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WO2025070429A1 - Ink - Google Patents

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Publication number
WO2025070429A1
WO2025070429A1 PCT/JP2024/034019 JP2024034019W WO2025070429A1 WO 2025070429 A1 WO2025070429 A1 WO 2025070429A1 JP 2024034019 W JP2024034019 W JP 2024034019W WO 2025070429 A1 WO2025070429 A1 WO 2025070429A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
isobutyl
pigment
solvent composition
total weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/034019
Other languages
French (fr)
Inventor
Andrew Mcvitie
John Hamilton
Derek Smith
Samantha Davies
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB2314902.4A external-priority patent/GB202314902D0/en
Priority claimed from GBGB2314905.7A external-priority patent/GB202314905D0/en
Priority claimed from GBGB2314906.5A external-priority patent/GB202314906D0/en
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Publication of WO2025070429A1 publication Critical patent/WO2025070429A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B32B27/205—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents the fillers creating voids or cavities, e.g. by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2471/00—Floor coverings

Definitions

  • the present invention relates to inks, processes for producing inks, methods of printing and printed articles.
  • Inkjet printing is used in a variety of printing applications, and can provide high resolution images on a range of substrates.
  • Growing interest in safety and environmentally-friendly technologies has led to increased demand for inks that utilise non-hazardous components which pose low or no risk to the environment.
  • use of volatile components, such as particular solvents, in inks is regarded as undesirable as substantial evaporation of such components or solvents can cause the ink to dry in the printhead, resulting in poor nozzle recovery.
  • the viscosity of inks can also be susceptible to change over time due to evaporation. Changes in viscosity over time will lead to inks being unsuitable for inkjet printing.
  • the present invention provides an ink comprising: (a) a solvent composition; and (b) a pigment dispersion; wherein said solvent composition comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate; wherein the total amount of said di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate is 50% or more by weight based on the total weight of the ink; and wherein said pigment dispersion comprises a pigment and a binder, said binder comprising a poly(vinyl chloride-vinyl acetate) copolymer.
  • the present invention further provides a process for preparing an ink comprising: (a) mixing a pigment dispersion with a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate to form a first mixture; and (b) mixing the first mixture with a second partial solvent composition comprising soy methyl ester and optionally comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate, thereby forming an ink.
  • a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate
  • the present invention further provides a method of printing comprising: - providing an ink; and - using an inkjet printer to print the ink onto a substrate.
  • the present invention further provides a printed article comprising a substrate and an ink.
  • the present inventors have surprisingly found that inclusion of soy methyl ester in a solvent composition of an ink as described above, which further comprises a pigment dispersion as described above, results in an ink that provides desirable viscosity stability and evaporation characteristics, and which also demonstrates good nozzle recovery in inkjet printing, and which does not utilise volatile, harmful, or environmentally detrimental solvents.
  • the present invention provides an ink comprising: (a) a solvent composition; and (b) a pigment dispersion; wherein said solvent composition comprises soy methyl ester, di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the ink of the present invention comprises a solvent composition which comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the ink of the present invention typically does not comprise volatile, harmful, or environmentally detrimental solvents.
  • the ink of the present invention typically does not comprise a solvent which is classified as flammable, corrosive, or harmful.
  • a solvent which is classified as flammable, corrosive, or harmful.
  • suitable solvent classifications include those in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS); Fourth revised edition, United Nations New York and Geneva, 2011.
  • the ink of the present invention does not comprise one or more solvents selected from the group consisting of cyclohexanone, butyl glycol acetate, and methoxypropanol acetate.
  • the ink of the present invention typically has desirable evaporation characteristics.
  • the ink of the present invention typically does not comprise a solvent which shows evaporation of 1% by weight or more at 30°C over 16 hours, for example as determined by the method described below: - weigh 2 g of test material into an open container (50 mm diameter); - place into an oven set to 30°C for a 16 hour period; and - assess weight loss at the end of the 16 hour period.
  • the ink of the present invention typically does not comprise a solvent which shows evaporation of 1% by weight or more at 150°C, for example as determined by the method described below: - using a moisture analyser (e.g. Ohaus MB45), set temperature to 150°C; - weigh 2 g of test material into pan on balance, - close the cover. - terminating test when amount of change is within 0.001g within 60 seconds.
  • a moisture analyser e.g. Ohaus MB45
  • the ink of the present invention does not comprise one or more solvents selected from the group consisting of cyclohexanone, butyl glycol acetate, methoxypropanol acetate, propylene glycol diacetate, and dimethyl adipate.
  • the solvent composition comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 50% or more by weight based on the total weight of the ink.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is from 50% to 99% by weight based on the total weight of the ink, such as from 50% to 97% by weight based on the total weight of the ink.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 61% or more by weight based on the total weight of the ink, such as from 61% to 99% by weight based on the total weight of the ink, or from 61% to 97% by weight based on the total weight of the ink.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 70% or more by weight based on the total weight of the ink, such as from 70% to 99% by weight based on the total weight of the ink, or from 70% to 97% by weight based on the total weight of the ink.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 79% or more by weight based on the total weight of the ink, such as from 79% to 99% by weight based on the total weight of the ink, or from 79% to 97% by weight based on the total weight of the ink.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink 90% or more by weight based on the total weight of the ink, such as from 90% to 99% by weight based on the total weight of the ink, or from 90% to 97% by weight based on the total weight of the ink.
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate by weight based on the total weight of the ink refers to the combined weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate components, relative to the total weight of the ink.
  • di-isobutyl succinate is present in an amount of 8w% by weight based on the total weight of the ink
  • di-isobutyl glutarate is present in an amount of 10% by weight based on the total weight of the ink
  • di-isobutyl adipate is present in an amount of 12% by weight based on the total weight of the ink
  • the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate would be 30% by weight based on the total weight of the ink.
