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WO2018069678A1 - Copolymère séquencé ramifié - Google Patents

Copolymère séquencé ramifié Download PDF

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Publication number
WO2018069678A1
WO2018069678A1 PCT/GB2017/053032 GB2017053032W WO2018069678A1 WO 2018069678 A1 WO2018069678 A1 WO 2018069678A1 GB 2017053032 W GB2017053032 W GB 2017053032W WO 2018069678 A1 WO2018069678 A1 WO 2018069678A1
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WO
WIPO (PCT)
Prior art keywords
solvent
branched
block copolymer
block
inkjet ink
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.)
Ceased
Application number
PCT/GB2017/053032
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English (en)
Inventor
Sarah Louise CANNING
Mark Geoghegan
Jonathan Morgan
Stuart William REYNOLDS
Stephen Rimmer
Trevor John Wear
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Domino UK Ltd
Original Assignee
Domino UK Ltd
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Publication date
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Publication of WO2018069678A1 publication Critical patent/WO2018069678A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • 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
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to a branched block copolymer, an onion micelle comprising the branched block copolymer, an inkjet ink comprising the branched block copolymer and an inkjet ink deposit comprising the branched block copolymer.
  • Methods of providing the copolymer, onion micelle, inkjet ink and inkjet ink deposit are also described.
  • the branched block copolymer is useful, in one embodiment, in the provision of a water-based inkjet ink having an improved drying time.
  • Linear amphiphilic block copolymers and branched amphiphilic block copolymers are known in the art.
  • onion-like micelles have been formed during the self-assembly of linear block copolymers; for example the stepwise aggregation of AB and BC diblock copolymers in solution (e.g. Prochazka, K.; Martin, T. J.; Webber, S. E.; Munk, P. Macromolecules 1996, 29 (20), 6526-6530; and Talingting, M. R.; Munk, P.; Webber, S. E.; Tuzar, Z.
  • onion-like micelles can be formed from a single block copolymer through applying shear to Pluronic® systems, and later by solvent exchange processes using either double-hydrophobic or amphiphilic block copolymers.
  • branched copolymers are subject to different mechanisms of self-assembly. This is because branching within copolymer molecules results in intra-molecular overall globular structures. Assembly of segments from different molecules is thus severely impaired. Therefore branched block copolymers tend to form unimolecular micelles in solution, that then undergo secondary aggregation into multimicellar aggregates. Such assembly processes in water are largely driven by the minimisation of interfacial energies.
  • branched polymers encompassing dendritic, multi- branched and highly branched architectures, exhibit unique properties in terms of solution behaviour and rheology in comparison to linear analogues (see, for example, Magnusson, H.; Malmstrom, E.; Hult, A.; Johansson, M. Polymer 2002, 43 (2), 301 -306; and Zhu, X.; Zhou, Y.; Yan, D. J. Polym. Sci. Part B Polym. Phys. 201 1 , 49 (18), 1277-1286).
  • One object of the present invention is therefore to provide a branched amphiphilic block copolymer which is able to form self-assemblies useful in a variety of applications.
  • Such applications include the effective delivery of agents to desired locations, with high loading capacities and preferably other advantages.
  • one such application is inkjet printing.
  • Inkjet printing is widely used for the coding and marking of products on production lines. Typically, ink is jetted onto a surface such that ink is deposited onto a substrate without physical contact between the printing device and the surface.
  • Two major systems for coding products are continuous and drop-on-demand inkjet printing.
  • Continuous inkjet printing systems normally employ inks that are based on volatile organic solvents such as methyl ethyl ketone and ethanol.
  • Ink droplets are formed by vibrating a stream of ink ejected from a nozzle under pressure. These droplets are charged and then deflected with an electrostatic charging device to form a pattern on the substrate. If the ink droplets are not printed, the ink is recycled for later use.
  • the inkjet inks are typically based upon water and glycols. These ink droplets are propelled from a nozzle by heat or by a pressure wave.
  • the drop-on-demand printers have a plurality of nozzles, which eject drops when required.
  • an ink has a number of desirable characteristics such as high optical density; short drying time of the ink on the substrate; good adhesion to the substrate; reliable droplet formation that is free of satellite droplets; indelibility or resistance of the ink to solvent or water after drying; good long-term storage stability; compatibility with the printing technology such that there is minimum corrosion of printer parts or nozzle clogging; and being easy to dispose of without creating hazardous waste.
  • Most inks fail to satisfy every one of these characteristics and represent a best fit compromise to a subset of these goals.
  • the inclusion of an ink component meant to satisfy one of the above characteristics can prevent another characteristic from being met.
  • EP1284200 relates to an aqueous ink containing a metalized dye for use with a coated porous substrate
  • US6773101 discloses a pigment-containing aqueous ink for printing onto a porous layer comprising alumina hydrate and a resin binder.
