueous inkjet ink composition and a printed matter obtained using the same. [0013] (1) As a binder resin, a group power consisting of a salt vinyl polymer, a salt vinyl bisacetate butyl copolymer and an ethylene acetate butyl copolymer is selected. A polyalkylene glycol dialkyl ether represented by the following general formula (I) as the organic solvent: 15-30% by mass in the total organic solvent. A non-aqueous inkjet ink composition characterized by

[0014] R ¹ — Ο (one CH— CHX— Ο) one R ² (I)

 2 η

[Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, η is an integer of 3 to 6, and η Xs are each independently a hydrogen atom or a methyl group] .

[0015] (2) The ink composition for non-aqueous ink jet according to the above (1), wherein triethylene glycol dialkyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I).

 [0016] (3) Item (1) or (2) above, wherein at least one of triethylene glycol dimethyl ether and triethylene glycol jetyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I). Item 10. A non-aqueous ink jet ink composition according to the item.

 [0017] (4) The colorant is a pigment having a functional group that reacts with a carbodiimide group, and the non-aqueous inkjet ink composition contains a force carbodiimide compound having a carbodiimide group as a pigment dispersant. The ink thread and composition for non-aqueous ink jets according to any one of items (1) to (3).

[0018] (5) The non-aqueous ink jet ink composition according to any one of (1) to (4), wherein a salty vinyl polymer is used as the vinyl polymer.

[0019] (6) The non-aqueous solution according to any one of the above items (1) to (5), wherein at least a surface layer is made of a vinyl chloride polymer or an ethylene vinyl acetate copolymer. Printed matter obtained by printing an ink composition for inkjet.

[0020] (7) A printed matter obtained by printing the non-aqueous ink jet ink composition described in the above item (5) on a base material having at least a surface vinyl chloride polymer strength.

BEST MODE FOR CARRYING OUT THE INVENTION [0021] Hereinafter, the present invention will be described in more detail.

 [0022] The non-aqueous inkjet ink composition of the present invention contains a binder resin, a colorant, and an organic solvent.

 [0023] The binder resin constituting the non-aqueous ink jet ink composition of the present invention is selected from a group power consisting of a chlorinated bull-based polymer, a vinyl chloride-vinyl acetate-based copolymer, and an ethylene-vinyl acetate-based copolymer. At least one vinyl polymer is used. Salt-bulb polymers include salt-bulb homopolymers (polysalt-bulls) and other small amounts of copolymerizable monomers such as vinyl acetate, ethylene, And a copolymer with a salty vinylidene, etc.). As the salt butyl-vinyl acetate copolymer and ethylene acetate butyl copolymer, those usually used in this type of ink can be used without particular limitation. The molecular weight of Noinda rosin is preferably about 2,000 to 100,000 in terms of weight average molecular weight from the viewpoints of solubility in solvents, viscosity of the resulting ink composition, ejection stability, and the like. If at least the surface layer is printed on a base material having a vinyl chloride polymer (especially polysalt vinyl) or ethylene acetate vinyl copolymer, the salt resin polymer (especially polysalt polymer) is used as a binder resin.匕 匕 Bull) is preferred.

 [0024] The amount of the above-mentioned Noinda rosin is preferably in the range of 1 to 15% by mass, more preferably 1 to 7% by mass, based on the total amount of the non-aqueous inkjet ink composition. If the amount of the binder resin used is less than the above range, the fixing property to the substrate is not sufficient. On the other hand, if the amount exceeds the above range, the solid content increases excessively, so that the discharge stability is lowered.

 [0025] It should be noted that, within the range where the performance does not deteriorate, a resin other than the above binder resin, for example, an acrylic resin, a styrene acrylic resin, a styrene maleic resin, a rosin resin, a rosin Ester resin, petroleum resin, coumarone indene resin, terpene phenol resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin Fat, alkyd resin, aliphatic hydrocarbon resin, petital resin, maleic acid resin, fumaric acid resin, etc. can be used in combination.

[0026] Next, as the colorant constituting the non-aqueous inkjet ink composition of the present invention, the dyes used in conventional non-aqueous inkjet ink compositions, and z or Pigments can be used without particular limitation.

 [0027] When a dye is used as a colorant, a conventionally known dye can be used, and specific examples include CI Direct Black 17, 19, 22, 32, 38, 51, 71. C.I.Direct Yellow 4, 26, 44, 50, CI Direct Red 1, 4, 23, 3 31, 37, 39, 75, 80, 81, 83 , 225, 226, 227, CI direct blue 1, 1, 15, 41, 71, 86, 87, 106, 108, 199, etc., and CI Acid Black 1, 2, 24, 26, 31, 52, 107, 109, 110, 119, 154, CI Acid Yellow 1, 7, 17, 19, 19, 23, 25, 29, 38, 42, 49, 61, 72, 78, 110, 127, 135, 141, 142, CI Acid Red 8, 9, 14, 14, 18. 26, 27, 35, 37, 51, 51 52, 57, 82, 83, 87, 92, 94, 111, 129, 131, 138, 186, 249, 254, 265, 276, CI Acid Violet 15, 17, 17, 9 CI Acid Blue 1, 7, 7, 9, 15, 22, 23, 25, 40, 41, 4 3, 62, 78, 83 , 90, 93, 100, 103, 104, 112, 113, 158, CI Acid Green 3, 9, 16, 25, 27, CI Acid Orange 56, etc. Food dyes such as CI Food Yellow 3, Malachite Green (CI 420 00), Vik HJ Ablue FB (CI 44045), Methyl Biolet® FN (CI 42535), Mouth Damine F4G (CI 45160), Rhodamine 6GCP (CI 45160 ) And other basic dyes. These dyes can be used singly or in combination of two or more, and the amount used is preferably in the range of 2 to 15% by weight, more preferably 5% to the total amount of the non-aqueous inkjet ink composition. ~ 10% by weight. When the amount of the dye used is less than the above range, the coloring power tends to be insufficient. On the other hand, when the amount exceeds the above range, the solid content tends to increase, and thus the discharge stability tends to decrease.

