JP5001855B2 - Non-aqueous inkjet ink composition and printed matter obtained using the same - Google Patents

Description

  The present invention has good wettability and fixability for a base sheet whose printing surface is mainly composed of a vinyl chloride polymer or an ethylene-vinyl acetate copolymer, and maintains high ejection stability for a long time. The present invention relates to a non-aqueous inkjet ink composition suitable for producing large-sized billboard advertisements and the like, and printed matter obtained using the same.

  In recent billboard advertisements, in addition to vivid and sophisticated logos and patterns, there are an increasing number of photo-like items such as the appearance of products and the faces of people. In addition, the size of the signboard is so large that it can be seen in large numbers so as to have a stronger impact on the viewer.

  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 are a number of problems such as requiring a lot of time and labor for production and requiring large equipment such as a printing machine. Therefore, in order to more easily produce a signboard with a clear image, 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.

  The ink jet system has a wide range of materials that can be used as a printing substrate, and is characterized in that it can be easily printed on sheets of paper, polymers, metals, and other hard and soft materials. In particular, billboard advertisements installed outdoors are lightweight, excellent in strength and durability, resistant to rain, and more inexpensive, so it is easy to print on polymer sheets with these characteristics. This is a huge advantage. In addition, recently, an ultra-wide format inkjet printer with a printing width of 2,000 mm or more has also appeared, making it easier to print large-format prints that have been supported by pasting together. Signs can be made.

  On the other hand, as an ink-jet ink, the water-based type has been the main development so far, but this type of ink is repelled on the surface of the polymer sheet and cannot be printed (insufficient wettability). Therefore, a non-aqueous inkjet ink for polymer sheets based on organic solvents has been newly developed. For example, a technique using a (poly) alkylene glycol derivative and a nitrogen-containing heterocyclic compound as an organic solvent (Japanese Patent Laid-Open No. 2005-23298). 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 drying property and adhesion to the substrate (usually referred to as fixing property) are necessary. Often the physical properties of these directly or indirectly affect their performance.

  Since the polymer sheet surface is impervious, drying mainly depends on the evaporation rate of the solvent, but an organic solvent with an excessive evaporation rate decreases the ejection stability in the ink jet system. Therefore, how to achieve the balance is an important issue for efficiently obtaining a good printed matter. Also, if the fixing property of the ink film to the printing substrate is not good, the ink film is immediately peeled off from the printing substrate, and it becomes impossible to maintain a clear printed matter for a long period of time. The fixability of the ink depends mainly on the performance of the fixing resin (binder resin), but the organic solvent must dissolve the fixing resin. In this case, the fixability is indirect to the physical properties of the organic solvent used. Will depend on. Furthermore, when an organic solvent that slightly dissolves the surface of the polymer sheet as a base material is used during printing and drying, the improvement in fixing property is recognized. Therefore, the fixing property is directly related to the physical properties of the organic solvent to be used. It can be said that it depends on. Since there are a wide variety of polymer sheets, it is necessary to individually design according to the type of polymer to be a printing substrate in order to obtain a good ink composition that satisfies the above conditions.

  In general, a polymer sheet called tarpaulin 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 polyvinyl chloride and ethylene-vinyl acetate copolymer are laminated on both sides. Therefore, as described above, a material having good wettability, drying property, fixing property, and the like is used for the ink whose tarpaulin is to be printed, as described above, with respect to the vinyl polymer that is the material of the sheet surface. It will be necessary.

  The ink described in the above Japanese Patent Application Laid-Open No. 2005-23298 is intended for a polyvinyl chloride sheet as a printing substrate, but an acrylic resin, a polyester resin, a polyurethane resin exemplified as a suitable binder resin, With nitrocellulose or the like, there is a limit to improving the fixability. On the other hand, a vinyl chloride resin similar to the base material has good fixability, but does not exhibit sufficient solubility in the solvent specifically exemplified in JP-A-2005-23298. However, there is a problem that the ink is the most important ink when used in an ink jet system and has low ejection stability.

  Further, the invention described in the above Japanese Patent Application Laid-Open No. 2005-36199 is also intended for a vinyl chloride polymer sheet, but from this point of view, it depends only on the evaporation rate of the organic solvent, and more specific formulas are used. It can be said that there is some effect on the ink performance that is satisfactory only when the conditions (1) to (3) are satisfied. However, with regard to performance such as wettability and fixability that change in any way due to factors that have nothing to do with the evaporation rate of the organic solvent (the water resistance and light resistance described as effective in this invention also change) However, no technique for obtaining a high level of performance is disclosed.

  Therefore, the problem to be solved by the present invention is that the printing surface has good wettability and fixability with respect to a base material mainly composed of a vinyl chloride polymer or an ethylene-vinyl acetate copolymer, and further the ink jet printing. It is an object of the present invention to provide a non-aqueous ink jet ink composition having excellent ejection stability even after a long period of time and after a long pause.

  As a result of intensive 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, a vinyl chloride polymer, chloride, Using at least one vinyl polymer selected from the group consisting of a vinyl-vinyl acetate copolymer and an ethylene-vinyl acetate copolymer, and using a specific polyalkylene glycol dialkyl ether as the organic solvent in the organic solvent The present inventors have found that the above-mentioned problems can be realized by containing a specific amount in the present invention, and have completed the present invention.

  That is, the present invention provides the following non-aqueous inkjet ink composition and a printed matter obtained using the same.

