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
  • C09D10/00—Correcting fluids, e.g. fluid media for correction of typographical errors by coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers

Definitions

• the present invention relates to photocurable water-based correction fluids.
• Correction fluids for correcting the marks made by a writing instrument, in particular a pen, are well known. Such fluids are applied to the mark on a paper and when they dry, provide a film, usually white, which covers the wrong mark. A correction mark can then be applied to the dry film.
• fluids with physical drying evaporation of solvents
• the patent application WO94 / 11450 describes a photocurable correction fluid having a short drying time, less than or equal to 10s.
• this fluid does not contain solvents, or it contains a volatile solvent, that is to say an organic solvent.
• a volatile solvent poses problems of VOC release.
• a correction fluid without solvent poses a problem of migration of the ink of the writing after deposition (the writing trace reappears through the correction fluid) due to a too weak cross-linking of the film due to the excessive concentration of photocurable material of this fluid.
• US2012 / 0041092 discloses an opaque coating composition comprising a resin capable of cross-linking to form a film under the action of UV. This composition is photocrosslinkable.
• EP2557094 also discloses an aqueous coating composition crosslinkable by radiation.
• a composition could not be used as a correction fluid, the pigment content described and exemplified in this document not being sufficient to have a good hiding power on marks left by ink roller pen or ballpoint pen or gel ink and in particular so that the film obtained after drying avoids the phenomenon of progressive reappearance of the ink.
• EP 2703459 discloses a photocurable ink. It is therefore not a correction fluid and the pigment content described and exemplified in this document is not sufficient to have a good hiding power on marks left by ink roller pen or pen ball or gel ink and in particular so that the film obtained after drying avoids the phenomena of progressive reappearance of the ink.
• compositions proposed may contain organic solvents of glycol, glycol ether and alcohol types. This type of solvent can either change the appearance of the writing trace to be covered (diffusion of the ink in the paper) or cause the problem of bleeding (migration of the writing trace through the correction fluid film ).
• Such correction fluids furthermore do not suffer from bleeding phenomenon, that is to say from progressive reappearance of the mark by diffusion of the ink through the dry film of the correction fluid and have a good covering power, regardless of the type of ink (ink for roller pen or for ballpoint pen or gel ink for example) and its color (blue or black for example).
• the present invention therefore relates to a water-based correction fluid comprising:
• e- optionally a photocurable acrylate and / or methacrylate monomer
• said fluid having a solids content of between 40 and 80% by weight relative to the total weight of the fluid, advantageously between 50 and 70%, more advantageously between 54 and 66%, and forming a film after drying comprising at least 40% by weight of opacifying agent with respect to the total weight of the film, more preferably between 40 and 80% by weight, in particular between 45 and 80% by weight.
• water-based correction fluid means any correction fluid whose solvent is water.
• a correction fluid does not contain an organic solvent.
• the water content of the correction fluid according to the present invention is between 20 and 60% by weight relative to the total weight of the fluid, advantageously between 30 and 50% by weight relative to the total weight of the fluid, more advantageously between 34 and 46% by weight relative to the total weight of the fluid.
• oligomer is intended to mean any small polymer chain advantageously consisting of at least two monomers and more advantageously at most 20 monomers.
• an oligomer has a low molecular weight, generally less than 4000 g / mol.
• acrylate oligomer and / or photocrosslinkable methacrylate means any oligomer as defined above having at least one acrylate and / or methacrylate unit and crosslinking by means of a radical reaction under the action of UV or visible light.
• the oligomer according to the present invention is chosen from acrylates, methacrylates, aliphatic acrylate polyurethanes, acrylate aromatic polyurethanes, acrylate polyesters, polyether acrylates, aliphatic methacrylate polyurethanes, methacrylate aromatic polyurethanes, methacrylate polyesters, methacrylate polyethers, and mixtures thereof, advantageously among acrylates, acrylate polyesters and acrylate aliphatic polyurethanes, still more advantageously among the aliphatic acrylate polyurethanes.
• the oligomer according to the present invention is a photocrosslinkable acrylate oligomer.