 [0028] When a pigment is used as the colorant, conventionally known inorganic pigments, organic pigments, and the like can be used.

[0029] Specific examples of inorganic pigments include carbon black, titanium oxide, zinc white, zinc oxide, tribon, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate. , Silica, alumina, cadmium red, bengara, moly Buden Red, Chrome Vermillion, Molybdate Orange, Yellow Lead, Chrome Yellow, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Chromium Oxide, Pyridian, Cobalt Green, Titanium Cobalt Green, Cobalt Chrome Green, Ultramarine Blue, Ultramarine Blue, Bitumen, Examples include cobalt blue, senorelian bunore, manganese violet, cobalt violet, and my strength.

 [0030] Examples of organic pigments include azo, azomethine, polyazo, phthalocyanine, quinatalidone, anthraquinone, indigo, indigo, quinophthalone, benzimidazolone, isoindoline, iso Organic pigments such as indolinone are listed. Specific examples are shown by color index: pigment black 7, pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, Pigment Neolet 19, 23, 29, 30, 37, 40, 50, Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 13 8, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, pigment orange 36, 43, 51, 55, 59, 61, 71, 74 etc.

 [0031] These pigments can be used singly or in combination of two or more, and the amount used is preferably 1 to: LO mass% with respect to the total amount of the non-aqueous inkjet ink composition, and more Preferably it is 2-7 mass%. If the amount of the pigment used is less than the above range, the coloring power tends to be insufficient. On the other hand, if it exceeds the above range, the viscosity tends to increase and the fluidity of the ink tends to decrease.

 [0032] As the colorant used in the non-aqueous inkjet ink composition of the present invention, it is preferable to use a pigment among the above colorants from the viewpoint of light resistance.

 [0033] When a pigment is used, it has a group (for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, etc.) that reacts with a carpositimide group as a pigment from the viewpoint of stably dispersing the pigment in an organic solvent. It is preferable to use a calpositimide compound having a carposimide group among the pigment dispersants described later as a pigment dispersant.

[0034] If there is no functional group that reacts with the carposimide group on the pigment surface, it can be introduced by surface treatment. For example, “Pigment dispersion stabilization and surface treatment technology” evaluation, technical information Incorporated, December 25, 2001, first edition issued, plasma treatment described on pages 76-85, oxygen Z ultraviolet treatment, low temperature plasma method described in JP-A-58-217559, etc.

 Next, as the organic solvent constituting the non-aqueous ink jet ink composition of the present invention, polyalkylene glycol dialkyl ether represented by the general formula (I) is used in the non-aqueous ink jet ink composition. Use by containing 15-30% by mass of the total organic solvent.

[0036] R ¹ — O (one CH—CHX— O) one R ² (I)

 2 n

[Wherein, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, n is an integer of 3 to 6, and n Xs are each independently a hydrogen atom or a methyl group] .

Here, n is the number of repeating structural units represented by (—CH—CHX—O 2). General

 2

In the formula (I), examples of the alkyl group having 1 to 3 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

 [0038] If the amount of polyalkylene glycol dialkyl ether represented by the general formula (I) is less than the above range, good wettability and fixability tend not to be obtained, while if more than the above range, When using a substrate whose surface layer is made of a salty bulle polymer or an ethylene acetate bur copolymer as the substrate, the surface of the substrate may be melted too much, resulting in unevenness on the surface of the printed material. It tends to occur or cause a decrease in gloss.

 [0039] Among the polyalkylene glycol dialkyl ethers represented by the general formula (I), triethylene glycol dimethyl ether, triethylene glycol jetyl ether, and the like from the viewpoint of solubility of the resin and printability. Of these, triethylene glycol dialkyl ether is preferred, and triethylene glycol dimethyl ether is preferred.

[0040] As the solvent other than the polyalkylene glycol dialkyl ether, those conventionally used in non-aqueous ink jet ink compositions can be used.

[0041] In addition to the polyalkylene glycol dialkyl ether represented by the general formula (I), an organic solvent in which the salt vinyl polymer and ethylene vinyl acetate copolymer in the surface layer of the substrate are soluble is used. Can be used together. Specific examples of such organic solvents include methyl ether. Noreketone, butinole acetate, dioxane, cyclohexane, cyclohexanone, β-latatam, 2-pyrrolidone, Ν-methyl-2-pyrrolidone, Ν, ジ メ チ ル dimethylformamide, Ν, Ν dimethylacetamide, etc. Of these, those having a boiling point of 150 ° C or higher are preferably used. When these organic solvents are used in combination, the total amount of the organic solvent and the polyalkylene glycol dialkyl ether represented by the general formula (I) is 30% by mass with respect to the total organic solvent in the non-aqueous inkjet ink composition. It is preferable to use it within the following range.

Examples of the organic solvent used in the non-aqueous inkjet ink composition of the present invention include the above-mentioned organic solvents in which the salt vinyl polymer and the ethylene acetate butyl copolymer are soluble in the surface layer of the substrate. An organic solvent can be used in combination with a salt vinyl polymer or ethylene vinyl acetate copolymer in the surface layer of the base material which is not dissolved at all or hardly dissolved. Such an organic solvent is not particularly limited, but in order to stably eject ink as an ink composition for a non-aqueous ink jet, a solvent having a boiling point of 140 ° C. or higher is used. preferable. The upper limit of the boiling point is not particularly limited, but is preferably 250 ° C. or less from the viewpoint of ink drying properties. Specific examples include glycols such as ethylene glycol, diethylene glycolate, triethylene glycol, propylene glycol, and dipropylene glycol mononole, ethylene glycol monomethyl enoenoate acetate, and ethylene glycol monomethinoatenoate acetate. , Ethylene glycol monobutinoreate norecetate, diethylene glycol nole monomethenoate ethere acetate, diethylene glycol nore monoethinoatenore acetate, diethylene glycol monobutyl ether acetate, propylene glycol nole monomethinoate noate acetate, dipropylene glycol Glycol alkyl ether acetates such as nomonomethyl ether acetate, ethylene glycol monobutinole Tenoré, propylene glycolenomonobutylenoateol, diethylene glycolenomonochinenoateolate, diethyleneglycolenomonobutinoylenotenole, diethyleneglycoldimethylether, diethyleneglycoljetylether, diethyleneglycolonebutinoateline, dipropyleneglycol Monomethyl ether, dipropylene glycolenomonoethylenole ether, dipropylene glycolenomonobutinoreether, triethylene glycolenomonomethylenoether, triethylene glycolenomonoethylenoether, triethylene glycol Examples thereof include glycol ethers such as ethylene glycol-monomonobutenoate ethere and tripropylene glycol monomethyl ether, and esters such as hexyl acetate, octyl acetate, methyl lactate, ethyl lactate, propyl lactate and butyl lactate. The organic solvent is preferably used in the range of 85 to 70% by mass with respect to the total organic solvent in the non-aqueous inkjet ink composition.