(1) As a binder resin, at least one vinyl polymer selected from the group consisting of a vinyl chloride polymer, a vinyl chloride-vinyl acetate copolymer, and an ethylene-vinyl acetate copolymer, a colorant, and A non-aqueous inkjet, comprising an organic solvent, and containing 15 to 30% by mass of a polyalkylene glycol dialkyl ether represented by the following general formula (I) as the organic solvent in the total organic solvent: Ink composition.

R ¹ —O — (— CH ₂ —CHX—O—) _n —R ² (I)
[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 non-aqueous inkjet ink composition according to (1), wherein triethylene glycol dialkyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I).

(3) The non-aqueous composition according to (1) or (2), wherein at least one of triethylene glycol dimethyl ether and triethylene glycol diethyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I). Ink-jet ink composition.

(4) The above item (1), wherein the 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 the non-aqueous inkjet ink composition. The ink composition for non-aqueous ink jets according to any one of items (3) to (3).

(5) The non-aqueous inkjet ink composition according to any one of (1) to (4), wherein a vinyl chloride polymer is used as the vinyl polymer.

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

(7) A printed matter obtained by printing the ink composition for non-aqueous inkjet according to the item (5) on a base material having at least a surface layer made of a vinyl chloride polymer.

  Hereinafter, the present invention will be described in more detail.

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

  The binder resin constituting the non-aqueous inkjet ink composition of the present invention is at least selected from the group consisting of vinyl chloride polymers, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate copolymers. One kind of vinyl polymer is used. Vinyl chloride polymers include vinyl chloride homopolymer (polyvinyl chloride) and vinyl chloride and other small copolymerizable monomers (for example, vinyl acetate, ethylene, vinylidene chloride, etc.) Coalescence is mentioned. As the vinyl chloride-vinyl acetate copolymer and the ethylene-vinyl acetate copolymer, those usually used in this type of ink can be used without particular limitation. The molecular weight of the binder resin is preferably about 2,000 to 100,000 in terms of weight average molecular weight from the viewpoints of solubility in a solvent, viscosity of the resulting ink composition, ejection stability, and the like. When at least the surface layer is printed on a substrate made of a vinyl chloride polymer (particularly polyvinyl chloride) or an ethylene-vinyl acetate copolymer, a vinyl chloride polymer (particularly polyvinyl chloride) is preferred as the binder resin. .

  The amount of the binder resin used 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. When the amount of the binder resin used is less than the above range, the fixing property with the substrate is not sufficient, while when it exceeds the above range, the solid content increases excessively, and thus the discharge stability is lowered.

  As long as the performance does not deteriorate, a resin other than the above binder resin, for example, acrylic resin, styrene-acrylic resin, styrene-maleic resin, rosin resin, 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, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid It is also possible to use a resin or the like together.

  Next, as the colorant constituting the non-aqueous inkjet ink composition of the present invention, dyes and / or pigments conventionally used in non-aqueous inkjet ink compositions can be used without particular limitation.

  When using a dye as a colorant, a conventionally known dye can be used. I. Direct Black 17, 19, 19, 22, 32, 38, 51, 71, C.I. I. Direct Yellow 4, 26, 44, 50, C.I. I. Direct Red 1, 4, 23, 31, 37, 39, 75, 80, 81, 83, 225, 226, 227, C.I. I. Direct blue 1, 15, 41, 71, 86, 87, 106, 108, 199, and the like; I. Acid Black 1, 2, 24, 26, 31, 31, 52, 107, 109, 110, 119, 154, C.I. I. Acid Yellow 1, 7, 17, 19, 23, 25, 29, 38, 42, 49, 61, 72, 78, 110, 127, 135, 141, 142, C.I. I. Acid Red 8, 9, 9, 14, 26, 27, 35, 37, 51, 52, 57, 82, 83, 87, 92, 94, 111, 129, 131, 138, 186, 249, 254, 265, 276, C.I. I. Acid Violet 15, 17, 49, C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 40, 41, 43, 62, 78, 83, 90, 93, 100, 103, 104, 112, 113, 158, C.I. I. Acid Green 3, 9, 16, 25, 27, C.I. I. Acid dyes such as Acid Orange 56, C.I. I. Food dyes such as Food Yellow 3, Malachite Green (C.I. 42000), Victoria Blue FB (C.I. 44545), Methyl Violet FN (C.I. 42535), Rhodamine F4G (C.I. 45160), And basic dyes such as rhodamine 6GCP (C.I. 45160). These dyes can be used alone or in combination of two or more, and the amount used thereof is preferably in the range of 2 to 15% by mass, more preferably 5 to 5% by mass with respect to the total amount of the non-aqueous inkjet ink composition. 10% by weight. If the amount of the dye 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 solid content tends to increase, and thus the discharge stability tends to decrease.

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

  Specific examples of inorganic pigments include carbon black, titanium oxide, zinc white, zinc oxide, tripone, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silica, alumina, cadmium red. , Bengara, molybdenum red, chrome vermilion, 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, ultramarine Examples include blue, bitumen, cobalt blue, cerulean blue, manganese violet, cobalt violet, and mica.

  Organic pigments such as azo, azomethine, polyazo, phthalocyanine, quinacridone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, isoindoline, isoindolinone 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 Violet 19, 23, 29, 30, 37, 40 , 50, Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 8 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, Pigment Orange 36 , 43, 51, 55, 59, 61, 71, 74, and the like.

  These pigments can be used alone or in combination of two or more, and the amount used is preferably 1 to 10% by mass, more preferably 2 to 2%, based on the total amount of the non-aqueous inkjet ink composition. 7% by 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 ink fluidity tends to decrease.