  • the di-isobutyl succinate is typically present in an amount of 15% to 30% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the di-isobutyl glutarate is typically present in an amount of 55% to 70% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the di-isobutyl adipate is typically present in an amount of 8% to 25% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the di-isobutyl succinate is present in an amount of 15% to 30% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate;
  • the di-isobutyl glutarate is present in an amount of 55% to 70% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate;
  • the di-isobutyl adipate is present in an amount of 8% to 25% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
  • the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate may be provided as a commercially available mixture of solvents, for example Coasol (registered trademark) available from Chemoxy International Ltd and Saiper Chemicals Pvt Ltd.
  • the solvent composition may further comprise soy methyl ester.
  • Soy methyl ester is derived from an acid (hereinafter the acid component of the soy methyl ester) and an alcohol (hereinafter the alcohol component of the soy methyl ester).
  • the acid component of the soy methyl ester is an unsaturated fatty acid.
  • the acid component of the soy methyl ester is a di-unsaturated fatty acid.
  • Di-unsaturated fatty acids may be obtained, for example, by hydrolysis of vegetable oils (e.g. soy oil).
  • suitable di-unsaturated fatty acids include linoleic acid, eicosadienoic acid, and docosadienoic acid.
  • Linoleic acid is preferred as the acid component of the first ester. Linoleic acid can be obtained by hydrolysis of soy oil.
  • the alcohol component of the first ester is a monohydric alcohol.
  • suitable monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n- butanol, i-butanol and t-butanol.
  • Methanol is the alcohol component of the soy methyl ester.
  • the soy methyl ester may be an ester of a di-unsaturated fatty acid and a monohydric alcohol, and examples of the soy methyl ester include methyl esters such as linoleic acid methyl ester, eicosadienoic acid methyl ester, docosadienoic acid methyl ester and linolelaidic acid. Linoleic acid methyl ester is preferred as the soy methyl ester.
  • soy methyl ester is present in an amount of 47% or less by weight based on the total weight of the ink, such as 1% to 47% by weight based on the total weight of the ink.
  • soy methyl ester is present in an amount of 37% or less by weight based on the total weight of the ink, such as 1% to 37% by weight based on the total weight of the ink.
  • soy methyl ester is present in an amount of 27% or less by weight based on the total weight of the ink, such as 1% to 27% by weight based on the total weight of the ink.
  • soy methyl ester is present in an amount of 19% or less by weight based on the total weight of the ink, such as 1% to 19% by weight based on the total weight of the ink. Most preferably, soy methyl ester is not present in the ink of the present invention.
  • the solvent composition may further comprise an ester, glycol ester, glycol ester acetate, glycol ether, glycol ether acetate, lactone, adipate, succinate, glutarate, or a mixture thereof.
  • the ink of the present invention comprises a pigment dispersion.
  • the pigment dispersion comprises a pigment and a binder.
  • the term pigment dispersion as used herein typically refers to the pigment and the binder. However it will be understood that the pigment is typically present in the form of a dispersion throughout the entire ink.
  • the pigment used in the pigment dispersion in the ink of the present invention is not particularly limited.
  • the pigment dispersion comprises a red pigment, a blue pigment, or a black pigment, or a mixture thereof.
  • the pigment may be a magenta pigment or a cyan pigment.
  • the pigment dispersion comprises a pigment selected from: Pigment Red 202, Pigment Red 144, Pigment Red 166, Pigment Red 185, Pigment Red 254, Pigment Blue 15:3, Pigment Blue 60, and Pigment Black 7, or a mixture thereof.
  • the pigment dispersion comprises Pigment Red 202.
  • the pigment dispersion comprises a mixture of Pigment Red 202 and one or more additional pigments selected from Pigment Red 144, Pigment Red 166, Pigment Red 185, and Pigment Red 254.
  • the pigment typically has a volume average particle size characterised by: (a) Dv50 of from 110 to 120 nm; and/or (b) Dv90 of less than 350 nm; as measured by dynamic light scattering, for example as measured using a Malvern Zetasizer Nano-ZS Dynamic Light Scattering particle size instrument.
  • the binder used in the pigment dispersion in the ink of the present invention is also not particularly limited.
  • the binder comprises poly(vinyl chloride-vinyl acetate) copolymer.
  • the poly(vinyl chloride-vinyl acetate) copolymer may have a random copolymer structure.
  • the poly(vinyl chloride-vinyl acetate) copolymer may have an alternating copolymer structure.
  • the poly(vinyl chloride-vinyl acetate) copolymer may have a block copolymer structure.
  • the poly(vinyl chloride-vinyl acetate) copolymer may have a graft copolymer structure.
  • the poly(vinyl chloride-vinyl acetate) copolymer may have a vinyl chloride:vinyl acetate monomer ratio of from 80:20 to 90:10 (typically wt:wt).
  • the poly(vinyl chloride-vinyl acetate) copolymer may have a molecular weight (Mw) of from 40000 g mol -1 to 50000 g mol -1 .
  • Mw molecular weight
  • the ratio of binder (e.g. the poly(vinyl chloride-vinyl acetate) copolymer described above) to the pigment is typically from 40:60 to 80:20 (typically wt:wt), e.g. from 50:50 to 70:30 (typically wt:wt), from 58:42 to 68:32 (typically wt:wt), from 60:40 to 66:34 (typically wt:wt), or about 63:37 (typically wt:wt).
  • binder e.g. the poly(vinyl chloride-vinyl acetate) copolymer described above
  • the pigment dispersion may be a commercially available pigment dispersion.
  • commercially available pigment dispersions that can be used in the ink of the present invention include Microlith (registered trademark)-K series (e.g. Magenta 4330 K, Magenta 4535 K, Blue 7080K, Blue 6480 K, and Black 0066K) available from BASF SE.
  • the pigment dispersion may be present in an amount of 1 to 20 wt%, based on the total weight of the ink, for example when the pigment dispersion comprises a coloured pigment.
  • the pigment dispersion is present in an amount of 1 to 10 wt%, based on the total weight of the ink, such as for example 1 to 6% 1 to 4 wt%, 2 to 6%, 3 to 5%, or about 4% based on the total weight of the ink.
  • the amounts of the pigment dispersion described above are typically the total amounts of the pigment and binder, as described above.
  • Preferred inks of the invention include those in which: - the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 50% to 97% by weight based on the total weight of the ink; - soy methyl ester is optionally present in the ink in an amount of 46% or less by weight based on the total weight of the ink; - the pigment dispersion is present in an amount of 3 to 5% by weight based on the total weight of the ink.
  • More preferred inks of the invention include those in which: - the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 70% to 97% by weight based on the total weight of the ink; - soy methyl ester is optionally present in the ink in an amount of 26% or less by weight based on the total weight of the ink; - the pigment dispersion is present in an amount of 3 to 5% by weight based on the total weight of the ink.
  • Particularly preferred inks of the invention include those in which: - the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 95% to 97% by weight based on the total weight of the ink; - soy methyl ester is not present in the ink; and - the pigment dispersion is present in an amount of 3 to 5% by weight based on the total weight of the ink.
  • the ink of the present invention typically has a desirable viscosity for inkjet printing.
  • the viscosity of the ink is from 7 to 20 cP at 25°C. More preferably, the viscosity of the ink is from 8 to 14 cP at 25°C.
  • Viscosity may be as determined using a cone and plate viscometer, such as for example a Brookfield DV3T viscometer with a CPA-40Z cone operating at 10 rpm.