 In the non-inkjet ink composition of the present invention, when a pigment is used as a colorant, it is preferable to use a pigment dispersant in combination with an organic solvent for the purpose of improving the dispersibility of the pigment.

 [0044] As the pigment dispersant, ionic or nonionic surfactants, anionic, power thione, or nonionic polymer compounds can be used.

 [0045] Among them, the pigment dispersant is preferably a polymer compound. For example, JP-A-2004-083872, republished WO2003Z076527, republished WO2004Z00 0950, calpositimide Compounds, Ajinomoto from Ajinomoto Co., Inc., SOLSPERSE from Zeneca, DISPERBY from Bicchemi, and F power from F Power Additives are preferred. These pigment dispersants can be used alone or in combination.

 Among these, from the viewpoint of dispersion stability of the pigment in an organic solvent, a pigment having a group (for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, etc.) that reacts with a calpositimide group is used as the pigment. As the pigment dispersant, use should be made of a pigment having a group that reacts with a carpositimide group and a carpositimide compound having a carpositimide group in the molecule, which is a pigment dispersant capable of having a strong binding force due to a covalent bond. Is most preferred.

 [0047] Specific examples of the above-mentioned carpositimide compounds having a carposimide group in the molecule are disclosed in JP-A-2004-083872 [Recited, re-published WO2003 / 076527, re-published WO2004Z000950] Among them, those having a carbodiimide group can be exemplified.

 [0048] Further, as the carpositimide compound, those having a side chain such as a polyester side chain, a polyether side chain, and a polyacryl side chain are more preferable than the point of pigment dispersion stability. In addition to the chain, it has a basic nitrogen-containing group.

[0049] Next, preferred and specific examples of the carpositimide compound used in the present invention will be described. To do. The carpositimide compound of the present invention is not limited to this.

 [0050] Preferred calpositimide compounds that can be used in the present invention are selected from the group consisting of a polyester chain, a polyether chain, and a polyacrylic chain by utilizing a reaction between a carpositimide group and a functional group capable of reacting with it. Group force consisting of a polyester side chain, a polyether side chain and a polyacryl side chain, having at least one side chain selected, and having a carbodiimide equivalent of 100 to It is of 50000.

[0051] More preferably, the carpositimide compound includes at least one side chain selected from a group power consisting of a polyester side chain, a polyether side chain, and a polyacryl side chain, and at least one basic group-containing group. In the molecule and has a calpositimide equivalent of 100 to 50,000.

 [0052] In the present invention, such a reaction between a carposimide group and a functional group is sometimes referred to as a graft-in reaction, and the side chain introduced by the method is introduced as a grafted side chain. The polyester side chain may be called a grafted polyester side chain, the polyether side chain may be called a grafted polyester side chain, and the polyacrylic side chain may be called a grafted polyester side chain.

 [0053] In the present specification, the carbodiimide equivalent means

 (Molecular weight of carpositimide compound) Z (carpositimide compound)

 Number of carbodiimide groups in the molecule)

 This means the numerical value represented by

 [0054] In the present invention, one or more kinds of calpositimide compounds can be used.

In the present specification, the “side chain” refers to a chain that is branched from the main chain when the carpositimide compound is used as the main chain. In addition, one side chain formed by combining one or more of a polyester chain and a polyether chain belongs to both the “polyester side chain” and the “polyether side chain”. A chain formed by combining at least one polyester chain and a polyacrylic chain belongs to both the “polyester side chain” and the “polyacrylic side chain”. A combination of at least one ether chain and a polyaryl chain belongs to both the “polyether side chain” and the “polyacryl side chain”. In addition, polyester chains and poly Those formed by combining one or more ether side chains and polyacryl chains belong to any of “polyester side chains”, “polyether side chains”, and “polyacryl side chains”. In addition, a polyester chain, a polyether chain, and a polyaryl chain are mixed in one side chain as described above. Of course, “group power consisting of a polyester side chain, a polyether side chain, and a polyacryl side chain is selected. It is a side chain that satisfies the condition of “at least one kind of side chain”.

 [0056] Further, the "basic group nitrogen-containing group" includes not only those containing nitrogen that forms a quaternary ammonium ion in water, but also those containing nitrogen that act as a Lewis base. A typical example is an amino group or a nitrogen-containing heterocyclic group.

[0057] First, the carposimide compound having the grafted side chain will be described.

[0058] As the above-mentioned carpositimide compound having a grafted side chain, first, a polyester side chain, a polyether side chain and a polyacrylic compound are obtained by a grafted-in reaction based on a compound having two or more carboxylidimide groups in the molecule. Examples of compounds obtained by a method of adding one or more side chains selected from a group force consisting of side chains (and also including one or more remaining carpositimide groups).

 [0059] Here, examples of the compound having two or more calpositimide groups in the molecule include compounds obtained by calpositimidizing a diisocyanate compound by decarboxylation reaction in the presence of a calpositimidization catalyst in an organic solvent. Specific examples of diisocyanate compounds to be decarboxylated include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, Cyclohexane diisocyanate, dicyclohexylenomethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, tetramethylxylylene diisocyanate, etc., aliphatic, alicyclic, aromatic And araliphatic diisocyanate compounds.

