EP3155055A1 - Photocrosslinkable correction fluid - Google Patents

Photocrosslinkable correction fluid

Info

Publication number
EP3155055A1
EP3155055A1 EP15732870.9A EP15732870A EP3155055A1 EP 3155055 A1 EP3155055 A1 EP 3155055A1 EP 15732870 A EP15732870 A EP 15732870A EP 3155055 A1 EP3155055 A1 EP 3155055A1
Authority
EP
European Patent Office
Prior art keywords
correction fluid
methacrylate
advantageously
film
acrylate
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.)
Withdrawn
Application number
EP15732870.9A
Other languages
German (de)
French (fr)
Inventor
Christelle DEBRAUWER
Coralie FRICOU
Khalid Zahouily
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.)
BIC SA
Original Assignee
BIC SA
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
Application filed by BIC SA filed Critical BIC SA
Publication of EP3155055A1 publication Critical patent/EP3155055A1/en
Withdrawn legal-status Critical Current

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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.

Abstract

The present invention relates to a water-based correction fluid including: a- a photocrosslinkable acrylate and/or methacrylate oligomer; b- a photoinitiator; c- an opacifying agent; and d- water; e- optionally a photocrosslinkable acrylate and/or methacrylate monomer; and d- optionally an additive, said fluid having a dry extract of 40 to 80 wt % relative to the total weight of the fluid, advantageously 54 to 66 wt %, and forming a film after drying which includes at least 40 wt % of opacifying agent relative to the total weight of the film, advantageously 40 to 80 wt %. The invention also relates to a device for applying a correction fluid and to a method for covering a mark on a paper substrate using the correction fluid.

