JP6075186B2 - Non-aqueous inkjet ink composition - Google Patents

Description

  The present invention relates to a non-aqueous ink-jet ink composition, which suppresses defects during printing such as bleeding, streaks, and mist, and relates to an ink composition excellent in decapability and printing stability.

  The ink composition used for inkjet printing is classified into a solvent type, an oily type, an aqueous type, an active energy ray curable type, and the like according to the composition. Among these, the solvent-type inkjet ink composition has characteristics such as excellent storage stability and good coating film resistance of printed matter such as scratch resistance and weather resistance compared to other ink compositions, It is used for various purposes including outdoor advertising.

  On the other hand, the solvent-based inkjet printing method requires a step of drying the organic solvent in the ink composition after printing, so depending on the substrate used and the printing conditions, productivity may decrease due to deterioration in drying properties. Or printed matter defects such as smearing of the printed matter.

  Therefore, in recent years, studies aiming to achieve both productivity and image quality have been conducted from both the ink composition and ink jet printing systems. In recent years, in particular, efforts have been made to improve drying properties by reducing the amount of ink composition droplets ejected from an inkjet head, and to increase image resolution by ejecting at a high frequency. However, when such an ink jet head is used, the ink composition dries before it completely spreads on the substrate, so that unevenness may occur in the printed matter.

  Conventionally, the use of an additive as an approach from an ink composition for avoiding the uneven stripe is known. For example, in Patent Documents 1 and 2, a polysiloxane additive is used, and in Patent Document 3, a fluorine additive is used. Each is used. By using an additive, the wetting spreadability of the ink composition can be improved and the unevenness can be improved.On the other hand, when the wetting spread is excessive, adjacent droplets are mixed with each other and bleeding occurs. When the surface tension of the ink composition is remarkably lowered, an image defect called mist may occur, in which ink droplets scatter and adhere to the image during ejection from the inkjet head.

  Under such circumstances, an ink composition containing an additive that can suppress defects during printing such as bleeding, stripe unevenness, and mist has been studied. For example, Patent Document 2 limits the type of organic solvent used in combination, and Patent Document 4 limits the amount of additives to be added, thereby controlling the wet spread and drying properties of the ink composition, and the printed matter defect. Trying to suppress. However, in any of the examples, it is difficult to say that the characteristics are completely controlled, and the printed matter defect may occur depending on a base material or an ink jet head to be used.

  As described above, a non-aqueous ink-jet ink composition that can suppress printing defects such as bleeding, stripe unevenness, and mist has not yet been obtained regardless of the substrate and printing conditions.

JP 2007-161892 A JP 2012-201838 A JP2011-219615A JP 2011-080043 A

  The present invention provides a non-aqueous ink-jet ink composition that suppresses defects during printing such as bleeding, stripe unevenness, and mist, and is excellent in decapability and printing stability.

The present inventor has intensively studied to provide an ink composition which is a non-aqueous ink jet ink composition and suppresses defects during printing such as bleeding, streaks, and mist, and is excellent in decapability and printing stability. As a result, at least a colorant, an organic solvent (A), a binder resin, and a siloxane additive (B) are contained in the ink composition, an arbitrary organic solvent (A) is selected, and the vinyl chloride base material is selected. The present invention has been accomplished by finding that the above-mentioned problems can be solved by designing the formulation of the ink composition so that the contact angle is larger than the contact angle with respect to the ink layer.

  The non-aqueous inkjet ink composition of the present invention is characterized by having the following constitution.

The present invention is a non-aqueous inkjet ink composition containing at least a colorant, an organic solvent (A), a binder resin, and a siloxane additive (B) and substantially free of water, wherein the organic solvent (A ) As R ₁ CO (OR ₂ ) _Z OR ₃ general formula (1)
R ₄ CO (OR ₅ ) _Z OCOR ₆ General formula (2)
R ₇ (OR ₈ ) _Z OR ₉ general formula (3),
And R ₁₀ (OR ₁₁ ) _Z OR ₁₂ general formula (4)
_{(Wherein, R 2, R 5, R} 8 represents an alkylene group having 2 to 4 carbon _{atoms, R 1, R 3, R} 4, R 6, R 7, R 9 is 1 to carbon atoms independently 4 represents an alkyl group, R ₁₀ and R ₁₂ both represent a hydrogen atom or one represents a hydrogen atom and one represents an alkyl group having 1 to 6 carbon atoms, and R ₁₁ represents an alkylene group having 1 to 10 carbon atoms. Z represents an integer of 1 to 3. The alkylene group and alkyl group may be linear or branched.
The non-aqueous inkjet ink composition contains at least one compound selected from the above, and the non-aqueous inkjet ink composition has a contact angle of CA1 (degrees) measured after dropping the non-aqueous inkjet ink composition onto a vinyl chloride base material after 1 second. When the contact angle measured after 1 second is dropped on the ink layer formed using CA2 is CA2 (degrees),
CA1> CA2
It is related with the non-aqueous inkjet ink composition characterized by these relationships being materialized.

The present invention also relates to a non-aqueous inkjet ink composition, wherein the siloxane additive (B) is a polyether-modified polysiloxane additive.
Furthermore, the present invention relates to a non-aqueous inkjet ink composition, wherein the siloxane-based additive (B) is soluble in water.

The present invention further relates to a non-aqueous ink-jet ink composition comprising at least one compound represented by the general formula (3) as the organic solvent (A).
Furthermore, the present invention relates to a non-aqueous ink-jet ink composition characterized by further containing at least one compound represented by the general formula (4) as the organic solvent (A).