  • the ink of the present invention demonstrates good nozzle recovery. Typically, the ink does not show any loss in nozzle jetting after standing idle at jetting temperature for at least a period of 4 days as determined using a Ricoh Gen5 printhead (MH5420) by the method described below.
  • MH5420 Ricoh Gen5 printhead
  • the ink of the present invention demonstrates good washing resistance. Typically, the colour change of the inks after washing for 5 cycles at 40°C were very little as determined by the method described below.
  • the present invention provides a process for preparing an ink according to the present invention comprising: (a) mixing a pigment dispersion with a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate to form a first mixture; and (b) mixing the first mixture with a second partial solvent composition comprising soy methyl ester and optionally comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate, thereby forming an ink.
  • a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate
  • the components of the first partial solvent composition may be added separately.
  • the components of the first partial solvent composition may be added simultaneously.
  • the components of the first partial solvent composition may be added sequentially.
  • the components of the second partial solvent composition may be added separately.
  • the components of the second partial solvent composition may be added simultaneously.
  • the components of the second partial solvent composition may be added sequentially.
  • the step (a) of mixing a pigment dispersion with a first partial solvent composition comprises adding the pigment dispersion to a vortex of the first partial solvent composition in a dissolver with a tip speed of 9 metres per second or more (e.g. 9 to 15 metres per second, 10 to 12 metres per second or about 10 metres per second) and mixing for 5 to 25 minutes (e.g. 8 to 22 minutes, 10 to 20 minutes, or about 15 minutes).
  • the step (b) of mixing the first mixture with a second partial solvent composition comprises adding the second partial solvent composition to a vortex of the first mixture in a dissolver with a tip speed of 1 to 8 metres per second (e.g. 2 to 7 metres per second or 3 to 6 metres per second) and mixing for 5 to 15 minutes (e.g. 7 to 13 minutes, 9 to 11 minutes or about 10 minutes).
  • the step (b) comprises adding the second partial solvent composition to a vortex of the first mixture in a dissolver with a tip speed of 3 to 6 metres per second and mixing for about 10 minutes.
  • the present invention also relates to methods of printing.
  • the present invention provides a method of printing comprising: - providing an ink of the present invention; and - using an inkjet printer to print the ink onto a substrate.
  • the substrate used in the methods of printing is not particularly limited.
  • the substrate may be formed of paper, non-woven fabric, plastic, wood, metal or combinations of these materials. Specific examples may be selected from natural paper, plastic film, synthetic paper, non-woven fabric, fleece, cloth, wood, semi-cure wallpaper (in which a solid resin layer is present in the form of a semi-gel), full-cure wallpaper, metal sheet, and metal thin film or any combination of these materials.
  • the substrate may comprise a fleece-backed paper.
  • the substrate may be semi-rigid polyvinyl chloride which is suitably used for flooring applications.
  • the substrate may be polyethylene, which is suitably used for packaging applications.
  • Multi-layered substrates may be used.
  • the top layer of the substrate is selected from paper, plastic film (e.g. polyvinyl chloride), wood or metal (e.g. aluminium).
  • plastic film e.g. polyvinyl chloride
  • wood e.g. aluminum
  • metal e.g. aluminium
  • the present invention also relates to printed articles.
  • the present invention provides a printed article comprising a substrate and an ink of the present invention.
  • the printed article of the present invention may be a textile.
  • the substrate in the printed article of the invention may be as described above with reference to the substrates in the method of printing in the present invention.
  • the printed article of the present invention may be obtainable by the methods of printing of the present invention, as described above.
  • Inks having the compositions set out in Tables 1 and 2 Magnetica Inks), Table 3 (Cyan Inks), and Table 4 (Black Inks) below were prepared according to the following procedure.
  • Stage 1 A first partial solvent composition of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate was added to a disperser and then stirred with a tip speed of 9 m sec -1 to create a vortex.
  • the pigment dispersion was added to the vortex of the first partial solvent composition and stirred for 10 to 20 minutes while maintaining a tip speed of 9 m sec -1 .
  • Stage 2 - Tip speed was reduced to 3 to 6 m sec -1 and a second partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate and optionally comprising soy methyl ester was added to the vortex of the composition of Stage 1 and stirred for 10 minutes.
  • a second partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate and optionally comprising soy methyl ester was added to the vortex of the composition of Stage 1 and stirred for 10 minutes.
  • Cone and plate viscometers of the Brookfield type DV3T are suitable for determining viscosity of the ink. Viscosity was determined using a Brookfield DV3T viscometer with a CPA-40Z cone operating at 10 rpm. Viscosities were measured at room temperature over a period of six months or one year, at 50°C over a period of two weeks, at 30°C over a period of six months or one year, and at 40°C over a period of six months.
  • the viscosity stability of inks were graded as “A**” if a viscosity change of less than 10% was recorded, as “A*” if a viscosity change of 10% to 20% was recorded, as “A” if a viscosity change of 20% to 30% was recorded, as “B” if a viscosity change of 30% to 50% was recorded, and as “C” if a viscosity change of more than 50% was recorded.
  • Nozzle recovery was assessed using a Ricoh Gen5 printhead (MH5420). Ink was delivered from a bottle with no back-channel flow through. A 9 pL droplet was used. Jetting frequency was 20 kHz. Jetting temperature was 30°C. A process was used as follows: 1) Print nozzle matrix test pattern on plain paper. 2) Check all nozzles (1280) are jetting. 3) Stop jetting. 4) Leave printhead for 4 days at jetting temperature. 5) Restart jetting and print nozzle matrix test pattern, check all nozzles (1280) are jetting.
  • the nozzle recovery was assessed and graded as “A**”, “A*”, “A”, “B”, or “C”.
  • Amounts of components shown in Tables 1 to 4 are weight percentages.
  • the components used and analysis outcomes are as follows:
  • Pigment dispersion Microlith (registered trademark)-K series (Microlith Magenta 4535 K, a 63:37 wt:wt dispersion of pigment in vinyl chloride/vinyl acetate binder, or Microlith Blue 7080 K, a 50:50 wt:wt dispersion of pigment in vinyl chloride/vinyl acetate binder, or Microlith Black 0066 K, a 48:52 wt:wt dispersion of pigment in vinyl chloride/vinyl acetate binder).
  • Coasol registered trademark
  • SME Soy methyl ester
  • inks of the present invention possess superior viscosity stability after both short-term and long-term storage at temperatures including room temperature and elevated temperature, and superior nozzle recovery.
  • ink Magenta Ink 10 (Table 1)
  • Printing was performed using the Ricoh Gen5 printhead (MH5420). Ink was delivered from the bottle with no back-channel flow through. A 10-20 pL droplet was used. Jetting frequency was 20 kHz.
  • cotton fabric RTP Apparel, Aeoon Technologies, 100% cotton
  • cotton thread (Guterman CA02776, 100% cotton)
  • polyester fabric (Polx SWSE wipes, 100% polyester)
  • polyester thread Coats Sylko AW, 100% polyester
  • the ink and the substrate were exposed to 200°C. Washing was then performed for 5 cycles at 40°C based on ISO105-C06 procedure. After that, colour measurement was performed using SpectroDens (Techkon GmbH).
  • inks of the present invention possess superior washing resistance.