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

  In the case of using a pigment, a pigment having a group that reacts with a carbodiimide group (for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, etc.) is used as the pigment from the viewpoint of stably dispersing the pigment in an organic solvent. It is preferable to use a carbodiimide compound having a carbodiimide group among the pigment dispersants described later as the pigment dispersant.

  In addition, when there is no functional group that reacts with the carbodiimide group on the pigment surface, it can be introduced by surface treatment. For example, “Pigment dispersion stabilization and surface treatment technology / evaluation”, Technical Information Association, December 25, 2001. It can be introduced by the first day printing, plasma treatment described on pages 76 to 85, oxygen / ultraviolet treatment, low temperature plasma method described in JP-A-58-217559, and the like.

  Next, as the organic solvent constituting the non-aqueous inkjet ink composition of the present invention, the polyalkylene glycol dialkyl ether represented by the general formula (I) is used as the total organic solvent in the non-aqueous inkjet ink composition. In contrast, it is used so as to be 15 to 30% by mass.

R ¹ —O — (— CH ₂ —CHX—O—) _n —R ² (I)
[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 ₂ —CHX—O—). In general 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.

  If the amount of the 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. When using a base material made of a vinyl chloride polymer or ethylene-vinyl acetate copolymer for the surface layer, the surface of the base material will be melted too much, resulting in unevenness on the surface of the printed matter or a decrease in gloss. There is a tendency to invite.

  Among the polyalkylene glycol dialkyl ethers represented by the above general formula (I), triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether from the viewpoint of solubility of the resin and printability. Among them, triethylene glycol dimethyl ether is preferable.

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

  In addition to the polyalkylene glycol dialkyl ether represented by the general formula (I), an organic solvent in which the vinyl chloride polymer or ethylene-vinyl acetate copolymer in the surface layer of the base material is soluble may be used in combination. it can. Specific examples of such organic solvents include methyl ethyl ketone, butyl acetate, dioxane, cyclohexane, cyclohexanone, β-lactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl. Examples thereof include acetamide, and among 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.

  As the organic solvent used in the non-aqueous inkjet ink composition of the present invention, in addition to the organic solvent in which the vinyl chloride polymer and the ethylene-vinyl acetate copolymer in the surface layer of the substrate are soluble, the above group is used. An organic solvent in which the vinyl chloride polymer and ethylene-vinyl acetate copolymer in the surface layer of the material are not dissolved at all or hardly dissolved can be used in combination. Such an organic solvent is not particularly limited, but it is preferable to use an organic solvent having a boiling point of 140 ° C. or higher in order to stably eject ink as a non-aqueous inkjet ink composition. The upper limit of the boiling point is not particularly limited, but is preferably 250 ° C. or lower from the viewpoint of ink drying properties. Specific examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Glycol alkyl ether acetates such as monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethyl Glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Examples include glycol ethers such as ethyl ether, triethylene glycol monobutyl ether, 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 the organic solvent for the purpose of improving the dispersibility of the pigment.

  As the pigment dispersant, an ionic or nonionic surfactant, an anionic, cationic or nonionic polymer compound can be used.

  Among them, the pigment dispersant is preferably a polymer compound, for example, carbodiimide compounds described in JP-A-2004-038772, re-published WO2003 / 0776527, re-published WO2004 / 000950, Ajinomoto Co., Ajisper, SOLSPERS manufactured by Zeneca, DISPERBYK manufactured by BYK Chemie, Fuka manufactured by Fuka Additives, and the like are preferable. These pigment dispersants can be used alone or in combination of two or more.

  Among these, from the viewpoint of dispersion stability of the pigment in an organic solvent, a pigment having a group that reacts with a carbodiimide group (for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, etc.) is used as a pigment. As the agent, it is most preferable to use a carbodiimide-based compound having a carbodiimide group in the molecule, which is a pigment dispersant capable of having a strong binding force due to a covalent bond with a pigment having a group that reacts with a carbodiimide group.

  Specific examples of the carbodiimide-based compound having a carbodiimide group in the molecule include those described in JP-A-2004 / 083872, re-publication WO2003 / 0776527, and re-publication WO2004 / 000950. Among them, those having a carbodiimide group can be exemplified.

  Further, as the carbodiimide-based compound, those having a side chain such as a polyester side chain, a polyether side chain, and a polyacryl side chain are preferable from the viewpoint of pigment dispersion stability, and more preferably basic other than the above side chains. It has a nitrogen-containing group.

  Next, the preferable specific example of the carbodiimide type compound used for this invention is demonstrated. In addition, the carbodiimide type compound of this invention is not limited to this.

  A preferred carbodiimide-based compound that can be used in the present invention is at least one selected from the group consisting of a polyester chain, a polyether chain, and a polyacryl chain by utilizing a reaction between a carbodiimide group and a functional group capable of reacting with the carbodiimide group. Having at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain, and a polyacryl side chain, and having a carbodiimide equivalent of 100 to 50,000.

  More preferred carbodiimide compounds have at least one side chain selected from the group consisting of polyester side chain, polyether side chain and polyacryl side chain, and at least one basic group-containing group in the molecule. And the carbodiimide equivalent is 100 to 50,000.

  In the present invention, such a reaction between a carbodiimide group and a functional group is sometimes referred to as a grafting reaction. The side chain introduced by the method is grafted and the introduced polyester side chain is grafted. The polyester side chain, the polyether side chain may be referred to as a grafted polyether side chain, and the polyacryl side chain may be referred to as a grafted polyacryl side chain.