Description

FLUIDE DE CORRECTION PHOTORETICULABLE  PHOTORETICULABLE CORRECTION FLUID
La présente invention concerne les fluides de correction à base aqueuse photoréticulables. The present invention relates to photocurable water-based correction fluids.
Les fluides de correction, pour corriger les marques faites par un instrument d'écriture, en particulier un stylo, sont bien connus. De tels fluides sont appliqués sur la marque présente sur un papier et lorsqu'ils sèchent, fournissent un film, en général de couleur blanche, qui couvre la marque erronée. Une marque de correction peut alors être appliquée sur le film sec. Actuellement sur le marché, on trouve des fluides à séchage physique (évaporation de solvants), qui sont de deux types : 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. Currently on the market, there are fluids with physical drying (evaporation of solvents), which are of two types:
- à base de solvant organique : sèchent rapidement mais libèrent des COV.  - based on organic solvent: dry quickly but release VOCs.
- à base aqueuse : non nocifs mais sèchent lentement, avec en général un temps de séchage > 120 s.  - water-based: non-harmful but dry slowly, with a drying time> 120 s in general.
Un autre système de correcteur existant est celui-du dérouleur, mais la formule est alors une formule sèche, et, bien que le séchage soit très rapide et ne libère pas de COV, la technologie est complètement différente.  Another existing corrector system is that of the unwinder, but the formula is then a dry formula, and although the drying is very fast and does not release VOC, the technology is completely different.
La demande de brevet WO94/11450 décrit un fluide de correction photoréticulable ayant une durée de séchage courte, inférieure ou égale à 10s. Toutefois soit ce fluide ne contient pas de solvants, soit il contient un solvant volatil c'est-à-dire un solvant organique. Or l'utilisation d'un solvant volatil pose des problèmes de libération de COV. En outre un fluide de correction sans solvant pose un problème de migration de l'encre de l'écriture après dépôt (la trace d'écriture réapparaît au travers du fluide correcteur) dû à une réticulation trop faible en profondeur du film en raison de la concentration trop importante en matières photoréticulables de ce fluide. La demande US2012/0041092 décrit une composition de revêtement opaque comprenant une résine pouvant réticuler pour former un film sous l'action des UV. Cette composition est donc photoréticulable. Toutefois, ce document ne décrit pas de fluide de correction. En effet les seuls exemples d'utilisation concernent les peintures. De plus la composition décrite n'est pas destinée à être utilisée sur du papier. Elle n'est en outre pas destinée à recouvrir des marques laissées par de l'encre pour stylo roller ou pour stylo à bille ou par une encre gel, sans que cette encre ne réapparaisse (bleeding), sans que la composition ne soit absorbée par le papier et tout en permettant par la suite une réécriture sur le film sec obtenu. En effet la teneur en pigment décrite et exemplifiée dans ce document n'est pas suffisante pour avoir un bon pouvoir couvrant sur de telles marques et en particulier pour que le film obtenu après séchage évite les phénomènes de réapparition progressive de l'encre. En outre ce document décrit au paragraphe [0071] que l'énergie de réticulation est de 100MJ/cm2 à 5000 MJ/cm2, ce qui est très important. Il semble difficile de proposer un produit d'écriture nécessitant une telle énergie de réticulation en raison des risques pour la sécurité du consommateur. Par ailleurs utiliser une énergie plus faible serait soit inefficace soit accroîtrait de façon trop importante le temps de séchage et de réticulation (plusieurs heures). Par ailleurs les compositions décrites dans ce document ne sont pas totalement exemptes de solvants organiques. The patent application WO94 / 11450 describes a photocurable correction fluid having a short drying time, less than or equal to 10s. However, either this fluid does not contain solvents, or it contains a volatile solvent, that is to say an organic solvent. However, the use of a volatile solvent poses problems of VOC release. In addition, 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. However, this document does not describe a correction fluid. Indeed the only examples of use concern the paintings. In addition, the composition described is not intended to be used on paper. It is also not intended to cover marks left by ink roller pen or ballpoint pen or gel ink, without this ink reappear (bleeding), without the composition is absorbed by the paper and while subsequently allowing a rewrite on the dry film obtained. Indeed, the pigment content described and exemplified in this document is not sufficient to have a good hiding power on such marks and in particular for the film obtained after drying avoids the phenomenon of progressive reappearance of the ink. In addition, this document describes in paragraph [0071] that the crosslinking energy is 100MJ / cm 2 to 5000 MJ / cm 2 , which is very important. It seems difficult to propose a writing product requiring such crosslinking energy because of the risks for the safety of the consumer. In addition, using a lower energy would be either inefficient or would increase the drying and curing time (several hours) too much. Moreover, the compositions described in this document are not completely free of organic solvents.