[0060] Under the conditions sufficient to have two or more carposimide groups in the molecule of the resulting compound, a monoisocyanate compound may be used in combination. Examples of monoisocyanate compounds include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, ferro-isocyanate, aliphatic, Alicyclic, aromatic, and araliphatic monoisocyanate compounds Can be mentioned.

 [0061] Further, usable organic solvents are those having a high boiling point and no active hydrogen that reacts with an isocyanate compound or a compound having a carpositimide group to be generated. Specifically, Aromatic hydrocarbons such as toluene, xylene, and jetylbenzene; ethylene glycoloresetic acetate, dipropylene glycol dibutyrate, hexylene glycoloresicetate, glyconoresiacetate, methinoreglycololeacetate, ethinoreglycol acetate Glycol ether esters such as butyl butyl alcohol acetate, ethyl diglycol acetate, buty diglycol acetate; ketones such as ethyl butyl ketone, acetophenone, propiophenone, diisoptyl ketone, cyclohexanone; amyl acetate Propyl propionate, and aliphatic esters such as butyric Echiru like.

 [0062] Further, examples of usable carpositimide catalysts include phospholenes, phospholenides, and the like. Specifically, 1-ethyl-3-methyl-3 phospholene oxide, 1-phenol 3- Examples thereof include methyl 3-phospholene oxide, 1-ferro-3-methyl 2-phospholene oxide, and the like.

 [0063] As a method for performing a decarboxylation reaction of an isocyanate group using these materials, a known method can be used. For example, the reaction can be performed at a reaction temperature of 100 to 200 ° C in a nitrogen atmosphere. Examples of other methods for obtaining the above compound having a carposimide group include, for example, US Pat. No. 2941956, JP-B-47-33279, JP-A-5-178954, JP-A-6-56950 And the like.

 [0064] Using such a method, for example, a compound obtained by decarboxylation of K (≥3) moles of diisocyanate compound is represented by the following general formula (1) 1 and (Κ 1 A compound obtained by decarboxylation of 2 mol of diisocyanate compound and 2 mol of monoisocyanate compound can be represented by the following general formula (1) 2. These are also referred to as polycarbozide imide compounds.

 [0065] OCN— (Α— N = C = N) — A— NCO (1) — 1

 k- 1

 A1— N = C = N— (A— N = C = N) — Al (1) — 2

 k- 1

[0066] In the above general formula, A is a residue excluding the isocyanate group of the diisocyanate one-toy compound used for the synthesis of the polycarposimide compound, and A1 is a synthesis of the polycarposimide compound. It is a residue excluding the isocyanate group of the monoisocyanate compound used in.

 [0067] Commercially available compounds having a carpositimide group represented by the above general formula (1) 1 include calpositrite V-03, V-05, etc. as carpositimide using tetramethylxylylene diisocyanate as a raw material (all Product name, manufactured by Nisshinbo Industries, Inc.).

 [0068] Further, for example, a general formula (2) obtained by reacting a compound obtained by decarboxylating a K '(≥2) mole of diisocyanate compound with a diol compound having two hydroxyl groups ( A compound having two or more carpositimide groups represented by 2) can also be used. This compound is also called a polycarbodiimide compound.

 [0069] OCN- (A-N = C = N) A— NHCOO— (B— OOCNH

 k-l

 One (N = C = N— A)) m— NCO (2)

 k-l

 [0070] In the above general formula, A is a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the polycarbopositimide compound, and B is a hydroxyl group of the diol compound having two hydroxyl groups. In the residues other than, m is an integer of 1 or more.

 [0071] Such a compound represented by the general formula (1) 1 or (2) has an isocyanate group in the molecule, but it is also possible to react a compound having a functional group capable of reacting with the isocyanate group. Yes, it can be used as a compound having two or more carpositimide groups in the molecule that forms the carpositimide compound of the present invention.

 [0072] As such a compound having a functional group capable of reacting with an isocyanate group, a compound having a low reactivity with the remaining force rubodiimide group and selectively reacting with an isocyanate group first is preferable. Low molecular monoalcohol compounds such as methanol and ethanol, polyester compounds having the above hydroxyl groups, polyalkylene glycol and monoalkyl ester compounds thereof, polymethyl metatalylate diol, polybutyl metatalylate diol, poly 2-ethylhexyl metatalylate Examples thereof include a hydroxyl group-containing compound such as a hydroxyl group-containing polyacryl compound such as a diol. Among them, preferred are positive estenore, positive ethenore and polyacrylol having a formula weight of 500 to 5,000.

[0073] A polyester side chain, a polyether side chain or a polyacryl side chain is further introduced into the compound having two or more carposimide groups in the molecule obtained by the method as described above by a graft polymerization reaction. In the molecule, there are calposimide groups, grafted polyester side chains, groups A carpositimide compound containing at least one kind of grafty side chain, which is selected from the group power consisting of rough toy polyether side chain and grafty side polyacrylic side chain, is used.

 [0074] And, as a typical method for introducing these side chains into the molecule by grafting reaction, functional groups capable of reacting with a carpositimide group such as carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, amino A method in which a polyester compound, a polyether compound or a polyacryl compound having a group or the like is reacted with a calpositimide group of a compound having a carpositimide group can be used.

 [0075] As the polyester compound having the above functional group, first, (1) a ring-opening polymerization compound of a cyclic ester compound using an oxycarboxylic acid, a monoalcohol, a low molecular diol compound or the like as an initiator (For example, using mono- or polyoxycarboxylic acid such as lactic acid, caproic acid, 12-hydroxystearic acid, dimethylolpropionic acid, dimethylolbutanoic acid as an initiator, ε-strength prolataton, γ-butyrolataton, 2-methyl Polyesters containing a carboxyl group and a hydroxyl group obtained by ring-opening polymerization of cyclic ester compounds such as caprolataton, 4-methylcaprolataton, 13-propiolatatone, δ-valerolataton, 13-methyl-1-δ-valerolatataton Hydride compound: Low molecular mono-rich compound such as methanol or ethanol is used as an initiator. Polyester monool compound containing a hydroxyl group obtained by ring-opening polymerization of a cyclic ester compound; a low molecular diol compound such as ethylene glycol or propylene glycol is used as an initiator, and the cyclic ester compound is subjected to ring-opening polymerization. And polyester diol compounds containing a hydroxyl group obtained).