  • special substrates is undesirable, as products are often printed directly and substrates are chosen not for their suitability for printing but for their ability to preserve or protect the product inside them.
  • one object of the present invention is to provide a water-based inkjet ink having improved or comparable adhesion to a variety of different substrates, including non- porous substrates.
  • one object of the present invention is to provide a water-based inkjet ink having a fast or comparable drying time on a variety of different substrates, including non- porous substrates.
  • a branched block copolymer comprising a hydrophobic block and a hydrophilic block, the hydrophobic block comprising a poly (alkyl methacrylate), wherein the alkyl group comprises from 1 to 20 carbon atoms; and the hydrophilic block comprising poly (acrylic acid).
  • the present inventors have surprisingly found that this branched amphiphilic block copolymer is useful in inkjet inks, specifically water-based inkjet inks.
  • the inkjet ink thereby provided displays good adhesion to substrates.
  • the present inventors have found that when the inkjet ink has a short or comparable drying time compared to other water-based inkjet inks and a short or comparable drying time compared to inkjet inks using a volatile organic solvent.
  • an onion micelle having two or more layers, the two or more layers comprising the branched block copolymer as described herein.
  • an inkjet ink comprising the branched block copolymer as described herein, a colourant, and water.
  • an inkjet ink deposit comprising the branched block copolymer as described herein, and a colourant.
  • a branched block copolymer comprising a hydrophobic block and a hydrophilic block, the method comprising:
  • hydrophilic monomer is acrylic acid
  • hydrophilic block is soluble in both the first solvent and the second solvent and the hydrophobic block is more soluble in the first solvent than in the second solvent;
  • hydrophobic block is soluble in both the first solvent and the second solvent and the hydrophilic block is more soluble in the first solvent than in the second solvent.
  • a method of making an inkjet ink comprising (a) dissolving the branched block copolymer of any of claims 1 to 9, comprising a hydrophobic block and a hydrophilic block, and a colourant in a first solvent to provide a first solution;
  • a method of making an inkjet ink comprising adding the branched block copolymer as described herein and a colourant to water.
  • a method of providing an inkjet ink deposit comprising depositing the inkjet ink as described herein onto a substrate; and exposing the deposited inkjet ink to an energy source to form the inkjet ink deposit.
  • the term 'branched polymer or copolymer' means a polymer or copolymer having at least one branch point intermediate between the boundary units.
  • the term 'onion micelle' means an organised auto-assembly having a layered structure composed of amphiphilic macromolecules.
  • Short drying time is typically achieved for an inkjet ink through the use of a volatile organic solvent as the carrier for a mixture of resins, colourants and other additives such as adhesion promoters, whereby, when the ink is printed, the volatile organic compounds evaporate to leave a dried deposit.
  • volatile organic chemicals present hazards in their use as they are typically highly flammable, and are often harmful to the environment. While the use of water as a solvent would be more environmentally friendly, water based inks in the art for use on various substrates, including non-porous substrates, are not fast drying. Further factors are discussed above.
  • branched block copolymer comprising a hydrophobic block and a hydrophilic block
  • a water-based inkjet ink provides an environmentally friendly ink that is fast drying on various substrates, including non-porous substrates.
  • the present inventors have surprisingly found that this branched amphiphilic block copolymer is useful in inkjet inks, specifically water-based inkjet inks.
  • the inkjet ink thereby provided displays good adhesion and has a short or comparable drying time compared to other water-based inkjet inks and a short or comparable drying time compared to inkjet inks using a volatile organic solvent.
  • the branched block copolymer of the present invention forms onion micelles. These onion micelles are thought to be formed by the successive alignment of hydrophobic and hydrophilic parts of the branched block copolymer to form a generally spherical structure comprising layers, similar in appearance to an onion. In inkjet ink applications, it is thought that a colourant may be located between the layers in either a hydrophilic or hydrophobic environment, depending on the colourant's structure.
  • a branched block copolymer comprising a hydrophobic block and a hydrophilic block, the hydrophobic block comprising a poly (alkyl methacrylate), wherein the alkyl group comprises from 1 to 20 carbon atoms; and the hydrophilic block comprising poly (acrylic acid).
  • the molar ratio of the poly (alkyl methacrylate) to the poly (acrylic acid) in the branched block copolymer is about 0.5:1 to about 2:1 . More preferably, the molar ratio is about 0.6:1 to about 1 .9:1 , or about 0.6:1 to about 1 .8:1 , or about 0.6:1 to about 1 .7:1 . More preferably still, the molar ratio is about 0.7:1 to about 1 .6:1 .
  • the molar ratio of the poly (alkyl methacrylate) to the poly (acrylic acid) in the branched block copolymer is measured by 1 H NMR.
