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
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
• • 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
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
• • 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
• • 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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

• This invention relates to inks and to ink-sets and their use in ink-jet printing, particularly in the commercial print sector.
• Ink-jet printing is a non-impact printing technique in which droplets of ink are ejected through a fine nozzle onto a substrate without bringing the nozzle into contact with the substrate.
• Desktop printers are commonly used in the home and small offices to print, for example, family photographs, children's homework and documents having a small number of pages such as letters.
• the print heads used in the commercial print sector are usually positioned in a wide, single array and are able to print substrates in a single pass.
• Commercial printers run continuously for long periods and so the inks need to be particularly stable since if even one nozzle becomes blocked this can lead to a blank band on a vast number of documents and the printer being off line while print head is cleaned.
• desktop printers usually have a much narrower print head and print substrates in multiple passes such that it is less noticeable if a single nozzle becomes blocked.
• Ink-jet printers in the commercial sector can print at high speeds, for example there are printers which are able to print 600 x 600 dpi resolution at a speed in excess of 200 metres/min. This imposes technical demands not present on desktop printers producing only a few pages per minute. Increasing print speed often means that the ink-jet ink should desirably dry more quickly such that the final print does not smudge when stacked. Inks with a quicker drying time, however, pose an increased risk of the ink drying and crusting over on the nozzles whilst the printer is not actively printing. To enable these printers to work at these high speeds the inks used must also show a low foaming potential and excellent drop formation.
• the substrates used in the commercial print sector are also much more varied than those used in desktop. In the desktop sector, expensive glossy and special coated papers are used when printing photographs and the occasional short document.
• the high volume printing of, for example, utility bills requires inexpensive substrates such as plain papers, thin paper of the kind used in newspapers and offset media which can be difficult to print effectively with aqueous inks.
• Customers in the commercial print sector expect inks to be suitable for a wide variety of substrates, from very thin absorbent substrates to substrates with much less absorbency.
• Thin substrates such as those used in newspapers can suffer from poor dot definition due to "feathering" of the ink across the paper. "Strike through” can also be a problem with conventional inks where the ink permeates right through the thin paper to become visible on the other side.
• Good drop definition and edge acuity are high priorities in the commercial print sector.
• an ink composition comprising:
• the ink composition has a viscosity of from 2.5 to 1 1 cP, more preferably of from 3 to 10 cP, especially of from 3.5 to 9 cP, more especially of from 4 to 8 cP, particularly of from 4 to 7 cP and more particularly of from 4 to 6 cP.
• the viscosity is measured at 32 ° C using a Brookfield spindle 18 at 60 rpm.
• the ink composition has a surface tension of from 25 to 45, more preferably of from 30 to 40 and especially of from 33 to 37 dynes/cm at 22°C.
• the surface tension of the ink composition is preferably measured using a Kibron Aquapi.
• the ink composition has a pH of from 6 to 10, more preferably of from 6.5 to 9.5 and especially of from 7 to 8.5.
• Component a) is preferably present in the ink composition in an amount of from 1 to 15 parts, more preferably of from 2 to 10 parts by weight and especially of from 3 to 8 parts by weight.
• Component a) is preferably diethylene glycol, propylene glycol or mixtures thereof, more preferably component a) is diethylene glycol.
• Component b) is preferably present in the ink composition in an amount of from 35 to 45 parts by weight and more preferably of from 36 to 42 parts by weight.
• Component c) is preferably present in the ink composition in an amount of from 1 to 8 parts by weight, more preferably of from 2 to 7 parts by weight, especially of from 3 to 6 parts by weight and more especially of from 4 to 6 parts by weight.
• the amount of component d) included in the ink composition will depend to some extent on the intensity of colour required for the ink. Typically however component d) is present in an amount of from 0.6 to 8 parts by weight, more preferably of from 1 to 7.5 parts by weight and especially of from 2 to 5 parts by weight.
• Component d) may be a single colourant or a mixture of colourants.
• Preferred colorants are dyes, especially water-soluble dyes. Acid and Direct dyes are particularly preferred and as examples there may be mentioned the dyes listed in the Colour Index International.
• component d) comprises a yellow colorant it is preferably selected from the group consisting of C. I. Direct Yellow 86, C. I. Direct Yellow 132, C. I. Direct Yellow 142, Acid Yellow 23 and Pro-Jet Yellow 746 and mixtures thereof, especially C. I. Direct Yellow 132.
