EP2118366B1 - Offset-printable coated white paper having a high fluorescence intensity and method for producing same - Google Patents

Offset-printable coated white paper having a high fluorescence intensity and method for producing same Download PDF

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Publication number
EP2118366B1
EP2118366B1 EP20080762016 EP08762016A EP2118366B1 EP 2118366 B1 EP2118366 B1 EP 2118366B1 EP 20080762016 EP20080762016 EP 20080762016 EP 08762016 A EP08762016 A EP 08762016A EP 2118366 B1 EP2118366 B1 EP 2118366B1
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EP
European Patent Office
Prior art keywords
dry weight
pigments
coated
coated sheet
sheet according
Prior art date
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Application number
EP20080762016
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German (de)
French (fr)
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EP2118366A2 (en
Inventor
Laurence Avazzeri
Michel Goguelin
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Arjo Wiggins Fine Papers Ltd
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Arjo Wiggins Fine Papers Ltd
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Publication of EP2118366A2 publication Critical patent/EP2118366A2/en
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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506Intermediate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/66Coatings characterised by a special visual effect, e.g. patterned, textured
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30Luminescent or fluorescent substances, e.g. for optical bleaching
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • D21H23/46Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
    • D21H23/48Curtain coaters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38Intermediate layers; Layers between substrate and imaging layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5227Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5254Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24909Free metal or mineral containing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • Y10T428/31899Addition polymer of hydrocarbon[s] only
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • Y10T428/31899Addition polymer of hydrocarbon[s] only
    • Y10T428/31902Monoethylenically unsaturated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • Y10T428/31906Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to an offset printable coated white sheet, at least the surface layer of which has a high fluorescence power by virtue of its composition. It also relates to its manufacturing process.
  • fluorescent whitening agents also known as optical brighteners
  • optical brighteners In the field of papers as well as in the case of plastic sheets treated by applying a pigmented layer to obtain offset printability, fluorescent whitening agents, also known as optical brighteners, have long been used, which act by absorbing natural light in the interior of the room. ultraviolet, as well as in the visible near below 420 nm, then re-emit light fluorescence at around 440 nm so in the blue or blue-violet part of the visible spectrum. They increase the whiteness of these leaves by moving strongly their shade from yellow to blue.
  • the weight of this layer after drying is at least 5 g / m 2 in dry weight per side to see an improvement in printability, preferably 10 g / m 2 per face and if we want a high level of offset printability, many more, possibly applied in several stages.
  • the problem with such layers is that the fluorescent whitening agents are poorly fixed by the components of the layers and that it is difficult to increase the fluorescence without causing the counter-whitening effect called "greening" which corresponds to an evolution of the shade of the leaf lying from blue to green.
  • This evolution can be quantified by the variation ⁇ a * of the tristimulus coordinate a * of the CIELAB space measured under the conditions of the ISO 11475: 2004 standard.
  • Another problem is that the layers based on their weight per square meter act more or less as a UV filter of the incident light vis-à-vis the fluorescent whitening agent present in the base sheet.
  • a first solution in the case of a paper sheet, is to confer on the fibrous base a high fluorescence power which is then more or less attenuated according to the composition and the layer thickness deposited thereon.
  • this route uses large amounts of fluorescent whitening agent and limits the deposition layer to about 8 g / m 2 dry weight per face if it is desired to maintain a high fluorescence intensity.
  • Another solution is to introduce into the layer composition chemical substances which are a carrier for the fluorescent whitening agent, that is to say which play a role of fixing the agent analogous to that of cellulose.
  • these carrier substances there may be mentioned starch, polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), etc ... which are macromolecules rich in groups. hydrophilic.
  • PVA polyvinyl alcohol
  • CMC carboxymethylcellulose
  • PVP polyvinylpyrrolidone
  • PEG polyethylene glycol
  • the amount of whitening agent is limited, the amount of 0.2 to less than 1% by dry weight of fluorescent whitening agent and 0.3 to 2% by weight is usually used relative to the total dry weight of pigments. dry of substance support.
  • the purpose of the present invention is to overcome the drawbacks of the prior art (defined by the documents WO-A1-01 / 07714 , DE-A1-100 55,592 , DE-A1-104 44 131 , EP-A1-1 416 088 , WO-A2-2006 / 035234 and EP-A1-1 577 438 ) and these alternatives to obtain coated sheets appearing very white and offset-printable, in particular by offset inks drying in the open air, without noticeable defect of mottle.
  • the coated sheet according to the invention is "offset-printable without mounded defects" that it does not present on its surface when it is printed by offset, in particular by in-line drying inks, noticeable mottling defect.
  • This mocking defect can be evaluated in particular by the test described in the examples presented below which gives a mock index.
  • Said coated sheet according to the invention has a high fluorescence power and therefore appears very white and moreover its surface is printable in offset, in particular by offset inks drying in the open air, without noticeable mottle defect.
  • said layer of The surface should be as uniform as possible, even if the surface of the base sheet and / or sub-layers are very irregular. This regularity of the deposition of the layer makes it possible to have a layer of composition that is homogeneous on the surface after drying and to avoid the flaw of molding during printing.
  • the support substance which is in fact water-soluble, migrates irregularly with water depending on the irregularities of the deposition of the layer, these irregularities are notably related to structural irregularities of the base on which it is applied and / or a certain uneven penetration of the layer, resulting in offset printing (especially with inks drying in the open air) a non-uniform ink-surface interaction , which gives an irregular appearance to the printing, which can explain the lack of mottle observed in the prior art when the support substances are used in greater quantity.
  • said coated sheet may comprise at least one sublayer comprising pigments and at least one binder disposed under said surface layer.
  • the weight of said surface layer is at least 5 g / m 2 dry, per side, preferably at least 10 g / m 2 , more particularly between 15 and 30 g / m 2 .
  • this most surface-deposited layer comprises a large quantity of fluorescent whitening agent and of support substance, the base sheet and / or the sub-layers possibly having intrinsically low fluorescence power, even zero in order to reduce the cost of these fluorescent whitening agents and carrier substances whose price is high.
  • the Applicant has unexpectedly found that the sheets according to the invention have a high fluorescence power, and that they do not exhibit offset printing of noticeable mottle defect.
  • the total amount of fluorescent whitening agent in said surface layer is greater than 1 and less than or equal to 4% by dry weight relative to the total dry weight of said coating pigments, in particular between 1.5 and 3. %.
  • the total amount of support substance in said surface layer is less than or equal to 10% by dry weight relative to the total dry weight of said coating pigments, in particular between 4 and 8%.
  • the total amount of fluorescent whitening agent in said surface layer is equal to 1% by dry weight relative to the total dry weight of said coating pigments, and the total amount of carrier substance in said surface layer is greater than 5% by dry weight relative to the total dry weight of said coating pigments.
  • said coated sheet according to the invention has a fluorescence power greater than 60, this power being measured according to the international standard ISO 11475: 2004 as previously described.
  • said base sheet optionally coated with one or more sub-layers, has a fluorescence power of between 0 and 20.
  • the coating pigments of said layer are chosen from calcium carbonates, kaolins, talcs, titanium dioxide and plastic pigments.
  • the plastic pigments are hollow microspheres of a (styrene-acrylic) copolymer having an average size of between 1 and 0.1 ⁇ m.
  • the surface layer comprises at least one coating binder chosen from acrylic polymers, styrene-butadiene polymers and possibly other monomers commonly used in coating, as well as other commonly used additives such as dyes. shading.
  • the coating binders are employed as a stabilized aqueous dispersion (latex).
  • the fluorescent whitening agent is more particularly chosen alone or as a mixture among the various derivatives of stilbene disulfonic acid having altogether 2, 4 or 6 sulphonic groups, especially as marketed. Possibly these may be commercial preparations already containing a very small amount of a carrier substance.
  • the support substance is chosen alone or in a mixture from polyvinyl alcohols (PVA), carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP) and N-vinylformamide-based polymers.
  • PVA polyvinyl alcohols
  • CMC carboxymethylcellulose
  • PVP polyvinylpyrrolidone
  • N-vinylformamide-based polymers are preferably chosen from those having a high degree of hydrolysis, especially greater than 98%.
  • the base sheet may be any fibrous sheet, particularly cellulosic and / or synthetic fiber based sheet, such as paper including cardboard.
  • the base sheet can also be a sheet or a plastic film, for example a said synthetic paper based on a polyolefin extruded film of POLYART ® brand, or extruded polypropylene sheet manufactured and sold by the company PRIPLAK ®.
  • the base sheet may also be a complex of a fibrous sheet, especially a paper and a film or plastic sheet or a paper coated with an extruded plastic layer.