 [0076] Further, (2) a self-polycondensation compound of an oxycarboxylic acid (for example, containing a carboxyl group and a hydroxyl group obtained by polycondensation of monooxycarboxylic acid such as lactic acid, caproic acid, 12-hydroxystearic acid, etc. And polyester compounds).

[0077] Further, (3) compounds obtained by polycondensation of a low molecular diol compound and a low molecular dicarboxylic acid compound (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol) 1, 6-hexanediol and other linear glycols, 1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethyl Low molecular diol compound components such as branched glycols such as tilpropane diol, and aromatics such as saturated or unsaturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and maleic acid, and phthalic acid A polyester diol compound containing a hydroxyl group obtained by reacting a low molecular diol compound component such as a dicarboxylic acid in the presence of an excess of a low molecular diol compound.

 [0078] Further, (4) a phosphoric ester compound of a ring-opening polymer of a cyclic ester compound using a monoalcohol as an initiator (for example, esterification reaction of the above-mentioned polyester mono-ol compound with phosphoric acid) (5) a ring-opening polymerization compound of a cyclic ester compound using an amino group-containing sulfonic acid compound as an initiator (for example, taurine). Examples thereof include polyester diol compounds containing a sulfonic acid obtained by ring-opening polymerization of the above cyclic ester compound using an amino group-containing sulfonic acid compound such as

 [0079] In addition, (6) a sulfurous acid gas adduct of a ring-opening polymer of a cyclic ester compound using a monoalcohol as an initiator (for example, adding a sulfurous acid gas to the above-mentioned polyester monool compound) And polyester diol compounds containing sulfonic acid obtained in this manner.

 [0080] Such a polyester compound is preferably a polyester compound obtained by ring-opening polymerization of poly-strength prolatatone.

 [0081] As the polyether compound having the above functional group, first,

(1) Ring-opening polymerization compounds of cyclic ether compounds starting from oxycarboxylic acids, monoalcohols, low molecular diol compounds, etc. (for example, lactic acid, cabronic acid, 12-hydroxy stearic acid, Obtained by ring-opening polymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran using mono- or polyoxycarboxylic acids such as dimethylolpropionic acid and dimethylolbutanoic acid as initiators. Polyether compound containing a carboxyl group and a hydroxyl group; containing a hydroxyl group obtained by ring-opening polymerization of the above cyclic ether compound using a low molecular monool compound such as methanol or ethanol as an initiator Polyether monool compound; ethylene glycol, propylene And the initiator of low molecular Jiorui 匕合 of such glycol And a polyether diol compound containing a hydroxyl group obtained by ring-opening polymerization of the above cyclic ether compound.

 [0082] In addition, (2) a phosphate ester compound of a ring-opening polymer of a cyclic ether compound using a monoalcohol as an initiator (for example, the polyether monool compound is subjected to an esterification reaction with phosphoric acid). Polyether compounds containing phosphate groups obtained by

[0083] (3) A ring-opening polymerization compound of a cyclic ether compound using an amino group-containing sulfonic acid compound as an initiator (for example, an amino group-containing sulfonic acid compound such as taurine is used as an initiator) As a polyether compound containing a sulfonic acid group obtained by ring-opening polymerization of the above cyclic ether compound.

 [0084] In addition, (4) a sulfurous acid gas adduct of a ring-opening polymer of a cyclic ether compound using a monoalcohol as an initiator (for example, adding a sulfurous acid gas to the polyether monool compound) And a polyethery compound containing a sulfonic acid group thus obtained).

 [0085] As the polyacrylic compound having the functional group,

(1) (meth) acrylic monomer power having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group and an amino group. Polymerization of a monomer component containing at least one selected. (Meth) acrylic polymer (for example, (meth) acrylic monomer having a carboxyl group: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cytocholanic acid (methylmaleic acid), itaconic acid, etc. ; (Meth) acrylic monomer having sulfonic acid group: (meth) acrylic acid sulfoethyl, (meth) acrylic acid sulfopropyl, etc .; (meth) acrylic monomer having phosphoric acid group: 2-methacryloyloxetyl acid Phosphate, trisacryloyloxychetyl phosphate, etc .; (meth) acrylic monomer having a hydroxyl group 2-Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypentyl (meth) acrylate, etc .; (meth) acrylic monomer having amino group: (meta ) Acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) ) Monomeric strength of acrylamide etc. At least one monomer component selected and as required Other than the above, (meth) acrylic polymers obtained by polymerizing known monomers such as alkyl esters and styrene monomers generally used as reaction components for acrylic resins can be mentioned.

 [0086] (2) In addition, an acid group-free radically polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer is added in the presence of an acid group-containing chain transfer agent. Examples thereof include polyacrylic compounds containing acid groups at the ends of the molecules obtained by polymerization.

 [0087] Further, a compound having the above functional group and including both a polyester chain and a polyether chain, a polyacryl compound having a polyester chain, and a polyacryl compound having a polyether chain may be used. For example, a compound obtained by reacting a cyclic ester compound using polyalkylene glycol or its monoalkyl ether compound as an initiator, a compound obtained by reacting a cyclic ether compound with a hydroxyl-containing polyester compound, a polyester chain Examples thereof include (meth) acrylic monomers containing in the molecule and polyacrylic chain compounds obtained using (meth) acrylic monomers containing polyether chains in the molecule.

 [0088] Among these polyester compounds, polyether compounds, and polyacryl compounds, it is more advantageous to have a carboxyl group, a sulfonic acid group, and a phosphoric acid group from the viewpoint of reactivity with a strong carbodiimide group.

 [0089] Further, in the case of the compound having a hydroxyl group, when the original polycarpositimide compound further has an isocyanate group, the reaction with the isocyanate group occurs before the carpositimide group, and it becomes difficult to control the reaction. Compounds with two or more hydroxyl groups can crosslink during the grafting reaction and cause gelation.