  • the alkyl group of the poly (alkyl methacrylate) comprises from 1 to 18 carbon atoms, or from 1 to 15 carbon atoms, or from 1 to 12 carbon atoms, or from 1 to 10 carbon atoms, or from 1 to 8 carbon atoms, or from 1 to 6 carbon atoms, or from 1 to 5 carbon atoms. More preferably, the alkyl group of the poly (alkyl methacrylate) comprises from 1 to 4 carbon atoms.
  • the alkyl group comprises 2 to 12 carbon atoms, or 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 1 to 6 carbon atoms, or 2 to 5 carbon atoms, or 3 to 4 carbon atoms.
  • the poly (alkyl methacrylate) is selected from poly (methyl methacrylate), poly (butyl methacrylate) and poly (lauryl methacrylate). Most preferably, the poly (alkyl methacrylate) is poly (butyl methacrylate).
  • the molar ratio of the poly (alkyl methacrylate) to the poly (acrylic acid) in the branched block copolymer is about 0.8:1 to about 1 .5:1 , more preferably about 0.9:1 to about 1 .3:1 , or about 1 :1 to about 1 .2:1 .
  • the molar ratio of the poly (alkyl methacrylate) to the poly (acrylic acid) in the branched block copolymer is about 0.8:1 to about 1 .8:1 , or about 0.9:1 to about 1 .7:1 , or about 1 :1 to about 1 .7:1 , more preferably about 1 .2:1 to about 1 .7:1 , most preferably about 1 .3:1 to about 1 .6:1 .
  • the molar ratio of the poly (alkyl methacrylate) to the poly (acrylic acid) in the branched block copolymer is about 0.4:1 to about 1 :1 , more preferably about 0.5:1 to about 0.9:1 , or about 0.6:1 to about 0.8:1 .
  • the degree of branching (DB) in the branched block copolymer is at least about 0.05, or at least about 0.06, or at least about 0.07, or at least about 0.08, or at least about 0.09. More preferably, the degree of branching (DB) in the branched block copolymer is at least about 0.1 , or at least about 0.1 1 .
  • the degree of branching (DB) in the branched block copolymer is about 0.05 to 0.5, or about 0.05 to about 0.4, or about 0.1 to about 0.3.
  • the degree of branching (DB) in the branched block copolymer is about 0.05 to about 0.25, or about 0.05 to about 0.2, or about 0.05 to about 0.15, or about 0.08 to about 0.15.
  • the branched block copolymer is a highly branched copolymer.
  • the branched block copolymer is not a dendritic or multi-branched copolymer.
  • the branched block copolymer has a dispersity (D) of about 1 to about 15, or about 2 to about 12, or about 3 to about 10. More preferably, the branched block copolymer has a dispersity (D) of about 3.5 to about 9.50. Alternatively, preferably, the branched block copolymer has a dispersity (D) of about 4 to about 10, or about 5 to about 10, or about 6 to about 10, or about 7 to about 10, or about 8 to about 10, more preferably about 9 to about 10.
  • the poly (alkyl methacrylate) comprises about 20 to about 100 alkyl
  • the poly (alkyl methacrylate) comprises about 25 to about 80 alkyl methacrylate monomers, or about 25 to about 70 alkyl methacrylate monomers, or about 25 to about 60 alkyl methacrylate monomers, most preferably about 30 to about 50 alkyl methacrylate monomers.
  • the poly (acrylic acid) comprises about 10 to about 200 acrylic acid monomers. More preferably, the poly (acrylic acid) comprises about 20 to about 100 acrylic acid monomers. Most preferably the poly (acrylic acid) comprises about 20 to about 40 acrylic acid monomers.
  • an onion micelle having two or more layers, the two or more layers comprising the branched block copolymer of any of the preceding claims.
  • the two or more layers of the onion micelle are formed from the branched block copolymer.
  • the onion micelle has three or more layers, or four or more layers, or five or more layers, or six or more layers, or seven or more layers. More preferably, the onion micelle has at least eight layers. More preferably still, the onion micelle has at least nine layers, or at least ten layers.
  • the onion micelle has about 2 to about 20 layers, or about 3 to about 19 layers, or about 4 to about 18 layers, or about 5 to about 17 layers, or from about 6 to about 16 layers, or about 7 to about 15 layers. More preferably, the onion micelle has about 8 to about 14 layers. More preferably still, the onion micelle has about 9 to about 13 layers, or about 10 to about 12 layers.
  • the more layers an onion micelle has, the higher loading capacity it may exhibit for example, the larger the volume and/or amount of agent(s) it may carry.
  • the agent may be a dye, for example).
  • the onion micelle has a diameter of from about 50 nm to about 300 nm, as determined by PALS. More preferably, the onion micelle has a diameter of from about 60 nm to about 250 nm, or from about 70 nm to about 225 nm, or from about 80 nm to about 200 nm, as determined by PALS.
  • an inkjet ink comprising the branched block copolymer as described herein, a colourant, and water.