  • the invention also relates to the method of manufacturing said coated sheet.
  • an outline method such as the curtain coating method contributes to the objects of the invention, in particular in the case of a substrate. substrate with a not very regular surface. Indeed, this method makes it possible to obtain a surface layer deposited with a very regular thickness and thus avoids, during drying, the non-homogeneous migration of the water-soluble support substance, and to avoid the mottle defect during offset printing.
  • the invention therefore also relates to a method of manufacturing said offset coated white sheet with the characteristics as described above according to the invention, comprising a step of forming said surface layer by depositing the pigmented composition defining it, and carried out in an aqueous medium, by a curtain coating on said base sheet, the latter being optionally coated with underlayer (s).
  • this coating method applies to a fibrous base sheet, especially a paper.
  • Curtain coating can be done online during paper making or offline.
  • the process is such that the pigmented composition of said surface layer is deposited simultaneously with that of a pigmented sub-layer described above by means of a multilayer curtain coating head.
  • the said underlayer (s) may be applied (s) by means of a gluing press for example on the paper machine on which the base of the paper is produced or offline for a plastic base sheet.
  • the gluing press may be of the conventional type or it may be a modified model, for example a "Speedsizer” as marketed by Voith.
  • Other coating methods may be used provided that they are suitable for the application of the desired layer weights, several sub-layers can be applied by different methods.
  • a first underlayer may be coated in a size press and a second pigmented sub-layer may be applied by blade coating, for example.
  • the total dry weight of all the layers of a sheet according to the invention is greater than 10 g / m 2 in sec per side and preferably 15 g / m 2 , or even 30 g / m 2 per side or more. .
  • the coated sheet according to the invention may comprise said surface layer on each of its faces.
  • the fluorescence power is measured according to ISO 11475: 2004 by difference between the values of the CIE whiteness under illuminant D65 and the value of this quantity measured after the interposition of a filter eliminating wavelengths below 420 nm.
  • the measurements of the diffuse reflectance factor in blue R457 according to ISO 2469: 1994 and ISO 2470: 1999 under illuminant D65 as well as the whitening power at 457 nm are indicated by difference with the value of diffuse reflectance.
  • the greening ⁇ a * is calculated by the difference between the value of the trichromatic coordinate a * in the presence of the filter at 420 mm for the coated sheet without fluorescent whitening brightener and that under the same conditions of measurement for the coated sheet with a given percentage of fluorescent whitening agent.
  • the homogeneity of the printing is evaluated by the melt index which is determined by image analysis on a KHEOPS device marketed by the company TECHPAP, the index being on a scale of 1 (perfect) to 9 (very bad), with considered unacceptable for this use from note 7.
  • Example 1 in connection with Table 1, comprises Comparative Examples 1a to 1c and Example 1d according to the invention.
  • Comparative Tests 1a-1c are coated by a drag-plate method (steel) and the aqueous compositions are adjusted to the same solids (66%) and viscosity.
  • the pigmented surface composition of the test 1d according to the invention is deposited by curtain coating.
  • Matt coated papers with a total coating weight of 47 g / m 2 dry per side are then obtained, as used for sheet-fed offset printing applications (sheet-by-sheet printing with air-drying inks). high quality.
  • coated papers of the tests 1a to 1d are tested in offset printing on the Roland 4-color machine and their roughness index is evaluated as described above.
  • Comparative test la illustrates a standard coated paper for offset printing, both in terms of its coating formulation and its coating process: It is found that the quality of printing is good but the fluorescence power is insufficient.
  • Comparative test 1b shows the negative effect of the percentage increase fluorescent whitening agent which leads after greening, the opposite effect of that sought.
  • Comparative test 1c shows that under standard coating conditions it is not possible to increase the percentage of carrier substance without unacceptably degrading the printability (mottle defect).
  • Test 1d illustrates the invention, a coated sheet appears very white because of a high fluorescence power and for which there is a good quality of offset printing without noticeable mottle defect.
  • Table 1 Trial 1a comparative 1b comparative 1c comparative 1d % substance support 1 1 6 6 % fluorescent whitening agent A 0.4 1.5 0.4 1.5 Sleeping type Blade Blade Curtain Fluorescence power of the reclining leaf 47 41 52 62 Puffiness index 4 3.5 8 3
  • the coated paper 1d according to the invention has a CIE whiteness of 136, a diffuse reflectance factor in the R457 blue of 107% and a bleaching power of 22%.
  • Example 2 in conjunction with Table 2, includes Comparative Examples 2a and 2b and Examples 2c and 2d with surface compositions in accordance with those defined for the invention.
  • Two aqueous pigment compositions for mat coating consisting of the same mixture of calcium carbonate pigments and a copolymer binder (styrene-butadiene) at a rate of 11% by dry weight relative to the dry weight of the pigments.
  • a copolymer binder styrene-butadiene
  • One of the surface compositions which is not in accordance with the invention, also comprises standard percentages according to the prior art (0.4%) of the carrier substance of Example 1 and of a fluorescent whitening agent B which is a tetrasulphonated stilbene derivative marketed by CLARIANT under the reference LEUCOPHOR LCPE.
  • the other composition includes the same products but with quantities according to the invention.
  • compositions are each coated at a rate of 15 g / m 2 dry per side on two fibrous bases (paper) of 120 g / m 2 weak (16) or strong (69) fluorescence power.
  • Table 2 shows that, unlike the surface compositions according to the invention (tests 2c and 2d), it is not possible with a standard coating composition of the prior art (tests 2a and 2b) to reconcile a deposit of a layer compatible with the printability requirement, that is to say a layer comprising a low level of support substance so as not to have a mottle defect, and a high fluorescence power of the coated sheet (greater than 55 ), even taking as a basis a paper having a very high fluorescence power (test 2b).
  • Table 2 Trial 2a 2b 2c 2d Fluorescence power of the fibrous base 16 69 16 69 % substance support 0.4 6 % fluorescent whitening agent B 0.7 1.3 Fluorescence power of the reclining leaf 45 51 59 63
  • Example 3 in conjunction with Table 3, includes Examples 3a and 3b with surface compositions in accordance with those defined for the invention.
  • Table 3 reports the results obtained by coating a fibrous base with the same pigmented composition as in Example 2, this time in the presence of 6% (by dry weight relative to the dry pigments) of the carrier substance and 2, 5% (dry weight relative to the dry pigments) of fluorescent whitening agent B.
  • Table 3 Trial 3a 3b Fluorescence power of the fibrous base 2 Layer weight (g / m 2 dry per side) 15 30 Fluorescence power of the reclining leaf 62 69
  • coated papers 3a and 3b according to the invention respectively have a whitening power of 22% and 25%.
  • Example 4 comprises Comparative Examples 4a to 4d and Examples 4 to 4q with surface compositions in accordance with those defined for the invention.
  • the fluorescent whitening agent may be the agent A (disulphonated stilbene derivative) or B (tetrasulphonated stilbene derivative) already mentioned in the preceding examples, or another agent C which is a stilbene derivative.
  • the fluorescent whitening agent may be the agent A (disulphonated stilbene derivative) or B (tetrasulphonated stilbene derivative) already mentioned in the preceding examples, or another agent C which is a stilbene derivative.
  • hexasulfonated marketed by ROBAMA under the reference of RESISTOL SLK (see Table 4).
  • the best quality / cost compromise will be chosen industrially to achieve the desired fluorescence power with a greening ⁇ a * of less than 1, preferably less than 0.6.
  • Table 4 Trial 4a 4b 4c 4d 4th 4f 4g 4h 4i 4d 4k 4l 4m 4n 4o 4p 4q % substance support 0.8 3 6 9 % fluorescent whitening agent A 0.4 1.5 2.5 4 1.5 1 1.5 2.5 4 1.5 2.5 4 % fluorescent whitening agent B 1 1.5 2.5 4 % fluorescent whitening agent C 1.5 Fluorescence power of the reclining leaf 47 40 36 31 59 63 64 63 59 58 63 66 68 65 66 67 63 ⁇ a * of the test 0.24 0.70 1.21 1.72 0.59 0.38 0.52 0.64 0.94 0.26 0.34 0.39 0.47 0.24 0.42 0.57 0.79
  • This example 5 in connection with Table 5, includes Examples 5a to 5c which illustrate the use of mixtures of carrier substances to produce pigmented compositions in accordance with those of the invention.
  • Example 4 The coating conditions of Example 4 are repeated with 2% (by dry weight relative to the dry weight of the pigments) of the fluorescent whitening agent A (stilbene disulfonated derivative), 0.8% (by dry weight per relative to the weight of the dry pigments) of the PVA carrier substance described in the previous examples and 5% (by dry weight relative to the dry weight of the pigments) of one of the following carrier substances:
  • S1 CMC marketed by HERCULES under the reference BLANOSE 7L1C1.
  • S2 polymer based on N-vinylformamide marketed by BASF under the reference LUPAMIN 4500.
  • S3 PVP marketed by BASF under the reference LUMITEN PPR 8450.
  • coated papers 5a, 5b and 5c according to the invention respectively have a measurement of the reflectance factor R457 of 104% (for 5a), 104.5% (for 5b) and 105% (for 5c). ), and a whitening power respectively of 21% (for 5a), 21% (for 5b) and 22% (for 5c).
  • This example 6 in conjunction with Table 6 illustrates the invention using as a base sheet a plastic sheet.
  • the coating composition of Test 4o (9% of carrier substance PVA in dry weight relative to dry pigments and 1.5% in dry weight relative to to the dry pigments of the fluorescent whitening agent A (disulfonated stilbene derivative)) with a coating weight of 23 g / m 2 dry per side deposited on a plastic sheet (based on an extruded polyolefin film coated with a pigmented precursor) of 150 g / m 2 marketed by the company ARJOBEX Ltd under the trademark POLYART®, having a fluorescence power of 8.
  • Table 6 shows that a sheet with a high fluorescence power is obtained.
  • Table 6 Trial 6 Fluorescence power of the reclining leaf 68 ⁇ a * of the test 0.6