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Abstract

Disclosed is an ink comprising: (a) a solvent composition; and (b) a pigment dispersion; wherein said solvent composition comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate, wherein the total amount of said di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate is 50% or more by weight based on the total weight of the ink, and wherein said pigment dispersion comprises a pigment and a binder, said binder comprising a poly(vinyl chloride-vinyl acetate) copolymer. Also disclosed are processes for producing inks, methods of printing, and printed articles.

Description

INK
The present invention relates to inks, processes for producing inks, methods of printing and printed articles.
Inkjet printing is used in a variety of printing applications, and can provide high resolution images on a range of substrates. Growing interest in safety and environmentally-friendly technologies has led to increased demand for inks that utilise non-hazardous components which pose low or no risk to the environment. Further, use of volatile components, such as particular solvents, in inks is regarded as undesirable as substantial evaporation of such components or solvents can cause the ink to dry in the printhead, resulting in poor nozzle recovery. The viscosity of inks can also be susceptible to change over time due to evaporation. Changes in viscosity over time will lead to inks being unsuitable for inkjet printing.
It remains a particular problem to provide inks that have advantages in terms of desirable viscosity stability and evaporation characteristics, which demonstrate good nozzle recovery in inkjet printing, and which do not utilise volatile, harmful, or environmentally detrimental solvents.
There is therefore a need for new inks which solve the above problems.
The present invention provides an ink comprising:
(a) a solvent composition; and
(b) a pigment dispersion;
wherein said solvent composition comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate;
wherein the total amount of said di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate is 50% or more by weight based on the total weight of the ink;
and wherein said pigment dispersion comprises a pigment and a binder, said binder comprising a poly(vinyl chloride-vinyl acetate) copolymer.
The present invention further provides a process for preparing an ink comprising:
(a) mixing a pigment dispersion with a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate to form a first mixture; and
(b) mixing the first mixture with a second partial solvent composition comprising soy methyl ester and optionally comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate,
thereby forming an ink.
The present invention further provides a method of printing comprising:
- providing an ink; and
- using an inkjet printer to print the ink onto a substrate.
The present invention further provides a printed article comprising a substrate and an ink.
The present inventors have surprisingly found that inclusion of soy methyl ester in a solvent composition of an ink as described above, which further comprises a pigment dispersion as described above, results in an ink that provides desirable viscosity stability and evaporation characteristics, and which also demonstrates good nozzle recovery in inkjet printing, and which does not utilise volatile, harmful, or environmentally detrimental solvents.
Ink
The present invention provides an ink comprising:
(a) a solvent composition; and
(b) a pigment dispersion;
wherein said solvent composition comprises soy methyl ester, di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
The ink of the present invention comprises a solvent composition which comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
The ink of the present invention typically does not comprise volatile, harmful, or environmentally detrimental solvents.
The ink of the present invention typically does not comprise a solvent which is classified as flammable, corrosive, or harmful. One of skill in the art will understand which substances are classified as flammable, corrosive, or harmful as part of their common general knowledge, and suitable solvent classifications include those in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS); Fourth revised edition, United Nations New York and Geneva, 2011.
Preferably, the ink of the present invention does not comprise one or more solvents selected from the group consisting of cyclohexanone, butyl glycol acetate, and methoxypropanol acetate.
The ink of the present invention typically has desirable evaporation characteristics. The ink of the present invention typically does not comprise a solvent which shows evaporation of 1% by weight or more at 30°C over 16 hours, for example as determined by the method described below:
- weigh 2 g of test material into an open container (50 mm diameter);
- place into an oven set to 30°C for a 16 hour period; and
- assess weight loss at the end of the 16 hour period.
The ink of the present invention typically does not comprise a solvent which shows evaporation of 1% by weight or more at 150°C, for example as determined by the method described below:
- using a moisture analyser (e.g. Ohaus MB45), set temperature to 150°C;
- weigh 2 g of test material into pan on balance,
- close the cover.
- terminating test when amount of change is within 0.001g within 60 seconds.
Preferably, the ink of the present invention does not comprise one or more solvents selected from the group consisting of cyclohexanone, butyl glycol acetate, methoxypropanol acetate, propylene glycol diacetate, and dimethyl adipate.
The solvent composition comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate. The total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 50% or more by weight based on the total weight of the ink. Typically, the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is from 50% to 99% by weight based on the total weight of the ink, such as from 50% to 97% by weight based on the total weight of the ink. More typically the, total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 61% or more by weight based on the total weight of the ink, such as from 61% to 99% by weight based on the total weight of the ink, or from 61% to 97% by weight based on the total weight of the ink. Preferably, the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 70% or more by weight based on the total weight of the ink, such as from 70% to 99% by weight based on the total weight of the ink, or from 70% to 97% by weight based on the total weight of the ink. More preferably, the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 79% or more by weight based on the total weight of the ink, such as from 79% to 99% by weight based on the total weight of the ink, or from 79% to 97% by weight based on the total weight of the ink. Still more preferably, the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink 90% or more by weight based on the total weight of the ink, such as from 90% to 99% by weight based on the total weight of the ink, or from 90% to 97% by weight based on the total weight of the ink.
As used herein the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate by weight based on the total weight of the ink refers to the combined weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate components, relative to the total weight of the ink. For example, if di-isobutyl succinate is present in an amount of 8w% by weight based on the total weight of the ink, di-isobutyl glutarate is present in an amount of 10% by weight based on the total weight of the ink, and di-isobutyl adipate is present in an amount of 12% by weight based on the total weight of the ink, then the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate would be 30% by weight based on the total weight of the ink.
The di-isobutyl succinate is typically present in an amount of 15% to 30% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate. The di-isobutyl glutarate is typically present in an amount of 55% to 70% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate. The di-isobutyl adipate is typically present in an amount of 8% to 25% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
Preferably, the di-isobutyl succinate is present in an amount of 15% to 30% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate; the di-isobutyl glutarate is present in an amount of 55% to 70% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate; and the di-isobutyl adipate is present in an amount of 8% to 25% by weight, based on the total weight of the di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate.