Furthermore, the present invention relates to a non-aqueous inkjet ink composition characterized by being for a vinyl chloride substrate.
The present invention further relates to a non-aqueous inkjet ink composition comprising at least a cyan ink, a magenta ink, a yellow ink, and a black ink.

  The ink composition contains at least a colorant, an organic solvent (A), a binder resin, and a siloxane additive (B), selects an arbitrary organic solvent (A), and determines the ink from the contact angle with respect to the vinyl chloride substrate. By designing the formulation of the ink composition so that the contact angle with the layer is larger, it is a non-aqueous inkjet ink composition that suppresses defects during printing such as bleeding, streaks, and mist, and has a decapability and An ink composition having excellent printing stability could be obtained.

  Hereinafter, the present invention will be described with reference to preferred embodiments. In the following description, “part” and “%” represent “part by weight” and “% by weight” unless otherwise specified.

  The present invention is a non-aqueous ink-jet ink composition that suppresses defects during printing by designing the ink composition prescription so that the contact angle with the ink layer is larger than the contact angle with the vinyl chloride substrate. In addition, an ink composition having excellent decapability and printing stability can be obtained.

  In this specification, “substantially no water” means that the ink composition does not intentionally contain water, and excludes a small amount of water contained in each compounding component. is not.

  “Excellent decapability” means that an ink jet head filled with an ink composition is left without a cap for a certain period of time and then printed without cleaning the head without causing defective ejection or flying bends. It means that.

  The siloxane-based additive (B) is used for the purpose of improving the wettability of the ink composition with respect to the substrate. Generally, this phenomenon occurs because the additive is oriented at the interface (solid-liquid interface) with the substrate immediately after the ink composition ejected from the ink jet head has landed on the substrate. Since the additive is also oriented on the ink layer surface (gas-liquid interface) at the same time, the surface energy of the ink layer after drying and the surface tension of the ink composition are reduced.

  Due to the influence of the additive oriented on the surface of the ink layer, the wet-spreading property of the ink composition newly landed on the ink layer is worse than that on the substrate. Further, along with this, the drying property of the ink composition on the ink layer is deteriorated, and as a result, adjacent droplets are mixed with each other and the printed matter is blurred.

  On the other hand, when the additive is not used, the above-mentioned bleeding phenomenon is less likely to occur, but the additive is no longer oriented at the solid-liquid interface, so that wetting spreadability when printed on the substrate is eliminated. As a result, the printed matter may be uneven.

  The present inventors have found that by selecting a suitable siloxane-based additive (B), only the orientation to the gas-liquid interface among the interface orientations of the additive can be suppressed. Although the detailed mechanism is not clear, in view of the above-mentioned theory, after the ink composition of the present invention has landed on the substrate, the siloxane additive (B) is mainly oriented at the solid-liquid interface, On the other hand, the ink composition that has landed on the ink layer by ensuring little wetting and spreading on the substrate by preventing little orientation at the gas-liquid interface, and preventing the surface energy of the ink layer from decreasing. It is considered that the film was sufficiently wet and spread, and it was possible to improve the drying property and to suppress the bleeding of the printed matter.

  On the other hand, depending on the type and amount of the organic solvent (A) used in combination, the siloxane-based additive (B) is dissolved in the organic solvent (A) or, on the contrary, completely separated. Since the orientation of the siloxane-based additive (B) at the interface is affected, not only the siloxane-based additive (B) but also the compatibility with the organic solvent (A) used together, that is, compatibility is important. Become.

  As described above, in order to maximize the effects of the present invention, not only the type of the organic solvent (A) and the siloxane additive (B) but also the blending ratio when combined is an important factor.

Whether or not the combination of the organic solvent (A) and the siloxane additive (B) described above is suitable was formed by using an ink composition as a mixture of both on the base material and the ink composition. This can be confirmed by measuring the contact angle on the ink layer. In the ink composition of the present invention, the contact angle measured 1 second after dropping on a vinyl chloride substrate is CA1 (degrees), and the contact angle measured 1 second after dropping on the ink layer is CA2 (degrees). In addition,
CA1> CA2
It is preferable that the relationship is established.

  When the above formula is satisfied, it is shown that the orientation of the siloxane additive (B) at the gas-liquid interface hardly occurs as described above because the ink layer is wet and spread more than the base material. . Here, when CA2 is larger than CA1, wetting and spreading on the ink layer is poor, and orientation of the siloxane-based additive (B) to the gas-liquid interface occurs, and as a result, as described above. In this case, bleeding of the printed part occurs.

  The CA1 is preferably 25 degrees or less. If it is 25 degrees or more, even if the above formula is satisfied, wetting and spreading on the substrate becomes insufficient, and as a result, unevenness occurs in the printed matter, which is not preferable.

  The contact angle can be measured using a CA-X contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

  In this invention, if it is a siloxane type additive (B) which has the above physical properties, it will not specifically limit, The siloxane type additive normally used for an inkjet ink composition can be used.

As shown in the following general formula (5), the general formula of the siloxane additive (B) is to adjust the physical properties by introducing organic groups into the side chain and terminal of the derivative having polydimethylsiloxane as a basic structure. I can do it.
Examples of the organic group to be introduced include polyethers, polyesters, alkyls, aralkyls, fatty acid esters, fatty acid amides and the like. In the present invention, the following poly (a) (b) (c) Ether or alkyl is preferably selected. In particular, in the present invention, R ₁₄ in the general formula (5) includes at least one (a) and at least one of b, c, d, and e is an integer of 1 or more, that is, poly Ether-modified products are preferably used. This is indispensable for introducing the polyether group into the siloxane-based additive (B) to change the hydrophobicity of the additive and exhibit the effects of the present invention. This is because the compatibility with the organic solvent (A) can be controlled.