Moreover, in this specification, carbodiimide equivalent is
(Molecular weight of carbodiimide compound) / (Number of carbodiimide groups in the carbodiimide compound molecule)
This means the numerical value represented by

  In the present invention, one or more carbodiimide compounds can be used.

  In the present specification, the “side chain” refers to a chain that is branched from the main chain when a carbodiimide 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 one or more of a 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 polyacryl chain belongs to both the “polyether side chain” and the “polyacryl side chain”. Further, one side chain formed by combining one or more of a polyester chain, a polyether side chain, and a polyacrylic chain is a “polyester side chain”, “polyether side chain”, “polyacrylic side” It belongs to any of the “chains”. And, in this way, those in which a polyester chain, a polyether chain, and a polyacryl chain are mixed in one side chain are of course selected from the group consisting of “polyester side chain, polyether side chain, and polyacryl side chain”. It is a side chain that satisfies the condition of “at least one kind of side chain”.

  The “basic group nitrogen-containing group” includes not only those containing nitrogen that forms a quaternary ammonium ion in water, but also includes groups containing nitrogen that acts as a Lewis base. Examples thereof include an amino group and a nitrogen-containing heterocyclic group.

  First, the carbodiimide compound having the grafted side chain will be described.

  The carbodiimide compound having a grafted side chain is first composed of a polyester side chain, a polyether side chain and a polyacryl side chain by a grafting reaction based on a compound having two or more carbodiimide groups in the molecule. Mention may be made of compounds obtained by a method in which at least one side chain selected from the group is added (the remaining carbodiimide group is also at least one).

  Here, as the compound having two or more carbodiimide groups in the molecule, for example, a compound obtained by carbodiimidizing a diisocyanate compound by decarboxylation reaction in the presence of a carbodiimidization catalyst in an organic solvent can be used. As the diisocyanate compound to be decarboxylated, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, tetramethylxylylene diisocyanate, aliphatic, Mention may be made of alicyclic, aromatic and araliphatic diisocyanate compounds.

  In addition, under conditions sufficient to have two or more carbodiimide groups in the molecule of the resulting compound, a monoisocyanate compound may be used in combination. Examples of the monoisocyanate compound that can be used in this case include methyl isocyanate, Examples include ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and phenyl isocyanate, and aliphatic, alicyclic, aromatic, and araliphatic monoisocyanate compounds.

  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 carbodiimide group to be generated. Specifically, toluene, xylene, diethylbenzene Aromatic hydrocarbons such as diethylene glycol diacetate, dipropylene glycol dibutyrate, hexylene glycol diacetate, glycol diacetate, methyl glycol acetate, ethyl glycol acetate, butyl glycol acetate, ethyl diglycol acetate, butyl diglycol acetate, etc. Glycol ether esters; ketones such as ethyl butyl ketone, acetophenone, propiophenone, diisobutyl ketone, cyclohexanone; amyl acetate, propyl propionate And aliphatic esters such as ethyl butyrate and the like.

  Examples of the carbodiimidization catalyst that can be used include phospholenes and phospholene oxides. Specifically, 1-ethyl-3-methyl-3-phospholene oxide, 1-phenyl-3-methyl- Examples include 3-phospholene oxide and 1-phenyl-3-methyl-2-phospholene oxide.

  As a method of 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 carbodiimide group include, for example, U.S. Pat. No. 2,941,956, JP-B-47-33279, JP-A-5-178954, JP-A-6-56950, and the like. The method of description is mentioned.

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

OCN- (A-N = C = N) _k-1 -A-NCO (1) -1
A1-N = C = N- (A-N = C = N) _k-1 -A1 (1) -2

  In the above general formula, A is a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the polycarbodiimide compound, and A1 is a residue excluding the isocyanate group of the monoisocyanate compound used for the synthesis of the polycarbodiimide compound. It is.

  As a commercial product of the compound having a carbodiimide group represented by the general formula (1) -1, carbodiimide using tetramethylxylylene diisocyanate as a raw material, carbodilite V-03, V-05, etc. (both trade names, Nisshinbo) Results (made by Co., Ltd.).

  In addition, for example, 2 carbodiimide groups represented by the general formula (2) obtained by reacting a compound obtained by decarboxylation of K ′ (≧ 2) moles of a diisocyanate compound with a diol compound having two hydroxyl groups. Two or more compounds can also be used. This compound is also referred to as a polycarbodiimide compound.

OCN- (A-N = C = N) _k-1 -A-NHCOO- (B-OOCNH
-(N = C = NA) _k-1 ) m-NCO (2)

  In the above general formula, A is a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the polycarbodiimide compound, B is a residue excluding the hydroxyl group of the diol compound having two hydroxyl groups, and m is It is an integer of 1 or more.

  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, It can utilize as a compound which has two or more carbodiimide groups in the molecule | numerator which will form the carbodiimide type compound of this invention.

  As such a compound having a functional group capable of reacting with an isocyanate group, a compound having low reactivity with the remaining carbodiimide group and preferentially reacting with an isocyanate group first is preferable. For example, methanol, ethanol, etc. Hydroxyl groups such as low molecular monoalcohol compounds, polyester compounds having the above hydroxyl groups, polyalkylene glycols and their monoalkyl ester compounds, polymethyl methacrylate diols, polybutyl methacrylate diols, poly-2-ethylhexyl methacrylate diol and other hydroxyl group-containing polyacrylic compounds The containing compound can be mentioned. Among them, a polyester chain, a polyether chain, and a polyacryl chain having a formula weight of 500 to 5000 are preferable.