The di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate may be provided as a commercially available mixture of solvents, for example Coasol (registered trademark) available from Chemoxy International Ltd and Saiper Chemicals Pvt Ltd.
The solvent composition may further comprise soy methyl ester. Soy methyl ester is derived from an acid (hereinafter the acid component of the soy methyl ester) and an alcohol (hereinafter the alcohol component of the soy methyl ester).
The acid component of the soy methyl ester is an unsaturated fatty acid. Preferably the acid component of the soy methyl ester is a di-unsaturated fatty acid. Di-unsaturated fatty acids may be obtained, for example, by hydrolysis of vegetable oils (e.g. soy oil). Examples of suitable di-unsaturated fatty acids include linoleic acid, eicosadienoic acid, and docosadienoic acid. Linoleic acid is preferred as the acid component of the first ester. Linoleic acid can be obtained by hydrolysis of soy oil.
The alcohol component of the first ester is a monohydric alcohol. Examples of suitable monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n- butanol, i-butanol and t-butanol. Methanol is the alcohol component of the soy methyl ester.
The soy methyl ester may be an ester of a di-unsaturated fatty acid and a monohydric alcohol, and examples of the soy methyl ester include methyl esters such as linoleic acid methyl ester, eicosadienoic acid methyl ester, docosadienoic acid methyl ester and linolelaidic acid. Linoleic acid methyl ester is preferred as the soy methyl ester.
Typically, if present, soy methyl ester is present in an amount of 47% or less by weight based on the total weight of the ink, such as 1% to 47% by weight based on the total weight of the ink. Preferably, if present, soy methyl ester is present in an amount of 37% or less by weight based on the total weight of the ink, such as 1% to 37% by weight based on the total weight of the ink. More preferably, if present, soy methyl ester is present in an amount of 27% or less by weight based on the total weight of the ink, such as 1% to 27% by weight based on the total weight of the ink. Still more preferably, if present, soy methyl ester is present in an amount of 19% or less by weight based on the total weight of the ink, such as 1% to 19% by weight based on the total weight of the ink. Most preferably, soy methyl ester is not present in the ink of the present invention.
The solvent composition may further comprise an ester, glycol ester, glycol ester acetate, glycol ether, glycol ether acetate, lactone, adipate, succinate, glutarate, or a mixture thereof.
The ink of the present invention comprises a pigment dispersion. The pigment dispersion comprises a pigment and a binder. Unless otherwise stated, the term pigment dispersion as used herein typically refers to the pigment and the binder. However it will be understood that the pigment is typically present in the form of a dispersion throughout the entire ink.
The pigment used in the pigment dispersion in the ink of the present invention is not particularly limited. Typically, the pigment dispersion comprises a red pigment, a blue pigment, or a black pigment, or a mixture thereof. The pigment may be a magenta pigment or a cyan pigment. Preferably, the pigment dispersion comprises a pigment selected from: Pigment Red 202, Pigment Red 144, Pigment Red 166, Pigment Red 185, Pigment Red 254, Pigment Blue 15:3, Pigment Blue 60, and Pigment Black 7, or a mixture thereof. More preferably the pigment dispersion comprises Pigment Red 202. Still more preferably the pigment dispersion comprises a mixture of Pigment Red 202 and one or more additional pigments selected from Pigment Red 144, Pigment Red 166, Pigment Red 185, and Pigment Red 254.
The pigment typically has a number average particle size (Dn50) of from 0.020 μm to 0.150 μm as measured by a disc centrifuging method, for example as measured using a CPS DC24000 Disc Centrifuge Particle Size Analyser.
The pigment typically has a volume average particle size characterised by:
(a) Dv50 of from 110 to 120 nm; and/or
(b) Dv90 of less than 350 nm;
as measured by dynamic light scattering, for example as measured using a Malvern Zetasizer Nano-ZS Dynamic Light Scattering particle size instrument.
The binder used in the pigment dispersion in the ink of the present invention is also not particularly limited. The binder comprises poly(vinyl chloride-vinyl acetate) copolymer. The poly(vinyl chloride-vinyl acetate) copolymer may have a random copolymer structure. The poly(vinyl chloride-vinyl acetate) copolymer may have an alternating copolymer structure. The poly(vinyl chloride-vinyl acetate) copolymer may have a block copolymer structure. The poly(vinyl chloride-vinyl acetate) copolymer may have a graft copolymer structure. The poly(vinyl chloride-vinyl acetate) copolymer may have a vinyl chloride:vinyl acetate monomer ratio of from 80:20 to 90:10 (typically wt:wt). The poly(vinyl chloride-vinyl acetate) copolymer may have a molecular weight (Mw) of from 40000 g mol-1 to 50000 g mol-1. Molecular weight (Mw) can be measured by methods well known to a skilled person, e.g. according to ISO 16014-3:2019.
The ratio of binder (e.g. the poly(vinyl chloride-vinyl acetate) copolymer described above) to the pigment is typically from 40:60 to 80:20 (typically wt:wt), e.g. from 50:50 to 70:30 (typically wt:wt), from 58:42 to 68:32 (typically wt:wt), from 60:40 to 66:34 (typically wt:wt), or about 63:37 (typically wt:wt).
The pigment dispersion may be a commercially available pigment dispersion. Examples of commercially available pigment dispersions that can be used in the ink of the present invention include Microlith (registered trademark)-K series (e.g. Magenta 4330 K, Magenta 4535 K, Blue 7080K, Blue 6480 K, and Black 0066K) available from BASF SE.
The pigment dispersion may be present in an amount of 1 to 20 wt%, based on the total weight of the ink, for example when the pigment dispersion comprises a coloured pigment. Preferably, the pigment dispersion is present in an amount of 1 to 10 wt%, based on the total weight of the ink, such as for example 1 to 6% 1 to 4 wt%, 2 to 6%, 3 to 5%, or about 4% based on the total weight of the ink. The amounts of the pigment dispersion described above are typically the total amounts of the pigment and binder, as described above.
Preferred inks of the invention include those in which:
- the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 50% to 97% by weight based on the total weight of the ink;
- soy methyl ester is optionally present in the ink in an amount of 46% or less by weight based on the total weight of the ink;
- the pigment dispersion is present in an amount of 3 to 5% by weight based on the total weight of the ink.
More preferred inks of the invention include those in which:
- the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 70% to 97% by weight based on the total weight of the ink;
- soy methyl ester is optionally present in the ink in an amount of 26% or less by weight based on the total weight of the ink;
- the pigment dispersion is present in an amount of 3 to 5% by weight based on the total weight of the ink.
Particularly preferred inks of the invention include those in which:
- the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 95% to 97% by weight based on the total weight of the ink;
- soy methyl ester is not present in the ink; and
- the pigment dispersion is present in an amount of 3 to 5% by weight based on the total weight of the ink.
The ink of the present invention typically has a desirable viscosity for inkjet printing. Preferably, the viscosity of the ink is from 7 to 20 cP at 25°C. More preferably, the viscosity of the ink is from 8 to 14 cP at 25°C. Viscosity may be as determined using a cone and plate viscometer, such as for example a Brookfield DV3T viscometer with a CPA-40Z cone operating at 10 rpm.
The ink of the present invention demonstrates good nozzle recovery. Typically, the ink does not show any loss in nozzle jetting after standing idle at jetting temperature for at least a period of 4 days as determined using a Ricoh Gen5 printhead (MH5420) by the method described below.
The ink of the present invention demonstrates good washing resistance. Typically, the colour change of the inks after washing for 5 cycles at 40°C were very little as determined by the method described below.