General formula (5)
In general formula (5), x is an integer of 1 to 800, preferably an integer of 1 to 400, more preferably an integer of 1 to 100, and y is an integer of 0 to 20, preferably 0 to 10. . The length of the main chain represented by x + y preferably does not exceed 800. When this value is exceeded, the compatibility with the organic solvent (A) is inferior, so that the orientation to the interface changes, and as a result, the wetting and spreading property to the substrate deteriorates. R ₁₃ represents an alkyl group or an aryl group, and R ₁₄ represents an alkyl group, an aryl group, or any substituent represented by the following (a) polyether, (b) alkyl, (c) reactive polyether. Indicates.

(A) Polyether
-(CH ₂ ) _a- (OC ₂ H ₄ ) _b- (OC ₃ H ₆ ) _c- (OC ₄ H ₈ ) _d- (OCH ₂ CH (C ₆ H ₅ )) _e -OR ₁₅
However, a is an integer of 1-10, b is an integer of 0-20, c is an integer of 0-50, d is an integer of 0-10, e is an integer of 0-10. . R ₁₅ represents any one of a hydrogen atom, an alkyl group, and an acyl group.

(B) Alkyl
-(CH ₂ ) _f -OR ₁₆
However, f is an integer of 2-20. R ₁₆ represents any one of a hydrogen atom, an alkyl group, an acyl group, and an ether group having a dimethylpropyl skeleton.

(C) Reactive polyether

However, g is an integer of 1-20, h is an integer of 0-50, i is an integer of 0-50. R ₁₇ represents a hydrogen atom or an alkyl group, and R ₁₈ represents a hydrogen atom, an alkyl group or an acyl group.

In the present invention, a commercially available siloxane additive (B) can be used, for example,
As the polyether modified product, KF-353A, KF-354L, KF6017, X-22-6551, AW-3 manufactured by Shin-Etsu Chemical Co., Ltd., SAG001, SAG002, SAG003, SAG005 manufactured by Nissin Chemical Industry Co., Ltd., SAG503A, SAG008, SAG010, 8019ADDITIVE, 8029ADDITIVE, 8032ADDITIVE, 8054ADDITIVE, 8526ADDITIVE, 8616ADDITIVE, 57ADDITIVE, 67ADDITZ, L7001, 04700Z BYK-300, 302, 306, 307, 330, 377, Bonikkudegusa manufactured by TEGO Glide 100,110,130,406,410,415,420,432,435,440,450
As a polyester modification, BYK-310, 313, 315, 370, 377 made by Big Chemie Japan Co., Ltd.
As the polyether polyester modification, BYK-375 manufactured by Big Chemie Japan Co., Ltd.
As aralkyl modification, BYK-322, 323 manufactured by Big Chemie Japan Co., Ltd.
Other organic modifications include TEGO Glide 411, 420 manufactured by Evonik Degussa.
Etc.

  Specific examples of the siloxane-based additive (B) suitably used in the present invention include BYK-302, 307, 333 by BYK-Chemie, KF354L by Shin-Etsu Silicone, Nissin Chemical Industry Co., Ltd., which are polyether modified products. SAG008, 503A made by Evonik Degussa and TEGO Glide 420 made by Evonik Degussa.

  The inventor has found that the compatibility with the organic solvent (A) can be easily confirmed by evaluating the solubility of the siloxane-based additive (B) in water. The siloxane additive (B) of the present invention is preferably soluble in water. Note that “soluble in water” means that when 99 parts by weight of water and 1 part by weight of the siloxane additive (B) are mixed, a uniform mixture is obtained without white turbidity or separation. If the siloxane-based additive (B) is not soluble in water, the orientation at the interface will be out of the preferred state, resulting in poor wetting and spreading to the substrate, resulting in streaks, This is not preferable because blurring is observed.

  The blending amount of the siloxane additive (B) with respect to the total amount of the ink composition is preferably 0.01 to 5%, more preferably 0.05 to 3%, and 0.1 to 2%. It is particularly preferably 5%. Here, if the blending amount of the siloxane additive (B) is less than 0.01%, the characteristics of the siloxane additive (B) cannot be fully exerted, and conversely if it exceeds 5%, the siloxane additive (B) is insufficient. Not only does the amount of additive (B) become excessive and the amount of orientation at the gas-liquid interface becomes relatively large, but also the ink composition affects the viscosity and boiling point of the siloxane additive (B). It is not preferable because it is received.

The ink composition of the present invention contains at least one compound selected from the following general formulas (1) to (4) as the organic solvent (A).
R ₁ CO (OR ₂ ) _Z OR ₃ General formula (1)
R ₄ CO (OR ₅ ) _Z OCOR ₆ General formula (2)
R ₇ (OR ₈ ) _Z OR ₉ general formula (3)
R ₁₀ (OR ₁₁ ) _Z OR ₁₂ general formula (4)
In the above formula, R ₂ , R ₅ and R ₈ represent an alkylene group having 2 to 4 carbon atoms, and R ₁ , R ₃ , R ₄ , R ₆ , R ₇ and R ₉ are each independently 1 to 1 carbon atoms. 4 represents an alkyl group, R ₁₀ and R ₁₂ both represent a hydrogen atom or one represents a hydrogen atom and one represents an alkyl group having 1 to 6 carbon atoms, and R ₁₁ represents an alkylene group having 1 to 10 carbon atoms. , Z represents an integer of 1 to 3. The alkylene group and alkyl group may be linear or branched.