  • the branched block copolymer in the inkjet ink is in the form of an onion micelle having two or more layers. More preferably, the branched block copolymer in the inkjet ink is in the form of an onion micelle having three or more layers, or four or more layers, or five or more layers, or six or more layers, or seven or more layers. Most preferably, the branched block copolymer in the inkjet ink is in the form of an onion micelle having eight or more layers, or nine or more layers, or ten or more layers.
  • the branched block copolymer in the inkjet ink is in the form of an onion micelle having about 2 to about 20 layers, or about 3 to about 19 layers, or about 4 to about 18 layers, or about 5 to about 17 layers, or from about 6 to about 16 layers, or about 7 to about 15 layers. More preferably, the branched block copolymer in the inkjet ink is in the form of an onion micelle having about 8 to about 14 layers. More preferably still, the branched block copolymer in the inkjet ink is in the form of an onion micelle having about 9 to about 13 layers, or about 10 to about 12 layers.
  • the colourant is at least partially located within the onion micelle. More preferably, the colourant is located entirely within the onion micelle.
  • the colourant when the colourant is at least partially located within the onion micelle, the colourant is at least partially located between two or more layers of the onion micelle, i.e. between two or more layers of the block copolymer. More preferably, when the colourant is located entirely within the onion micelle, the colourant is located entirely between two or more layers of the onion micelle, i.e. between two or more layers of the block copolymer, and there is no colourant present outside the onion micelle, e.g. on the outer layer of the micelle, or elsewhere in any solution/dispersion containing the onion micelle.
  • This may be advantageous as it may assist in using a solvent to carry an agent, e.g. a dye, in which the agent would otherwise be insoluble or less soluble.
  • an agent e.g. a dye
  • the inkjet ink further comprises one or more of the group consisting of an adhesion promoter, a humectant and a plasticiser.
  • the inkjet ink further comprises two or more of the group consisting of an adhesion promoter, a humectant and a plasticiser.
  • the inkjet ink further comprises other additives such as an adhesion promoter, a humectant and a plasticiser.
  • Suitable adhesion promoters are known in the art. Any suitable adhesion promoter known in the art can be used. For example, adhesion promoters such as rosins, rosin esters (both modified and unmodified materials), terpenes (modified and unmodified) and terpene phenolic resins may be used. Suitable humectants are known in the art. Humectants are typically hydrophilic solvents having high boiling points, preferably above 100 °C, and more preferably from 150 °C to 250 °C. Any suitable humectant known in the art can be used.
  • humectants examples include glycols such as ethylene glycol, propylene glycol, glycerin, diglycerin, and diethylene glycol; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethylether, propyleneglycol methylether, cellosolve, diethylene glycol monoethylether (Carbitol), diethylene glycol dimethylether, and diethylene glycol diethylether; dialkyl sulfoxides such as dimethyl sulfoxide, and other solvents such as sulfolane and N- methylpyrrolidone.
  • the humectant may be present in an amount of from about 0 to about 10 % by weight of the ink, or from about 0.1 to about 8 % by weight of the ink, and preferably from about 1 to about 5% by weight of the ink.
  • plasticisers are known in the art. Any suitable plasticiser known in the art can be used.
  • plasticisers may be selected from the adipate, citrate or epoxy based families, and provided at a concentration of about 0.1 to about 2 % by weight of the ink.
  • the ionic strength of the inkjet ink is about 1 x 10 ⁇ 5 M to about 10 x 10 ⁇ 5 M, more preferably about 3 x 10 ⁇ 5 M to about 9 x 10 ⁇ 5 M.
  • an inkjet ink deposit comprising the branched block copolymer as described herein, and a colourant.
  • a method (I) of making a branched block copolymer comprising a hydrophobic block and a hydrophilic block comprising:
  • hydrophobic monomer an alkyl methacrylate, wherein the alkyl group comprises from 1 to 20 carbon atoms;
  • hydrophilic monomer is acrylic acid.
  • RAFT Reversible Addition-Fragmentation chain Transfer
  • chain (growth) polymerisation is propagated by radicals that are deactivated reversibly, bringing them into active/dormant equilibria of which there might be more than one.
  • the RAFT agent comprises 4-vinylbenzyl-1 -pyrrole carbodithioate and the chain end groups are pyrrole dithioester chain end groups.
  • step (2) is carried out at a temperature of about 50 °C to about 70 °C. More preferably, step (2) is carried out at a temperature of about 55 °C to about 65 °C, or from about 58 °C to about 62 °C.
  • step (3) is carried out at a temperature of about 50 °C to about 70 °C. More preferably, step (3) is carried out at a temperature of about 55 °C to about 65 °C, or from about 58 °C to about 62 °C.
  • a reaction scheme exemplifying method (I) is shown in Figure 1 .
  • a method (II) of making a dispersion of onion micelles comprising:
  • hydrophilic block is soluble in both the first solvent and the second solvent and the hydrophobic block is more soluble in the first solvent than in the second solvent;
  • hydrophobic block is soluble in both the first solvent and the second solvent and the hydrophilic block is more soluble in the first solvent than in the second solvent.