Landscapes

  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Duplication Or Marking (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

White coated sheet material comprises a base sheet and a printable surface layer comprising a white pigment, a binder, an optical brightener and a support for the optical brightener. The optical brightener is present in an amount of at least 1% by weight of pigment and the support is present in an amount of more than 2% by weight of pigment. Producing coated sheet material as above by applying an aqueous pigment composition by curtain coating.

Description

La présente invention concerne une feuille couchée blanche imprimable par offset dont au moins la couche de surface possède de par sa composition un haut pouvoir de fluorescence. Elle concerne également son procédé de fabrication.The present invention relates to an offset printable coated white sheet, at least the surface layer of which has a high fluorescence power by virtue of its composition. It also relates to its manufacturing process.

Dans le domaine des papiers ainsi que dans celui des feuilles plastiques traitées par application d'une couche pigmentée pour obtenir l'imprimabilité offset, on utilise depuis longtemps des agents blanchissants fluorescents, appelés aussi azurants optiques, qui agissent en absorbant la lumière naturelle dans l'ultraviolet, ainsi que dans le proche visible en-dessous de 420 nm, puis re-émettent la lumière par fluorescence aux alentours de 440 nm donc dans la partie du bleu ou bleu-violet du spectre visible. Ils augmentent ainsi la blancheur de ces feuilles couchées en déplaçant fortement leur nuance du jaune vers le bleu.In the field of papers as well as in the case of plastic sheets treated by applying a pigmented layer to obtain offset printability, fluorescent whitening agents, also known as optical brighteners, have long been used, which act by absorbing natural light in the interior of the room. ultraviolet, as well as in the visible near below 420 nm, then re-emit light fluorescence at around 440 nm so in the blue or blue-violet part of the visible spectrum. They increase the whiteness of these leaves by moving strongly their shade from yellow to blue.

La mise en oeuvre de ces agents blanchissants fluorescents, des molécules organiques insaturés comportant deux à six groupes sulfonés, a été abondamment décrite, notamment vis-à-vis de la nécessité, au niveau de la feuille, d'une bonne fixation de ces molécules sous leur forme isomérique trans qui est seule active.The use of these fluorescent whitening agents, unsaturated organic molecules containing two to six sulphonated groups, has been abundantly described, in particular with regard to the need, at the level of the sheet, for a good fixation of these molecules. in their trans isomeric form which is only active.

Parmi les matières premières existantes, la plus performante pour assurer cette fixation est de loin la cellulose en raison des interactions entre les électrons des groupements hydroxyles et la structure insaturée de l'agent blanchissant fluorescent. De fait, il est facile d'obtenir des papiers non couchés visuellement très blancs par l'addition d'une quantité suffisante d'un agent blanchissant fluorescent approprié, lesdits papiers ayant un haut pouvoir de fluorescence d'au moins 55, voire de l'ordre de 60 à 70 tel que mesuré selon la norme internationale ISO 11475 : 2004.Among the existing raw materials, the most efficient to ensure this fixation is by far the cellulose because of the interactions between the electrons of the hydroxyl groups and the unsaturated structure of the fluorescent whitening agent. In fact, it is easy to obtain visually very white uncoated papers by the addition of a sufficient amount of a suitable fluorescent whitening agent, said papers having a high fluorescence power of at least 55, or even more. from 60 to 70 as measured according to International Standard ISO 11475: 2004.

Dans le domaine de l'imprimabilité offset, il est connu que pour un bon rendu d'impression, notamment une interaction encre - surface le plus homogène possible et un temps de séchage des encres plus court, il est nécessaire d'appliquer en surface de la feuille de base une couche composée d'au moins un pigment minéral ou organique et d'au moins un liant naturel ou synthétique. Selon la composition et le procédé d'application, le poids de cette couche après séchage est d'au moins 5 g/m2 en poids sec par face pour apercevoir une amélioration de l'imprimabilité, de préférence 10 g/m2 par face et si l'on souhaite un haut niveau d'imprimabilité offset, beaucoup plus, éventuellement appliqués en plusieurs étapes.In the field of offset printability, it is known that for a good rendering of printing, in particular an ink-surface interaction as homogeneous as possible and a shorter ink drying time, it is necessary to apply on the surface of the base sheet a layer composed of at least one inorganic or organic pigment and at least one natural or synthetic binder. According to the composition and the method of application, the weight of this layer after drying is at least 5 g / m 2 in dry weight per side to see an improvement in printability, preferably 10 g / m 2 per face and if we want a high level of offset printability, many more, possibly applied in several stages.

Le problème avec de telles couches est que les agents blanchissants fluorescents sont mal fixés par les composants des couches et qu'il est difficile d'augmenter la fluorescence sans provoquer l'effet contre-blanchissant appelé « verdissement » qui correspond à une évolution de la nuance de la feuille couchée du bleu vers le vert. Cette évolution peut être quantifiée par la variation Δa* de la coordonnée trichromatique a* de l'espace CIELAB mesurée dans les conditions de la norme ISO 11475 : 2004.The problem with such layers is that the fluorescent whitening agents are poorly fixed by the components of the layers and that it is difficult to increase the fluorescence without causing the counter-whitening effect called "greening" which corresponds to an evolution of the shade of the leaf lying from blue to green. This evolution can be quantified by the variation Δa * of the tristimulus coordinate a * of the CIELAB space measured under the conditions of the ISO 11475: 2004 standard.

Un autre problème est que les couches en fonction de leur poids par mètre carré agissent plus ou moins comme filtre UV de la lumière incidente vis-à-vis de l'agent blanchissant fluorescent présent dans la feuille de base.Another problem is that the layers based on their weight per square meter act more or less as a UV filter of the incident light vis-à-vis the fluorescent whitening agent present in the base sheet.

Pour remédier à ces deux problèmes plusieurs solutions, décrites ci-après, ont été proposées dans l'art antérieur et sont mises en oeuvre seules ou en combinaison.To remedy these two problems several solutions, described below, have been proposed in the prior art and are implemented alone or in combination.

Une première solution, lorsqu'il s'agit d'une feuille papetière, est de conférer à la base fibreuse un pouvoir de fluorescence élevé qui est ensuite plus ou moins atténué selon la composition et l'épaisseur de couche déposée dessus. Dans la pratique, cette voie utilise une grande quantité d'agent blanchissant fluorescent et limite le dépôt de couche à environ 8 g/m2 en poids sec, par face si on souhaite conserver un pouvoir de fluorescence élevé.A first solution, in the case of a paper sheet, is to confer on the fibrous base a high fluorescence power which is then more or less attenuated according to the composition and the layer thickness deposited thereon. In practice, this route uses large amounts of fluorescent whitening agent and limits the deposition layer to about 8 g / m 2 dry weight per face if it is desired to maintain a high fluorescence intensity.