  By using the above-mentioned solvent, it is possible not only to suppress the generation of mist during printing, to improve decapability and printing stability, but also to have excellent storage stability and substrate adhesion. Can be obtained.

In the present invention, at least a compound represented by the general formula (3) as the organic solvent (A) from the viewpoint of good compatibility with the siloxane-based additive (B) and a small odor peculiar to the solvent. It is preferable to contain 1 or more types.
The content of the organic solvent (A) represented by the general formula (3) is preferably 20 to 95% by weight and more preferably 30 to 80% by weight with respect to the total amount of the ink composition.

Furthermore, from the viewpoint of controlling the compatibility with the siloxane-based additive (B) that is soluble in water as described above, and from the point that the decapability and print stability of the ink composition can be improved, it is more general. It is particularly preferable to use at least one compound represented by formula (4) in combination.
The content of the organic solvent (A) represented by the general formula (4) is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, based on the total amount of the ink composition. Particularly preferred is 50% by weight.

  In the present invention, when the compound represented by the general formula (3) and the compound represented by the general formula (4) are used in combination, the weight ratio of the general formula (3): general formula (4) = 5: 95 to 95: 5 is preferable, 10:90 to 90:10 is more preferable, and 20:80 to 80:20 is particularly preferable. When it deviates from this range, the effect of a solvent with a small blending amount cannot be obtained sufficiently, which is not preferable.

In addition, when the compound represented by the general formula (1) and / or the general formula (2) is used in combination with the compound represented by the general formula (3) or the compound represented by the general formula (4), The ratio is preferably {sum of general formulas (1) to (3)}: general formula (4) = 10: 90 to 90:10, more preferably 15:85 to 85:15, : 80-80: 20 is particularly preferable.
The total content of the organic solvent (A) represented by the general formulas (1) to (4) is preferably 50 to 99% by weight, and preferably 60 to 90% by weight with respect to the total amount of the ink composition. Is more preferable.

  Specific examples of the solvent corresponding to the general formula (1) include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol monobutyl ether propionate, diethylene glycol monomethyl ether propionate, diethylene glyco Monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, ethylene glycol monoethyl ether butyrate, ethylene glycol monobutyl ether There are glycol monoacetates such as butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol monomethyl ether butyrate, dipropylene glycol monomethyl ether butyrate and methoxybutyl acetate.

  Solvents corresponding to general formula (2) include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, ethylene glycol propio. Nate butyrate, ethylene glycol dipropionate, ethylene glycol acetate dibutyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, diethylene glycol propionate butyrate, diethylene glycol dipropionate, diethylene glycol acetate dibutyrate, propylene glycol acetate propionate , Propylene glycol Tate butyrate, propylene glycol propionate butyrate, propylene glycol dipropionate, propylene glycol acetate dibutyrate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyrate, dipropylene glycol propionate butyrate, dipropylene There are glycol diacetates such as glycol dipropionate and dipropylene glycol acetate dibutyrate.

Furthermore, as a solvent corresponding to the general formula (3), for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, Examples include glycol dialkyl ethers such as triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

  In the present invention, the solvent corresponding to the general formula (1) from the viewpoints of compatibility with the siloxane-based additive (B), suppression of mist during printing, improvement of decapability, solubility of binder resin, odor, and safety. As ethylene glycol monobutyl ether acetate, as solvent corresponding to general formula (2), ethylene glycol diacetate, and as solvent corresponding to general formula (3), at least one of diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether It is particularly preferred to use more than one.

  In recent years, according to the US Environmental Protection Agency, concerns have been announced that the new use of glymes (symmetric glycol diethers) may have a detrimental effect on reproduction and development. From this point, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether and the like are preferably used.

Solvents corresponding to the general formula (4) include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, propylene glycol monomethyl ether (1-methoxy -2-propanol), propylene glycol monobutyl ether, propylene glycol n-propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dip Pyrene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether Glycol monoalkyl ethers such as tripropylene glycol monobutyl ether, 3-methoxy-3-methylbutanol, 3-methoxybutanol,
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethylhexanediol, etc. Examples include alkanediol.
Of these, glycol monoalkyl ethers are preferably used from the viewpoint of decapability, binder resin solubility, and odor, and among them, 3-methoxy-3-methylbutanol and 3-methoxybutanol are particularly preferable.

  Furthermore, in this invention, even if it is other than what was shown by General formula (1)-(4), it can be used as an organic solvent (A). The solvent that can be used in the ink composition of the present invention can be selected without particular limitation as long as it does not corrode the ink jet head or dissolves the pigment.

  Examples of other solvents include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, Methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, Ketones such as methylcyclohexanone and isophorone, methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, hexyl acetate , Acetate esters such as octyl acetate, lactate esters such as methyl lactate, ethyl lactate, butyl lactate, propyl lactate, ethyl hexyl lactate, amyl lactate, isoamyl lactate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol Glycols such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane and other saturated hydrocarbons, 1-hexene, 1-heptene, 1-octene and other unsaturated hydrocarbons, cyclohexane, cycloheptane , Cyclic saturated hydrocarbons such as cyclooctane, cyclodecane and decalin, cyclounsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene, benzene Aromatic hydrocarbons such as toluene and xylene, 3-alkyl-2-oxazolidinones such as 3-methyl-2-oxazolidinone and 3-ethyl-2-oxazolidinone, N-methyl-2-pyrrolidone, N-ethyl-2 N-alkylpyrrolidones such as pyrrolidone, lactones such as γ-butyrolactone, ε-caprolactone, nitrogen-containing solvents such as β-alkoxypropionamide, terpene solvents, ether solvents, and cyclic imides. Mention may be made of solvents.