• component d) comprises a magenta colorant it is preferably selected from the group consisting of Acid Red 249; a xanthene dye such as C. I. Acid Red 52; and monoazo dyes of Formula (1 ), and salts thereof:
• Ar 1 is optionally substituted phenyl or optionally substituted naphthyl
• Z 1 is an optionally substituted nitrogen containing heterocyclic group which is attached to the triazine ring by a bond to a nitrogen atom in the heterocyclic group;
• R 1 is H or Ci-4-alkyl optionally substituted by -OH, -COOH or -SO 3 H; and t is 0 or 1 :
• Z 1 is an optionally substituted 5- or 6-membered heterocyclic group. It is especially preferred that Z 1 is free from primary or secondary amino groups. More especially Z 1 is morpholino or pyrrolidinyl each of which is optionally substituted by Ci -4 -alkyl, carboxy or sulfo.
• groups represented by Ar 1 include 2-carboxyphenyl, 3,5-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 2-carboxy-4-sulfophenyl, 3,4- dimethyl-6-sulfophenyl, 4-amino-2-hydroxyphenyl, 4-carboxy-2-hydroxyphenyl, 1 ,5-disulfonaphth-2-yl, 1 -sulfonaphth-2-yl, 3,6,8-trisulfonapth-2-yl, 8-hydroxy-2,4- disulfonaphth-1 -yl, 1 -amino-8-hydroxy-3,6-disulfonaphth-2-yl, 2-amino-8-hydroxy- 6-sulfonaphth-1 -yl, 2-amino-8-hydroxy-6-sulfonaphth-7-yl, 2-amino-8-hydroxy-3,6- sulfyl
• Ar 1 is phenyl or naphthyl each of which is optionally substituted by one or more of -OH, -SO 3 H, - COOH, -NH 2 , Ci-4-alkyl, Ci -4 -alkoxy or nitro.
• the floating sulfo group in Formula (1 ) is preferably attached at the 3- or 4- position in the naphthalene ring. More preferably t is 1 and the floating sulfo group is attached at the 3-position.
• a particularly preferred dye of Formula (1 ) is of Formula (2) and salts thereof:
• component d) comprises a cyan colorant it is preferably selected from the group consisting of C. I. Direct Blue 86, C. I. Direct Blue 199 and mixtures thereof, especially C. I. Direct Blue 199.
• component d) comprises a black colorant it is preferably selected from the group consisting of C. I. Direct Black 19, C. I. Direct Black 168, Mobay Black SP, Bayscript Black SP, Steiner Black SP, or a compound of the Formula (3) or (4) (whether in free acid or salt form) and mixtures thereof wherein Formula (3) is:
• each T independently is an azo containing group
• Q is an optionally substituted, optionally metallised 1 ,8-dihydroxynaphthyl group; and L is a divalent organic linker group:
• W 1 is carboxy
• W 2 is H, carboxy, sulfo, halo, hydroxy, Ci -4 -alkoxy or C i -4 -alkyl;
• Y and Z are each independently H, carboxy or sulfo
• R 2 and R 3 are each independently H, Ci -4 -alkyl or Ci -4 -alkyl carrying a carboxy or sulfo group.
• L is preferably of Formula (5):
• L 1 is a single covalent bond or optionally substituted phenyl or naphthyl
• L 2 is optionally substituted phenyl or naphthyl
• X is O, 1 or 2.
• Preferred optional substituents on A, L, L 1 , L 2 and Ar 1 include halogen
• R 5 is H, Ci-6-alkyl optionally substituted by -OH, -SO 3 H or -COOH, or phenyl optionally substituted by Ci- -alkyl, -OH, -SO 3 H, -COOH, -NH 2 or -NO 2 ;
• R 6 and R 7 are each independently H, -CO(Ci -6 -alkyl), -CONH 2 , C 1-6 -alkyl optionally substituted by -OH, -SO 3 H or -COOH, or phenyl optionally substituted by Ci- -alkyl, -OH, -SO 3 H, -COOH, -NH 2 or -NO 2 ; or R 6 and R 7 together with the nitrogen to which they are attached form a 5- or 6- membered ring (preferably morpholine or piperazine).
• Especially preferred optional substituents on A, L, L 1 , L 2 and Ar 1 include one or more of Ci -4 -alkyl, Ci- -alkoxy, -OH, -COOH, -PO 3 H 2 , -SO 3 H, nitro, -CI, -F,- CF 3 , amino and -COOCi -4 -alkyl.