Une autre solution est d'introduire dans la composition de couche des substances chimiques qui sont un support de l'agent blanchissant fluorescent, c'est-à-dire qui jouent un rôle de fixation de l'agent analogue à celui de la cellulose. Parmi ces substances support, on peut citer l'amidon, l'alcool polyvinylique (PVA), la carboxyméthylcellulose (CMC), la polyvinylpyrrolidone (PVP), le polyéthylène glycol (PEG), etc... qui sont des macromolécules riches en groupements hydrophiles. Dans la pratique, la quantité d'agent blanchissant est limitée, on utilise couramment par rapport au poids total sec de pigments, 0,2 à moins de 1 % en poids sec d'agent blanchissant fluorescent et 0,3 à 2 % en poids sec de substance support. En effet si l'on veut accroître la quantité d'agent blanchissant fluorescent, on observe un verdissement très critique à partir et au-delà d'une valeur de 1 du Δa* On peut corriger la nuance en ajoutant des colorants, mais ceci diminue la luminosité, donc la perception de blancheur. Si l'on veut accroître la quantité de substance support au-delà de 2 %, pour repousser cette limite de verdissement, on observe alors un autre problème lié à la qualité de l'impression offset (notamment avec des encres séchant à l'air libre) due à une interaction encre-surface non uniforme, qui donne un aspect irrégulier, nuageux à l'impression, appelé « défaut de moutonnement » ou « mottling ».Another solution is to introduce into the layer composition chemical substances which are a carrier for the fluorescent whitening agent, that is to say which play a role of fixing the agent analogous to that of cellulose. Among these carrier substances, there may be mentioned starch, polyvinyl alcohol (PVA), carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), etc ... which are macromolecules rich in groups. hydrophilic. In practice, the amount of whitening agent is limited, the amount of 0.2 to less than 1% by dry weight of fluorescent whitening agent and 0.3 to 2% by weight is usually used relative to the total dry weight of pigments. dry of substance support. Indeed, if we want to increase the amount of fluorescent whitening agent, we observe a very critical greening from and above a value of 1 of the Δa * We can correct the shade by adding dyes, but this decreases brightness, so the perception of whiteness. If we want to increase the amount of support substance beyond 2%, to push back this greening limit, then we observe another problem related to the quality of offset printing (especially with inks drying in the air free) due to a non-uniform ink-surface interaction, which gives an irregular, cloudy appearance to printing, called "mottling defect" or "mottling".

Le but de la présente invention est de remédier aux inconvénients de l'art antérieur (défini par les documents WO-A1-01/07714 , DE-A1-100 55 592 , DE-A1-104 44 131 , EP-A1-1 416 088 , WO-A2-2006/035234 et EP-A1-1 577 438 ) et de ces alternatives pour obtenir des feuilles couchées paraissant très blanches et imprimables par offset, notamment par des encres offset séchant à l'air libre, sans défaut notable de moutonnement.The purpose of the present invention is to overcome the drawbacks of the prior art (defined by the documents WO-A1-01 / 07714 , DE-A1-100 55,592 , DE-A1-104 44 131 , EP-A1-1 416 088 , WO-A2-2006 / 035234 and EP-A1-1 577 438 ) and these alternatives to obtain coated sheets appearing very white and offset-printable, in particular by offset inks drying in the open air, without noticeable defect of mottle.

La demanderesse y remédie en fournissant des feuilles papetières mais également des feuilles plastiques, lesdites feuilles étant couchées et présentant un haut pouvoir de fluorescence grâce à l'incorporation d'agent blanchissant fluorescent et de substance support en quantités relativement élevées par rapport à celles utilisées dans l'art antérieur. L'homme du métier n'était pas enclin à utiliser de telles quantités pour les raisons exposées précédemment.The applicant remedies by providing paper sheets but also plastic sheets, said sheets being coated and having a high fluorescence power by incorporating fluorescent whitening agent and carrier substance in relatively high amounts compared to those used in the prior art. The person skilled in the art was not inclined to use such quantities for the reasons set out above.

L'invention fournit ainsi une feuille couchée blanche ayant un pouvoir de fluorescence supérieur à 55, mesuré selon la norme internationale ISO 11475 : 2004 par différence entre la valeur de la blancheur CIE sous illuminant D65 et la valeur de cette même blancheur CIE après interposition d'un filtre éliminant les longueurs d'onde inférieures à 420 nm, et étant imprimable par impression offset sans défaut de moutonnement, ladite feuille couchée comprenant au moins une feuille de base et une couche de surface blanche imprimable dont la composition pigmentée comporte :

  • au moins des pigments de couchage blancs et au moins au liant de couchage,
  • au moins un agent blanchissant fluorescent en une quantité totale supérieure ou égale à 1% en poids sec par rapport au poids sec desdits pigments,
  • au moins une substance support dudit agent blanchissant en une quantité totale en poids sec supérieure à 2% par rapport au poids sec desdits pigments.
The invention thus provides a white coated sheet having a fluorescence power greater than 55, measured according to International Standard ISO 11475: 2004, by difference between the value of CIE whiteness under illuminant D65 and the value of this same whiteness CIE after interposition of a filter eliminating wavelengths shorter than 420 nm, and being printable by offset printing without mounded defects, said coated sheet comprising at least one base sheet and a printable white surface layer whose pigmented composition comprises:
  • at least white coating pigments and at least the coating binder,
  • at least one fluorescent whitening agent in a total amount greater than or equal to 1% by dry weight relative to the dry weight of said pigments,
  • at least one support substance of said whitening agent in a total amount by dry weight greater than 2% relative to the dry weight of said pigments.

On entend par le fait que la feuille couchée selon l'invention est « imprimable par offset sans défaut de moutonnement » qu'elle ne présente pas à sa surface lors de son impression par offset, notamment par des encres séchant à l'air libre, de défaut de moutonnement notable. Ce défaut de moutonnement peut être évalué notamment par le test décrit dans les exemples présentés plus loin qui donne un indice de moutonnement.It is meant by the fact that the coated sheet according to the invention is "offset-printable without mounded defects" that it does not present on its surface when it is printed by offset, in particular by in-line drying inks, noticeable mottling defect. This mocking defect can be evaluated in particular by the test described in the examples presented below which gives a mock index.

Ladite feuille couchée selon l'invention présente un haut pouvoir de fluorescence et paraît donc très blanche et de plus sa surface est imprimable en offset, notamment par des encres offset séchant à l'air libre, sans défaut de moutonnement notable.Said coated sheet according to the invention has a high fluorescence power and therefore appears very white and moreover its surface is printable in offset, in particular by offset inks drying in the open air, without noticeable mottle defect.

Plus particulièrement la Demanderesse a mis en évidence que ladite couche de surface doit être d'une épaisseur la plus régulière possible, même si en dessous la surface de la feuille de base, et/ou des sous-couches, est très irrégulière. Cette régularité du dépôt de la couche permet d'avoir une couche de composition homogène en surface après le séchage et d'éviter le défaut de moutonnement lors de l'impression. En effet, il a été constaté que lors du séchage de la couche déposée en milieu aqueux, la substance support qui est de fait hydrosoluble, migre irrégulièrement avec l'eau en fonction des irrégularités du dépôt de la couche, ces irrégularités sont notamment liées aux irrégularités structurelles de la base sur laquelle elle est appliquée et/ou à une certaine pénétration irrégulière de la couche, ce qui entraîne lors de l'impression offset (notamment avec des encres séchant à l'air libre) une interaction encre-surface non uniforme, qui donne un aspect irrégulier à l'impression, ce qui peut expliquer le défaut de moutonnement observé dans l'art antérieur quand les substances support sont employées en plus grande quantité.More particularly, the Applicant has demonstrated that said layer of The surface should be as uniform as possible, even if the surface of the base sheet and / or sub-layers are very irregular. This regularity of the deposition of the layer makes it possible to have a layer of composition that is homogeneous on the surface after drying and to avoid the flaw of molding during printing. Indeed, it has been found that during the drying of the layer deposited in an aqueous medium, the support substance which is in fact water-soluble, migrates irregularly with water depending on the irregularities of the deposition of the layer, these irregularities are notably related to structural irregularities of the base on which it is applied and / or a certain uneven penetration of the layer, resulting in offset printing (especially with inks drying in the open air) a non-uniform ink-surface interaction , which gives an irregular appearance to the printing, which can explain the lack of mottle observed in the prior art when the support substances are used in greater quantity.

Selon un cas particulier de l'invention, ladite feuille couchée peut comprendre au moins une sous-couche comportant des pigments et au moins un liant, disposée sous ladite couche de surface.According to a particular case of the invention, said coated sheet may comprise at least one sublayer comprising pigments and at least one binder disposed under said surface layer.

Plus particulièrement selon l'invention le poids de ladite couche de surface est d'au moins 5 g/m2 en sec, par face, de préférence d'au moins 10 g/m2, plus particulièrement compris entre 15 et 30g/m2.More particularly according to the invention the weight of said surface layer is at least 5 g / m 2 dry, per side, preferably at least 10 g / m 2 , more particularly between 15 and 30 g / m 2 .