La demande EP2557094 décrit également une composition de revêtement aqueuse réticulable par les radiations. Pour les mêmes raisons que précédemment, une telle composition ne pourrait pas être utilisée en tant que fluide de correction, la teneur en pigment décrite et exemplifiée dans ce document n'étant pas suffisante pour avoir un bon pouvoir couvrant sur des marques laissées par de l'encre pour stylo roller ou pour stylo à bille ou par une encre gel et en particulier pour que le film obtenu après séchage évite les phénomènes de réapparition progressive de l'encre. La demande EP 2703459 décrit une encre photoréticulable. Il ne s'agit donc pas d'un fluide de correction et la teneur en pigment décrite et exemplifiée dans ce document n'est pas suffisante pour avoir un bon pouvoir couvrant sur des marques laissées par de l'encre pour stylo roller ou pour stylo à bille ou par une encre gel et en particulier pour que le film obtenu après séchage évite les phénomènes de réapparition progressive de l'encre. EP2557094 also discloses an aqueous coating composition crosslinkable by radiation. For the same reasons as above, such 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.
En outre d'après ce document, il est possible que les compostions proposées puissent contenir des solvants organiques de types glycol, glycol éther et alcool. Ce type de solvant peut soit modifier l'apparence de la trace d'écriture à recouvrir (diffusion de l'encre dans le papier) soit engendrer le problème de bleeding (migration de la trace d'écriture à travers le film de fluide de correction). In addition, according to this document, it is possible that the 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 ).
Ainsi aucun des documents de l'art antérieur ne décrit ni ne suggère qu'il soit possible d'obtenir un fluide de correction à base aqueuse qui sèche rapidement, c'est dire ayant un temps de séchage entre 5 et 30 secondes. Les inventeurs se sont aperçus de façon surprenante, qu'il était possible de formuler des fluides de correction à base aqueuse ayant une durée de séchage courte à condition d'utiliser des oligomères photoréticulables. En effet grâce à l'irradiation UV ou visible, les oligomères réticulent ce qui permet de sécher rapidement le fluide de correction sans libérer de solvants volatiles et donc de COV. De tels fluides de correction en outre ne souffrent pas de phénomène de bleeding, c'est-à-dire de réapparition progressive de la marque par diffusion de l'encre à travers le film sec du fluide de correction et ont un bon pouvoir couvrant, quel que soit le type d'encre (encre pour stylo roller ou pour stylo à bille ou encre gel par exemple) et sa couleur (bleue ou noire par exemple). La présente invention concerne donc un fluide de correction à base aqueuse comprenant : Thus none of the documents of the prior art describes or suggests that it is possible to obtain a water-based correction fluid which dries rapidly, that is to say having a drying time between 5 and 30 seconds. The inventors have surprisingly found that it is possible to formulate water-based correction fluids having a short drying time provided that photocrosslinkable oligomers are used. Indeed, thanks to UV or visible irradiation, the oligomers crosslink which allows to quickly dry the correction fluid without releasing volatile solvents and therefore VOC. 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:
a- un oligomère acrylate et/ou méthacrylate photoréticulable, b- un photoamorceur,  a-a photocrosslinkable acrylate and / or methacrylate oligomer, b- a photoinitiator,
c- un agent opacifiant et  c- an opacifying agent and
d- de l'eau,  d- water,
e- éventuellement un monomère acrylate et/ou méthacrylate photoréticulable et  e- optionally a photocurable acrylate and / or methacrylate monomer and
d- éventuellement un additif,  d- possibly an additive,
ledit fluide présentant un extrait sec compris entre 40 et 80 % en poids par rapport au poids total du fluide, avantageusement entre 50 et 70 %, plus avantageusement entre 54 et 66 %, et formant un film après séchage comprenant au moins 40 % en poids d'agent opacifiant par rapport au poids total du film, plus avantageusement entre 40 et 80 % en poids, en particulier entre 45 et 80 % en poids. 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.
Au sens de la présente invention on entend par « fluide de correction à base aqueuse », tout fluide de correction dont le solvant est de l'eau. Avantageusement un tel fluide de correction ne contient pas de solvant organique. En particulier la teneur en eau du fluide de correction selon la présente invention est comprise entre 20 et 60 % en poids par rapport au poids total du fluide, avantageusement entre 30 et 50 % en poids par rapport au poids total du fluide, plus avantageusement entre 34 et 46 % en poids par rapport au poids total du fluide. For the purposes of the present invention, the term "water-based correction fluid" means any correction fluid whose solvent is water. Advantageously, such a correction fluid does not contain an organic solvent. In particular, 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.