 [0090] Therefore, for a compound having only a hydroxyl group as a functional group, a polyester compound containing one carboxyl group is further reacted with an acid anhydride such as phthalic anhydride, maleic anhydride, or succinic anhydride. After obtaining the compound, it is desirable to carry out a graft reaction.

[0091] The polyester compound, the polyether compound, or the polyacryl compound exemplified above, wherein at least one compound is introduced into the molecule by graft polymerization, must further have at least one carposimide group. For example, when a side chain is introduced into the polyforce carbodiimide compound represented by the general formula (1) 1 by a graft reaction, the following general formula (3) To obtain a carpositimide compound represented by the formula (K-1 = m + n)

[0092] [Chemical 1]

Here, Α is a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the polycarbodiimide compound. X is the same or different and is a trivalent linking group obtained by reacting a carpositimide group with a functional group capable of reacting with it. Y is the same or different and is a polyester chain, a polyether chain or a polyacrylic chain. Yes, m and n each represent an integer of 1 or more.

 [0094] As the trivalent linking group represented by X, for example, the linking group formed from the reaction of a carbodiimide group and a carboxyl group is represented by the following general formulas (4), (5), The linking group formed from the reaction between the group and the hydroxyl group is represented by the following general formulas (6) and (7), and the linking group formed from the reaction between the carpositimide group and the amino group is represented by the following general formula (8), The linking group formed from the reaction between the carpositimide group and the sulfonic acid group is represented by the following general formula (9), and the linking group formed from the reaction between the carpositimide group and the phosphoric acid group is represented by the following general formula (10). expressed.

[0095] [Chemical 2]

(0 I)

 ■ == 0 ~ R-

 O

 (I) Q i. HM-

(9)

^ / 900Zdf / e :) d 03 _ooz OA [0096] In the above general formula, R represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms.

[0097] Furthermore, the carpositimide compound represented by the general formula (3) has an isocyanate group in the molecule, but it is also possible to react a compound having a functional group capable of reacting with the isocyanate group. The compound represented by the formula (11) can also be used as a carpositimide compound in the present invention.

[0098] [Chemical 3]

Z ¹ — OCNH— (A— N = C = N) _m — (A— X) _n — A—NHCO together (1 1)

[0099] In the above general formula, Z ¹ and Z ² are each independently an active hydrogen of the functional group of a compound having a functional group capable of reacting with an isocyanate group, which may have a different structure. Represents a residue excluding one. A is a residue excluding the isocyanate group of the diisocyanate compound used in the synthesis of the polycarposimide compound. X is the same or different, and a trivalent linking group obtained by reacting a carpositimide group with a functional group capable of reacting with it, Y is the same or different, and is a polyester chain, a polyether chain or a polyacryl chain, m and n each represents an integer of 1 or more.

 [0100] As such a compound having a functional group capable of reacting with an isocyanate group, a compound having a low reactivity with the remaining force rubodiimide group and selectively reacting with an isocyanate group first is preferable. Low molecular monoalcohol compounds such as methanol and ethanol, polyester compounds containing the above hydroxyl groups, polyalkylene glycol and its monoalkyl ester compounds, polymethyl metatalylate diol, polybutyl metatalylate diol, poly 2-ethylhexyl meta Examples thereof include a hydroxyl group-containing compound such as a hydroxyl group-containing polyacryl compound such as tallylate diol. Among them, a polyester chain, a polyether chain or a polyacryl chain having a formula weight of 500 to 5000 is preferably formed.

[0101] The above-described reactions, that is, the ring-opening reaction of the cyclic ester compound using the above hydroxyl group-containing compound as an initiator, the polycondensation reaction of oxycarboxylic acid, the low molecular diol compound and the low molecular dicarboxylic acid. A polycondensation reaction with an acid compound, a hydroxyl group-containing ester compound and Ring opening reaction of acid anhydride, ring opening reaction of cyclic ether compound, ring opening reaction of hydroxyl group-containing ether compound and acid anhydride, reaction of carpositimide group with carboxyl group, hydroxyl group, etc., and isocyanate group Conventional methods can be used for the reaction with a hydroxyl group or the like.

 [0102] The above-mentioned carpositimide-based compound is a compound containing at least one carposimide group and a grafted polyester chain, a daffodied polyether chain, or a grafted polyacrylic chain, and reacts each reaction material. Even if the order in which they are made is different, the performance obtained is not different if the finally obtained compounds have the same molecular structure.

[0103] Therefore, in the compound of the general formula (11), a compound having at least one chain selected from the group consisting of a polyester chain having a functional group that reacts with a carpositimide group, a polyether chain, and a polyacryl chain. ) And a carpositimide group (compound having) to introduce the side chain into the molecule, that is, to introduce a grafted polyester chain, a grafted polyether chain or a grafted polyacrylic chain, First, a functional group-containing polyester compound that reacts with a carbodiimide group, a functional group-containing polyether compound that reacts with a carbodiimide group, or a functional group-containing polyether compound that reacts with a carbodiimide group is synthesized and then reacted with a carbodiimide group. Explains the method of making the side chain described above. As another method for introducing a compound into a molecule of a carpositimide compound, after reacting a compound having a functional group that reacts with a carpositimide group and a carposimide group (compound having a), a polyester chain, a polyether chain, It can also be carried out by introducing into the molecule a compound that forms at least one selected group force consisting of acrylic chains.

[0104] For example, in the case of introducing a grafted polyester side chain or a grafted polyether side chain, an oxycarboxylic acid is first reacted with a carpositimide group, and a hydroxyl group is introduced into the molecule of the force rubodiimide compound. Thereafter, a method of ring-opening polymerization of a cyclic polyester compound or a cyclic polyether compound and graft-bonding the polyester chain or the polyether chain may be used. Also, in the case of introducing a grafted polyacrylic chain, a method of grafting a polyacrylic chain after first reacting an oxycarboxylic acid with a carpositimide group to introduce a hydroxyl group into the molecule of the compound having a carposimide group. so There may be.

