Ink composition

Abstract

-C 16 ~C 18 methyl esters of fatty acids, - 0.40kgL -1 a β-type copper phthalocyanine having a bulk density of at least -C 14 ~C 18 Hydrocarbons, - a fatty acid amine salt of sulfonated copper phthalocyanine; An ink composition comprising: C 14 ~C 18 An ink composition is disclosed in which the weight ratio of hydrocarbon to fatty acid amine salt of sulfonated copper phthalocyanine is from 6:1 to 45:1. Methods of making the ink compositions, printing methods, and printed articles are also disclosed.

Description

[Technical Field]

[0001] The present invention relates to ink compositions, methods of making ink compositions, printing methods, and printed articles. [Background technology]

[0002] Increasing interest in sustainability and environmentally friendly technologies has led to a growing demand for plant-based inks. Additionally, concerns about the flammability of ink ingredients have led to a growing demand for inks with non-flammable ingredients. Changes in particle size and viscosity over time make the ink unsuitable for inkjet printing. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special table Hei 11-501353 [Patent Document 2] Special table Hei 10-507487 [Patent Document 3] Patent Publication No. 2005-290064 Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, new ink compositions are needed that address the above problems. [Means for solving the problem]

[0005] In one aspect, the present invention provides: -C 16 ~C 18 methyl esters of fatty acids; - 0.40kgL -1 β-type copper phthalocyanine having a bulk density of not less than 1000 ppm; -C 14 ~C 18 hydrocarbons; and - fatty acid amine salts of sulfonated copper phthalocyanine; An ink composition comprising: C 14 ~C 18 The ink composition has a weight ratio of hydrocarbon to fatty acid amine salt of sulfonated copper phthalocyanine of 6:1 to 45:1.

[0006] In another aspect, the present invention provides a method for producing a pharmaceutical composition comprising: -C 16 ~C 18 Providing methyl esters of fatty acids; - 0.40kgL -1 To provide a β-type copper phthalocyanine having a bulk density of at least -C 14 ~C 18 Providing hydrocarbons; and - providing a fatty acid amine salt of sulfonated copper phthalocyanine; 1. A method for producing an ink composition comprising: C 14 ~C 18 The method provides a method in which the weight ratio of the hydrocarbon to the fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 45:1.

[0007] In a further aspect, the present invention provides a method for producing a pharmaceutical composition comprising: - providing an ink composition of the present invention; and - printing the ink composition onto a substrate using an inkjet printer; A printing method including the steps of:

[0008] In yet another aspect, the present invention provides a printed article comprising a substrate and an ink composition of the present invention. [Effects of the Invention]

[0009] Advantages of the ink compositions of the present invention will become apparent from the detailed description of the invention below and include good particle size stability and good viscosity stability when using plant-derived carrier fluids and high flash point dispersants. DETAILED DESCRIPTION OF THE INVENTION

[0010] In one aspect, the present invention provides: -C 16 ~C 18 methyl esters of fatty acids; - 0.40kgL -1 β-type copper phthalocyanine having a bulk density of not less than 1000 ppm; -C 14 ~C 18 hydrocarbons; and - fatty acid amine salts of sulfonated copper phthalocyanine; An ink composition comprising: C 14 ~C 18 The ink composition has a weight ratio of hydrocarbon to fatty acid amine salt of sulfonated copper phthalocyanine of 6:1 to 45:1.

[0011] The ink composition of the present invention is 16 ~C 18 The ink composition includes a methyl ester of a fatty acid (hereinafter referred to as the first ester), which can act as a carrier fluid in the ink composition.

[0012] As used herein, C 16 ~C 18 Fatty acid methyl esters are fatty acids having 16 to 18 carbon atoms in which the -OH group of the acid moiety is replaced with an -O-CH group. The first ester may be a single compound or a mixture of compounds. The first ester is obtained from a fatty acid or a mixture of a fatty acid (hereinafter, the acid component of the first ester) and methanol. The first ester may be a plant-derived material. As used herein, a plant-derived material is a material that can be obtained by processing vegetable matter, for example, by hydrolysis of a vegetable oil such as soybean oil. Plant-derived materials suitable for the first ester include, for example, the plant-derived oils described in the CRC Handbook of Chemistry and Physics, edited by Robert C. Weast and Melvin J. Astle, CRC Press, 1979.

[0013] The acid component of the first ester may be branched or unbranched, and may be linear or cyclic. Typically, the acid component of the first ester may be linear and unbranched. The acid component of the first ester may be saturated or unsaturated. Suitable acid components of the first ester include polyunsaturated acids (examples of which include linoleic acid and linolenic acid), monounsaturated acids (examples of which include oleic acid), saturated acids (examples of which include palmitic acid and stearic acid), and mixtures thereof. In some embodiments, the acid component of the first ester is linoleic acid, oleic acid, palmitic acid, linolenic acid, stearic acid, or a mixture thereof.