Au sens de la présente invention on entend par «oligomère », toute chaîne polymérique de petite taille, avantageusement constituée d'au moins deux monomères et plus avantageusement d'au plus 20 monomères. En particulier un oligomère présente une faible masse moléculaire, en général inférieure à 4000g/mol. Au sens de la présente invention on entend par «oligomère acrylate et/ou méthacrylate photoréticulable », tout oligomère tel que défini ci-dessus présentant au moins un motif acrylate et/ou méthacrylate et réticulant par le biais d'une réaction radicalaire sous l'action des UV ou de la lumière visible. Avantageusement l'oligomère selon la présente invention est choisi parmi les acrylates, les méthacrylates, les polyuréthanes aliphatiques acrylates, les polyuréthanes aromatiques acrylates, les polyesters acrylates, les polyéthers acrylates, les polyuréthanes aliphatiques méthacrylates, les polyuréthanes aromatiques méthacrylates, les polyesters méthacrylates, les polyéthers méthacrylates, et leurs mélanges, avantageusement parmi les acrylates, les polyesters acrylates et les polyuréthanes aliphatiques acrylates, encore plus avantageusement parmi les polyuréthanes aliphatiques acrylates. De façon particulièrement avantageuse, l'oligomère selon la présente invention est un oligomère acrylate photoréticulable. For the purposes of the present invention, the term "oligomer" is intended to mean any small polymer chain advantageously consisting of at least two monomers and more advantageously at most 20 monomers. In particular, an oligomer has a low molecular weight, generally less than 4000 g / mol. For the purposes of the present invention, the term "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. Advantageously, 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. In a particularly advantageous manner, the oligomer according to the present invention is a photocrosslinkable acrylate oligomer.
Les oligomères selon la présente invention peuvent présenter des fonctionnalités en bout de chaînes allant de 2 à 18, en particulier 6, et une viscosité pouvant aller de 70 à 4000 mPa.s mesurée à 25°C, en particulier entre 70 et 1000 mPa.s. L'oligomère selon la présente invention peut par exemple être un oligomère diacrylate, en particulier un polyuréthane aliphatique diacrylate. Ces oligomères sont disponibles commercialement, par exemple auprès de la société Kromachem sous la dénomination commerciale Etercure® DR-W401. L'oligomère selon l'invention peut aussi être un acrylate. Ces oligomères sont disponibles commercialement par exemple auprès de la société Alberdingk Boley sous la dénomination commerciale Alberdingk® LUX 515. Ces oligomères peuvent se trouver sous la forme d'une dispersion aqueuse. 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.
Le fluide de correction selon l'invention peut contenir (en poids par rapport au poids total du fluide de correction) entre 2 et 25 % de l'oligomère acrylate et/ou méthacrylate photoréticulable, avantageusement entre 2,5 et 20 %, encore plus avantageusement entre 3 et 18%, de façon particulièrement préférée entre 3,5 et 16%. 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%.
Au sens de la présente invention on entend par «monomère acrylate et/ou méthacrylate photoréticulable », tout monomère présentant au moins un motif acrylate et/ou méthacrylate et réticulant par le biais d'une réaction radicalaire sous l'action des UV ou de la lumière visible. For the purposes of the present invention, the term "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.
Avantageusement le monomère selon la présente invention est choisi parmi les acrylates mono ou polyfonctionnalisés, les méthacrylates mono ou polyfonctionnalisés et leurs mélanges, avantageusement parmi les acrylates polyfonctionnalisés. Il peut en particulier s'agir d'un monomère de mono-, di- , tri-, tétra-, penta- acrylates et méthacrylates (hydroxylés, éthoxylés, propoxylés), aromatique ou aliphatique, possédant ou non des chaînes polymères courtes de type polyéther, polyuréthane, polyesters, polyépoxy, modifiés ou non par des groupements aminés. Ces monomères peuvent présenter des fonctionnalités en bout de chaîne allant de 2 à 6 et en particulier une viscosité pouvant aller de 40 à 1000 mPa.s mesurée à 25°C, en particulier de 100 à 500 mPa.s. Le monomère n'est pas obligatoirement présent dans le fluide de correction selon la présente invention. De façon avantageuse il n'est pas présent. Advantageously, 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.
Au sens de la présente invention on entend par « photoamorceur » tout produit qui permet d'amorcer la réaction de réticulation par voie radicalaire des oligomères et des monomères éventuellement présents dans le fluide de correction selon l'invention lors de leur irradiation par une source UV ou visible. En effet le photoamorceur, en absorbant l'énergie des photons émis, va devenir une espèce excitée (sous forme radicalaire). Ainsi cette espèce réagit avec les fonctions réactives des oligomères et des éventuels monomères du fluide de correction, entraînant une réticulation de la matière. Le photoamorceur est donc avantageusement un photoamorceur absorbant dans les UV ou le visible, plus avantageusement un photoamorceur absorbant dans les UV-A. En particulier le photoamorceur selon la présente invention permettra un amorçage en surface et/ou en profondeur de la réaction de polymérisation radicalaire. Plus particulièrement le photoamorceur selon la présente invention absorbe les longueurs d'onde d'émission des lampes/LED, et/ou les longueurs d'onde choisies dans la gamme comprise entre 230 et 410 nm, avantageusement entre 278 et 410 nm, en particulier entre 362 et 410 nm, plus particulièrement entre 400 et 410 nm, tel que par exemple 278, 360-400nm, 365, 382 et 405 nm. Dans un mode de réalisation particulier le photoamorceur est de type I, avantageusement il s'agit d'un photoamorceur de type acyle phosphine oxyde, plus particulièrement il s'agit de l'éthyl-2,4,6-triméthylbenzoylphenyl phosphinate. Ces photoamorceur sont disponibles commercialement par exemple auprès de la société BASF sous la dénomination commerciale Lucirin TPO-L. For the purposes of the present invention, 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. In particular, 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. In a particular embodiment, 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.