Process for preparing ink
The present invention provides a process for preparing an ink according to the present invention comprising:
(a) mixing a pigment dispersion with a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate to form a first mixture; and
(b) mixing the first mixture with a second partial solvent composition comprising soy methyl ester and optionally comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate,
thereby forming an ink.
The components of the first partial solvent composition may be added separately. The components of the first partial solvent composition may be added simultaneously. The components of the first partial solvent composition may be added sequentially.
The components of the second partial solvent composition may be added separately. The components of the second partial solvent composition may be added simultaneously. The components of the second partial solvent composition may be added sequentially.
Typically, the step (a) of mixing a pigment dispersion with a first partial solvent composition comprises adding the pigment dispersion to a vortex of the first partial solvent composition in a dissolver with a tip speed of 9 metres per second or more (e.g. 9 to 15 metres per second, 10 to 12 metres per second or about 10 metres per second) and mixing for 5 to 25 minutes (e.g. 8 to 22 minutes, 10 to 20 minutes, or about 15 minutes).
Typically, the step (b) of mixing the first mixture with a second partial solvent composition comprises adding the second partial solvent composition to a vortex of the first mixture in a dissolver with a tip speed of 1 to 8 metres per second (e.g. 2 to 7 metres per second or 3 to 6 metres per second) and mixing for 5 to 15 minutes (e.g. 7 to 13 minutes, 9 to 11 minutes or about 10 minutes). Preferably, the step (b) comprises adding the second partial solvent composition to a vortex of the first mixture in a dissolver with a tip speed of 3 to 6 metres per second and mixing for about 10 minutes