  Among them, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-methyl-2-pyrrolidone, N-ethyl are used because the surface of the printing medium is dissolved to improve the fixability and weather resistance of the ink. -2-pyrrolidone, γ-butyrolactone, ε-caprolactone, β-alkoxypropionamide (M100, B100: manufactured by Idemitsu Kosan Co., Ltd.) are preferable.

The addition amount of the other solvent with respect to the total amount of the ink composition is preferably 1 to 10%, more preferably 3 to 8%.
Here, if it is less than 1%, the amount of the solvent is too small relative to the ink composition, and thus the above-described effects cannot be sufficiently obtained. On the other hand, if it exceeds 10%, materials such as pigments and dispersants are dissolved, and as a result, the storage stability of the ink composition deteriorates, which is not preferable.

In the present invention, it is preferable to use a binder resin together for the purpose of improving the substrate adhesion of the printed matter, the coating film resistance, and the like. Known binder resins can be used such as acrylic resins, styrene-acrylic resins, styrene-maleic resins, vinyl chloride resins, rosin resins, rosin ester resins, Ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic carbonization Examples thereof include a hydrogen resin, a butyral resin, a maleic acid resin, and a fumaric acid resin.
Specifically, BR-50, BR-52, MB-2539, BR-60, BR-64, BR-73, BR-75, MB-2389, BR-80 as acrylic resins manufactured by Mitsubishi Rayon Co., Ltd. BR-82, BR-83, BR-84, BR-85, BR-87, BR-88, BR-90, BR-95, BR-96, BR-100, BR-101, BR-102, BR- 105, BR-106, BR-107, BR-108, BR-110, BR-113, MB-2389, MB-2660, MB-2952, MB-3012, MB-3015, MB-7033, BR-115, MB-2478, BR-116, BR-117, BR-118, BR-122, ER-502,
As acrylic resins manufactured by Dow Chemical Company, PARALOID A-11, A-14, A-21, B-44, B-48N, B-60, B-64, B-66, B-67, B- 72, B-82, B-99N, DM-55,
As the acrylic resin manufactured by BASF, JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL683, JONCRYL690, JONCRYL819, JONCRYLJDX-C3000C80D
As a vinyl acetate resin made by Nissin Chemical Industry Co., Ltd., Solvain CL, CNL, C5R, TA3, TA5R,
Wacker Chemie AG's PVC resin E15 / 45, H14 / 36, H40 / 43, E15 / 45M, E15 / 40M,
Arakawa Chemical Co., Ltd. Superester 75, Ester Gum HP, Malkid 33, Yasuhara YS Polystar T80, Mitsui Chemicals Hirtts HRT200X,
An example is SMA 2625P manufactured by Sartomer. The above binder resins may be used alone or in combination of two or more.

  Among the above-mentioned binder resins, acrylic resins and vinyl chloride resins are particularly preferably selected from the viewpoints of adhesion to the substrate and excellent film resistance such as scratch resistance, chemical resistance, and weather resistance of printed matter. Is done.

  The binder resin is preferably contained in the ink composition in an amount of 0.1 to 20% by weight. If the addition amount is less than 0.1% by weight, the adhesion to the surface of the printing medium is poor, and the resistance of the coating film is reduced. If the addition amount exceeds 20% by weight, the viscosity is too high, so the printability is reduced. This is not preferable.

  In order to stably discharge the ink composition from the ink jet head, when the binder resin is used in the present invention, the weight average molecular weight Mw is preferably 70,000 or less, particularly preferably 10,000 to 50,000. The weight average molecular weight Mw can be determined as a styrene equivalent molecular weight by gel permeation chromatography.

  As the colorant used in the present invention, various pigments used in printing inks, paints and the like can be used. As the pigment, in addition to achromatic pigments such as carbon black, titanium oxide, and calcium carbonate, chromatic organic pigments can be used. Examples of the organic pigment include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red, soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, alizarin, indanthrone, Derivatives from vat dyes such as thioindigo maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, isoindo Isoindolinone organic pigments such as Linon Yellow and Isoindolinone Orange, and pyranthrone organic pigments such as Pilanthrone Red and Pilanthrone Orange Thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow, isoindoline organic pigments such as isoindoline yellow, and other pigments such as flavanthron yellow and acylamide yellow Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and the like.

When organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 8893, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153 154, 155, 166, 168, 180, 185, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 146, 149, 168, 177, 180, 185, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 269, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, and the like.

  Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline organic pigments, etc. are light resistant. Is preferable because it is excellent.

  The organic pigment is preferably a fine pigment having an average particle diameter of 10 to 300 nm as measured by laser scattering. When the average particle size of the pigment is less than 10 nm, the light resistance is lowered due to the small particle size, and when it exceeds 200 nm, it is difficult to maintain stable dispersion and the pigment is likely to precipitate.

  In the present invention, it is preferable to add a pigment dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink composition. The pigment dispersant is mainly classified into an acidic dispersant having an acidic group as a pigment adsorption site and a basic dispersant having a basic group. In the present invention, the affinity for the organic solvent (A) From the viewpoint of storage stability of the ink composition, it is preferable to select a basic dispersant.