 [0105] Furthermore, after the isocyanate group remaining in the molecule of the compound having a carposimide group previously reacts with a reactive functional group as described above, grafting may be performed. As for the reaction sequence, it is desirable to synthesize under conditions that minimize the number of undesirable side reaction products.

 Next, the force rubodiimide compound having the grafted side chain and having the basic group-containing group in the molecule will be described.

[0107] Typical specific examples of the carboimide compound having the grafted side chain and having the basic group-containing group in the molecule include (1) the above general formula (1) 1 or (2 ), A tertiary amine amino group or a basic nitrogen that does not participate in the reaction between the isocyanate group of the polycarbodiimide compound, a hydroxyl group suitable as a functional group capable of selectively reacting with the isocyanate group, and a carpositimide group or an isocyanate group. Select a group force consisting of a polyester chain, a polyether chain, and a polyacrylic chain by utilizing the reaction between the carpositimide group of the compound obtained by reacting a compound having a heterocyclic group and a functional group capable of reacting with it. And (2) the calpositimide group of the polycarbopositimide compound of the above general formula (1) 1 or (2), And the isocyanate group of the compound in which at least one selected from the group force consisting of a polyester chain, a polyether chain, and a polyacrylic chain is introduced into the molecule using the reaction with a functional group capable of reacting with A compound having a hydroxyl group suitable as a functional group capable of selectively reacting with the isocyanate group, and a tertiary amino group or basic nitrogen-containing heterocyclic group not involved in the reaction between the carpositimide group and the isocyanate group. (3) a compound obtained by decarboxylating the above K ′ (≥2) moles of diisocyanate compound and a diol compound having two hydroxyl groups. The resulting polycarbopositimide compound having two or more calpositimide groups represented by the general formula (2) is a diol compound having two hydroxyl groups. Based on a polycarbopositimide compound that has a basic group-containing group in the molecule obtained by using a compound having a non-group, the reaction between the carpositimide group of this compound and a functional group capable of reacting with it Utilizing the group power consisting of polyester chain, polyether chain and polyacrylic chain, introduce at least one selected in the molecule And the like.

 [0108] In the above (1) to (3), when an isocyanate group remains, a compound having a functional group capable of reacting with the isocyanate group can be reacted.

 [0109] As such a compound having a functional group capable of reacting with an isocyanate group, a compound having a low reactivity with the remaining force rubodiimide group and selectively reacting with an isocyanate group first is preferred. For example, methanol , Low molecular monoalcohol compounds such as ethanol, polyester compounds having the above hydroxyl groups, polyalkylene glycols and monoalkyl ester compounds thereof, polymethyl methacrylate diol, polybutyl methacrylate diol, poly 2-ethyl Examples thereof include hydroxyl group-containing compounds such as hydroxyl group-containing polyacryl compounds such as xylmetatalylate diol.

 [0110] Compound having a hydroxyl group suitable as a functional group capable of selectively reacting with the above isocyanate group, and a tertiary amino group or basic nitrogen-containing heterocyclic group not involved in the reaction between the carbodiimide group and the isocyanate group Specifically, examples of the compound having one hydroxyl group and a tertiary amino group include N, N-dialkylalkanolamines such as N, N-dimethylethanolamine and N, N-jetylethanolamine. Examples include compounds, ethylene oxide adducts of secondary amine compounds, and reactants of secondary amine compounds and epoxy compounds. Examples of the compound having two hydroxyl groups and a tertiary amino group include, for example, N-alkyldianolamine compounds such as N-methyljetanolamine and N-ethyljetanolamine, and primary amine compounds. And ethylene oxide adducts, reaction products of primary amine compounds and epoxy compounds, and the like.

 [0111] Further, examples of the compound having a hydroxyl group and a basic nitrogen-containing heterocyclic group include tertiary basic nitrogen such as hydroxypyridine, pyridinemethanol, pyridineethanol, pyridine, pyrazine, triazine, quinoline and the like. Compounds containing a heterocyclic ring and a hydroxyl group can be used. Also, even heterocyclic compounds containing secondary basic nitrogen such as piperidine or piperazine can be used by alkylating to tertiary and adding a hydroxyl group.

[0112] The number average molecular weight of the carpositimide compound used in the present invention is preferably 1,000 or more and 1,000,000 or less. High number average molecular weight of carbodiimide compounds When it becomes too much, it becomes difficult to obtain an ink composition having an appropriate viscosity as a non-aqueous ink jet printing ink composition.

 [0113] The dispersant is appropriately selected according to the type of pigment and the type of organic solvent to be used.

 [0114] Further, in the non-aqueous ink jet ink composition of the present invention, various additives such as a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, and an antioxidant are used as necessary. can do.

 Next, a method for producing the non-aqueous inkjet ink composition of the present invention using these materials will be described.

 [0116] The ink thread composition for non-aqueous inkjet according to the present invention includes, for example, a wet circulation mill, a bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, and a high pressure homogenizer. (Micro fluidizer 1, Nanomizer 1, Optimizer 1, Genus PY, DeBEE2000, etc.) Disperse and mix using a disperser such as a pearl mill, and the viscosity of the non-aqueous ink jet ink composition is 2 to: LOmPa's It can be obtained by adjusting as follows. The content of the total organic solvent in the non-aqueous inkjet ink composition of the present invention is determined based on the total amount of the ink composition, binder resin, colorant (including pigment dispersant when a pigment is used), and if necessary. It is an amount obtained by subtracting the total amount of other additives, but it is preferable to appropriately change the ink viscosity to be within the above range.

 [0117] The method for obtaining the printed matter of the present invention will be described. Using the above ink composition for non-aqueous ink jet on a base material having at least a surface layer of vinyl chloride polymer or ethylene acetate butyl copolymer. It can be obtained by printing with an inkjet printer.

 Example

[0118] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" is meaning taste "mass _^0/0", "parts" means parts by weight.

[0119] Examples 1 to 5 and Comparative Examples 1 to 2 <Manufacture of base ink for non-aqueous inkjet>

 20 parts of the following pigment dispersant (carpositimide compound) is dissolved in 60 parts of diethylene glycol jetyl ether, and carbon black MA-7 (manufactured by Mitsubishi Igaku Co., Ltd., which reacts with calpositimide) as a pigment. After mixing 20 parts by stirring and mixing, the mixture was kneaded using a bead mill to obtain a base ink for non-aqueous inkjet.