  • the hydrophilic block is soluble in both the first solvent and the second solvent and the hydrophobic block is more soluble in the first solvent than in the second solvent.
  • the second solvent is water. More preferably, in method (II), the second solvent is deionised water.
  • the dispersion is a unimodal or a bimodal dispersion of onion micelles.
  • the micelles are one population of particles having the same or a similar diameter.
  • the dispersion comprises two populations of particles, the two particles exhibiting a different average particle size.
  • the dispersion is a bimodal dispersion of onion micelles comprising a first population of micelles having a diameter of about 60 nm to about 100 nm, as determined by PALS, and a second population of micelles having a diameter of about 180 to 230 nm, as determined by PALS. More preferably, the dispersion is a bimodal dispersion of onion micelles comprising a first population of micelles having a diameter of about 70 nm to about 90 nm, as determined by PALS, and a second population of micelles having a diameter of about 190 to 220 nm, as determined by PALS.
  • the ionic strength of the dispersion is about 1 x 10 ⁇ 5 M to about 10 x 10 ⁇ 5 M, more preferably about 3 x 10 "5 M to about 9 x 10 "5 M.
  • a method (IV) of making an inkjet ink comprising (a) dissolving the branched block copolymer as described herein, comprising a hydrophobic block and a hydrophilic block, and a colourant in a first solvent to provide a first solution;
  • the colourant may comprise a dye or pigment, for example a fine pigment dispersion.
  • the colourant comprises a dye. Any dye which is soluble in the carrier solvent and which is compatible with the other raw materials may be used. Mixtures of dyes may be used to achieve the desired colour.
  • the colourant comprises one or more dyes selected from the group consisting of rhodamine B, Solvent Black 3, Solvent Black 27, Solvent Black 28, Solvent Black 29, Solvent Black 35, Solvent red 8, Solvent red 18, Solvent red 1 18, Solvent red 122, Solvent red 125, Solvent red 132, Solvent blue 5, Solvent blue 44, Solvent blue 45, Solvent blue 67, Solvent blue 70, Acid yellow 42, Solvent yellow 29, Solvent yellow 79, Solvent yellow 82, Solvent yellow 83:1 .
  • the colourant comprises a pigment.
  • the colourant comprises one or more pigments selected from the group consisting of titanium dioxide, carbon black, CI Pigment Red 176, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 272, CI Pigment Red 254, CI Pigment Orange 64, CI Pigment Orange 73, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 151 , CI Pigment Yellow 154, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Green 3, CI Pigment Violet 23 and CI Pigment Violet 37.
  • the pigment concentration is preferably about 2 - 25 wt % by weight of the ink, and the pigment preferably has an average particle size of less than 1 ⁇ .
  • the colourant comprises one or more of the above dyes and one or more of the above pigments.
  • the pH of the second solution is about 3 to about 8. More preferably, the pH of the second solution is about 4 to about 7. More preferably still, the pH of the second solution is about 4.5 to about 6.5, or about 5 to about 6, or about 5.5 to about 6.
  • the ionic strength of the first solution is about 1 x 10 "5 M to about 10 x 10 "5 M, more preferably about 3 x 10 "5 M to about 9 x 10 "5 M.
  • the ionic strength of the second solution is about 1 x 10 "5 M to about 10 x 10 "5 M, more preferably about 3 x 10 "5 M to about 9 x 10 "5 M.
  • the ionic strength of the inkjet ink is about 1 x 10 "5 M to about 10 x 10 "5 M, more preferably about 3 x 10 "5 M to about 9 x 10 "5 M.
  • the ionic strengths of the first solution, the second solution and the inkjet ink are maintained as constant (i.e. the same).
  • the polymer concentration in the first solution is about 0.1 to about 1 .0 w/v %. More preferably, the polymer concentration in the first solution is about 0.2 to about 0.9 w/v %, or about 0.3 to about 0.8 w/v %, or about 0.4 to about 0.7 w/v %. More preferably still, the polymer concentration in the first solution is about 0.4 to about 0.6 w/v %, or about 0.45 to about 0.55 w/v %.
  • the polymer concentration in the second solution is about 0.1 to about 1 .0 w/v %. More preferably, the polymer concentration in the second solution is about 0.2 to about 0.9 w/v %, or about 0.3 to about 0.8 w/v %, or about 0.4 to about 0.7 w/v %. More preferably still, the polymer concentration in the second solution is about 0.4 to about 0.6 w/v %, or about 0.45 to about 0.55 w/v %.
  • the first solvent is an organic solvent. More preferably, the first solvent is an organic solvent which is miscible with water.
  • the first solvent is selected from the group consisting of tetrahydrofuran (THF), ethanol and dioxane. Most preferably, the first solvent is tetrahydrofuran (THF).