• the oligomers according to the present invention may have end-of-chain functionalities ranging from 2 to 18, in particular 6, and a viscosity ranging from 70 to 4000 mPa.s measured at 25 ° C., in particular between 70 and 1000 mPa. s.
• the oligomer according to the present invention may for example be a diacrylate oligomer, in particular an aliphatic polyurethane diacrylate. These oligomers are commercially available, for example from Kromachem under the trade name Etercure® DR-W401.
• the oligomer according to the invention may also be an acrylate. These oligomers are commercially available for example from Alberdingk Boley under the trade name Alberdingk® LUX 515. These oligomers can be in the form of an aqueous dispersion.
• the correction fluid according to the invention may contain (by weight relative to the total weight of the correction fluid) between 2 and 25% of the acrylate oligomer and / or photocrosslinkable methacrylate, advantageously between 2.5 and 20%, more preferably between 3 and 18%, particularly preferably between 3.5 and 16%.
• acrylate monomer and / or photocrosslinkable methacrylate means any monomer having at least one acrylate and / or methacrylate unit and crosslinking by means of a radical reaction under the action of UV or visible light.
• the monomer according to the present invention is chosen from mono or polyfunctionalized acrylates, mono or polyfunctionalized methacrylates and mixtures thereof, advantageously from polyfunctionalized acrylates. It may in particular be a monomer of mono-, di-, tri-, tetra-, penta- acrylates and methacrylates (hydroxylated, ethoxylated, propoxylated), aromatic or aliphatic, with or without short polymer chains of the type polyether, polyurethane, polyesters, polyepoxy, modified or not with amino groups.
• These monomers may have functionalities at the end of the chain ranging from 2 to 6 and in particular a viscosity ranging from 40 to 1000 mPa.s measured at 25 ° C., in particular from 100 to 500 mPa.s.
• the monomer is not necessarily present in the correction fluid according to the present invention. Advantageously it is not present.
• the term "photoinitiator” means any product which makes it possible to initiate the crosslinking reaction by radical route of the oligomers and monomers possibly present in the correction fluid according to the invention during their irradiation with a UV source. or visible. Indeed the photoinitiator, by absorbing the energy of the photons emitted, will become an excited species (in radical form). Thus this species reacts with the reactive functions of the oligomers and any monomers of the correction fluid, resulting in crosslinking of the material.
• the photoinitiator is therefore advantageously an absorbing photoinitiator in the UV or the visible, more advantageously an absorbing photoinitiator in the UV-A.
• the photoinitiator according to the present invention will allow surface and / or in-depth priming of the radical polymerization reaction. More particularly, the photoinitiator according to the present invention absorbs the emission wavelengths of the lamps / LEDs, and / or the selected wavelengths in the range between 230 and 410 nm, advantageously between 278 and 410 nm, in particular between 362 and 410 nm, more particularly between 400 and 410 nm, such as for example 278, 360-400 nm, 365, 382 and 405 nm.
• the photoinitiator is of type I, advantageously it is a photoinitiator of the acyl phosphine oxide type, more particularly it is ethyl-2,4,6-trimethylbenzoylphenyl phosphinate.
• These photoinitiators are commercially available for example from BASF under the trade name Lucirin TPO-L.
• the correction fluid according to the invention may contain (in% by weight relative to the dry extract of the correction fluid) between 3 and 10% of the photoinitiator, advantageously between 5 and 7%, in particular about 6%.
• the term "opacifying agent” means any pigment which makes it possible to confer on the correction fluid its covering power, that is to say its capacity to completely cover and hide a writing mark.
• the opacifying agent is chosen from kaolin, calcium carbonate and titanium oxide. It is advantageously titanium oxide which has an opacifying power superior to kaolin and calcium carbonate.
• the titanium oxide may be chosen from rutile titanium oxide, anatase titanium oxide or mixtures thereof and may optionally have undergone an organic or inorganic surface treatment, for example using aluminum oxide. or zirconium oxide. he can have an average particle size of between 0.2 ⁇ and 0.4 ⁇ , advantageously 0.21 ⁇ .