[0014] In some embodiments, the acid component of the first ester is an unsaturated fatty acid. Preferably, the acid component of the first ester is a monounsaturated fatty acid. The monounsaturated fatty acid can be obtained, for example, by hydrolysis of vegetable oil (e.g., soybean oil). A preferred example of a suitable monounsaturated fatty acid is a C 10 fatty acid such as oleic acid. 18 Contains monounsaturated fatty acids such as oleic acid. 18 Monounsaturated fatty acids can be obtained by hydrolysis of soybean oil.

[0015] Therefore, in a preferred embodiment, C in the ink composition of the present invention 16 -C 18 Methyl esters of fatty acids include C methyl oleate, etc. 18 It is a methyl ester of a monounsaturated fatty acid and has, for example, the CAS number 67762-38-3.

[0016] Suitable C 16 ~C 18 Methyl esters of fatty acids are commercially available, such as METHYL OLEATE P, available from Mosselman SA. 16 ~C 18 The methyl ester of fatty acid is METHYL OLEATE P available from Mosselman SA.

[0017] C present in the ink composition of the present invention 16 ~C 18 The amount of methyl ester of fatty acid present in the ink composition of the present invention is not particularly limited. 16 ~C 18 The amount of methyl ester of fatty acid may be about 60 wt% or more based on the total weight of the composition, for example, 65 wt% or more, 70 wt% or more, or 75 wt% or more based on the total weight of the composition. 16 ~C 18 The amount of methyl ester of fatty acid may be about 95 wt% or less based on the total weight of the composition, for example, 90 wt% or less, 85 wt% or less, or 80 wt% or less based on the total weight of the composition. 16 ~C 18 The amount of methyl ester of fatty acid may be from 60 wt% to 90 wt%, from 65 wt% to 85 wt%, or from 70 wt% to 80 wt%, based on the total weight of the composition.

[0018] The ink composition of the present invention contains β-type copper phthalocyanine. β-type copper phthalocyanine can function as a cyan pigment in the ink composition. Therefore, the ink composition of the present invention is typically a cyan ink.

[0019] Copper phthalocyanine, also known as CuPc or phthalocyanine blue, has the CAS number 147-14-8 and the following chemical structure:

[0020] [ka] It is a blue phthalocyanine pigment having the formula: As can be seen from the above structure, copper phthalocyanine contains a phthalocyanine macrocyclic ligand with four isoindole units and Cu(II).

[0021] Copper phthalocyanine is generally crystalline and can exist in different crystalline forms. These crystalline forms include α, β, γ, η, and χ polymorphs. The copper phthalocyanine in the ink composition of the present invention is in the β crystalline form, referred to as β-type copper phthalocyanine. The β crystalline form is well known in the art and is described, for example, by J.M. Robertson, J. Chem. Soc. (1935) 615. The β crystalline form of copper phthalocyanine can be characterized by an XRPD (CuKα) spectrum containing peaks at 7.1±0.2°2θ, 9.1±0.2°2θ, 10.6±0.2°2θ, 28.5±0.2°2θ, and 31.9±0.2°2θ. Beta-form copper phthalocyanine pigments are widely available from commercial sources, for example, as Heliogen Blue L7101F (15:4) from Sun Chemical Colors & Effects GmbH and as Lionol Blue FG-7400-G (15:4) available from Toyocolor Co., Ltd.

[0022] The β-type copper phthalocyanine in the ink composition of the present invention is 0.40 kg / L -1 As used herein, the bulk density of β-form copper phthalocyanine is typically measured in accordance with ASTM D1895-17.

[0023] In the ink composition of the present invention, the β-type copper phthalocyanine is 0.40 kgL -1 Preferably, the β-type copper phthalocyanine has a bulk density of 0.42 kg / L or more. -1 More than 0.44 kgL, preferably 0.44 kgL -1 More preferably, 0.46 kg / L -1 Above, most preferably 0.48 kgL -1 β-type copper phthalocyanine typically has a bulk density of 1.50 kg / L or more. -1 Preferably, the bulk density is 1.00 kg / L or less. -1 Less than or equal to 0.80 kgL, preferably 0.80 kgL -1 Less than or equal to 0.60 kgL, and even more preferably 0.60 kgL -1Below 0.50 kgL, most preferably -1 Typically, β-type copper phthalocyanine has a bulk density of 0.40 kg L -1 from 1.50 kg L -1 , preferably 0.42 kg L -1 to 1.00 kg L -1 , more preferably 0.44 kg L -1 from 0.80 kg L -1 , and even more preferably 0.46 kg L -1 from 0.60 kg L -1 , most preferably 0.48 kg L -1 from 0.50 kgL -1 The bulk density of β-type copper phthalocyanine is 0.40 kg / L. -1 When the ink composition of the present invention has a bulk density equal to or greater than the above, and particularly when the ink composition has a bulk density in the above-mentioned typical and preferred amount, it exhibits advantageous properties such as particle size stability and viscosity stability.