  • the second solvent is preferably deionised water.
  • the second solvent is added dropwise.
  • the first solvent is evaporated at a temperature of about 15 °C to about 25 °C. More preferably, the first solvent is evaporated at a temperature of about 17 °C to about 23 °C, or about 18 °C to about 22 °C.
  • a method (V) of making an inkjet ink comprising adding the branched block copolymer as described herein and a colourant to water, preferably deionised water.
  • each of methods (III), (IV) and (V) further comprises adding to the inkjet ink one or more of the group consisting of an adhesion promoter, a humectant and a plasticiser.
  • each of methods (III), (IV) and (V) further comprises adding to the inkjet ink two or more of the group consisting of an adhesion promoter, a humectant and a plasticiser.
  • each of methods (III), (IV) and (V) further comprises adding to the inkjet ink an adhesion promoter, a humectant and a plasticiser. Suitable adhesion promoters, humectants and plasticisers are listed above.
  • a method (VI) of providing an inkjet ink deposit comprising depositing the inkjet ink as described herein onto a substrate; and exposing the deposited inkjet ink to an energy source to form the inkjet ink deposit.
  • the energy source is a light source or a heat source. Most preferably, the energy source is a light source.
  • the substrate is a non-porous substrate.
  • the substrate comprises a polymer, preferably a non-porous polymer. More preferably, the substrate comprises polypropylene and/or high density polyethylene.
  • Figure 1 shows the synthesis of branched PnMA-b-PAA Block Copolymers with Pyrrole Chain Ends in a Two-Step RAFT-SCVP Polymerisation
  • Figure 2 is a comparison of molecular weight distributions obtained from GPC: A) branched PMMA (dashed line) and branched PMMA-b-PAA (solid line), B) branched PBMA (dashed line) and branched PBMA-b-PAA (solid line) and C) branched PLMA (dashed line) and branched PLMA-b-PAA (solid line).
  • Figure 3 shows TEM micrographs of dispersions of branched block PnMA-b-PAA copolymers in water, stained with uranyl formate: A branched PMMA-b-PAA, B branched PBMA-b-PAA and C branched PLMA-b-PAA.
  • Figure 4 shows SEM images of the spheres formed by branched PBMA-b-PAA.
  • Figure 5 shows TEM images of onion micelles formed from branched PBMA-b-PAA dispersed in water A) immediately following preparation and B) after 5 weeks storage at ambient conditions.
  • Figure 6 provides representative TEM images of copolymers A: branched PMMA-b-PAA, B: branched PBMA-b-PAA and C: branched PLMA-b-PAA self-assembled in water and D: branched PMMA-b-PAA, E: branched PBMA-b-PAA and F: branched PLMA-b-PAA following annealing at 45 °C for 12 hours. Samples were stained with uranyl formate prior to imaging. Inset text displays the results of particle sizing measurements.
  • Figure 7 provides representative TEM images of branched PBMA-b-PAA copolymers with varying ratios of BMA to AA self-assembled in water: A) 0.5:1 .0, B) 0.75:1 .0, C) 1 .0:1 .0, D) 1 .5:1 .0, E) 2.0:1 .0. Samples were stained with uranyl formate prior to imaging.
  • Acrylic acid (99%, Aldrich) was distilled under reduced pressure to remove inhibitors.
  • Dimethyl formamide (DMF) was obtained from the Grubb's dry solvent system.
  • MEHQ inhibitors were removed from methyl methacrylate (99%, Aldrich), butyl methacrylate (99%, Aldrich) and lauryl methacrylate (96%, Lancaster) by running through a column packed with inhibitor removing beads (Aldrich). Deionized water was used in all experiments.
  • MMA (1 g, 9.99 mmol)
  • 4-vinylbenzyl-1 -pyrrole carbodithioate 0.852g, 0.329 mmol
  • dioxane 10 g, 10% w/w
  • the resulting solution was transferred into a glass ampoule and freeze-pump-thawed on a high vacuum line (10-4 mbar, three cycles) then flame- sealed and heated in a water bath set 60 °C by a thermostat for up to 36 h to undergo polymerization.
  • Dispersions were prepared using a solvent switch method. Copolymer was dissolved in THF at a concentration of 5 mg ml-1 (0.5% w/v) and stirred overnight. A Razel R-99 syringe pump was used to add an equal volume of ultrapure H20 at a constant rate of 0.1 ml min- 1 . The dispersion was then stirred uncovered for 3 h to allow the THF to evaporate. Study by 1 H NMR showed that no residual THF was present after this time.
  • Copolymer dispersions prepared as above were sealed in sample tubes to prevent evaporation and placed into an oil bath set to 45 °C whilst stirring for 12 h.