Plus particulièrement selon l'invention, seule cette couche déposée la plus en surface comporte une forte quantité d'agent blanchissant fluorescent et de substance support, la feuille de base et/ou les sous-couches pouvant avoir intrinsèquement un pouvoir de fluorescence faible, voire nul afin de réduire le coût de ces agents blanchissants fluorescents et substances support dont le prix est élevé.More particularly according to the invention, only this most surface-deposited layer comprises a large quantity of fluorescent whitening agent and of support substance, the base sheet and / or the sub-layers possibly having intrinsically low fluorescence power, even zero in order to reduce the cost of these fluorescent whitening agents and carrier substances whose price is high.

En effet, malgré le pouvoir de fluorescence faible de la base et/ou des éventuelles sous-couches, la Demanderesse a constaté de manière inattendue que les feuilles selon l'invention ont un haut pouvoir de fluorescence, et qu'elles ne présentent pas à l'impression offset de défaut de moutonnement notable.Indeed, despite the low fluorescence power of the base and / or any sub-layers, the Applicant has unexpectedly found that the sheets according to the invention have a high fluorescence power, and that they do not exhibit offset printing of noticeable mottle defect.

De préférence la quantité totale d'agent blanchissant fluorescent dans ladite couche de surface est supérieure à 1 et inférieure ou égale à 4 % en poids sec par rapport au poids total en sec desdits pigments de couchage, en particulier comprise entre 1,5 et 3 %.Preferably, the total amount of fluorescent whitening agent in said surface layer is greater than 1 and less than or equal to 4% by dry weight relative to the total dry weight of said coating pigments, in particular between 1.5 and 3. %.

De préférence, la quantité totale de substance support dans ladite couche de surface est inférieure ou égale à 10 % en poids sec par rapport au poids total sec desdits pigments de couchage, en particulier comprise entre 4 et 8%.Preferably, the total amount of support substance in said surface layer is less than or equal to 10% by dry weight relative to the total dry weight of said coating pigments, in particular between 4 and 8%.

Selon un cas particulier de l'invention, la quantité totale d'agent blanchissant fluorescent dans ladite couche de surface est égale à 1 % en poids sec par rapport au poids total en sec desdits pigments de couchage, et la quantité totale de substance support dans ladite couche de surface est supérieure à 5 % en poids sec par rapport au poids total sec desdits pigments de couchage.According to a particular case of the invention, the total amount of fluorescent whitening agent in said surface layer is equal to 1% by dry weight relative to the total dry weight of said coating pigments, and the total amount of carrier substance in said surface layer is greater than 5% by dry weight relative to the total dry weight of said coating pigments.

De préférence ladite feuille couchée selon l'invention a un pouvoir de fluorescence supérieur à 60, ce pouvoir étant mesuré selon la norme internationale ISO 11475 : 2004 comme décrit précédemment.Preferably said coated sheet according to the invention has a fluorescence power greater than 60, this power being measured according to the international standard ISO 11475: 2004 as previously described.

Selon un cas particulier de l'invention, ladite feuille de base, le cas échéant revêtue d'une ou plusieurs sous-couches, a un pouvoir de fluorescence compris entre 0 et 20.According to a particular case of the invention, said base sheet, optionally coated with one or more sub-layers, has a fluorescence power of between 0 and 20.

Selon un cas particulier de l'invention, les pigments de couchage de ladite couche sont choisis parmi les carbonates de calcium, les kaolins, les talcs, le dioxyde de titane et les pigments plastiques. Par exemple les pigments plastiques sont des microsphères creuses d'un copolymère (styrène-acrylique) ayant une taille moyenne comprise entre 1 et 0,1 µm.According to a particular case of the invention, the coating pigments of said layer are chosen from calcium carbonates, kaolins, talcs, titanium dioxide and plastic pigments. For example, the plastic pigments are hollow microspheres of a (styrene-acrylic) copolymer having an average size of between 1 and 0.1 μm.

Plus particulièrement la couche de surface comporte au moins un liant de couchage choisi parmi les polymères acryliques, les polymères de styrène-butadiène et éventuellement d'autres monomères couramment utilisés en couchage, ainsi que d'autres additifs d'usage commun tels que les colorants de nuançage. Les liants de couchage sont employés sous forme de dispersion aqueuse stabilisée (latex).More particularly, the surface layer comprises at least one coating binder chosen from acrylic polymers, styrene-butadiene polymers and possibly other monomers commonly used in coating, as well as other commonly used additives such as dyes. shading. The coating binders are employed as a stabilized aqueous dispersion (latex).

Selon l'invention, l'agent blanchissant fluorescent est plus particulièrement choisi seul ou en mélange parmi les divers dérivés de l'acide stilbène disulfonique présentant en tout 2, 4 ou 6 groupes sulfoniques, notamment tels que commercialisés. Eventuellement il peut s'agir de préparations commerciales comportant déjà une très petite quantité d'une substance support.According to the invention, the fluorescent whitening agent is more particularly chosen alone or as a mixture among the various derivatives of stilbene disulfonic acid having altogether 2, 4 or 6 sulphonic groups, especially as marketed. Possibly these may be commercial preparations already containing a very small amount of a carrier substance.

Selon l'invention, la substance support est choisie seule ou en mélange parmi les alcools polyvinyliques (PVA), la carboxyméthylcellulose (CMC), la polyvinylpyrrolidone (PVP) et les polymères à base de N-vinylformamide. Les PVA sont de préférence choisis parmi ceux ayant un haut degré d'hydrolyse, notamment supérieur à 98 %.According to the invention, the support substance is chosen alone or in a mixture from polyvinyl alcohols (PVA), carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP) and N-vinylformamide-based polymers. The PVAs are preferably chosen from those having a high degree of hydrolysis, especially greater than 98%.

La feuille de base peut être toute feuille fibreuse, en particulier une feuille à base de fibres cellulosiques et/ou synthétiques, tel qu'un papier y compris un carton.The base sheet may be any fibrous sheet, particularly cellulosic and / or synthetic fiber based sheet, such as paper including cardboard.

La feuille de base peut être aussi une feuille ou un film plastique, par exemple un papier dit synthétique à base d'un film extrudé de polyoléfme de la marque POLYART® ou une feuille à base de polypropylène extrudé fabriquée et commercialisée par la société PRIPLAK®.The base sheet can also be a sheet or a plastic film, for example a said synthetic paper based on a polyolefin extruded film of POLYART ® brand, or extruded polypropylene sheet manufactured and sold by the company PRIPLAK ®.

La feuille de base peut être aussi un complexe d'une feuille fibreuse, notamment un papier et d'un film ou feuille plastique ou encore un papier revêtu d'une couche de plastique extrudée.The base sheet may also be a complex of a fibrous sheet, especially a paper and a film or plastic sheet or a paper coated with an extruded plastic layer.

L'invention concerne aussi le procédé de fabrication de ladite feuille couchée.The invention also relates to the method of manufacturing said coated sheet.

La Demanderesse a trouvé aussi que parmi les différents moyens de déposer une composition pigmentée en milieu aqueux sur un substrat, un procédé contour tel que le procédé de couchage à rideau contribue à atteindre les buts de l'invention, notamment dans le cas d'un substrat avec une surface pas très régulière. En effet ce procédé permet d'obtenir une couche de surface déposée avec une épaisseur très régulière et évite ainsi lors du séchage la migration non homogène de la substance support hydrosoluble, et d'éviter le défaut de moutonnement lors de l'impression offset.The Applicant has also found that among the various means of depositing an aqueous-pigmented composition on a substrate, an outline method such as the curtain coating method contributes to the objects of the invention, in particular in the case of a substrate. substrate with a not very regular surface. Indeed, this method makes it possible to obtain a surface layer deposited with a very regular thickness and thus avoids, during drying, the non-homogeneous migration of the water-soluble support substance, and to avoid the mottle defect during offset printing.

L'invention concerne donc aussi un procédé de fabrication de ladite feuille couchée blanche et imprimable par offset avec les caractéristiques telles que décrites précédemment conformément à l'invention, comprenant une étape consistant à former ladite couche de surface en déposant la composition pigmentée la définissant, et réalisée en milieu aqueux, par un couchage à rideau sur ladite feuille de base, cette dernière étant le cas échéant revêtue de sous-couche(s).The invention therefore also relates to a method of manufacturing said offset coated white sheet with the characteristics as described above according to the invention, comprising a step of forming said surface layer by depositing the pigmented composition defining it, and carried out in an aqueous medium, by a curtain coating on said base sheet, the latter being optionally coated with underlayer (s).