The pigment dispersant used in the present invention can be selected from known materials. Specifically, Solspers 11200, Solspers 13240, Solspors 13650, Solspurs 13940, Solspurs 16000, Solspurz 17000, Solspurs 18000, Solspurs 20000, Solspurs 24000SG, Solspurs 24000GR, Solspurs 28000, Solspurs 31845 manufactured by Lubrizol as a basic dispersant. Solspurs 32000, Solspurs 32500, Solspurs 32550, Solspers 32600, Solspers 33000, Solspers 34750, Solspers 35100, Solspers 35200, Solspers 37500, Solspers 38500, Solspers 39000, Solspers 56000, Solspers 71000, Solspers 76400, Solspers 76500, Solspers X300, Solspers 9000, Solspers J200, DISPERBYK-108, DISPERBYK-109, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-161, DISPERDIBBY-162, manufactured by Big Chemie , DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2008, DISPERB PERBYK-2022, DISPERBYK-2050, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-9077, Ajinomoto Fine-Techno Co. AJISPER PB821, PB822, PB823, PB824, PB827, and the like. Further, as an acidic dispersant, Solspurs 3000, Solspurs 21000, Solspers 26000, Solspers 36600, Solspers 36600, Solspers 41000, Solspers 41090, Solspers 43000, Solspers 44000, Solspers 46000, Solspers 47000, Solspers 55000, manufactured by Big Chemie DISPERBYK-102, DISPERBYK-111, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2096, BYK-P104, BYK-P104S, BYK-P105, and BYK-220S. Furthermore, as a dispersant containing both an acidic group and a basic group in the molecule, Solspers 26000, Solspers 53095, manufactured by Lubrizol, DISPERBYK-101, DISPERBYK-106, DISPERBYK-140, DISPERBYK-142, manufactured by BYK Chemie. , DISPERBYK-180, DISPERBYK-2001, DISPERBYK-2025, DISPERBYK-2070, and BYK-9076.
The above dispersants may be used alone or in combination of two or more.

  The pigment dispersant is preferably contained in the ink composition in an amount of 0.1 to 10% by weight, more preferably 0.1 to 5% by weight.

  The ink composition of the present invention is preferably provided as an ink set comprising at least a cyan ink, a magenta ink, a yellow ink, and a black ink. In addition to the above four colors, for example, light cyan ink, light magenta ink, white ink, gray ink, light gray ink, in addition to the above four colors, for the purpose of improving the color gamut of the printed matter or improving the color developability on a substrate other than white. Violet ink, green ink, etc. can be used in combination.

  In addition to the siloxane-based additive (B), the ink composition of the present invention includes additives such as ultraviolet light inhibitors, light stabilizers, antioxidants, and hydrolysis inhibitors, in order to enhance printability and printed matter resistance. Can be used as needed.

  The ink composition of the present invention is a concentrated liquid containing a high concentration of pigment in advance by thoroughly dispersing a part of the colorant, pigment dispersant, and organic solvent (A) using a normal dispersing machine such as a sand mill. It is preferable to prepare by diluting with the remaining organic solvent (A), adding the siloxane-based additive (B), and further mixing and dissolving a binder resin and other additives as necessary. . This method enables sufficient dispersion even in dispersion using a normal disperser, and does not require excessive dispersion energy, and does not require a large amount of dispersion time, so that it is difficult to cause material deterioration during dispersion, and as a result An ink composition having excellent stability can be prepared.

  In order to prevent clogging in the head, the ink composition of the present invention is preferably filtered through a filter having a pore diameter of 3 μm or less, preferably 1 μm or less after dispersion and / or after dissolution of the binder resin.

The ink composition of the present invention preferably has a viscosity at 25 ° C. of 3 to 20 mPa · s and a surface tension of 15 to 40 mN / m. If it is this viscosity area | region, the stable discharge characteristic will be shown also in the head of the high frequency of 10-50 KHz especially from the head which has a frequency of normal 4-10 KHz.
When the viscosity is less than 3 mPa · s, a decrease in the followability of the discharge is recognized in the high-frequency ink jet head, and when it exceeds 20 mPa · s, the discharge amount decreases, resulting in poor discharge stability. In the end, it is not preferable because the discharge cannot be performed at all.

  The printing substrate used in the present invention is not particularly limited. For example, soft vinyl chloride, hard vinyl chloride, polystyrene, polystyrene foam, PMMA, polypropylene, polyethylene, PET, polycarbonate and other plastic substrates, mixed products or modified products thereof, and high-quality products. Examples thereof include paper base materials such as paper, art paper, coated paper and cast coated paper, and metal base materials such as glass and stainless steel. Especially in this invention, it uses suitably with respect to vinyl chloride base materials, such as a soft vinyl chloride and a hard vinyl chloride.

[Example]
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the embodiments of the present invention are not limited to these examples. In the following, all parts represent parts by weight. The detailed conditions of the following Examples and Comparative Examples are shown in Tables 1 and 2 below, and the results are shown in Table 3.