• Titanium oxide is commercially available from Tronox under the trade name CR-813.
• the correction fluid according to the present invention may comprise an additive f), advantageously chosen from an optical brightener, a dye-modifying pigment, for example carbon black to gray out the hue, a cationic resin, a physically drying resin, a dispersant, a photosensitizer, for example of the thiolated additive type, a crosslinking accelerator, a drying agent, a wetting agent, a filler, a co-solvent, a biocide, an antifreeze, a coalescing agent, a preservative, a polyvinyl alcohol and mixtures thereof.
• an additive f advantageously chosen from an optical brightener, a dye-modifying pigment, for example carbon black to gray out the hue, a cationic resin, a physically drying resin, a dispersant, a photosensitizer, for example of the thiolated additive type, a crosslinking accelerator, a drying agent, a wetting agent, a filler, a co-solvent, a biocide, an
• the correction fluid according to the present invention may contain as an additive f) a physically drying resin, that is to say crosslinking through an increase in temperature.
• a physically drying resin that is to say crosslinking through an increase in temperature.
• a resin makes it possible to improve the drying time of the correction fluid.
• It may be for example an acrylic copolymer, in particular in the form of an aqueous dispersion.
• Such resins are commercially available from Alberdingk Boley under the trade name Alberdingk® AC2524.
• the content of physically drying resin in the correction fluid according to the present invention may be between 10 and 20% by weight relative to the total weight of the correction fluid, advantageously between 15 and 17%.
• the weight ratio resin with physical drying / acrylate oligomer and / or photocrosslinkable methacrylate may be about 1/1.
• the correction fluid according to the present invention may also contain as an additive f) an optical brightener (such as for example the 2495T -EZE- PG or LAMP BLACK 8592 from EPS / CCA or TINT AYD WD 2018 from Elementis specialities) which makes the film look more or less white.
• an optical brightener such as for example the 2495T -EZE- PG or LAMP BLACK 8592 from EPS / CCA or TINT AYD WD 2018 from Elementis specialities
• the content of optical brightener in the correction fluid according to the present invention in percentage by weight relative to the solids content is between 3 and 7%, advantageously between 4 and 6%, in particular it is 5%.
• the correction fluid according to the present invention may contain as an additive f) a cationic polymer.
• the cationic polymer makes it possible to avoid or limit the migration of the inks present on the paper and in particular from the mark which has been covered by the correction fluid, in the film during the application of the fluid or during time. It may be, for example, a quaternary hydroxy functional copolymer, advantageously being in the form of an aqueous dispersion. Such polymers are commercially available from Indulor under the trade name Induquat ECR 466L.
• the content of cationic polymer in the correction fluid according to the present invention may be between 1 and 10% by weight relative to the total weight of the correction fluid, advantageously between 2 and 4%.
• the weight ratio cationic polymer / acrylate oligomer and / or photocrosslinkable methacrylate may be about 1/1.
• the correction fluid according to the present invention may contain as an additive f) polyvinyl alcohol.
• Polyvinyl alcohol is commercially available from Fluka.
• the content of polyvinyl alcohol in the correction fluid according to the present invention may be between 1 and 10% by weight relative to the total weight of the correction fluid, advantageously between 2 and 4%.
• the weight ratio polyvinyl alcohol / acrylate oligomer and / or photocrosslinkable methacrylate may be about 1/1.
• the correction fluid comprises as additive f) a mixture of cationic polymer and polyvinyl alcohol, in particular cationic polymer / polyvinyl alcohol mass ratio of about 1/1. More preferably, the cationic polymer / polyvinyl alcohol / acrylate oligomer and / or photocrosslinkable methacrylate weight ratio is about 1/1/1.
• the correction fluid according to the present invention may contain as an additive f) a fountain additive. It may be for example a silicone surfactant such as in particular a polyether-modified acryl functional siloxane. Such additives are commercially available from BYK CHEMIE under the trademark BYK-UV 3530.