Plus particulièrement ce procédé de couchage s'applique à une feuille de base fibreuse, notamment un papier. Le couchage par rideau peut être fait en ligne lors de la fabrication du papier ou encore hors ligne.More particularly, this coating method applies to a fibrous base sheet, especially a paper. Curtain coating can be done online during paper making or offline.

Selon un cas particulier de l'invention le procédé est tel que la composition pigmentée de ladite couche de surface est déposée simultanément à celle d'une sous-couche pigmentée décrite plus avant au moyen d'une tête de couchage rideau multicouche.According to a particular case of the invention, the process is such that the pigmented composition of said surface layer is deposited simultaneously with that of a pigmented sub-layer described above by means of a multilayer curtain coating head.

Toutefois, selon un cas particulier du procédé de fabrication, la ou les dite(s) sous-couche(s) peuvent être appliquée(s) au moyen d'une presse encolleuse par exemple sur la machine à papier sur laquelle la base du papier est produite ou hors ligne pour une feuille de base en plastique. La presse encolleuse peut être du type classique ou il peut s'agir d'un modèle modifié, par exemple une « Speedsizer » telle que commercialisée par Voith. D'autres procédés d'enduction peuvent être utilisés pour autant qu'ils soient appropriés pour l'application des poids de couche souhaités, plusieurs sous-couches pouvant être appliquées selon des procédés différents. Une première sous-couche peut être enduite en presse encolleuse et une seconde sous-couche pigmentée peut être appliquée par couchage par lame par exemple.However, according to a particular case of the manufacturing process, the said underlayer (s) may be applied (s) by means of a gluing press for example on the paper machine on which the base of the paper is produced or offline for a plastic base sheet. The gluing press may be of the conventional type or it may be a modified model, for example a "Speedsizer" as marketed by Voith. Other coating methods may be used provided that they are suitable for the application of the desired layer weights, several sub-layers can be applied by different methods. A first underlayer may be coated in a size press and a second pigmented sub-layer may be applied by blade coating, for example.

Plus particulièrement le poids sec total de l'ensemble des couches d'une feuille selon l'invention est supérieure à 10 g/m2 en sec par face et préférentiellement 15 g/m2, voire 30 g/m2 par face ou plus.More particularly, the total dry weight of all the layers of a sheet according to the invention is greater than 10 g / m 2 in sec per side and preferably 15 g / m 2 , or even 30 g / m 2 per side or more. .

La feuille couchée selon l'invention peut comporter ladite couche de surface sur chacune de ses faces.The coated sheet according to the invention may comprise said surface layer on each of its faces.

L'invention sera mieux comprise à l'aide des exemples non limitatifs ou comparatifs et des tests présentés ci-après.The invention will be better understood with the aid of the non-limiting or comparative examples and the tests presented below.

LES TESTS:THE TESTS:

Le pouvoir de fluorescence est mesuré selon ISO 11475 : 2004 par différence entre les valeurs de la blancheur CIE sous illuminant D65 et la valeur de cette grandeur mesurée après interposition d'un filtre éliminant les longueurs d'onde en-dessous de 420 nm.The fluorescence power is measured according to ISO 11475: 2004 by difference between the values of the CIE whiteness under illuminant D65 and the value of this quantity measured after the interposition of a filter eliminating wavelengths below 420 nm.

A titre indicatif, sont éventuellement mentionnées les mesures du facteur de réflectance diffuse dans le bleu R457 selon les normes ISO 2469 : 1994 et ISO 2470 : 1999 sous illuminant D65 ainsi que le pouvoir blanchissant à 457 nm par différence avec la valeur de la réflectance diffuse R457 après interposition d'un filtre éliminant les longueurs d'onde en-dessous de 420 nm.As an indication, the measurements of the diffuse reflectance factor in blue R457 according to ISO 2469: 1994 and ISO 2470: 1999 under illuminant D65 as well as the whitening power at 457 nm are indicated by difference with the value of diffuse reflectance. R457 after interposition of a filter eliminating wavelengths below 420 nm.

Le verdissement Δa* est calculé par la différence entre la valeur de la coordonnée trichromatique a* en présence du filtre à 420 mm pour la feuille couchée sans azurant blanchissant fluorescent et celle dans les mêmes conditions de mesure pour la feuille couchée avec un pourcentage donné d'agent blanchissant fluorescent.The greening Δa * is calculated by the difference between the value of the trichromatic coordinate a * in the presence of the filter at 420 mm for the coated sheet without fluorescent whitening brightener and that under the same conditions of measurement for the coated sheet with a given percentage of fluorescent whitening agent.

L'homogénéité de l'impression, réalisée par impression offset sur une machine 4 couleurs ROLAND 200 avec des encres offset séchant à l'air libre NOVAFIT 918 SUPREME BIO de la société FLINT GROUP GERMANY Gmbh , est évaluée par l'indice de moutonnement qui est déterminé par analyse d'image sur un appareil KHEOPS commercialisé par la société TECHPAP, l'indice étant sur une échelle de 1 (parfait) à 9 (très mauvais), avec considéré comme inacceptable pour cet usage à partir de la note 7.The homogeneity of the printing, achieved by offset printing on a ROLAND 200 4-color machine with NOVAFIT 918 SUPREME BIO free-air offset inks from FLINT GROUP GERMANY GmbH, is evaluated by the melt index which is determined by image analysis on a KHEOPS device marketed by the company TECHPAP, the index being on a scale of 1 (perfect) to 9 (very bad), with considered unacceptable for this use from note 7.

EXEMPLE 1 :EXAMPLE 1

L'exemple 1, en liaison avec le tableau 1, comporte les exemples comparatifs 1a à 1c et l'exemple 1d selon l'invention.Example 1, in connection with Table 1, comprises Comparative Examples 1a to 1c and Example 1d according to the invention.

Sur une base fibreuse (papier) déjà préalablement surfacée et précouchée, le poids de couche total de 30 g/m2 sec par face, avec des compositions pigmentées de carbonate de calcium, de liants amidon et copolymère de (styrène-butadiène) et ayant un pouvoir de fluorescence de 39, on couche à nouveau, à raison de 17 g/m2 en sec par face, une composition pigmentée de surface réalisée en milieu aqueux et comprenant essentiellement :

  • un mélange de pigments carbonate de calcium (95 parts) et de talc (5 parts)
  • un liant copolymère (styrène-butadiène), à raison de 7 % en poids sec par rapport au poids sec des pigments
  • un agent blanchissant fluorescent A, qui est un dérivé stilbènique disulfoné commercialisé par 3Vsigma sous la référence d'OPTIBLANC NL, en quantité en poids sec par rapport au poids total des pigments tel qu'indiqué dans le Tableau 1,
  • une substance support de l'agent blanchissant, qui est un alcool polyvinylique basse viscosité à haut degré d'hydrolyse du type 4 - 98, en quantité en poids sec par rapport au poids total des pigments tel qu'indiqué dans le Tableau 1.
On a fibrous base (paper) already pre-surfaced and precoated, the total layer weight of 30 g / m 2 dry per side, with pigmented compositions of calcium carbonate, styrene-butadiene starch and copolymer binders and having a fluorescence power of 39, is coated again, at a rate of 17 g / m 2 dry per side, a surface pigmented composition made in an aqueous medium and comprising essentially:
  • a mixture of calcium carbonate (95 parts) and talc (5 parts) pigments
  • a copolymeric binder (styrene-butadiene), at a rate of 7% by dry weight relative to the dry weight of the pigments
  • a fluorescent whitening agent A, which is a disulphonated stilbene derivative marketed by 3Vsigma under the reference of OPTIBLANC NL, in an amount by dry weight relative to the total weight of the pigments as indicated in Table 1,
  • a carrier substance for the whitening agent, which is a polyvinyl alcohol of low viscosity with a high degree of hydrolysis of type 4 - 98, in an amount by dry weight relative to the total weight of the pigments as indicated in Table 1.

Les compositions de surface des essais comparatifs 1a à 1c sont couchées par procédé à lame traînante (acier) et les compositions aqueuses sont ajustées à matières sèches (66 %) et à viscosité identiques.The surface compositions of Comparative Tests 1a-1c are coated by a drag-plate method (steel) and the aqueous compositions are adjusted to the same solids (66%) and viscosity.

La composition pigmentée de surface de l'essai 1d selon l'invention est déposée par couchage rideau.The pigmented surface composition of the test 1d according to the invention is deposited by curtain coating.