  A polyester side chain, a polyether side chain or a polyacryl side chain is further introduced into the compound having two or more carbodiimide groups in the molecule obtained by the method as described above by grafting reaction. A carbodiimide group containing at least one carbodiimide group and at least one grafted side chain selected from the group consisting of a grafted polyester side chain, a grafted polyether side chain, and a grafted polyacryl side chain This is a compound.

  As a typical method for introducing these side chains into the molecule by grafting reaction, a functional group capable of reacting with a carbodiimide group, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amino group, etc. The method of making the polyester compound, polyether compound, or polyacryl compound which has it react with the carbodiimide group of the compound which has a carbodiimide group can be utilized.

  As the polyester compound having the above functional group, first, (1) a ring-opening polymerization compound of a cyclic ester compound starting from oxycarboxylic acid, monoalcohol, low molecular diol compound or the like (for example, lactic acid, caproic acid, 12- Mono- or polyoxycarboxylic acid such as hydroxystearic acid, dimethylolpropionic acid, dimethylolbutanoic acid or the like is used as an initiator, and ε-caprolactone, γ-butyrolactone, 2-methylcaprolactone, 4-methylcaprolactone, β-propiolactone Polyester compounds containing carboxyl groups and hydroxyl groups obtained by ring-opening polymerization of cyclic ester compounds such as δ-valerolactone and β-methyl-δ-valerolactone; low molecular monool compounds such as methanol and ethanol as initiators Used as the above cyclic ester compound Polyester monool compound containing a hydroxyl group obtained by ring-opening polymerization; polyester containing a hydroxyl group obtained by ring-opening polymerization of the cyclic ester compound using a low molecular diol compound such as ethylene glycol or propylene glycol as an initiator Diol compounds and the like).

  (2) Self-polycondensation compound of oxycarboxylic acid (for example, polyester compound containing carboxyl group and hydroxyl group obtained by polycondensation of monooxycarboxylic acid such as lactic acid, caproic acid, 12-hydroxystearic acid, etc.) Can be mentioned.

  (3) Compounds obtained by polycondensation of low molecular diol compounds and low molecular dicarboxylic acid compounds (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol) Low molecular weight diol compound components such as linear glycols such as 1,2-propanediol, neopentyl glycol, branched glycols such as 3-methyl-1,5-pentanediol, ethylbutylpropanediol, and succinic acid A low molecular diol compound in an excess of a low molecular diol compound, and a low molecular diol compound component such as a saturated or unsaturated aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, maleic acid, and aromatic dicarboxylic acid such as phthalic acid. Polyester diol compound containing a hydroxyl group obtained by reacting with .

  And (4) a phosphoric ester compound of a ring-opening polymer of a cyclic ester compound using a monoalcohol as an initiator (for example, containing a phosphoric acid group obtained by esterifying the above-mentioned polyester monool compound with phosphoric acid) Polyester diol compounds, etc.), (5) ring-opening polymerization compounds of cyclic ester compounds using amino group-containing sulfonic acid compounds as initiators (for example, cyclic ester compounds using amino group-containing sulfonic acid compounds such as taurine as initiators) And polyester diol compounds containing a sulfonic acid obtained by ring-opening polymerization.

  (6) A sulfurous acid gas adduct of a ring-opening polymer of a cyclic ester compound using a monoalcohol as an initiator (for example, a polyester diol containing a sulfonic acid obtained by adding sulfurous acid gas to the above-mentioned polyester monool compound) Compounds).

  Such a polyester compound is preferably a polyester compound obtained by ring-opening polymerization of polycaprolactone.

As the polyether compound having the 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, caproic acid, 12-hydroxystearic acid, dimethylolpropionic acid, dimethylolbutane) Poly-containing a carboxyl group and a hydroxyl group obtained by ring-opening polymerization of a cyclic ether compound such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran and tetrahydropyran using a mono- or polyoxycarboxylic acid such as an acid as an initiator. Ether compounds; polyether monool compounds containing hydroxyl groups obtained by ring-opening polymerization of the above cyclic ether compounds using low molecular monool compounds such as methanol and ethanol as initiators; ethylene glycol, propylene glycol, etc. Using a low molecular weight diol compound as an initiator, it may be mentioned polyether diol compounds) having a hydroxyl group obtained by ring-opening polymerization of the cyclic ether compound.

  And (2) a phosphate ester compound of a ring-opening polymer of a cyclic ether compound using a monoalcohol as an initiator (for example, containing a phosphate group obtained by esterifying the polyether monool compound with phosphoric acid) Polyether compound).

  (3) Ring-opening polymerization compound of a cyclic ether compound using an amino group-containing sulfonic acid compound as an initiator (for example, ring-opening polymerization of the cyclic ether compound using an amino group-containing sulfonic acid compound such as taurine as an initiator) And polyether compounds containing sulfonic acid groups obtained in this way).

  (4) A sulfurous acid gas adduct of a ring-opening polymer of a cyclic ether compound using a monoalcohol as an initiator (for example, a polysulfuric acid group-containing polysulfide group obtained by adding sulfurous acid gas to the polyether monool compound) Ether compounds).

As a polyacryl compound having the above functional group,
(1) Polymerizing a monomer component containing at least one selected from (meth) acrylic monomers 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 (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 a sulfonic acid group: (meth) acrylic acid sulfoethyl, sulfopropyl (meth) acrylic acid, etc .; (meth) acrylic monomer having a phosphoric acid group: 2-methacryloyloxyethyl acid phosphate, Trisacryloyloxyethyl phosphate, etc .; (meth) acrylic group having a hydroxyl group Nomer: (meth) acrylic acid hydroxyalkyl ester such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxypentyl (meth) acrylate; (meth) acrylic monomer having amino group: (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, etc. It is obtained by polymerizing at least one monomer component selected from a monomer and a known monomer such as an alkyl ester or a styrene monomer generally used as a reaction component of an acrylic resin other than the above, if necessary. Acrylic heavy Mention may be made of the body, etc.).