[0024] In some embodiments, the β-form copper phthalocyanine in the ink composition of the present invention is Lionol Blue FG-7400-G (15:4) available from Toyocolor Co., Ltd.

[0025] The amount of β-copper phthalocyanine present in the ink composition of the present invention is not particularly limited. The amount of β-copper phthalocyanine present in the ink composition of the present invention may be about 2 wt% or more based on the total weight of the composition, for example, 4 wt% or more, 6 wt% or more, or 8 wt% or more based on the total weight of the composition. The amount of β-copper phthalocyanine present in the ink composition of the present invention may be about 18 wt% or less based on the total weight of the composition, for example, 16 wt% or less, 14 wt% or less, or 12 wt% or less based on the total weight of the composition. The amount of β-copper phthalocyanine present in the ink composition of the present invention may be 2 wt% to 18 wt%, 4 wt% to 16 wt%, 6 wt% to 14 wt%, or 8 wt% to 12 wt% based on the total weight of the composition.

[0026] The ink composition of the present invention is14 ~C 18 Contains hydrocarbons. C 14 ~C 18 The hydrocarbon may act as a dispersant in the ink composition of the present invention.

[0027] As used herein, C 14 ~C 18 Hydrocarbons are compounds containing 14 to 18 carbon atoms and containing only carbon and hydrogen atoms. 14 ~C 18 The hydrocarbons may be branched or unbranched. 14 ~C 18 Hydrocarbons are C 14 ~C 18 Contains isoalkanes. Unbranched C 14 ~C 18 Hydrocarbons are C 14 ~C 18 Contains n-alkanes. 14 ~C 18 The hydrocarbon may be saturated or unsaturated. 14 ~C 18 The hydrocarbon may be linear or cyclic. 14 ~C 18 The hydrocarbon comprises one or more cyclic moieties and, optionally, further comprises one or more linear moieties. The one or more cyclic moieties may be aromatic or non-aromatic.

[0028] C 14 ~C 18 The hydrocarbon preferably has a flash point of 93°C or higher, for example, 93°C to 120°C, 93°C to 110°C, or 93°C to 100°C. 14 ~C 18 The flash point of a hydrocarbon can be measured by any suitable technique known in the art, for example according to ISO 2719:2016.

[0029] C 14 ~C 18 The hydrocarbon may be a single compound or a mixture of compounds. 14 ~C 18 Hydrocarbons are: -C 14 ~C 18 n-alkanes; -C 14 ~C 18 isoalkanes; - non-aromatic cyclic C 14 ~C 18 hydrocarbons; and - Aromatic C 14 ~C 18 hydrocarbons; The compound is a mixture of compounds selected from the group comprising:

[0030] C 14 ~C 18 The hydrocarbon is a mixture of compounds, containing one or more aromatic C 14 ~C 18 If hydrocarbons are included, aromatic C 14 ~C 18 The hydrocarbon is preferably C 14 ~C 18 It is present in an amount of 2 wt% to 30 wt% based on the total weight of the hydrocarbons.

[0031] More preferably, C 14 ~C 18 Hydrocarbons are mixtures of compounds, consisting of one or more C 14 ~C 18 n-alkanes, one or more C 14 ~C 18 Isoalkanes, one or more non-aromatic cyclic C 14 ~C 18 Hydrocarbons and one or more aromatic C 14 ~C 18 Even more preferably, C 14 ~C 18 Hydrocarbons are mixtures of compounds, consisting of one or more C 14 ~C 18 n-alkanes, one or more C 14 ~C 18 Isoalkanes, one or more non-aromatic cyclic C 14 ~C 18 Hydrocarbons and one or more aromatic C 14 ~C 18 Contains hydrocarbons and one or more aromatic C 14 ~C18 Hydrocarbons are C 14 ~C 18 It is present in an amount of 2 wt% to 30 wt% based on the total weight of the hydrocarbons.