On obtient alors des papiers couchés mats d'un poids total de couche de 47 g/m2 sec par face, tels qu'utilisés pour les applications impression offset feuilles (impression feuille à feuille avec des encres séchant à l'air ambiant) de haute qualité.Matt coated papers with a total coating weight of 47 g / m 2 dry per side are then obtained, as used for sheet-fed offset printing applications (sheet-by-sheet printing with air-drying inks). high quality.

Les papiers couchés des essais 1a à 1d sont testés en impression offset sur la machine Roland 4 couleurs et on évalue leur indice de moutonnement comme décrit ci-dessus.The coated papers of the tests 1a to 1d are tested in offset printing on the Roland 4-color machine and their roughness index is evaluated as described above.

L'essai comparatif la illustre un papier couché standard pour impression offset, tant au niveau de sa formulation de couche que de son procédé de couchage : On constate que la qualité de l'impression est bonne mais le pouvoir de fluorescence insuffisant.Comparative test la illustrates a standard coated paper for offset printing, both in terms of its coating formulation and its coating process: It is found that the quality of printing is good but the fluorescence power is insufficient.

L'essai comparatif 1b montre l'effet négatif de l'augmentation du pourcentage d'agent blanchissant fluorescent qui conduit suite au verdissement, à l'effet inverse de celui recherché.Comparative test 1b shows the negative effect of the percentage increase fluorescent whitening agent which leads after greening, the opposite effect of that sought.

L'essai comparatif 1c montre que dans des conditions standard de couchage il n'est pas possible d'augmenter le pourcentage de substance de support sans dégrader de manière inacceptable l'imprimabilité (défaut de moutonnement).Comparative test 1c shows that under standard coating conditions it is not possible to increase the percentage of carrier substance without unacceptably degrading the printability (mottle defect).

L'essai 1d illustre l'invention, on obtient une feuille couchée paraissant très blanche du fait d'un fort pouvoir de fluorescence et pour laquelle on constate une bonne qualité d'impression offset sans défaut de moutonnement notable. Tableau 1 Essai 1a comparatif 1b comparatif 1c comparatif 1d % substance support 1 1 6 6 % agent blanchissant fluorescent A 0,4 1,5 0,4 1,5 Type de couchage Lame Lame Lame Rideau Pouvoir de fluorescence de la feuille couchée 47 41 52 62 Indice de moutonnement 4 3,5 8 3 Test 1d illustrates the invention, a coated sheet appears very white because of a high fluorescence power and for which there is a good quality of offset printing without noticeable mottle defect. Table 1 Trial 1a comparative 1b comparative 1c comparative 1d % substance support 1 1 6 6 % fluorescent whitening agent A 0.4 1.5 0.4 1.5 Sleeping type Blade Blade Blade Curtain Fluorescence power of the reclining leaf 47 41 52 62 Puffiness index 4 3.5 8 3

Il convient de noter que le papier couché 1d selon l'invention à une blancheur CIE de 136, un facteur de réflectance diffuse dans le bleu R457 de 107 % et un pouvoir blanchissant de 22%.It should be noted that the coated paper 1d according to the invention has a CIE whiteness of 136, a diffuse reflectance factor in the R457 blue of 107% and a bleaching power of 22%.

EXEMPLE 2 :EXAMPLE 2

L'exemple 2, en liaison avec le tableau 2, comporte les exemples comparatifs 2a et 2b et les exemples 2c et 2d avec des compositions de surface conformes à celles définies pour l'invention.Example 2, in conjunction with Table 2, includes Comparative Examples 2a and 2b and Examples 2c and 2d with surface compositions in accordance with those defined for the invention.

On prépare deux compositions pigmentées aqueuses pour couchage mat constituées d'un même mélange de pigments carbonate de calcium et d'un liant copolymère (styrène-butadiène) à raison de 11 % en poids sec par rapport au poids en sec des pigments.Two aqueous pigment compositions for mat coating are prepared consisting of the same mixture of calcium carbonate pigments and a copolymer binder (styrene-butadiene) at a rate of 11% by dry weight relative to the dry weight of the pigments.

L'une des compositions de surface, non conforme à l'invention, comporte en outre des pourcentages standard selon l'art antérieur (0,4%) de la substance support de l'exemple 1 et d'un agent blanchissant fluorescent B qui est un dérivé stilbènique tétrasulfoné commercialisé par CLARIANT sous la référence de LEUCOPHOR LCPE.One of the surface compositions, which is not in accordance with the invention, also comprises standard percentages according to the prior art (0.4%) of the carrier substance of Example 1 and of a fluorescent whitening agent B which is a tetrasulphonated stilbene derivative marketed by CLARIANT under the reference LEUCOPHOR LCPE.

L'autre composition comprend les mêmes produits mais avec des quantités conformes à l'invention.The other composition includes the same products but with quantities according to the invention.

Ces deux compositions sont chacune couchées à raison de 15 g/m2 sec par face sur deux bases fibreuses (papier) de 120 g/m2 de faible (16) ou fort (69) pouvoir de fluorescence.These two compositions are each coated at a rate of 15 g / m 2 dry per side on two fibrous bases (paper) of 120 g / m 2 weak (16) or strong (69) fluorescence power.

Le tableau 2 montre que, contrairement aux compositions de surface conforme à l'invention (essais 2c et 2d), il n'est pas possible avec une composition de couchage standard de l'art antérieur (essais 2a et 2b) de concilier un dépôt de couche compatible avec l'exigence d'imprimabilité, c'est-à-dire une couche comprenant un faible taux de substance support pour ne pas avoir de défaut de moutonnement, et un fort pouvoir de fluorescence de la feuille couchée (supérieur à 55), même en prenant pour base un papier ayant un pouvoir de fluorescence très élevé (essai 2b). Tableau 2 Essai 2a 2b 2c 2d Pouvoir de fluorescence de la base fibreuse 16 69 16 69 % substance support 0,4 6 % agent blanchissant fluorescent B 0,7 1,3 Pouvoir de fluorescence de la feuille couchée 45 51 59 63 Table 2 shows that, unlike the surface compositions according to the invention (tests 2c and 2d), it is not possible with a standard coating composition of the prior art (tests 2a and 2b) to reconcile a deposit of a layer compatible with the printability requirement, that is to say a layer comprising a low level of support substance so as not to have a mottle defect, and a high fluorescence power of the coated sheet (greater than 55 ), even taking as a basis a paper having a very high fluorescence power (test 2b). Table 2 Trial 2a 2b 2c 2d Fluorescence power of the fibrous base 16 69 16 69 % substance support 0.4 6 % fluorescent whitening agent B 0.7 1.3 Fluorescence power of the reclining leaf 45 51 59 63

EXEMPLE 3 :EXAMPLE 3

L'exemple 3, en liaison avec le tableau 3, comporte les exemples 3a et 3b avec des compositions de surface conformes à celles définies pour l'invention.Example 3, in conjunction with Table 3, includes Examples 3a and 3b with surface compositions in accordance with those defined for the invention.

Ces exemples illustrent que même à partir d'une base avec un pouvoir de fluorescence quasi-nul, les compositions pigmentées selon l'invention permettent l'obtention de feuilles couchées à pouvoir de fluorescence très élevé.These examples illustrate that even from a base with a virtually zero fluorescence power, the pigmented compositions according to the invention allow the production of coated sheets with very high fluorescence power.

Le tableau 3 rapporte les résultats obtenus en couchant une base fibreuse avec la même composition pigmentée qu'à l'exemple 2, en présence cette fois de 6 % (en poids sec par rapport aux pigments secs) de la substance support et de 2,5 % (en poids sec par rapport aux pigments secs) de l'agent blanchissant fluorescent B. Tableau 3 Essai 3a 3b Pouvoir de fluorescence de la base fibreuse 2 Poids de couche (g/m2 en sec par face) 15 30 Pouvoir de fluorescence de la feuille couchée 62 69 Table 3 reports the results obtained by coating a fibrous base with the same pigmented composition as in Example 2, this time in the presence of 6% (by dry weight relative to the dry pigments) of the carrier substance and 2, 5% (dry weight relative to the dry pigments) of fluorescent whitening agent B. Table 3 Trial 3a 3b Fluorescence power of the fibrous base 2 Layer weight (g / m 2 dry per side) 15 30 Fluorescence power of the reclining leaf 62 69

Les papiers couchés 3a et 3b selon l'invention ont respectivement un pouvoir blanchissant de 22% et de 25%.The coated papers 3a and 3b according to the invention respectively have a whitening power of 22% and 25%.

EXEMPLE 4 :EXAMPLE 4

L'exemple 4 comporte les exemples comparatifs 4a à 4d et les exemples 4e à 4q avec des compositions de surface conformes à celles définies pour l'invention.Example 4 comprises Comparative Examples 4a to 4d and Examples 4 to 4q with surface compositions in accordance with those defined for the invention.