Moreover, the abbreviations described in Tables 1 and 2 represent the following materials, respectively.
LIONOL BLUE FG-7400G: Toyocolor Co., Ltd. Phthalocyanine Organic Pigment Fast Gen Super Magenta RG: DIC Corporation Quinacridone Organic Pigment
YELLOW PIGMENT E4GN: Nickel complex azo-based organic pigment SP32000 manufactured by LANXESS: Basic dispersant Solspurs 32000 manufactured by Lubrizol
BP821: Ajinomoto Fine Techno Co., Ltd. Basic dispersant DEDG: Diethylene glycol diethyl ether BGAc: Ethylene glycol monobutyl ether acetate
EGDA: ethylene glycol diacetate MEDG: diethylene glycol methyl ethyl ether DMTeG: tetraethylene glycol dimethyl ether MB: 3-methoxybutanol MMB: 3-methoxy-3-methylbutanol GBL: γ-butyrolactone MOZ: 3-methyl-2-oxazolidinone BR83, MB2389 BR87, BR113: Mitsubishi Rayon Co., Ltd. acrylic resin J586: BASF Co. acrylic resin E15 / 45: Wacker Chemie AG Co. vinyl acetate resin SAG503A: Nisshin Chemical Co., Ltd. siloxane additive (polyether modified) Soluble in water)
TG420: Organic modified siloxane additive Tego Glide420 (non-polyether modified, insoluble in water) manufactured by Evonik Degussa
TG450: siloxane additive Tego Glide450 (polyether modified, insoluble in water) manufactured by Evonik Degussa
BYK361N: acrylic additive manufactured by Big Chemie (insoluble in water)

[Example 1]
(Preparation of pigment dispersion 1)
After stirring the materials described in Table 1 with a high-speed mixer until uniform, the resulting mill base was dispersed for about 30 minutes with a horizontal sand mill to obtain pigment dispersion 1. Pigment dispersions 1-1 to 1-3 were prepared for cyan, magenta, and yellow, respectively.

(Preparation of ink composition 1)
The materials listed in Table 2 were added and mixed with sequential stirring, and gently mixed until the resin was dissolved, then filtered through a membrane filter with a pore size of 1 μm to remove coarse particles, whereby ink composition 1 was obtained. Obtained. An ink composition was similarly prepared for each of the pigment dispersants 1-1 to 1-3, and performance evaluation was performed using three ink compositions of cyan, magenta, and yellow as one ink set.

[Example 2 to Example 12]
In the same manner as in Example 1, after preparing pigment dispersions 1 and 2 as shown in Table 1, ink sets were prepared as shown in Table 2.

[Comparative Example 1 and Comparative Example 2]
In the same manner as in Example 1, after preparing pigment dispersions 1 and 2, ink sets were prepared as shown in Table 2.

The evaluation method of the ink composition produced above is as follows.
[Contact angle]
Prior to the contact angle measurement, the head of Color Painter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format ink jet printer) was filled with a cyan ink composition in an environment of 25 ° C. A solid print was created by printing 100% at 720 dpi × 720 dpi. Using the polyvinyl chloride sheet substrate and the solid printed material as a substrate sample, the contact angle of the ink composition was measured using a CA-X contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).
Specifically, 20 μL of the cyan ink composition was formed in a pendant shape at the tip of the dropping nozzle, and then dropped on the substrate sample by slowly lowering the nozzle. After capturing the droplet immediately after dropping as a continuous image, the contact angle was calculated by analyzing the droplet diameter and height of the droplet one second after dropping.
Using the method described above, the contact angle when using a polyvinyl chloride sheet substrate as a substrate sample is CA1 (degrees), the contact angle when using a solid print is CA2 (degrees), and the following evaluation criteria Comparison and evaluation were performed according to the above.
○: CA1> CA2 ×: CA1 ≦ CA2

[Smear]
Under an environment of 25 ° C., a color painter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format ink jet printer) is filled with an ink set, and a color image is printed on a surface of an untreated polyvinyl chloride sheet substrate. The presence or absence of bleeding between colors was observed with a magnifying glass. The evaluation criteria at this time are as follows.
◎: Bleeding cannot be confirmed by visual observation or observation with a 10 × magnifier. ○: Blurring cannot be confirmed by visual observation, but dot bleeding can be confirmed when viewed with a 10 × magnifier. Δ: Slightly blurred. X can be confirmed: Blur can be clearly seen visually, and the image is dirty

[Sujimura]
In a 25 ° C environment, the color set is filled into the head of a ColorPainter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format inkjet printer), and the surface is untreated, and 100% printing is performed. It was observed visually. The evaluation criteria at this time are as follows.
○: The ground is not visible at all. Δ: The ground is slightly exposed, but streaky unevenness is not visible. X: Clearly streaks can be confirmed.

[mist]
Under a 25 ° C environment, the color painter is filled into the head of ColorPainter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format ink jet printer) with a cyan ink composition, and a lattice pattern is printed on a non-processed polyvinyl chloride sheet base material. The part was observed visually. The evaluation criteria at this time are as follows.
○: No mist (scattering of ink composition) in non-printing area Δ: Slight mist can be confirmed in non-printing area ×: Mist in non-printing area can be clearly confirmed, and image is dirty

[Decap]
In a 25 ° C. environment, the color set of ColorPainter 64S (manufactured by Seiko I Infotech Co., Ltd., large inkjet printer) is filled with an ink set and left for 10 minutes with the cap open. The time that can be normally discharged was evaluated. The evaluation criteria at this time are as follows.
◎: All nozzles can be ejected without head cleaning. ○: Less than 10 nozzles are missing without head cleaning.
When all the nozzles are ejected by performing the cleaning once, no more than 10 nozzles are missing without the head cleaning, but all the nozzles are ejected by performing the head cleaning once. No nozzle missing occurs without cleaning, and nozzle missing does not recover even if head cleaning is performed once.

[Printing stability]
Under an environment of 25 ° C, a color painter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format ink jet printer) is filled with an ink set, and images are continuously printed on a non-treated surface of a polyvinyl chloride sheet. The frequency of occurrence of bending or ink scattering was evaluated. The evaluation criteria at this time are as follows, and Δ or higher is regarded as good printing stability.
○: After 50 hours of continuous printing, nozzle missing, flying bent or ink splashes occurred less than 10 times Δ: After 50 hours of continuous printing, nozzle missing, flying bent or ink splashed occurred 10 times or more and less than 20 times × : After 50 hours of continuous printing, nozzles missing, flying bent or ink splattered 20 times or more

  Table 3 shows the evaluation results for the ink compositions prepared in Examples 1 to 12 and Comparative Examples 1 and 2.