  • Particle diameters were calculated using Phase Analysis Light
  • PES particle size (diameter) analysis was carried out on a Brookhaven Instruments Corporation ZetaPALS Zeta Potential Analyzer with the 90Plus/BI-MAS Multi Angle Particle Sizing Option. 15 ⁇ of copolymer dispersion was added to 3 ml of 10 mmol KCI solution, sonicated for 20 seconds, and filtered through a 1 ⁇ filter. Measurements were made at 25 °C. 10 analysis runs were made in triplicate for each sample. For zeta potential measurement, 15 ⁇ of copolymer dispersion was added to 1.5 ml of 1 mmol KCI solution. Measurements were made at 25 °C in triplicate for each sample in 5 cycles of 2 minute runs.
  • the LOQ instrument uses incident neutron wavelengths from 2.2 to 10.0 A, which covers a scattering wavevector, Q, range of 0.009 to 1 .3 A "1 at a sample-detector distance of 4.1 m.
  • Polymer samples were prepared as 0.5% solutions, 5 mg of polymer in 1 ml D 2 0. All samples were transferred to 2 mm path-length quartz Hellma cells. The temperature was controlled by using circulating fluid baths to maintain constant temperature at 25 °C. Scattering intensities were reduced and normalized using the standard procedures on MantidPlot software to obtain the differential scattering cross section, d ⁇ /dQ, in absolute units (cm 1 ), which is referred to here as l(Q).
  • TEM imaging was carried out using a Philips CM 100 instrument operating at 100 kV.
  • Polymer samples dispersed in ultrapure H 2 0 as described above were prepared for TEM by adsorbing a 5 ⁇ drop of sample onto a glow-discharged carbon-coated grid for 1 min.
  • the grid was blotted, washed in a drop of distilled water and blotted again.
  • the grid was then washed in a drop of uranyl formate, blotted and then negatively stained by holding the grid in a drop of uranyl formate for 20 s before blotting.
  • Particle diameters were obtained using Image J analysis software to measure enough particles to represent a statistically significant sample; where possible at least 100 particles were required.
  • a TEM grid as described with sample adsorbed was applied to an aluminium stub of 1 .27 cm diameter using a carbonised sticky tab as an adhesive.
  • Stubs were sputter-coated with gold using an Edwards S150b coater and viewed using a Philips XL-20 SEM operating at 20 kV.
  • the dispersity of the branched polymer or copolymer is determined by GPC (THF, PMMA standards). Results and Discussion
  • Branched polymers of three different alkyl methacrylates (methyl, butyl and lauryl) were synthesized by RAFT solution polymerisation in dioxane at 60 °C using the RAFT CTA 4- vinylbenzyl-1 -pyrrole carbodithioate, a dithioate ester that also possesses alkene functionality.
  • the dual action of the CTA enabled branching to occur during the polymerisation, due to the occurrence of both copolymerisation with the styryl double bond and reversible addition-fragmentation chain transfer with the dithioate group.
  • the molar ratio of the poly (alkyl methacrylate) to the poly (acrylic acid), the degree of branching (DB), Number Average Molecular Weight (M n ), Weight Average Molecular Weight (M w ) and dispersity (D) of the polymers are provided in Table 1 .
  • Table 1 displays the results of the syntheses of both the homopolymer macro-CTAs (Examples 1 -3), and also the copolymers (Examples 4-6).
  • the ratio of methacrylate to acrylic acid within the copolymers could also be calculated from the 1 H NMR spectra.
  • Equal mass fractions of PnMA and PAA were targeted for each copolymer, in addition to equal molecular weights for all three
  • branched copolymers (Examples 4-6) were dispersed into water via the dropwise addition of deionised water at a controlled rate of 0.1 ml min "1 using a syringe pump into a stirring solution of the amphiphilic copolymer in THF, which is a good solvent for both the hydrophilic block and the hydrophobic block. This was followed by evaporation of the THF to form an aqueous dispersion of self-assembled copolymer particles. The self-assemblies were carried out at the pH of the deionized water (pH 5) without any addition of acid, base or salts to buffer pH to simplify the system, and all dispersions were prepared at the same concentration (0.5 w/v%).
  • Example 3 are TEM micrographs of dispersions of branched block PnMA-b-PAA copolymers in water, stained with uranyl formate:
  • Example 8 A greater dispersity in particle size was observed for the branched PBMA-b-PAA (Example 8) dispersion, shown to be a biomodal dispersion, with populations of larger (191 ⁇ 1 nm) and smaller (82 ⁇ 1 nm) onion micelle structures visible in the TEM image in Figure 3.
  • the branched PLMA-b-PAA dispersion (Example 9) was notably uniform. All three dispersions were shown to be stable by the zeta potential results, which indicate negative charge on the particle surfaces due to ionisation of the carboxylic acid groups of the PAA segments. At the native pH of the deionised water ( ⁇ pH 5) the PAA is partially ionized.
  • SEM Scanning electron microscopy
  • Table 3 summarises the values of the fitting parameters obtained from the model.