Methods of printing
The general process of inkjet printing is well known to a skilled person. Having described the ink of the present invention herein, a skilled person can therefore readily apply the ink to a suitable substrate in an inkjet printing method, based on their common general knowledge.
The present invention also relates to methods of printing. The present invention provides a method of printing comprising:
- providing an ink of the present invention; and
- using an inkjet printer to print the ink onto a substrate.
The substrate used in the methods of printing is not particularly limited. The substrate may be formed of paper, non-woven fabric, plastic, wood, metal or combinations of these materials. Specific examples may be selected from natural paper, plastic film, synthetic paper, non-woven fabric, fleece, cloth, wood, semi-cure wallpaper (in which a solid resin layer is present in the form of a semi-gel), full-cure wallpaper, metal sheet, and metal thin film or any combination of these materials. The substrate may comprise a fleece-backed paper. The substrate may be semi-rigid polyvinyl chloride which is suitably used for flooring applications. The substrate may be polyethylene, which is suitably used for packaging applications.
Multi-layered substrates may be used. Preferably the top layer of the substrate is selected from paper, plastic film (e.g. polyvinyl chloride), wood or metal (e.g. aluminium).

Printed articles
The present invention also relates to printed articles. The present invention provides a printed article comprising a substrate and an ink of the present invention. The printed article of the present invention may be a textile. The substrate in the printed article of the invention may be as described above with reference to the substrates in the method of printing in the present invention.
The printed article of the present invention may be an article of flooring. The printed article of the present invention may be wallpaper.
The printed article of the present invention may be obtainable by the methods of printing of the present invention, as described above.
The invention is illustrated below by means of the following non-limiting examples.

Examples
Inks having the compositions set out in Tables 1 and 2 (Magenta Inks), Table 3 (Cyan Inks), and Table 4 (Black Inks) below were prepared according to the following procedure.
Stage 1 － A first partial solvent composition of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate was added to a disperser and then stirred with a tip speed of 9 m sec-1 to create a vortex. The pigment dispersion was added to the vortex of the first partial solvent composition and stirred for 10 to 20 minutes while maintaining a tip speed of 9 m sec-1.
Stage 2 － Tip speed was reduced to 3 to 6 m sec-1 and a second partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate and optionally comprising soy methyl ester was added to the vortex of the composition of Stage 1 and stirred for 10 minutes.
Inks were analysed for viscosity stability of the ink and nozzle recovery.
Cone and plate viscometers of the Brookfield type DV3T are suitable for determining viscosity of the ink. Viscosity was determined using a Brookfield DV3T viscometer with a CPA-40Z cone operating at 10 rpm. Viscosities were measured at room temperature over a period of six months or one year, at 50°C over a period of two weeks, at 30°C over a period of six months or one year, and at 40°C over a period of six months.
The viscosity stability of inks were graded as “A**” if a viscosity change of less than 10% was recorded, as “A*” if a viscosity change of 10% to 20% was recorded, as “A” if a viscosity change of 20% to 30% was recorded, as “B” if a viscosity change of 30% to 50% was recorded, and as “C” if a viscosity change of more than 50% was recorded.
Nozzle recovery was assessed using a Ricoh Gen5 printhead (MH5420). Ink was delivered from a bottle with no back-channel flow through. A 9 pL droplet was used. Jetting frequency was 20 kHz. Jetting temperature was 30°C. A process was used as follows:
1) Print nozzle matrix test pattern on plain paper.
2) Check all nozzles (1280) are jetting.
3) Stop jetting.
4) Leave printhead for 4 days at jetting temperature.
5) Restart jetting and print nozzle matrix test pattern, check all nozzles (1280) are jetting.
No purging, wiping, or capping of the printhead were used during the nozzle recovery test.
The nozzle recovery was assessed and graded as “A**”, “A*”, “A”, “B”, or “C”.
Amounts of components shown in Tables 1 to 4 are weight percentages. The components used and analysis outcomes are as follows:
Pigment dispersion: Microlith (registered trademark)-K series (Microlith Magenta 4535 K, a 63:37 wt:wt dispersion of pigment in vinyl chloride/vinyl acetate binder, or Microlith Blue 7080 K, a 50:50 wt:wt dispersion of pigment in vinyl chloride/vinyl acetate binder, or Microlith Black 0066 K, a 48:52 wt:wt dispersion of pigment in vinyl chloride/vinyl acetate binder).
Coasol (registered trademark): mixture of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate
SME: Soy methyl ester