  (2) Also obtained by polymerizing an acid group-free radical polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer in the presence of an acid group-containing chain transfer agent. A polyacrylic compound containing an acid group at the end of the molecule to be produced can be mentioned.

  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. A compound obtained by reacting a cyclic ester compound with a glycol or its monoalkyl ether compound as an initiator, a compound obtained by reacting a cyclic ether compound with a hydroxyl group-containing polyester compound, or a (meth) acryl containing a polyester chain in the molecule A polyacrylic chain compound obtained by using a (meth) acrylic monomer containing a monomer or a polyether chain in the molecule can be mentioned.

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

  In addition, the compound having a hydroxyl group, when the original polycarbodiimide compound further has an isocyanate group, the reaction with the isocyanate group occurs before the carbodiimide group, and the control of the reaction becomes difficult. The compound that has it may crosslink during the grafting reaction and cause gelation.

  Therefore, for a compound having only a hydroxyl group as a functional group, a polyester compound containing one carboxyl group is obtained by further reacting an acid anhydride such as phthalic anhydride, maleic anhydride, succinic anhydride, etc., before grafting. It is desirable to carry out the reaction.

  The compound in which at least one polyester compound, polyether compound or polyacryl compound exemplified above is introduced into the molecule by grafting must further have at least one carbodiimide group. For example, the above general formula (1) When a side chain is introduced into the polycarbodiimide compound represented by -1 by grafting reaction, a carbodiimide compound represented by the following general formula (3) is obtained (provided that K-1 = m + n). ).

  Here, A 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 carbodiimide 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.

  In addition, as a trivalent coupling group represented by said X, for example, the coupling group formed from the reaction of a carbodiimide group and a carboxyl group includes the following general formulas (4) and (5), carbodiimide group and hydroxyl group: The linking group formed from the reaction of the following general formulas (6) and (7), the linking group formed from the reaction of the carbodiimide group and the amino group is the following general formula (8), carbodiimide group and sulfone The linking group formed from the reaction with the acid group is represented by the following general formula (9), and the linking group formed from the reaction between the carbodiimide group and the phosphoric acid group is represented by the following general formula (10).

  In the above general formula, R represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms.

  Furthermore, although the carbodiimide type compound represented by General formula (3) has an isocyanate group in a molecule | numerator, it is also possible to react the compound which has a functional group which can react with an isocyanate group, and following General formula (11) ) Can also be used as the carbodiimide compound in the present invention.

In the above general formula, Z ¹ and Z ² are each independently a residue of a compound having a functional group capable of reacting with an isocyanate group, which may have a different structure, excluding one active hydrogen of the functional group. Represents a group. A 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 carbodiimide 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.

  As such a compound having a functional group capable of reacting with an isocyanate group, a compound having low reactivity with the remaining carbodiimide group and preferentially reacting with an isocyanate group first is preferable. For example, methanol, ethanol, etc. Low molecular monoalcohol compounds, polyester compounds containing the above hydroxyl groups, polyalkylene glycol and its monoalkyl ester compounds, polyacrylic compounds containing hydroxyl groups such as polymethyl methacrylate diol, polybutyl methacrylate diol, poly 2-ethylhexyl methacrylate diol, etc. A hydroxyl-containing compound can be mentioned. Among them, a polyester chain, a polyether chain or a polyacryl chain having a formula weight of 500 to 5000 is preferably formed.

  In addition, the reactions mentioned above, 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 polycondensation of a low molecular diol compound and a low molecular dicarboxylic acid compound Reaction, ring-opening reaction of a hydroxyl group-containing ester compound and an acid anhydride, ring-opening reaction of a cyclic ether compound, a ring-opening reaction of a hydroxyl group-containing ether compound and an acid anhydride, a reaction between a carbodiimide group, a carboxyl group, a hydroxyl group, and the like, Furthermore, a conventional method can be used for the reaction between an isocyanate group and a hydroxyl group.

  The carbodiimide-based compound may be a compound containing at least one carbodiimide group and a grafted polyester chain, a grafted polyether chain, or a grafted polyacryl chain, and the order of reacting each reaction material is different. However, as long as the finally obtained compounds have the same molecular structure, the obtained performance is not different.

  Therefore, in the compound of the general formula (11), at least one chain selected from the group consisting of a polyester chain having a functional group that reacts with a carbodiimide group, a polyether chain, and a polyacryl chain (compound having), In order to introduce the side chain into the molecule by reaction with a carbodiimide group (compound having), that is, in order to introduce a grafted polyester chain, a grafted polyether chain or a grafted polyacryl chain, the carbodiimide group is first introduced. Explains how to synthesize 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 polyacryl compound that reacts with a carbodiimide group, and then reacts with a carbodiimide group to form the side chain. However, the side chain was As another method of introducing into the molecule of the imide compound, after reacting a compound having a functional group that reacts with a carbodiimide group and a carbodiimide group (compound having), a polyester chain, a polyether chain, and a polyacryl chain It can also be carried out by introducing into the molecule a compound that forms at least one selected from the group consisting of:

  For example, in the case of introducing a grafted polyester side chain or a grafted polyether side chain, after reacting an oxycarboxylic acid with a carbodiimide group first and introducing a hydroxyl group into the carbodiimide compound molecule, a cyclic polyester compound Alternatively, it may be a method in which a cyclic polyether compound is subjected to ring-opening polymerization and a polyester chain or a polyether chain is grafted. If a grafted polyacrylic chain is to be introduced, the oxycarboxylic acid is first reacted with a carbodiimide group, the hydroxyl group is introduced into the molecule of the compound having a carbodiimide group, and then the polyacrylic chain is grafted. It may be a method.