[0032] Suitable C 14 ~C 18 Hydrocarbons are commercially available and include Solsperse 13940 from The Lubrizol Corporation. In some embodiments, the C 14 ~C 18 The hydrocarbon is Solsperse 13940 from The Lubrizol Corporation.

[0033] In the ink composition of the present invention, 14 ~C 18 The absolute amount of hydrocarbons present in the ink composition of the present invention is not particularly limited. 14 ~C 18 The amount of hydrocarbon may be about 4 wt% or more based on the total weight of the composition, for example, 6 wt% or more, 8 wt% or more, or 10 wt% or more based on the total weight of the composition. 14 ~C 18 The amount of hydrocarbon may be about 18 wt% or less based on the total weight of the composition, for example, 16 wt% or less, 14 wt% or less, or 12 wt% or less based on the total weight of the composition. 14 ~C 18 The amount of hydrocarbon may be from 4 wt% to 18 wt%, from 6 wt% to 16 wt%, from 8 wt% to 14 wt%, or from 10 wt% to 12 wt%, based on the total weight of the composition.

[0034] The ink composition of the present invention includes a fatty acid amine salt of sulfonated copper phthalocyanine. The fatty acid amine salt of sulfonated copper phthalocyanine can act as a dispersant synergist in the ink composition of the present invention. The presence of the fatty acid amine salt of sulfonated copper phthalocyanine in the ink composition of the present invention provides advantageous properties such as particle size stability and viscosity stability.

[0035] As used herein, the fatty acid amine salt of sulfonated copper phthalocyanine comprises a copper phthalocyanine sulfonate anion and a quaternary ammonium cation.

[0036] The copper phthalocyanine sulfonate anion comprises one or more sulfonic acid groups bonded to a carbon atom in an isoindole unit of the phthalocyanine macrocycle. The copper phthalocyanine sulfonate anion may have, for example, one, two, three, or four sulfonic acid groups. Each sulfonic acid group can be bonded to a carbon atom in an isoindole unit of the phthalocyanine macrocycle. In some embodiments, the copper phthalocyanine sulfonate anion has one sulfonic acid group bonded to a carbon atom in an isoindole unit of the phthalocyanine macrocycle.

[0037] The quaternary ammonium cation in fatty acid amine salts is C8 to C 22 Contains a hydrocarbon group, where n is 1 to 4. n is C8 to C 22 In addition to the hydrocarbon group, the quaternary ammonium cation in the fatty acid amine salt contains 4 to n other groups attached to the quaternary nitrogen atom. The 4 to n other groups may be independently selected from, for example, hydrogen and C1 to C7 alkyl. The quaternary ammonium cation in the fatty acid amine salt may be, for example: - One C8 to C bonded to a quaternary nitrogen atom 22 a hydrocarbon group, and three groups independently selected from hydrogen and C1 to C7 alkyl attached to a quaternary nitrogen atom; or - Two C8 to C attached to a quaternary nitrogen atom 22 a hydrocarbon group, and two groups independently selected from hydrogen and C1 to C7 alkyl attached to a quaternary nitrogen atom; or - Three C8 to C attached to a quaternary nitrogen atom 22 a hydrocarbon group, and one group independently selected from hydrogen and C1 to C7 alkyl attached to a quaternary nitrogen atom; or - Four C8 to C attached to a quaternary nitrogen atom22 a hydrocarbon group (no further groups attached to the quaternary nitrogen atom); may include:

[0038] n C8 to C in quaternary ammonium cations in fatty acid amine salts 22 The hydrocarbon groups may be the same or different and each may be, for example, C 14 From C 22 Hydrocarbon group, C 16 From C 20 Hydrocarbon group, or C 18 It may be a hydrocarbon group, for example, C 14 From C 22 Alkyl group, C 16 From C 20 Alkyl group or C 18 The other groups 4 to n in the quaternary ammonium cation in the fatty acid amine salt may be the same or different, and each may be, for example, a hydrogen atom or a C1 to C2 alkyl group, such as a methyl group. In some embodiments, the quaternary ammonium cation has two C 18 It contains an alkyl group and two methyl groups attached to a quaternary nitrogen atom.

[0039] In some embodiments, the fatty acid amine salt of sulfonated copper phthalocyanine comprises a copper phthalocyanine sulfonate anion having one, two, three, or four sulfonic acid groups and a C to C bonded to a quaternary nitrogen atom. 22 The fatty acid amine salt of sulfonated copper phthalocyanine comprises a quaternary ammonium cation having a hydrocarbon group and 4 to n groups selected from hydrogen and C1 to C7 alkyl, where n is 1 to 4. In some embodiments, the fatty acid amine salt of sulfonated copper phthalocyanine comprises a copper phthalocyanine sulfonate anion having one sulfonic acid group and two C groups bonded to the quaternary nitrogen atom. 16 From C 20 and a quaternary ammonium cation having a hydrocarbon group and two groups selected from hydrogen and C1 to C2 alkyl.