  • the model fit gives a layer spacing of 11 .4 nm for the branched PBMA-b-PAA onion micelles (Example 8), which is consistent with the spacing obtained from the Bragg peak, and demonstrates some associated dispersity which can be observed in the TEM images.
  • the model suggests an average of ten layers for this sample which also agrees with the TEM results.
  • the scattering length density (SLD) of the layers is approximately 2.07 x 10 "6 A "2 . This shows that there is water within the layered structure as the calculated SLD for the copolymer alone is 1 .4 x 10 "6 A "2 .
  • Onion micelle structures were also indicated for branched PMMA-b-PAA (Example 7) and branched PLMA-b-PAA (Example 9), but with fewer layers.
  • the results suggest a mixture of bi- and tri-layered micelles, with much thicker layers than calculated for branched PBMA- b-PAA.
  • Increased values of SLD again indicate the presence of D 2 0 within the micelle structure.
  • Table 4 suggests some growth or swelling of the onion micelles had occurred during the storage period; but significantly the onion micelle structure was maintained. The onion micelles were thus found to be stable when stored at room temperature over a period of five weeks.
  • the layered onion micelle structure was no longer present, with more of a vesicle-like structure observed.
  • PMMA has a high T g of 105°C, similar to that of PAA (106°C), and PLMA has a low T g of -65°C.
  • PBMA has a known T g of 25°C i.e. at or close to ambient temperature at which the onion micelles are assembled. When the temperature of the dispersion is increased to 45°C, this has little effect on the self-assembled branched PMMA-b-PAA (Example 7) and branched PLMA-b-PAA (Example 9) micelle structures since they remain well above or well below their respective T g .
  • the PBMA segment of branched PBMA-b-PAA within the onion micelles (Example 8) is heated to above its T g during the annealing process and hence the layers are able to coalesce to form an amorphous 'vesicular' structure.
  • Branched PBMA-b-PAA copolymers with varying molar ratios of BMA to AA monomer were synthesized according to the method described above. Five different polymers were prepared, with BMA:AA molar ratios of 0.84:1 .0 (Example 10), 1 .51 :1 .0 (Example 1 1 ), 1 .69:1 .0 (Example 12), 1 .72:1 .0 (Example 13) and 1 .80:1 .0 (Example 14). Dispersions in water were prepared as described above.
  • Example 8 The dispersion of Example 8 was printed onto a substrate using an inkjet ink printer. The printed deposit on the substrate was analysed and the onion micelle structure was found to be maintained. As mentioned above with regard to temperature dependency, subjecting the onion micelles to a heat source causes the onion micelle structure to unravel.
  • a branched P(BMA-b-AA) copolymer (poly (butyl methacrylate)-block-poly (acrylic acid)) was made as per Example 5 above. 10 mg of the branched P(BMA-b-AA) copolymer was dissolved in 2 ml of THF (tetrahydrofuran) to provide a first solution. Meanwhile, a 0.2 mg ml "1 solution of Rhodamine B in deionized water was prepared.
  • the inkjet ink thereby formed was found to contain onion micelle structures with
  • Rhodamine B encapsulated between their layers.
  • Example 16 proves the concept that a dye may be encapsulated within the onion micelles and then released in a controlled manner upon subjection to a trigger (e.g. heat).
  • a trigger e.g. heat

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Abstract

La présente invention concerne un copolymère séquencé ramifié comprenant un bloc hydrophobe et un bloc hydrophile, le bloc hydrophobe comprenant un poly(méthacrylate d'alkyle), le groupe alkyle comprenant de 1 à 20 atomes de carbone ; et le bloc hydrophile comprenant de poly(acide acrylique).
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WO2001096429A1 (fr) * 2000-06-15 2001-12-20 Noveon Ip Holdings Corp. Copolymeres ramifies/sequences destines au traitement de substrats keratineux
EP1371696A1 (fr) * 2002-06-14 2003-12-17 Canon Kabushiki Kaisha Composition de particules, méthode d'enregistrement et appareil d'enregistrement utilisant cette composition de particules
WO2010019563A1 (fr) * 2008-08-11 2010-02-18 The University Of Akron Synthèse de polymères arborescents par polymérisation raft (reversible addition-fragmentation chain transfer) contrôlée du type inimère

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WO2001096429A1 (fr) * 2000-06-15 2001-12-20 Noveon Ip Holdings Corp. Copolymeres ramifies/sequences destines au traitement de substrats keratineux
EP1371696A1 (fr) * 2002-06-14 2003-12-17 Canon Kabushiki Kaisha Composition de particules, méthode d'enregistrement et appareil d'enregistrement utilisant cette composition de particules
WO2010019563A1 (fr) * 2008-08-11 2010-02-18 The University Of Akron Synthèse de polymères arborescents par polymérisation raft (reversible addition-fragmentation chain transfer) contrôlée du type inimère

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