  Furthermore, grafting may be carried out after reacting the isocyanate group remaining in the molecule of the compound having a carbodiimide group with a reactive functional group as described above, and the reaction of these reactions. As for the order, it is desirable to synthesize under conditions that minimize the number of undesirable side reaction products.

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

  Typical examples of the carbodiimide compound having the grafted side chain and having the basic group-containing group in the molecule include (1) the above-mentioned general formula (1) -1 or (2) An isocyanate group of a carbodiimide compound, a hydroxyl group suitable as a functional group capable of selectively reacting with the isocyanate group, a tertiary amino group or a basic nitrogen-containing heterocyclic group not involved in the reaction with the carbodiimide group or the isocyanate group. Using a reaction between a carbodiimide group of a compound obtained by reacting a compound having a functional group capable of reacting with the compound, at least one selected from the group consisting of a polyester chain, a polyether chain and a polyacryl chain is formed as a molecule. A carbodiimide compound introduced into the interior, (2) a carbodiimide of the polycarbodiimide compound of the above general formula (1) -1 or (2) An isocyanate group of a compound in which at least one selected from the group consisting of a polyester chain, a polyether chain, and a polyacrylic chain is introduced into the molecule by utilizing a reaction between a group and a functional group capable of reacting therewith, Obtained by reacting 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 with a carbodiimide group or an isocyanate group. (3) Carbodiimide represented by the general formula (2) obtained by reacting a compound obtained by decarboxylating the above-mentioned K ′ (≧ 2) mol of the diisocyanate compound with a diol compound having two hydroxyl groups. A polycarbodiimide-based compound having two or more groups, and a diol compound having two hydroxyl groups, two hydroxyl groups Based on a polycarbodiimide compound having a basic group-containing group in the molecule obtained by using a compound having a tertiary amino group and a carbodiimide group of this compound, and a functional group capable of reacting with the compound And carbodiimide compounds in which at least one selected from the group consisting of a polyester chain, a polyether chain, and a polyacrylic chain is introduced into the molecule.

  In addition, in said (1)-(3), when the isocyanate group remains, it is also possible to make the compound which has a functional group which can react with an isocyanate group react.

  As such a compound having a functional group capable of reacting with an isocyanate group, a compound having low reactivity with the remaining carbodiimide group and preferentially reacting with an isocyanate group first is preferable. Hydroxyl-containing compounds such as molecular monoalcohol compounds, polyester compounds having the above hydroxyl groups, polyalkylene glycols and monoalkyl ester compounds thereof, polymethyl methacrylate diols, polybutyl methacrylate diols, poly-2-ethylhexyl methacrylate diols and other hydroxyl group-containing polyacrylic compounds A compound can be mentioned.

  Specific examples of the 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 with a carbodiimide group or an isocyanate group include Examples of the compound having one hydroxyl group and a tertiary amino group include N, N-dialkylalkanolamine compounds such as N, N-dimethylethanolamine and N, N-diethylethanolamine, and secondary amine compounds. Examples thereof include an ethylene oxide adduct, a reaction product of a secondary amine compound and an epoxy compound. Examples of the compound having two hydroxyl groups and a tertiary amino group include N-alkyl dialkanolamine compounds such as N-methyldiethanolamine and N-ethyldiethanolamine, ethylene oxide adducts of primary amine compounds, and primary amines. The reaction material of a compound and an epoxy compound etc. can be mentioned.

  Furthermore, examples of the compound having a hydroxyl group and a basic nitrogen-containing heterocyclic group include a heterocyclic ring containing tertiary basic nitrogen such as hydroxypyridine, pyridinemethanol, pyridineethanol, etc., pyridine, pyrazine, triazine, quinoline and the like. And compounds having a hydroxyl group can be used. Further, even a heterocyclic compound containing secondary basic nitrogen such as piperidine or piperazine can be used by alkylating and tertiaryizing and containing a hydroxyl group.

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

  In addition, the said dispersing agent is suitably selected and used according to the kind of pigment and the kind of organic solvent to be used.

  Furthermore, in the non-aqueous inkjet 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 may be used as necessary. it can.

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

  The non-aqueous inkjet ink composition of 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, a high-pressure homogenizer (microfluidizer, nanomizer). , Optimizer, Genus PY, DeBEE2000, etc.), disperse and mix using a pearl mill or the like, and adjust the viscosity of the non-aqueous inkjet ink composition to 2-10 mPa · s. it can. The content of the total organic solvent in the non-aqueous inkjet ink composition of the present invention is determined from the total amount of the ink composition, the binder resin, the colorant (including the pigment dispersant when a pigment is used), and other components used as necessary. The total amount of these additives is subtracted, but it is preferable to appropriately change the ink viscosity so that it falls within the above range.

  The method for obtaining the printed matter of the present invention will be described. An ink jet printer using the above non-aqueous ink jet ink composition on a substrate having at least a surface layer made of a vinyl chloride polymer or an ethylene-vinyl acetate copolymer. It can be obtained by printing.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%” and “part” means mass part.