As can be seen from the evaluations set out in the Tables above, inks of the present invention possess superior viscosity stability after both short-term and long-term storage at temperatures including room temperature and elevated temperature, and superior nozzle recovery.
Further, color change due to washing were examined using ink (Magenta Ink 10 (Table 1)). Printing was performed using the Ricoh Gen5 printhead (MH5420). Ink was delivered from the bottle with no back-channel flow through. A 10-20 pL droplet was used. Jetting frequency was 20 kHz. As a substrate, cotton fabric (RTP Apparel, Aeoon Technologies, 100% cotton), cotton thread (Guterman CA02776, 100% cotton), polyester fabric (Polx SWSE wipes, 100% polyester), and polyester thread (Coats Sylko AW, 100% polyester) were used. After the printing, the ink and the substrate were exposed to 200°C. Washing was then performed for 5 cycles at 40°C based on ISO105-C06 procedure. After that, colour measurement was performed using SpectroDens (Techkon GmbH).
As can be seen from the above evaluation, inks of the present invention possess superior washing resistance.
According to the colour measurement, it was observed that the colour change of the inks due to the washing were very little (DE2000 < 3).
The invention is described above with reference to certain embodiments. However, those embodiments are merely illustrative and a skilled person will appreciate that various modifications are possible, including combinations of features which are described above with reference to separate embodiments, without departing from the scope of the invention as defined in the following claims (with due account being taken of equivalents thereto).
The present application is based on and claims priority of Great British Patent Application No. 2314902.4 filed on September 28, 2023, Great British Patent Application No. 2314905.7 filed on September 28, 2023, and Great British Patent Application No. 2314906.5 filed on September 28, 2023, the entire contents of which are hereby incorporated herein by reference.

Claims (17)

  1. An ink comprising:
    (a) a solvent composition; and
    (b) a pigment dispersion;
    wherein said solvent composition comprises di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate;
    wherein the total amount of said di-isobutyl succinate, di-isobutyl glutarate, and di- isobutyl adipate is 50% or more by weight based on the total weight of the ink;
    and wherein said pigment dispersion comprises a pigment and a binder, said binder comprising a poly(vinyl chloride-vinyl acetate) copolymer.
  2. An ink according to claim 1 wherein said ink is a magenta ink, a cyan ink, or a black ink.
  3. An ink according to claim 1 or claim 2 wherein said pigment is Pigment Red 202, or a mixture comprising Pigment Red 202 and one or more additional pigments selected from Pigment Red 144, Pigment Red 166, Pigment Red 185, Pigment Red 254, Pigment Blue 15:3, Pigment Blue 60, and Pigment Black 7.
  4. An ink according to any one of claims 1 to 3 wherein the total amount of di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate present in the ink is 61% or more by weight based on the total weight of the ink, preferably 79% or more by weight based on the total weight of the ink, more preferably 90% or more by weight based on the total weight of the ink.
  5. An ink according to any one of claims 1 to 4 wherein said solvent composition additionally comprises soy methyl ester.
  6. An ink according to any one of claims 1 to 5 wherein the pigment dispersion is present in an amount of 1% to 20% by weight based on the total weight of the ink.
  7. An ink according to any one of claims 1 to 6 wherein the pigment has a particle size (Dn50) of from 0.020 μm to 0.150 μm as measured by a disc centrifuging method.
  8. An ink according to any one of claims 1 to 7 wherein the pigment has a particle size distribution characterised by having:
    (a) Dv50 of from 110 to 120 nm; and/or
    (b) Dv90 of less than 350 nm; as measured by dynamic light scattering.
  9. An ink according to any one of claims 1 to 8 wherein the poly(vinyl chloride-vinyl acetate) copolymer has:
    (a) a random copolymer structure, an alternating copolymer structure, a block copolymer structure, or a graft copolymer structure;
    (b) a vinyl chloride:vinyl acetate monomer ratio of from 80:20 to 90:10; and/or
    (c) a Mw of from 40000 g mol-1 to 50000 g mol-1.
  10. An ink according to any one of claims 1 to 9 wherein the viscosity of the ink is from 7 to 20 cP at 25°C.
  11. An ink according to any one of claims 1 to 10 wherein the ink does not comprise a solvent which:
    - shows evaporation of 1% by weight or more at 30 °C for 16 hours or at 150°C for 60 seconds; or
    - is classified as flammable, corrosive, or harmful.
  12. A process for preparing an ink as defined in any one of claims 1 to 11 comprising:
    (a) mixing a pigment dispersion as defined in any one of claims 1 and 4 to 7 with a first partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate to form a first mixture; and
    (b) mixing the first mixture with a second partial solvent composition comprising di-isobutyl succinate, di-isobutyl glutarate, and di-isobutyl adipate and optionally comprising soy methyl ester,
    thereby forming an ink as defined in any one of claims 1 to 11.
  13. A process according to claim 12 wherein part (a) comprises adding the pigment dispersion to a vortex of the first partial solvent composition in a dissolver with a tip speed of 9 metres per second or more and mixing for 5 to 25 minutes.
  14. A process according to claim 12 or 13 wherein part (b) comprises adding the second partial solvent composition to a vortex of the first mixture in a dissolver with a tip speed of 1 to 8 metres per second or more and mixing for 5 to 25 minutes.
  15. A method of printing comprising:
    - providing an ink as defined in any one of claims 1 to 11; and
    - using an inkjet printer to print the ink onto a substrate.
  16. A printed article comprising a substrate and an ink as defined in any one of claims 1 to 11.
  17. A printed article according to claim 16 which is a textile, flooring or wallpaper.
PCT/JP2024/034019 2023-09-28 2024-09-24 Ink Pending WO2025070429A1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB2314902.4 2023-09-28
GB2314906.5 2023-09-28
GBGB2314902.4A GB202314902D0 (en) 2023-09-28 2023-09-28 Ink
GBGB2314905.7A GB202314905D0 (en) 2023-09-28 2023-09-28 Multilayer structure
GBGB2314906.5A GB202314906D0 (en) 2023-09-28 2023-09-28 Ink
GB2314905.7 2023-09-28

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PCT/JP2024/033975 Pending WO2025070412A1 (en) 2023-09-28 2024-09-24 Multilayer structure suitable for flooring
PCT/JP2024/034015 Pending WO2025070426A1 (en) 2023-09-28 2024-09-24 Ink
PCT/JP2024/034019 Pending WO2025070429A1 (en) 2023-09-28 2024-09-24 Ink

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PCT/JP2024/034015 Pending WO2025070426A1 (en) 2023-09-28 2024-09-24 Ink

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