• the compound of Formula (4) contains at least as many carboxy groups as sulfo groups.
• the compounds of Formula (4) may be prepared as described in US 5,203,912.
• the black colorant preferably comprises Direct Black 168 and/or Direct Black 19.
• the black colourant may also comprise a small amount of another coloured dye for shading purposes.
• the black colourant is Direct Black 168 and in another preferred embodiment the black colourant is a mixture of Direct Black 19 and a magenta colourant of Formula (1 ) as described and preferred above.
• Component e water
• the water is preferably deionised.
• the surfactant used as component f) may be ionic or, more preferably, non- ionic.
• Acetylenic diol surfactants are preferred (especially 2,4,7,9-tetramethyl-5- decyne-4,7-diol and ethylene oxide condensates thereof), for example Surfynol® surfactants and especially Surfynol® 465 available from Air Products.
• Component f) is preferably present in the composition in an amount of 0.001 to 2.5 parts, more preferably 0.01 to 2 parts, especially 0.05 to 1 parts and more especially 0.1 to 0.5 parts.
• any biocide (or mixture of biocides) which is stable in the ink may be used such as, for example Proxel ® GXL available from Lonza.
• Component g) is preferably present in the composition in an amount of 0.001 to 1 .5 parts, more preferably 0.01 to 0.5 parts, especially 0.01 to 0.3 parts.
• the ink composition may optionally comprise one or more ink additives.
• Preferred additives suitable for UP inks are pH adjusters and/or buffers, anti-kogation agents, rheology modifiers, corrosion inhibitors and chelating agents and additional dyes.
• the total amount of all such additives is no more than 10 parts by weight.
• the ink is free from pigments. In a further embodiment the ink is free from acrylic binders.
• a particularly preferred ink comprises
• the viscosity is 3 to 10 cP
• the surface tension is 25 to 45 dynes/cm
• the pH is 6 to 10.
• a particularly preferred ink comprises
• the viscosity is 4 to 7 cP
• the surface tension is 30 to 40 dynes/cm
• the pH is 7 to 9.5.
• the number of parts of a) to g) preferably add up to 100. This is not to say that additional ingredients cannot be present, it merely defines the relative amounts of the specified components relative to one another. However, in one preferred embodiment no additional components are present.
• the inks of the present invention comprise less than 3 parts, more preferably less than 2 parts, especially less than 1 part, more especially is free from ethylene glycol mono butyl ether.
• the ink composition has been filtered through a filter having a mean pore size of less than 10 microns, more preferably less than 5 microns and especially less than 1 micron.
• an ink-set comprising a yellow ink, a magenta ink, a cyan ink and one or two black inks, wherein each ink independently is as hereinbefore described.
• the colorants used in the yellow ink, magenta ink, cyan ink and black ink of the ink-set are preferably as described and preferred above in relation to the first aspect of the present invention.
• the ink-set according to the second aspect of the invention comprises:
• a yellow ink which comprises C. I. Direct Yellow 86, C. I. Direct Yellow 132, C. I. Direct Yellow 142, Acid Yellow 23, Pro-Jet Yellow 746 or a mixture comprising two or more thereof, especially C. I. Direct Yellow 132;
• magenta ink which comprises C. I. Acid Red 249, C. I. Acid Red 52, a monoazo dye of Formula (1 ) (whether in free acid or salt form) as hereinbefore defined or a mixture thereof. It is particularly preferred that the magenta ink comprises C. I. Acid Red 249 and/or a monoazo dye of Formula (1 );
• a cyan ink which comprises C. I. Direct Blue 86 or C. I. Direct Blue 199, especially C. I. Direct Blue 199, or a mixture thereof;
• one or two black ink(s) which comprise, if more than one ink independently, C. I. Direct Black 19, C. I. Direct Black 168, Mobay Black SP, Bayscirpt Black SP, Steiner Black SP, or a dye of the Formula (3) or (4) (whether in free acid or salt form) or a mixture thereof, especially a mixture of dyes of the Formula (2) and (5) (whether in free acid or salt form) or a mixture thereof.
• the black ink comprises C. I. Direct Black 19. In a second preferred embodiment the black ink comprises C. I. Direct Black 168 and C. I. Acid Red 249. If there are two black inks then preferably they comprise different colorants or different mixtures of colorants.