[0120] Manufacture of Pigment Dispersant (Carposiimide Compound)>

 In a four-necked flask equipped with a reflux condenser, a nitrogen gas inlet, a stirrer, and a thermometer, a toluene solution of a polycarbodiimide compound having a carbodiimide equivalent of 316 having an isocyanate group (solid content 50%) 1823 parts, N-methyl Charge 178 parts of jetanolamine, hold it at about 100 ° C for 3 hours to react isocyanate group with hydroxyl group, and then 2915 parts of 2000-molecular weight polylatatone having a carboxyl group at the end, propylene glycol monomer Charge 5104 parts of tilether acetate, hold at about 80 ° C for 2 hours, and react with calpositimide group and carboxyl group to give a pigment dispersant with a number average molecular weight of about 10800 and a calpositimide equivalent of 2800 (solid content 40%) Got.

[0121] Manufacturing of non-aqueous inkjet ink composition>

 According to the composition shown in Table 1 (the blending ratio of each material is mass%), the materials were stirred and mixed, and the viscosity at 25 ° C was about 4 mPa · s. Examples 1 to 5 and Comparative Examples 1 and 2 An ink composition for an aqueous ink jet was obtained.

[0122] <Printing method and printed matter>

 Commercially available inkjet printer (SOLJET PRO II manufactured by Roland DG Co., Ltd.)

SC-540) was loaded with the non-aqueous inkjet ink compositions of Examples 1 to 5 and Comparative Examples 1 and 2, and printed on a polychlorinated bull sheet (trade name: Capjet Dalos Burner, Film Lux). Printed materials of Examples 1 to 5 and Comparative Examples 1 and 2 were obtained.

[0123] <Evaluation>

 The following properties were evaluated for the ink compositions and printed materials of Examples 1 to 5 and Comparative Examples 1 and 2. In the following evaluation, A and B are practical levels, and C and D are levels that are supported by product use.

[0124] (Viscosity) The viscosity at 25 ° C. of each of the non-aqueous ink jet ink compositions of Examples 1 to 5 and Comparative Examples 1 and 2 was measured using a viscometer (RE100L type manufactured by Toki Sangyo Co., Ltd.).

[0125] (Glossy)

 The gloss of each printed matter of Examples 1 to 5 and Comparative Examples 1 and 2 was measured at 60 degrees with a variable angle gloss meter (VGS-300A) manufactured by Nippon Denshoku Industries Co., Ltd.

 Evaluation criteria

 A: Gloss value 40 or more

 B: Gloss value less than 40 to 20 or more

 C: Gloss value less than 20

[0126] (Set property)

 Using the ink compositions for non-aqueous ink jets of Examples 1 to 5 and Comparative Examples 1 and 2, solid printing was performed on a polysalt bull sheet (trade name: Capjet Gloss Burner, manufactured by FilmLux), 30 ° The time until drying with C was measured. Dryness was determined by touching the finger and not pushing it.

 Evaluation criteria

 A: Less than 3 minutes

 B: 3 minutes to less than 5 minutes

 C: 5 minutes or more

[0127] (Discharge stability)

 Using the ink compositions for non-aqueous ink jets of Examples 1 to 5 and Comparative Examples 1 and 2, printing was performed on a polysalt bull sheet (trade name: Capjet Daros Burner, FilmLux). Evaluation was made based on the number of wrinkles.

 Evaluation criteria

 A: Unprinted wrinkles occur after the 71st sheet, or unprinted wrinkles do not occur until the 100th sheet.

 B: Not printed, part occurs on the 51st to 71st sheets.

 C: Unprinted part occurs on the 31st to 50th sheets.

D: Not printed, part occurs by the 30th sheet. table 1

Industrial applicability

 [0129] The non-aqueous inkjet ink composition of the present invention has good wettability and adhesion to a substrate whose printing surface is mainly composed of a vinyl chloride vinyl polymer or an ethylene vinyl acetate copolymer. Furthermore, it has excellent ejection stability during ink jet printing and even after a long pause.

[0130] Therefore, by printing the non-aqueous inkjet ink composition of the present invention on a substrate such as turbolin, large-sized signboard advertisements with good print quality can be easily produced.

Claims

The scope of the claims

 [1] Group power consisting of a salt vinyl polymer, a salt vinyl vinyl monoacetate copolymer, and an ethylene acetate butyl copolymer as Noinder resin, at least one type of beer system selected A polymer, a colorant, and an organic solvent are contained, and the polyalkylene glycol dialkyl ether represented by the following general formula (I) is contained as the organic solvent in an amount of 15 to 30% by mass in the total organic solvent. A non-aqueous inkjet ink composition characterized by the above.

R ¹ — O (One CH— CHX— O) One R ² (I)

 2 n

(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, n is an integer of 3 to 6, and n Xs are each independently a hydrogen atom or a methyl group) .

[2] The ink composition for non-aqueous ink jets according to claim 1, wherein triethylene glycol dialkyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I).

[3] The non-claim according to claim 1 or 2, wherein at least one of triethylene glycol dimethyl ether and triethylene glycol jetyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I). Water-based inkjet ink thread.

 [4] The above colorant is a pigment having a functional group that reacts with a carbodiimide group, and contains a carbodiimide-based compound having a carbodiimide group as a pigment dispersant in a non-aqueous inkjet ink composition. Item 4. The non-aqueous inkjet ink thread according to any one of Items 1 to 3.

[5] The non-aqueous ink jet ink composition according to any one of claims 1 to 4, wherein a salty bulle polymer is used as the bulle polymer.

[6] The non-aqueous ink jet ink according to any one of claims 1 to 5, wherein at least a surface layer is made of a vinyl chloride polymer or ethylene vinyl acetate copolymer. Printed matter obtained by printing the composition.

[7] A printed matter obtained by printing the non-aqueous ink jet ink composition according to claim 5 on a base material having at least a surface vinyl chloride polymer strength.