Le fluide de correction selon l'invention peut contenir (en % poids par rapport à l'extrait sec du fluide de correction) entre 3 et 10 % du photoamorceur, avantageusement entre 5 et 7 %, en particulier environ 6 %.  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%.
Au sens de la présente invention on entend par « agent opacifiant », tout pigment qui permet de conférer au fluide de correction son pouvoir couvrant, c'est-à-dire sa capacité de complètement recouvrir et cacher une marque d'écriture. En particulier l'agent opacifiant est choisi parmi le kaolin, le carbonate de calcium et l'oxyde de titane. Il s'agit avantageusement de l'oxyde de titane qui possède un pouvoir opacifiant supérieur au kaolin et au carbonate de calcium. L'oxyde de titane peut être choisi parmi l'oxyde de titane rutile, l'oxyde de titane anatase ou leurs mélange et peut éventuellement avoir subi un traitement de surface organique ou minérale, par exemple à l'aide d'oxyde d'aluminium ou oxyde de zirconium. Il peut avoir une taille des particules moyennes comprises entre 0,2 μηη et 0,4 μιη, avantageusement 0,21 μιτι. Il peut posséder une absorption moyenne d'huile de 37 (quantité d'huile de lin absorbée en gramme pour 100 gramme d'oxyde de titane). Il peut se trouver sous la forme d'une dispersion aqueuse. L'oxyde de titane est disponible commercialement auprès de la société Tronox, sous la dénomination commerciale CR-813. For the purposes of the present invention, 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. In particular, 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 μηη and 0.4 μιη, advantageously 0.21 μιτι. It can have an average oil absorption of 37 (amount of linseed oil absorbed per gram per 100 grams of titanium oxide). It can be in the form of an aqueous dispersion. Titanium oxide is commercially available from Tronox under the trade name CR-813.
Le fluide de correction selon la présente invention peut comprendre un additif f), avantageusement choisi parmi un azurant optique, un pigment modificateur de teintes, par exemple du noir de carbone pour griser la teinte, une résine cationique, une résine à séchage physique, un dispersant, un photosensibilisateur, par exemple du type additif thiolé, un accélérateur de réticulation, un siccatif, un agent de mouillage, une charge, un co-solvant, un biocide, un antigel, un agent de coalescence, un conservateur, de l'alcool polyvinylique et leurs mélanges. 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.
En particulier, le fluide de correction selon la présente invention peut contenir en tant qu'additif f) une résine à séchage physique, c'est-à-dire réticulant par le biais d'une augmentation de la température. Une telle résine permet d'améliorer le temps de séchage du fluide de correction. Il peut s'agir par exemple d'un copolymère acrylique, en particulier sous forme de dispersion aqueuse. De telles résines sont disponibles commercialement auprès de la société Alberdingk Boley sous la dénomination commerciale Alberdingk® AC2524. La teneur en résine à séchage physique dans le fluide de correction selon la présente invention peut être comprise entre 10 et 20 % en poids par rapport au poids total du fluide de correction, avantageusement entre 15 et 17 %. Le ratio massique résine à séchage physique/oligomère acrylate et/ou méthacrylate photoréticulable peut être d'environ 1/1.  In particular, 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. Such 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.
Le fluide de correction selon la présente invention peut également contenir en tant qu'additif f) un azurant optique (tel que par exemple le 2495T -EZE- PG ou le LAMP BLACK 8592 de la société EPS/CCA ou le TINT AYD WD 2018 de la société Elementis specialities) qui permet de faire paraître le film plus ou moins blanc. La teneur en azurant optique dans le fluide de correction selon la présente invention en pourcentage en poids par rapport à l'extrait sec est comprise entre 3 et 7 %, avantageusement entre 4 et 6 % en particulier elle est de 5 %. 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. 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%.
Le fluide de correction selon la présente invention peut contenir en tant qu'additif f) un polymère cationique. Le polymère cationique permet d'éviter ou de limiter la migration des encres présentes sur le papier et en particulier à partir de la marque qui a été recouverte par le fluide de correction, dans le film lors de l'application du fluide ou au cours du temps. Il peut s'agir par exemple d'un copolymère hydroxy fonctionnel quaternaire, avantageusement se trouvant sous forme de dispersion aqueuse. De tels polymères sont disponibles commercialement auprès de la société Indulor sous la dénomination commerciale Induquat ECR 466L. La teneur en polymère cationique dans le fluide de correction selon la présente invention peut être comprise entre 1 et 10 % en poids par rapport au poids total du fluide de correction, avantageusement entre 2 et 4 %. Le ratio massique polymère cationique/oligomère acrylate et/ou méthacrylate photoréticulable peut être d'environ 1/1.  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.