• the content of wetting additive in the correction fluid according to the present invention may be between 0.2 and 2% by weight relative to to the solids content of the photo-crosslinkable oligomer a), advantageously between 0.5 and 1.5%, more advantageously it is 1%.
• the correction fluid according to the present invention may contain as additive f) a dispersant. It may be for example a solution of ammonium polyacrylate or sodium polyphosphate. Such dispersants are commercially available from Indulor under the trade name Indunal A and Indunal NHMP.
• the dispersant content in the correction fluid according to the present invention in percentage by weight relative to the solids content is between 0.1 and 2%, advantageously between 0.2 and 1.5%.
• the present invention further relates to a device for applying a correction fluid for applying the correction fluid according to the present invention.
• All devices for applying a liquid correction fluid can be used to apply the correction fluid according to the present invention.
• the fluid application system of the application device according to the invention may for example be chosen from a foam brush or hair, an applicator roller, a ball with large channels, a needle or a tab. It allows in particular an application homogeneous, with a thickness that can vary between 10 and 75 ⁇ , more preferably between 10 and 50 pm.
• the application device according to the invention may be provided with a UV or visible radiation source.
• the UV or visible irradiation source which allows the crosslinking of the correction fluid according to the invention can emit a mono or polydisperse wavelength, in particular monodisperse, advantageously chosen in the range between 230 and 410 nm, advantageously between 278 and and 410 nm, in particular between 362 and 410 nm, more particularly between 400 and 410 nm, such as for example 278, 360-400 nm, 365, 382 and 405 nm.
• the irradiation source may thus be a monodisperse light emitting diode (LED) or a polydisperse metal halide lamp, such as for example a doped mercury vapor lamp, or both.
• the present invention further relates to a method for covering a mark on a paper medium comprising the step of:
• the UV or visible irradiation source that can be used in step B is as defined above.
• step B provides an irradiation dose of at least 20 mJ / cm 2 , advantageously between 20 and 40 mJ / cm 2 , more advantageously at a wavelength of between 230 and 410. nm.
• the mark to be covered by the process according to the present invention is obtained from a roller pen or ballpoint pen ink or a gel ink, advantageously from a ballpoint pen ink.
• the degree of crosslinking of the correction fluid obtained in step B varies between 50 and 70% at depth of the film and between 70 and 100% at the surface for thicknesses of 25 ⁇ m.
• Oligomer LUX515 ES 50% 31,86 photocrosslinkable
• Opacifying agent Ti0 2 Tronox CR 813 200 31.86
• Dispersant Indunal A 1 0.32 Dispersant Indunal NHMP 0.2 0.06
• the formulation of the correction fluid is applied via a 20 ⁇ m thick polyester blank on a white paper sheet (Clairefontaine, 80 g) on which text is written with a pen.
• This pen can be a pen with a blue ink or a black ink. It can be a ballpoint pen or a gel ink pen.
• Using a calibrated bar of 25 ⁇ we pass on the polyester film to apply the formulation.
• the film is then dried for a maximum of 30 seconds at room temperature and then irradiated under a 400 nm LED for 40 seconds (5000 mJ / cm 2 ). This application allows to evaluate the coverage of the film and to observe the appearance of the applied films.
• the coverage is perfect on the blue or black ink ballpoint pen or the blue or black gel ink pen stroke.
• the film has a brilliant appearance.
• Example 2 There is no phenomenon of migration of the writing through the bleeding fluid film for more than 50 days after application.

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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)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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• 2014
  • 2014-06-16 FR FR1455493A patent/FR3022252B1/fr not_active Expired - Fee Related
• 2015
  • 2015-06-12 WO PCT/FR2015/051558 patent/WO2015193589A1/fr active Application Filing
  • 2015-06-12 EP EP15732870.9A patent/EP3155055A1/de not_active Withdrawn
  • 2015-06-12 US US15/319,531 patent/US10662341B2/en active Active
  • 2015-06-12 JP JP2016573494A patent/JP6687546B2/ja not_active Expired - Fee Related
  • 2015-06-12 CN CN201580031861.9A patent/CN107075282A/zh active Pending

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