[0040] Suitable fatty acid amine salts of sulfonated copper phthalocyanine are commercially available and include Solsperse 5000S available from The Lubrizol Corporation. In some embodiments, the fatty acid amine salt of sulfonated copper phthalocyanine in the ink composition of the present invention is Solsperse 5000S available from The Lubrizol Corporation.

[0041] The absolute amount of the sulfonated copper phthalocyanine fatty acid amine salt in the ink composition of the present invention is not particularly limited. The amount of the sulfonated copper phthalocyanine fatty acid amine salt present in the ink composition of the present invention may be about 0.06 wt% or more based on the total weight of the composition, for example, 0.09 wt% or more, 0.12 wt% or more, or 0.15 wt% or more based on the total weight of the composition. The amount of the sulfonated copper phthalocyanine fatty acid amine salt present in the ink composition of the present invention may be about 0.50 wt% or less based on the total weight of the composition, for example, 0.45 wt% or less, 0.40 wt% or less, or 0.35 wt% or less based on the total weight of the composition. The amount of the fatty acid amine salt of sulfonated copper phthalocyanine present in the ink composition of the present invention may be from 0.06 wt % to 0.50 wt %, from 0.09 wt % to 0.45 wt %, from 0.12 wt % to 0.40 wt %, or from 0.15 wt % to 0.35 wt %, based on the total weight of the composition.

[0042] The presence of the fatty acid amine salt of sulfonated copper phthalocyanine in the ink composition of the present invention, particularly in the compositions and amounts described above, provides advantageous properties such as particle size stability and viscosity stability.

[0043] The ink composition of the present invention may further comprise an alkyd resin. As used herein, the alkyd resin comprises an ester (hereinafter referred to as the second ester). The second ester is derived from an acid (hereinafter referred to as the acid component of the second ester) and an alcohol (hereinafter referred to as the alcohol component of the second ester). The second ester may be a plant-derived material as described elsewhere herein.

[0044] In some embodiments, the acid component of the second ester is an unsaturated fatty acid. Preferably, the acid component of the second ester is a di-unsaturated fatty acid. Di-unsaturated fatty acids can be obtained, for example, by hydrolysis of vegetable oils (such as soybean oil). Examples of suitable di-unsaturated fatty acids include linoleic acid, eicosadienoic acid, docosadienoic acid, and linoleic acid. Linoleic acid is preferred as the acid component of the second ester. Linoleic acid can be obtained by hydrolysis of soybean oil.

[0045] In some embodiments, the alcohol component of the second ester is a polyhydric alcohol. Examples of suitable polyhydric alcohols include glycerol, trimethylolpropane, and pentaerythritol. Pentaerythritol is preferred as the alcohol component of the second ester.

[0046] The second ester may be an ester of a diunsaturated fatty acid and a polyhydric alcohol, and examples of the second ester include glyceryl esters of linoleic acid (e.g., glyceryl monolinleate, glyceryl dilonleate, glyceryl trilinoleate, or any mixture thereof), glyceryl esters of eicosadienoic acid (e.g., glyceryl monoeicosadienoate, glyceryl dieicosadienoate, glyceryl trieicosadienoate, or any mixture thereof), trimethylolpropyl esters of linoleic acid (e.g., trimethylolpropyl monolinoleate, trimethylolpropyl dilinoleate, trimethylolpropyl esters of eicosadienoic acid (e.g., trimethylolpropyl monoeicosadienoate, trimethylolpropyl dieicosadienoate, trimethylolpropyl trieicosadienoate, or any mixture thereof), trimethylolpropyl esters of docosadienoic acid (e.g., trimethylolpropyl monodocosadienoate, trimethylolpropyl didocosadienoate, trimethylolpropyl tridocosadienoate, or any mixture thereof),tridocosadienoate, or any mixture thereof), pentaerythrityl esters of linoleic acid (e.g., pentaerythrityl monolinoleate, pentaerythrityl dilinoleate, pentaerythrityl trilinoleate, pentaerythrityl tetralinoleate, or any mixture thereof), pentaerythrityl esters of eicosadienoic acid (e.g., pentaerythrityl monoeicosadienoate, pentaerythrityl dieicosadienoate, pentaerythrityl trieicosadienoate, Examples of the second ester include pentaerythrityl esters of docosadienoic acid (e.g., pentaerythrityl monodocosadienoate, pentaerythrityl didocosadienoate, pentaerythrityl tridocosadienoate, pentaerythrityl tetradocosadienoate, or any mixture thereof), and pentaerythrityl esters of docosadienoic acid (e.g., pentaerythrityl monodocosadienoate, pentaerythrityl didocosadienoate, pentaerythrityl tridocosadienoate, pentaerythrityl tetradocosadienoate, or any mixture thereof). Pentaerythrityl esters of tetralinoleic acid are preferred as the second ester. A mixture containing pentaerythrityl monolinoleate and pentaerythrityl dilinoleate is particularly preferred.