Le fluide de correction selon la présente invention peut contenir en tant qu'additif f) de l'alcool polyvinylique. L'alcool polyvinylique est disponible commercialement auprès de la société Fluka. La teneur en alcool polyvinylique dans le fluide de correction selon la présente invention peut être comprise entre 1 et 10 % en poids par rapport au poids total du fluide de correction, avantageusement entre 2 et 4 %. Le ratio massique alcool polyvinylique/oligomère acrylate et/ou méthacrylate photoréticulable peut être d'environ 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.
De façon avantageuse le fluide de correction comprend en tant qu'additif f) un mélange de polymère cationique et d'alcool polyvinylique, en particulier de ratio massique polymère cationique/alcool polyvinylique d'environ 1/1. Plus avantageusement le ratio massique polymère cationique/alcool polyvinylique/oligomère acrylate et/ou méthacrylate photoréticulable est d'environ 1/1/1. Advantageously, 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.
Le fluide de correction selon la présente invention peut contenir en tant qu'additif f) un additif de mouillage. Il peut s'agir par exemple d'un tensioactif siliconé tel qu'en particulier un siloxane à fonction acryle modifié par un polyéther. De tels additif sont disponibles commercialement auprès de la société BYK CHEMIE sous la dénomination commerciale BYK-UV 3530. La teneur en additif de mouillage dans le fluide de correction selon la présente invention peut être comprise entre 0,2 et 2 % en poids par rapport à l'extrait sec de l'oligomère photoréticulable a), avantageusement entre 0,5 et 1,5 %, plus avantageusement elle est de 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%.
Le fluide de correction selon la présente invention peut contenir en tant qu'additif f) un dispersant. Il peut s'agir par exemple d'une solution de polyacrylate d'ammonium ou d'un polyphosphate de sodium. De tels dispersants sont disponibles commercialement auprès de la société Indulor sous la dénomination commerciale Indunal A et Indunal NHMP. La teneur en dispersant dans le fluide de correction selon la présente invention en pourcentage en poids par rapport à l'extrait sec est comprise entre 0,1 et 2 %, avantageusement entre 0,2 et 1,5 %.  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%.
La présente invention concerne en outre un dispositif d'application d'un fluide de correction permettant l'application du fluide de correction selon la présente invention. Tous les dispositifs d'application d'un fluide de correction liquide peuvent être utilisables pour appliquer le fluide de correction selon la présente invention. Le système d'application du fluide du dispositif d'application selon l'invention peut par exemple être choisi parmi un pinceau en mousse ou poil, un rouleau applicateur, une bille avec de larges canaux, une aiguille ou une languette. Il permet en particulier une application homogène, avec une épaisseur pouvant varier entre 10 et 75 μιτι, plus avantageusement entre 10 et 50 pm. 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 μιτι, more preferably between 10 and 50 pm.
Le dispositif d'application selon l'invention peut être muni d'une source d'irradiation UV ou visible. La source d'irradiation UV ou visible qui permet la réticulation du fluide de correction selon l'invention peut émettre une longueur d'onde mono ou polydisperse, en particulier monodisperse, avantageusement choisie dans la gamme comprise entre 230 et 410 nm, avantageusement entre 278 et 410 nm, en particulier entre 362 et 410 nm, plus particulièrement entre 400 et 410 nm, tel que par exemple 278, 360- 400nm, 365, 382 et 405 nm. La source d'irradiation peut ainsi être une diode électroluminescente (LED) monodisperse ou une lampe aux halogénures métalliques polydisperse, tel que par exemple une lampe à vapeur de mercure dopé, ou les deux. La présente invention concerne en outre un procédé pour couvrir une marque sur un support papier comprenant l'étape de :  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:
A - appliquer le fluide de correction selon la présente invention de façon à former un film couvrant la marque sur le support papier, avantageusement présentant une épaisseur comprise entre 10 et 75 pm, en particulier entre 10 et 50 pm ; A - applying the correction fluid according to the present invention so as to form a film covering the mark on the paper support, preferably having a thickness of between 10 and 75 pm, in particular between 10 and 50 pm;
B - irradier le film à l'aide d'une source d'irradiation UV ou visible de façon à sécher le film et à provoquer une réticulation de l'oligomère acrylate et/ou méthacrylate photoréticulable, avantageusement pendant une durée comprise entre 5 et 30 s.  B - irradiating the film with a UV or visible irradiation source so as to dry the film and to cause a crosslinking of the photocurable acrylate oligomer and / or methacrylate, advantageously for a period of between 5 and 30 s.
La source d'irradiation UV ou visible utilisable à l'étape B est telle que définie ci-dessus. The UV or visible irradiation source that can be used in step B is as defined above.
Dans un mode de réalisation particulier l'étape B fournie une dose d'irradiation d'au moins 20 mJ/cm2, avantageusement comprise entre 20 et 40 mJ/cm2, plus avantageusement à une longueur d'onde comprise entre 230 et 410 nm. En particulier la marque à couvrir par le procédé selon la présente invention est obtenue à partir d'une encre pour stylo roller ou pour stylo à bille ou d'une encre gel, avantageusement d'une encre pour stylo à bille. In a particular embodiment, 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. In particular, 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.