• a more preferred ink-set according to the second aspect of the invention comprises:
• magenta ink which comprises C. I. Acid Red 249, C. I. Acid Red 52, a monoazo dye of Formula (2) (whether in free acid or salt form) as hereinbefore defined or a mixture thereof. It is particularly preferred that the magenta ink comprises C. I. Acid Red 249 and/or a monoazo dye of Formula (2);
• black ink(s) which comprise, if more than one ink independently, C. I. Direct Black 19, C. I. Direct Black 168, Mobay Black SP or a mixture thereof.
• the black ink comprises C. I. Direct Black 19.
• the black ink comprises C. I. Direct Black 168 and C. I. Acid Red 249. If there are two black inks then preferably they comprise different colorants or different mixtures of colorants.
• the inks of the ink-set are each independently as described and preferred above in relation to the first aspect of the present invention.
• a process for printing an image on a substrate comprising applying an ink according to the first aspect of the present invention or an ink-set according to the second aspect of the present invention to a substrate by means of an ink-jet printer.
• the substrate is preferably a paper, a plastic film or a textile material.
• the paper may be a plain or treated paper, and may have an acid, alkaline or neutral character.
• a material printed by means of a process according to the third aspect of the invention is provided.
• the material is preferably a paper, a plastic film or a textile material.
• the paper may be a plain or treated paper, and may have an acid, alkaline or neutral character.
• an ink- jet printer comprising one or more ink vessels each comprising a chamber and an ink according to the first aspect of the present invention or an ink-set according to the second aspect of the present invention, wherein said ink is present in the one or more chambers.
• the inks of the present invention are particularly useful for commercial printers, especially piezo ink-jet printers. They have a low tendency to block nozzles and are suitable for a wide variety of substrates. Good drop definition can be achieved with a low strike-through rate. This means the inks are suitable for use with light and/or thin substrates.
• Inks 1 to 4 were prepared by mixing the components specified in Table 1 in the number of parts indicated.
• the colorant column describes the number of parts of the bracketed colorant(s) included and the weight ratio where more than one colorant is included.
• Example 1 Yellow Ink
• Example 2 Cyan Ink Ink Component Example 1
• Surfynol ® 465 is a surfactant from Air Products.
• DY 132 is C. I. Direct Yellow 132.
• DB199 is C. I. Direct Blue 199.
• AR 249 is C. I. Acid Red 249
• Example 7- Black Ink 3 Ink Component Example 5 Example 6 Example 7
• DB 19 is C. I. Direct Black 19
• DB 168 is C. I. Direct Black 168
• Example Inks 1 , 2, 4 and 6 were printed by means of an ink-jet printer onto the following printing papers: Relative Optical Density (ROD) and CIE L * a * b * color space parameters measured at 100% depth.
• ROD Relative Optical Density
• CIE L * a * b * color space parameters measured at 100% depth were printed by means of an ink-jet printer onto the following printing papers: Relative Optical Density (ROD) and CIE L * a * b * color space parameters measured at 100% depth.
• ROD Relative Optical Density
• the ability of the aged ink to re-dissolve after standing may be assessed as follows.
• the ink under evaluation may be warmed to 40°C in the open air and maintained at this temperature for 24 hours.
• the remaining residue (0.2g) should be weighed into a vial of capacity 10cm 3 containing water (2cm 3 ).
• the vial can then be shaken at a frequency of 120 cycles per minute and the time taken for the residue to re-dissolve recorded. A longer time to re-dissolve indicates a higher likelihood of crusting and nozzle blockage.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Ink Jet (AREA)

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Citations (7)

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• 2012
  • 2012-08-15 GB GBGB1214552.0A patent/GB201214552D0/en not_active Ceased
• 2013
  • 2013-08-05 KR KR1020157006141A patent/KR20150046101A/ko not_active Withdrawn
  • 2013-08-05 CN CN201380043394.2A patent/CN104769055A/zh active Pending
  • 2013-08-05 EP EP13745897.2A patent/EP2885357B1/en not_active Not-in-force
  • 2013-08-05 JP JP2015527020A patent/JP6316814B2/ja not_active Expired - Fee Related
  • 2013-08-05 MX MX2015001813A patent/MX2015001813A/es unknown
  • 2013-08-05 US US14/421,491 patent/US9540532B2/en not_active Expired - Fee Related
  • 2013-08-05 WO PCT/GB2013/052086 patent/WO2014027179A1/en not_active Ceased
  • 2013-08-14 TW TW102129165A patent/TWI599623B/zh not_active IP Right Cessation

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