Examples 1-5 and Comparative Examples 1-2
<Manufacture of base ink for non-aqueous inkjet>
20 parts of the following pigment dispersant (carbodiimide compound) is dissolved in 60 parts of diethylene glycol diethyl ether, and carbon black MA-7 (manufactured by Mitsubishi Chemical Co., Ltd., which reacts with carbodiimide itself) as a pigment has a carboxyl group and the like. 1) After stirring and mixing 20 parts, the mixture was kneaded using a bead mill to obtain a base ink for non-aqueous inkjet.

<Manufacture of pigment dispersant (carbodiimide compound)>
In a four-necked flask equipped with a reflux condenser, a nitrogen gas inlet, a stirrer, and a thermometer, 1823 parts of a toluene solution of a polycarbodiimide compound having a carbodiimide equivalent of 316 having an isocyanate group (solid content 50%), N-methyldiethanolamine 178 The mixture was charged at about 100 ° C. for 3 hours to react an isocyanate group with a hydroxyl group, and then charged with 2915 parts of polycaprolactone having a carboxyl group at the end and a molecular weight of 2000 and 5104 parts of propylene glycol monomethyl ether acetate, The mixture was held at ° C. for 2 hours, and a carbodiimide group and a carboxyl group were reacted to obtain a pigment dispersant (solid content 40%) having a number average molecular weight of about 10800 and a carbodiimide equivalent of 2800.

<Production of non-aqueous inkjet ink composition>
The non-aqueous inkjets of Examples 1 to 5 and Comparative Examples 1 and 2 having a viscosity of about 4 mPa · s at 25 ° C. by stirring and mixing the materials in accordance with the formulations shown in Table 1 (the mixing ratio of each material is mass%) An ink composition was obtained.

<Printing method and printed matter>
A commercially available inkjet printer (SOLJET PRO II SC-540 manufactured by Roland DG Co., Ltd.) was loaded with the non-aqueous inkjet ink compositions of Examples 1 to 5 and Comparative Examples 1 and 2, and a polyvinyl chloride sheet ( (Trade name: Capjet Gross Burner, manufactured by Filmlook Co., Ltd.) and printed materials of Examples 1 to 5 and Comparative Examples 1 and 2 were obtained.

<Evaluation>
The following characteristics 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 can be used for products.

(viscosity)
The viscosity at 25 ° C. of each of the non-aqueous inkjet 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.).

(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 of 40 or more B: Gloss value of less than 40 to 20 or more C: Gloss value of less than 20

(Set property)
Using each of the non-aqueous inkjet ink compositions of Examples 1 to 5 and Comparative Examples 1 and 2, solid printing was performed on a polyvinyl chloride sheet (trade name: Capjet Gross Burner, manufactured by FilmLux) at 30 ° C. The time until drying was measured. Dryness was determined by touching and not touching the finger.
Evaluation criteria A: Less than 3 minutes B: 3 minutes or more to less than 5 minutes C: 5 minutes or more

(Discharge stability)
Using each of the nonaqueous inkjet ink compositions of Examples 1 to 5 and Comparative Examples 1 and 2, printing was performed on a polyvinyl chloride sheet (trade name: Capjet Gross Burner, manufactured by FilmLux Co., Ltd.). Evaluation was based on the number of sheets generated.
Evaluation criteria A: A non-printed portion occurs after the 71st sheet or a non-printed portion does not occur until the 100th sheet.
B: A portion not printed occurs on the 51st to 71st sheets.
C: The non-printed part occurs on the 31st to 50th sheets.
D: An unprinted part occurs up to the 30th sheet.

  The non-aqueous inkjet ink composition of the present invention has good wettability and fixability to a substrate whose printing surface is mainly composed of a vinyl chloride polymer or an ethylene-vinyl acetate copolymer, and is further suitable for inkjet printing. Excellent ejection stability even during long periods and after long periods of rest.

  Accordingly, by printing the non-aqueous inkjet ink composition of the present invention on a substrate such as tarpaulin, a large-sized signboard advertisement with good print quality can be easily produced.

Claims (7)

As the binder resin, at least one vinyl polymer selected from the group consisting of a vinyl chloride polymer, a vinyl chloride-vinyl acetate copolymer and an ethylene-vinyl acetate copolymer, a colorant, and an organic solvent are used. A non-aqueous inkjet ink composition comprising, as the organic solvent, a polyalkylene glycol dialkyl ether represented by the following general formula (I) in an amount of 15 to 30% by mass in the total organic solvent: .
R ¹ —O — (— CH ₂ —CHX—O—) _n —R ² (I)
(In the formula, 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). The non-aqueous inkjet ink composition according to claim 1, wherein triethylene glycol dialkyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I). The non-aqueous inkjet ink according to claim 1 or 2, wherein at least one of triethylene glycol dimethyl ether and triethylene glycol diethyl ether is used as the polyalkylene glycol dialkyl ether represented by the general formula (I). Composition. The above-mentioned 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 ink jet ink composition. Item 4. The non-aqueous inkjet ink composition according to any one of items 3 to 4. The non-aqueous inkjet ink composition according to any one of claims 1 to 4, wherein a vinyl chloride polymer is used as the vinyl polymer. The non-aqueous inkjet ink composition according to any one of claims 1 to 5 is printed on a base material having at least a surface layer made of a vinyl chloride polymer or an ethylene-vinyl acetate copolymer. Printed matter. The printed matter obtained by printing the ink composition for non-aqueous inkjets of Claim 5 on the base material which a surface layer consists of a vinyl chloride polymer at least.