[0047] The alkyd resin may be a single material or a mixture of different materials, and the one or more additional materials may be other esters (e.g., other esters of unsaturated fatty acids and polyhydric alcohols) or other materials of the type commonly found in alkyd resins.

[0048] In a particular embodiment, the alkyd resin is Vilkyd 782 available from Vil Resins Ltd.

[0049] In some embodiments, the alkyd resin, when present, is present in an amount of 0.5 wt% or more based on the total weight of the composition. In preferred embodiments of the ink composition of the present invention, the alkyd resin, when present, is present in an amount of 0.5 to 8 wt% based on the total weight of the composition. In some preferred embodiments, the alkyd resin, when present, is present in an amount of 1 to 6 wt% based on the total weight of the composition. In particularly preferred embodiments, the alkyd resin, when present, is present in an amount of 2 to 4 wt% based on the total weight of the composition.

[0050] In the ink composition of the present invention, 14 ~C 18 The weight ratio of the hydrocarbon to the fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 45:1. 14 ~C 18 The weight ratio of the hydrocarbon to the fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 40:1. 14 ~C 18 The weight ratio of the hydrocarbon to the fatty acid amine salt of sulfonated copper phthalocyanine is 6.25:1 to 40:1. 14 ~C 18 When the weight ratio of the hydrocarbon to the fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 45:1, particularly 6:1 to 40:1 or 6.25:1 to 40:1, the ink composition of the present invention exhibits advantageous properties such as particle size stability and viscosity stability.

[0051] In some embodiments, the ink composition comprises: -C16 ~C 18 methyl esters of monounsaturated fatty acids; - 0.42kgL -1 to 1.00 kg L -1 β-type copper phthalocyanine having a bulk density of -C 14 ~C 18 n-alkanes, C 14 ~C 18 Isoalkanes, non-aromatic cyclic C 14 ~C 18 Hydrocarbons and aromatic C 14 ~C 18 C, a mixture of compounds selected from the group including hydrocarbons 14 ~C 18 hydrocarbons; - Copper phthalocyanine sulfonate anions with one, two, three, or four sulfonic acid groups and n C8 to C attached to a quaternary nitrogen atom 22 a fatty acid amine salt of sulfonated copper phthalocyanine containing a hydrocarbon group and a quaternary ammonium cation having 4 to n groups selected from hydrogen and C1 to C7 alkyl, where n is 1 to 4; and - Alkyd resin (C 14 ~C 18 the weight ratio of hydrocarbon to fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 45:1; Includes:

[0052] In some embodiments, the ink composition comprises: -C 18 methyl esters of monounsaturated fatty acids; - 0.46kgL -1 from 0.60 kg L -1 β-type copper phthalocyanine having a bulk density of - One or more C's 14 ~C 18 n-alkanes, one or more C 14 ~C 18 Isoalkanes, one or more non-aromatic cyclic C 14 ~C 18 Hydrocarbons and one or more aromatic C 14 ~C 18C, a mixture of hydrocarbons 14 ~C 18 hydrocarbons; - Copper phthalocyanine sulfonate anion with one sulfonic acid group and two C bonded to the quaternary nitrogen atom 16 From C 20 a fatty acid amine salt of sulfonated copper phthalocyanine containing a hydrocarbon group and a quaternary ammonium cation having two groups selected from hydrogen and C1 to C2 alkyl; and - alkyd resins containing esters of diunsaturated fatty acids and polyhydric alcohols (C 14 ~C 18 the weight ratio of hydrocarbon to fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 45:1; Includes:

[0053] In some embodiments, the ink composition comprises: - 60wt% to 90wt% C based on the total weight of the composition 16 ~C 18 methyl esters of monounsaturated fatty acids; - 0.42kgL -1 to 1.00 kg L -1 2 wt % to 18 wt %, based on the total weight of the composition, of β-type copper phthalocyanine having a bulk density of -C 14 ~C 18 n-alkanes, C 14 ~C 18 Isoalkanes, non-aromatic cyclic C 14 ~C 18 Hydrocarbons and aromatic C 14 ~C 18 4 wt% to 18 wt% C based on the total weight of the composition, which is a mixture of compounds selected from the group including hydrocarbons 14 ~C 18 hydrocarbons; - Copper phthalocyanine sulfonate anions with one, two, three, or four sulfonic acid groups and n C8 to C attached to a quaternary nitrogen atom 220.06 wt % to 0.50 wt %, based on the total weight of the composition, of a fatty acid amine salt of sulfonated copper phthalocyanine, comprising a hydrocarbon group and a quaternary ammonium cation having 4 to n groups selected from hydrogen and C1 to C7 alkyl, where n is 1 to 4; and - 1 wt% to 6 wt% of alkyd resin (C 14 ~C 18 the weight ratio of hydrocarbon to fatty acid amine salt of sulfonated copper phthalocyanine is 6:1 to 45:1; Includes:

[0054] In some embodiments, the ink composition comprises: - 70wt% to 80wt% C based on the total weight of the composition 18 methyl esters of monounsaturated fatty acids; - 0.46kgL -1 from 0.60 kg L -1 6 wt % to 14 wt %, based on the total weight of the composition, of β-type copper phthalocyanine having a bulk density of - One or more C's 14 ~C 18 n-alkanes, one or more C 14 ~C 18 Isoalkanes, one or more non-aromatic cyclic C 14 ~C 18 Hydrocarbons and one or more aromatic C 14 ~C 18 8 wt% to 14 wt% C based on the total weight of the composition, which is a mixture of hydrocarbons 14 ~C 18 Hydrocarbons (one or more aromatic C 14 ~C 18 Hydrocarbons are C 14 ~C 18 present in an amount of 2 wt% to 30 wt% based on the total weight of hydrocarbons); - Copper phthalocyanine sulfonate anion with one sulfonic acid group and two C bonded to the quaternary nitrogen atom 16 From C 200.12 wt % to 0.40 wt %, based on the total weight of the composition, of a fatty acid amine salt of sulfonated copper phthalocyanine, the fatty acid amine salt comprising a hydrocarbon group and a quaternary ammonium cation having two groups selected from hydrogen and C1 to C2 alkyl; and - 2 wt. % to 4 wt. % of an alkyd resin (C), based on the total weight of the composition, comprising an ester of a diunsaturated fatty acid and a polyhydric alcohol. 14 ~C 18 the weight ratio of hydrocarbon to sulfonated copper phthalocyanine fatty acid amine salt is 6:1 to 40:1 (or 6.25:1 to 40:1); Includes:

[0055] The ink compositions of the present invention can be prepared by techniques known in the art, for example, by providing the components of the composition, which may be milled and / or subjected to ultrasonic dispersion (e.g., in an ultrasonic dispersion bath).

[0056] The ink compositions of the present invention can be used as inkjet inks. For example, they can be printed onto a substrate using an inkjet printer according to techniques known in the art. The substrate is not particularly limited and includes, for example, paper, card, and board. A printed article comprising a substrate and the ink composition of the present invention can be obtained by printing the ink onto the substrate, for example, by inkjet printing. [Example]

[0057] The present invention will now be illustrated by the following non-limiting examples. All examples and comparative examples were carried out using methyl oleate (METHYL OLEATE P from Mosselman SA) as the carrier and C 1000 (C 1000) with a flash point of 96°C as the dispersant. 14 ~C 18 A hydrocarbon (Solsperse 13940 from The Lubrizol Corporation) and an alkyd resin (Vilkyd 782) were used as the resin.

[0058] Examples 1 through 4 and Comparative Examples 2 and 3 used a fatty acid amine salt of sulfonated copper phthalocyanine as the dispersant synergist (Solsperse 5000S from The Lubrizol Corporation; Dispersant Synergist 1). Comparative Example 4 used a VOC-free fatty acid-based polymer as the dispersant synergist (ADD-6245 from ADD Additives BV; Dispersant Synergist 2).

[0059] In Examples 1 to 4 and Comparative Examples 1, 2, and 4, the pigment was 0.48 kgL -1 A β-type copper phthalocyanine having a bulk density of 0.33 kg L (Lionol Blue FG-7400G (15:4) from Toyocolor Co., Ltd.; bulk density was measured according to ASTM D1895-17; Pigment 1) was used. Comparative Example 3 used a β-type copper phthalocyanine having a bulk density of 0.33 kg L as the pigment. -1 A β-form copper phthalocyanine having a bulk density of 15:4 (Heliogen Blue L 7101F (15:4) from Sun Chemical Colors & Effects GmbH; bulk density measured according to ASTM D1895-17; Pigment 2) was used.