In Examples 1 to 4, the compound represented by the general formula (3) and the compound represented by the general formula (4) are used in combination as the organic solvent (A), and water is used as the siloxane-based additive (B). In this system, a polyether-modified siloxane additive soluble in water was used, and the contact angle was CA1> CA2. In addition, as shown in Table 3, in all evaluations, good results were obtained, in which bleeding was ◯ or more, streaky was ◯ or more, mist was ◯, decapability was ◎, and printing stability was ◯.

  On the other hand, Example 5 was a system using a non-polyether-modified siloxane additive insoluble in water as the siloxane additive (B), and it was confirmed that CA1> CA2 was established as a contact angle. As a result of evaluation, the blur was ◯, the stripe was △, the mist was △, the decapability was ◎, and the printing stability was ◯. The result was slightly inferior. Although the detailed reason is unknown, it was a result showing that selecting a water-soluble polyether-modified siloxane additive as the siloxane additive (B) contributes to further improvement in image quality.

  Examples 6-12 are the systems which changed the compounding ratio of the organic solvent (A), and all established CA1> CA2 as a contact angle. Of these, Examples 6 to 10 are systems in which the compound represented by the general formula (3) and the compound represented by the general formula (4) are used in combination as the organic solvent (A). Good results were obtained in all evaluations, although there were items that were not more than Examples 1-4, such as ◯ or more, streaky ◯ or more, mist ○, decapability ◯ or more, and printing stability △ or more. It was.

  Further, Example 11 is a system using the compounds represented by the general formulas (2) and (3) as the organic solvent (A). As a result of the evaluation, the blur is ○, the stripe is ○, the mist is Δ, the decap. Although the properties were Δ and the printing stability was Δ and all items were good, the results were slightly inferior in mist, decapability and printing stability as compared with Examples 1 to 4. Furthermore, in Example 12, the organic solvent (A) was a system in which neither the compound represented by the general formula (3) nor the compound represented by the general formula (4) was used. The results were slightly inferior in quality compared to other examples, although Δ was good in all items and good in all items. The above results suggest that the image quality can be further improved by using the compound represented by the general formula (3) and the compound represented by the general formula (4) as the organic solvent (A). Is.

On the other hand, in Comparative Examples 1 and 2, as a result of measuring the contact angle of the ink composition, CA1 ≦ CA2. In any of these systems, bleeding and / or streaking were insufficient. From this result, it was confirmed that in order to improve the image quality, it is essential to establish CA1> CA2 as the contact angle.

  Further, Comparative Example 2 is a system in which neither the compound represented by the general formula (3) nor the compound represented by the general formula (4) was used as the organic solvent (A). Not only that, but also about the mist. From this result, it was confirmed that the compound represented by the general formula (3) and the compound represented by the general formula (4) are suitably used as the organic solvent (A) in the present invention.

The non-aqueous ink-jet ink composition of the present invention is excellent in image quality and printing stability, and therefore is suitably used for, for example, ink-jet printing for industrial use and industrial use, particularly printing requiring high productivity and high image quality. be able to.

Claims (5)

A non-aqueous inkjet ink composition containing at least a colorant, an organic solvent (A), a binder resin, and a siloxane-based additive (B) and substantially free of water, wherein the organic solvent (A ) As R ₁ CO (OR ₂ ) _Z OR ₃ general formula (1)
R ₄ CO (OR ₅ ) _Z OCOR ₆ General formula (2)
R ₇ (OR ₈ ) _Z OR ₉ general formula (3),
And R ₁₀ (OR ₁₁ ) _Z OR ₁₂ general formula (4)
(Wherein R ₂ , R ₅ and R ₈ represent an alkylene group having 2 to 4 carbon atoms, and R ₁ , R ₃ , R ₄ , R ₆ , R ₇ and R ₉ each independently represent 1 to 4 represents an alkyl group, R ₁₀ and R ₁₂ are both hydrogen atoms or one is a hydrogen atom and one represents an alkyl group having 1 to 6 carbon atoms, and R ₁₁ represents an alkylene group having 1 to 10 carbon atoms. , Z represents an integer of 1 to 3. The alkylene group and the alkyl group may contain at least one compound selected from the group consisting of a linear or branched group, and the non-aqueous inkjet ink composition may be chlorinated. The contact angle measured 1 second after dropping on the vinyl substrate was CA1 (degrees), and the contact angle measured 1 second after dropping on the ink layer formed using the non-aqueous inkjet ink composition was CA2 (degrees). When
CA1> CA2
The relationship is established ,
The organic solvent (A) contains at least one compound represented by the general formula (3) and further contains at least one compound represented by the general formula (4). The weight ratio of the compound represented by 3) and the compound represented by the general formula (4) is 20:80 to 80:20
A non-aqueous inkjet ink composition.   The non-aqueous inkjet ink composition according to claim 1, wherein the siloxane additive (B) is a polyether-modified polysiloxane additive.   The non-aqueous inkjet ink composition according to claim 1, wherein the siloxane-based additive (B) is soluble in water. The non-aqueous inkjet ink composition according to any one of claims 1 to 3 , wherein the composition is for a vinyl chloride substrate. At least cyan ink, wherein the magenta ink, yellow ink, black ink, a non-aqueous inkjet ink composition according to any one of claims 1-4.