Avantageusement grâce au procédé selon la présente invention le taux de réticulation du fluide de correction obtenue à l'étape B varie entre 50 et 70 % en profondeur du film et entre 70 et 100 % en surface pour des épaisseurs de 25 μιτι. Advantageously, thanks to the process according to the present invention, 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 μm.
On s'est aperçu que grâce au fluide de correction selon la présente invention, on peut déposer un film qui possède une couvrance idéale (le trait de stylo est entièrement couvert) et aucune auréole n'apparaît avec le temps c'est-à- dire qu'il n'y a pas de migration de l'encre à l'intérieur du film de fluide de correction.  It has been found that, thanks to the correction fluid according to the present invention, it is possible to deposit a film which has an ideal coverage (the pen stroke is entirely covered) and no halo appears with time, that is to say say that there is no migration of the ink inside the correction fluid film.
L'invention sera mieux comprise à la lecture des exemples qui suivent qui sont donnés à titre indicatif non limitatif. The invention will be better understood on reading the examples which follow, which are given by way of non-limiting indication.
Exemple 1 : Example 1
Un fluide de correction ayant la formulation suivante a été testé  A correction fluid having the following formulation has been tested
Nom commercial %/Extrait sec (ES) % de l'oligomère massique photoréticulable a)  Trade name% / Dry extract (ES)% of photocurable mass oligomer a)
Oligomère LUX515 ES = 50% 31,86 photoréticulable  Oligomer LUX515 ES = 50% 31,86 photocrosslinkable
Photoamorceur Lucirin TPO 6 0,96  Photoinitiator Lucirin TPO 6 0.96
Agent opacifiant : Ti02 Tronox CR 813 200 31,86Opacifying agent: Ti0 2 Tronox CR 813 200 31.86
Résine à séchage AC 2524 (ES = 48%) 100 33,19 physique Drying resin AC 2524 (ES = 48%) 100 33.19 physical
Additif de mouillage BYK UV 3530 1 0,16  Wetting additive BYK UV 3530 1 0,16
Azurant optique Dilution de 2459T- 5 1,59  Optical brightener Dilution of 2459T- 5 1.59
EZE PG 1% dans  EZE PG 1% in
99% d'eau  99% water
Dispersant Indunal A 1 0,32 Dispersant Indunal NHMP 0,2 0,06 Dispersant Indunal A 1 0.32 Dispersant Indunal NHMP 0.2 0.06
Formulation ES (%) 65,2  ES formulation (%) 65.2
% Ti02 31,9 % Ti0 2 31.9
Film % liant 51,2  Film% binder 51.2
% Ti02 48,8 % Ti0 2 48.8
La formulation du fluide de correction est appliquée via un cache en polyester de 20 pm d'épaisseur sur une feuille de papier blanc (Clairefontaine, 80 g) sur laquelle on écrit du texte à l'aide d'un stylo. Ce stylo peut être un stylo ayant une encre bleue ou une encre noire. Il peut s'agir d'un stylo-bille ou d'un stylo à encre gel. À l'aide d'une barre calibrée de 25 μιτι, on passe sur le film de polyester pour appliquer la formulation. Le film est ensuite séché durant 30 secondes maximum à température ambiante puis il est irradié sous une LED de 400 nm durant 40 secondes (5000 mJ/cm2). Cette application permet d'évaluer la couvrance du film et d'observer l'aspect des films appliqués. The formulation of the correction fluid is applied via a 20 μm 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 μιτι, 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.
Les résultats obtenus sont les suivants :  The results obtained are as follows:
La couvrance est parfaite sur le trait de stylo-bille à encre bleue ou noire ou le trait de stylo à encre gel bleue ou noire.  The coverage is perfect on the blue or black ink ballpoint pen or the blue or black gel ink pen stroke.
Le film présente un aspect brillant.  The film has a brilliant appearance.
II est possible de réécrire très rapidement (30 secondes après application). Il n'y a pas d'évolution de la trace dans le temps.  It is possible to rewrite very quickly (30 seconds after application). There is no evolution of the trace in time.
On n'observe pas de phénomène de migration de l'écriture à travers le film de fluide de correction (bleeding) pendant plus de 50 jours après application. Exemple 2 :  There is no phenomenon of migration of the writing through the bleeding fluid film for more than 50 days after application. Example 2
Un fluide de correction ayant la formulation suivante a été testé  A correction fluid having the following formulation has been tested
Nom commercial %/Extrait sec (ES) % de l'oligomère massique photoréticulable a)  Trade name% / Dry extract (ES)% of photocurable mass oligomer a)
Oligomère photoréticulable Etercure DR-W401A ES = 38% 9,6  Photocrosslinkable oligomer Etercure DR-W401A ES = 38% 9.6
Photoamorceur Lucirin TPO 6 0,22 Agent opacifiant : Ti02 Tronox CR 813 1200 43,75Photoinitiator Lucirin TPO 6 0,22 Opacifying agent: Ti0 2 Tronox CR 813 1200 43,75
Résine cationique Induquat ECR 766L 100 11,39 Cationic resin Induquat ECR 766L 100 11.39
(ES = 32%)  (ES = 32%)
Additif de mouillage BYK UV 3530 1 0,04 Wetting additive BYK UV 3530 1 0,04
Azurant optique Dilution de 2459T-EZE 5 2,19 Optical brightener Dilution of 2459T-EZE 5 2.19
PG 1% dans 99%  PG 1% in 99%
d'eau  water
Alcool Polyvinylique PVA 12-03 (ES = 20%) 100 18,23 Polyvinyl Alcohol PVA 12-03 (ES = 20%) 100 18.23
Solvant Eau 14,58Solvent Water 14.58
Formulation ES (%) 55 ES formulation (%) 55
% Ti02 43,8 % Ti0 2 43.8
Film % liant 20,4  Film% binder 20.4
% Ti02 79,6 % Ti0 2 79.6
Le test de couvrance est le même que celui utilisé l'exemple 1. Les résultats obtenus sont similaires.  The coverage test is the same as that used in Example 1. The results obtained are similar.