[0060] Ink compositions having the ingredients listed in Table 1 were prepared as Examples 1 to 4. Ink compositions having the ingredients listed in Table 2 were prepared as Comparative Examples 1 to 4. The compositions of Examples 1, 2, and 4 and Comparative Examples 1, 2, and 3 were prepared by milling the ingredients in a MiniZeta laboratory mill. The compositions of Example 3 and Comparative Example 4 were prepared by dispersion in an ultrasonic bath.

[0061] [Table 1]

[0062] [Table 2] The inks of Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated for particle size stability and viscosity stability. The results are presented in Table 3.

[0063] [Table 3] As can be seen from the examples, the combination of dispersant synergist and dispersant according to the present invention provides good particle size and viscosity stability when using a vegetable-derived carrier fluid and a high flash point dispersant.

[0064] The present invention has been described with reference to particular embodiments. However, those embodiments are merely exemplary, and those skilled in the art will appreciate that various modifications, including combinations of features described with reference to different embodiments, are possible without departing from the scope of the invention as set forth in the appended claims (with full regard for equivalents thereof).

[0065] This application claims priority from UK priority application no. GB ​​2218413.9, filed December 7, 2022, the entire contents of which are incorporated herein by reference.

Claims

1. - C １６ ~C １８ Methyl esters of fatty acids, - 0.40 kg L －１ a β-type copper phthalocyanine having a bulk density of at least - C １４ ~C １８ Hydrocarbons, - a fatty acid amine salt of sulfonated copper phthalocyanine; An ink composition comprising: Said C １４ ~C １８ The ink composition comprises a hydrocarbon and a fatty acid amine salt of the sulfonated copper phthalocyanine in a weight ratio of 6:1 to 45:

1.

2. Said C １４ ~C １８ 2. The ink composition of claim 1, wherein the weight ratio of hydrocarbon to the fatty acid amine salt of sulfonated copper phthalocyanine is from 6.25:1 to 40:

1.

3. Said C １６ ~C １８ 3. The ink composition of claim 1, wherein the methyl ester of a fatty acid is present in an amount of from 60 wt% to 90 wt% based on the total weight of the composition.

4. Said C １６ ~C １８ 4. The ink composition according to claim 1, wherein the fatty acid methyl ester is a plant-derived material.

5. 5. The ink composition of claim 1, wherein the beta copper phthalocyanine is present in an amount of 2 wt% to 18 wt% based on the total weight of the composition.

6. The β-type copper phthalocyanine was 0.42 kgL －１ to 1.00 kg L －１ The ink composition according to claim 1 , having a bulk density of

7. Said C １４ ~C １８ 7. The ink composition of claim 1, wherein the hydrocarbon is present in an amount of from 4 wt% to 18 wt% based on the total weight of the composition.

8. Said C １４ ~C １８ The hydrocarbon is C １４ ~C １８ n-alkanes, C １４ ~C １８ Isoalkane, non-aromatic cyclic C １４ ~C １８ Hydrocarbons and aromatic C １４ ~C １８ 8. An ink composition according to claim 1, which is a mixture of compounds selected from the group comprising hydrocarbons.

9. - Alkyd resin The ink composition according to claim 1 , further comprising:

10. 10. The ink composition of claim 9, wherein the alkyd resin is present in an amount of 1 wt% to 6 wt%, based on the total weight of the composition.

11. 10. The ink composition of claim 9, wherein the alkyd resin is present in an amount of 1 wt% to 6 wt%, based on the total weight of the composition.

12. - C １６ ~C １８ Providing a methyl ester of a fatty acid; - 0.40 kg L －１ To provide a β-type copper phthalocyanine having a bulk density of at least - C １４ ~C １８ providing a hydrocarbon; and - providing a fatty acid amine salt of sulfonated copper phthalocyanine; 1. A method for producing an ink composition comprising: Said C １４ ~C １８ The method, wherein the weight ratio of hydrocarbon to said sulfonated copper phthalocyanine fatty acid amine salt is from 6:1 to 45:

1.

13. Said C １６ ~C １８ a methyl ester of a fatty acid, the β-type copper phthalocyanine, the C １４ ~C １８ 13. The method of claim 12, wherein the hydrocarbon and / or fatty acid amine salt of the sulfonated copper phthalocyanine is as defined in any one of claims 2 to 11.

14. - providing an ink composition according to any one of claims 1 to 11, and - printing said ink composition onto a substrate using an inkjet printer; A printing method including:

15. A printed article comprising a substrate and the ink composition of any one of claims 1 to 11.

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