Claims

REVENDICATIONS
1. Fluide de correction à base aqueuse comprenant : A water-based correction fluid comprising:
a- un oligomère acrylate et/ou méthacrylate photoréticulable, b- un photoamorceur,  a-a photocrosslinkable acrylate and / or methacrylate oligomer, b- a photoinitiator,
c- un agent opacifiant et  c- an opacifying agent and
d- de l'eau,  d- water,
e- éventuellement un monomère acrylate et/ou méthacrylate photoréticulable et  e- optionally a photocurable acrylate and / or methacrylate monomer and
d- éventuellement un additif,  d- possibly an additive,
ledit fluide présentant un extrait sec compris entre 40 et 80 % en poids par rapport au poids total du fluide, avantageusement entre 54 et 66 %, et formant un film après séchage comprenant au moins 40 % en poids d'agent opacifiant par rapport au poids total du film, avantageusement entre 40 et 80 % en poids. said fluid having a solids content of between 40 and 80% by weight relative to the total weight of the fluid, advantageously between 54 and 66%, and forming a film after drying comprising at least 40% by weight of opacifying agent relative to the weight total film, advantageously between 40 and 80% by weight.
2. Fluide de correction selon la revendication 1, caractérisé en ce que l'agent opacifiant est du Ti02. 2. correction fluid according to claim 1, characterized in that the opacifying agent is Ti0 2 .
3. Fluide de correction selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que l'oligomère acrylate et/ou méthacrylate photoréticulable est choisi parmi les acrylates, les méthacrylates, les polyuréthanes aliphatiques acrylates, les polyuréthanes aromatiques acrylates, les polyesters acrylates, les polyéthers acrylates, les polyuréthanes aliphatiques méthacrylates, les polyuréthanes aromatiques méthacrylates, les polyesters méthacrylates, les polyéthers méthacrylates et leurs mélanges, avantageusement parmi les acrylates, les polyesters acrylates et les polyuréthanes aliphatiques acrylates. 3. correction fluid according to any one of claims 1 or 2, characterized in that the photocrosslinkable acrylate oligomer and / or methacrylate is selected from acrylates, methacrylates, aliphatic polyurethanes acrylates, acrylate aromatic polyurethanes, polyesters acrylates, polyether acrylates, aliphatic methacrylate polyurethanes, methacrylate aromatic polyurethanes, methacrylate polyesters, methacrylate polyethers and mixtures thereof, advantageously from acrylates, acrylate polyesters and aliphatic acrylate polyurethanes.
4. Fluide de correction selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'oligomère acrylate et/ou méthacrylate photoréticulable se trouve sous la forme d'une dispersion aqueuse. 4. correction fluid according to any one of claims 1 to 3, characterized in that the acrylate oligomer and / or photocrosslinkable methacrylate is in the form of an aqueous dispersion.
5. Fluide de correction selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le photoamorceur est de type I, en particulier il s'agit de l'éthyl 2,4,6-triméthylbenzoylphenylphosphinate, avantageusement présent en une teneur comprise entre 3 et 10 % en poids par rapport à l'extrait sec du fluide de correction. 5. correction fluid according to any one of claims 1 to 4, characterized in that the photoinitiator is of type I, in particular it is ethyl 2,4,6-trimethylbenzoylphenylphosphinate, advantageously present in a content between 3 and 10% by weight relative to the solids content of the correction fluid.
6. Fluide de correction selon l'une quelconque des revendications 1 à 5, caractérisé en ce que I' additif f) est choisi parmi un azurant optique, un pigment modificateur de teintes, une résine cationique, une résine à séchage physique, un dispersant, un photosensibilisateur, un accélérateur de réticulation, un siccatif, un agent de mouillage, une charge, un co-solvant, un biocide, un antigel, un agent de coalescence, un conservateur, de l'alcool polyvinylique et leurs mélanges. 6. correction fluid according to any one of claims 1 to 5, characterized in that the additive f) is selected from an optical brightener, a hue modifier pigment, a cationic resin, a physical drying resin, a dispersant , a photosensitizer, a crosslinking accelerator, a drying agent, a wetting agent, a filler, a co-solvent, a biocide, an antifreeze, a coalescing agent, a preservative, polyvinyl alcohol and mixtures thereof.
7. Fluide de correction selon l'une quelconque des revendications 1 à 6, caractérisé en ce que sa durée de séchage, après application sous forme d'un film d'épaisseur comprise entre 10 et 75 Mm sur un support papier, est comprise entre 5 et 30 secondes sous irradiation UV ou visible. 7. correction fluid according to any one of claims 1 to 6, characterized in that its drying time, after application in the form of a film of thickness between 10 and 75 Mm on a paper support, is between 5 and 30 seconds under UV or visible irradiation.
8. Dispositif d'application d'un fluide de correction caractérisé en ce qu'il permet l'application du fluide de correction selon l'une quelconque des revendications 1 à 7. 8. Apparatus for applying a correction fluid characterized in that it allows the application of the correction fluid according to any one of claims 1 to 7.
9. Dispositif selon la revendication 8, caractérisé en ce qu'il est muni d'une source d'irradiation UV ou visible. 9. Device according to claim 8, characterized in that it is provided with a UV or visible radiation source.
10. Dispositif selon la revendication 9, caractérisé en ce que la source d'irradiation UV ou visible émet une longueur d'onde mono ou polydisperse, en particulier monodisperse choisie dans la gamme comprise entre 230 et 410 nm, plus particulièrement entre 400 et 410nm. 10. Device according to claim 9, characterized in that the UV or visible irradiation source emits a mono or polydisperse wavelength, in particular monodisperse selected in the range between 230 and 410 nm, more particularly between 400 and 410 nm. .
11. Procédé pour couvrir une marque sur un support papier comprenant l'étape de : 11. A method of covering a mark on a paper medium comprising the step of:
A - appliquer le fluide de correction selon l'une quelconque des revendications 1 à 7 de façon à former un film couvrant la marque sur le support papier, avantageusement présentant une épaisseur comprise entre 10 et 75 μιη;  A - applying the correction fluid according to any one of claims 1 to 7 so as to form a film covering the mark on the paper support, preferably having a thickness between 10 and 75 μιη;
B - irradier le film à l'aide d'une source d'irradiation UV ou visible de façon à sécher le film et à provoquer une réticulation de l'oligomère acrylate et/ou méthacrylate photoréticulable, avantageusement pendant une durée comprise entre 5 et 30 s.  B - irradiating the film with a UV or visible irradiation source so as to dry the film and to cause a crosslinking of the photocurable acrylate oligomer and / or methacrylate, advantageously for a period of between 5 and 30 s.
12. Procédé selon la revendication 11 caractérisé en ce que l'étape B fournie une dose d'irradiation d'au moins 20 mJ/cm2, avantageusement comprise entre 20 et 40 mJ/cm2, plus avantageusement à une longueur d'onde comprise entre 230 et 410 nm. 12. The method of claim 11 characterized in that step B provides an irradiation dose of at least 20 mJ / cm 2 , preferably between 20 and 40 mJ / cm 2 , more preferably at a wavelength. between 230 and 410 nm.
13. Procédé selon l'une quelconque des revendications 11 ou 12 caractérisé en ce que la marque à couvrir est obtenue à partir d'une encre pour stylo roller ou pour stylo à bille ou d'une encre gel, avantageusement d'une encre pour stylo à bille. 13. Method according to any one of claims 11 or 12 characterized in that the mark to be covered is obtained from a roller pen ink or ballpoint pen or a gel ink, preferably an ink for ballpoint pen.
EP15732870.9A 2014-06-16 2015-06-12 Photocrosslinkable correction fluid Withdrawn EP3155055A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1455493A FR3022252B1 (en) 2014-06-16 2014-06-16 PHOTORETICULABLE CORRECTION FLUID
PCT/FR2015/051558 WO2015193589A1 (en) 2014-06-16 2015-06-12 Photocrosslinkable correction fluid

Publications (1)

Publication Number Publication Date
EP3155055A1 true EP3155055A1 (en) 2017-04-19

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ID=51417472

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US (1) US10662341B2 (en)
EP (1) EP3155055A1 (en)
JP (1) JP6687546B2 (en)
CN (1) CN107075282A (en)
FR (1) FR3022252B1 (en)
WO (1) WO2015193589A1 (en)

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US10662341B2 (en) 2020-05-26
WO2015193589A1 (en) 2015-12-23
JP2017525787A (en) 2017-09-07
CN107075282A (en) 2017-08-18
FR3022252A1 (en) 2015-12-18
FR3022252B1 (en) 2016-07-01
JP6687546B2 (en) 2020-04-22

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