Ces exemples montrent que contrairement aux conditions habituelles, les compositions de surface conformes à celles définies pour l'invention ne présentent pas de verdissement critique.These examples show that, contrary to the usual conditions, the surface compositions conforming to those defined for the invention do not exhibit critical greening.

Sur une base fibreuse (papier) préalablement surfacée et précouchée , pour une poids de couche total de 15 g/m2 sec par face, avec des compositions pigmentées de carbonate de calcium et d'un mélange de liants amidon et copolymère (styrène- butadiène), ladite base précouchée ayant un pouvoir de fluorescence de 43, on couche à raison de 12 g/m2 par face, une composition pigmentée de surface réalisée en milieu aqueux comprenant essentiellement :

  • des pigments de carbonate de calcium,
  • un liant copolymère (styrène-butadiène) à raison de 8 % en poids sec par rapport au poids des pigments,
  • un agent blanchissant fluorescent en quantité en poids sec par rapport au poids total des pigments tel qu'indiqué dans le Tableau 4,
  • une substance support en quantité en poids sec par rapport au poids total des pigments tel qu'indiqué dans le Tableau 4.
On a fibrous base (paper) previously surfaced and precoated, for a total layer weight of 15 g / m 2 dry per side, with pigmented compositions of calcium carbonate and a mixture of binders starch and copolymer (styrene-butadiene) ), said precoated base having a fluorescence power of 43, is coated at a rate of 12 g / m 2 per side, a surface pigmented composition produced in an aqueous medium essentially comprising:
  • calcium carbonate pigments,
  • a copolymer binder (styrene-butadiene) at a rate of 8% by dry weight relative to the weight of the pigments,
  • a fluorescent whitening agent in an amount by dry weight relative to the total weight of the pigments as indicated in Table 4,
  • a support substance in an amount by dry weight relative to the total weight of the pigments as indicated in Table 4.

La substance support employée est celle mentionnée aux exemple précédents, l'agent blanchissant fluorescent peut être l'agent A (dérivé stilbènique disulfoné) ou B (dérivé stilbènique tétrasulfoné) déjà mentionné aux exemples précédents, ou un autre agent C qui est un dérivé stilbènique hexasulfoné commercialisé par ROBAMA sous la référence de RESISTOL SLK (voir Tableau 4).The support substance employed is that mentioned in the preceding examples, the fluorescent whitening agent may be the agent A (disulphonated stilbene derivative) or B (tetrasulphonated stilbene derivative) already mentioned in the preceding examples, or another agent C which is a stilbene derivative. hexasulfonated marketed by ROBAMA under the reference of RESISTOL SLK (see Table 4).

On obtient des feuilles de papier couchées demi mates.Semi-matte coated sheets of paper are obtained.

Seuls les essais 4e à 4q avec des compositions pigmentées de surface conformes à celles de l'invention, comparativement aux essais comparatifs 4a à 4d, présentent à la fois un pouvoir de fluorescence élevé et un verdissement Δa* inférieur à 1.Only tests 4e to 4q with pigmented surface compositions in accordance with those of the invention, compared with comparative tests 4a to 4d, have both a high fluorescence power and a greening Δa * less than 1.

Selon le mode de conception de la feuille couchée, on choisira industriellement le meilleur compromis qualité / coût permettant d'atteindre le pouvoir de fluorescence souhaité avec un verdissement Δa* inférieur à 1, de préférence inférieur à 0,6. Tableau 4 Essai 4a 4b 4c 4d 4e 4f 4g 4h 4i 4j 4k 4l 4m 4n 4o 4p 4q % substance support 0,8 3 6 9 % agent blanchissant fluorescent A 0,4 1,5 2,5 4 1,5 1 1,5 2,5 4 1,5 2,5 4 % agent blanchissant fluorescent B 1 1,5 2,5 4 % agent blanchissant fluorescent C 1,5 Pouvoir de fluorescence de la feuille couchée 47 40 36 31 59 63 64 63 59 58 63 66 68 65 66 67 63 Δa* de l'essai 0,24 0,70 1,21 1,72 0,59 0,38 0,52 0,64 0,94 0,26 0,34 0,39 0,47 0,24 0,42 0,57 0,79 According to the design mode of the coated sheet, the best quality / cost compromise will be chosen industrially to achieve the desired fluorescence power with a greening Δa * of less than 1, preferably less than 0.6. Table 4 Trial 4a 4b 4c 4d 4th 4f 4g 4h 4i 4d 4k 4l 4m 4n 4o 4p 4q % substance support 0.8 3 6 9 % fluorescent whitening agent A 0.4 1.5 2.5 4 1.5 1 1.5 2.5 4 1.5 2.5 4 % fluorescent whitening agent B 1 1.5 2.5 4 % fluorescent whitening agent C 1.5 Fluorescence power of the reclining leaf 47 40 36 31 59 63 64 63 59 58 63 66 68 65 66 67 63 Δa * of the test 0.24 0.70 1.21 1.72 0.59 0.38 0.52 0.64 0.94 0.26 0.34 0.39 0.47 0.24 0.42 0.57 0.79

EXEMPLE 5 :EXAMPLE 5

Cet exemple 5, en liaison avec le tableau 5, comportent les exemples 5a à 5c qui illustrent l'utilisation des mélanges de substances support pour réaliser des compositions pigmentées conformes à celles de l'invention.This example 5, in connection with Table 5, includes Examples 5a to 5c which illustrate the use of mixtures of carrier substances to produce pigmented compositions in accordance with those of the invention.

On reprend les conditions de couchage de l'exemple 4, avec 2 % (en poids sec par rapport au poids en sec des pigments) de l'agent blanchissant fluorescent A (dérivé stilbènique disulfoné), 0,8 % (en poids sec par rapport au poids des pigments en sec) du PVA substance support décrit aux exemples précédents et 5 % (en poids sec par rapport au poids en sec des pigments) de l'une des substances support suivantes :
S1 = CMC commercialisée par HERCULES sous la référence BLANOSE 7L1C1.
S2 = polymère à base de N-vinylformamide commercialisé par BASF sous la référence LUPAMIN 4500.
S3 = PVP commercialisée par BASF sous la référence LUMITEN PPR 8450. Tableau 5 Essai 5a 5b 5c Substance support S1 S2 S3 Pouvoir de fluorescence de la feuille couchée 59 60 62 Blancheur CIE de la feuille couchée 141 142 144
The coating conditions of Example 4 are repeated with 2% (by dry weight relative to the dry weight of the pigments) of the fluorescent whitening agent A (stilbene disulfonated derivative), 0.8% (by dry weight per relative to the weight of the dry pigments) of the PVA carrier substance described in the previous examples and 5% (by dry weight relative to the dry weight of the pigments) of one of the following carrier substances:
S1 = CMC marketed by HERCULES under the reference BLANOSE 7L1C1.
S2 = polymer based on N-vinylformamide marketed by BASF under the reference LUPAMIN 4500.
S3 = PVP marketed by BASF under the reference LUMITEN PPR 8450. Table 5 Trial 5a 5b 5c Substance support S1 S2 S3 Fluorescence power of the reclining leaf 59 60 62 Whiteness CIE of the reclining leaf 141 142 144

Il convient de noter que les papiers couchés 5a, 5b et 5c selon l'invention ont respectivement une mesure du facteur de réflectance R457 de 104 % (pour 5a), de 104,5 % (pour 5b) et de 105 % (pour 5c), et un pouvoir blanchissant respectivement de 21% (pour 5a), de 21 % ( pour 5b) et de 22 % (pour 5c).It should be noted that the coated papers 5a, 5b and 5c according to the invention respectively have a measurement of the reflectance factor R457 of 104% (for 5a), 104.5% (for 5b) and 105% (for 5c). ), and a whitening power respectively of 21% (for 5a), 21% (for 5b) and 22% (for 5c).

EXEMPLE 6EXAMPLE 6

Cet exemple 6 en liaison avec le tableau 6 illustre l'invention utilisant comme feuille de base une feuille plastique.This example 6 in conjunction with Table 6 illustrates the invention using as a base sheet a plastic sheet.

On applique la composition de couchage de l'essai 4o (9 % de substance support PVA en poids sec par rapport aux pigments secs et 1,5 % en poids sec par rapport aux pigments secs de l'agent blanchissant fluorescent A (dérivé stilbènique disulfoné)) avec un poids de couche de 23 g/m2 en sec par face déposée sur une feuille plastique (à base d'un film de polyoléfine extrudé revêtu d'une précouche pigmentée) de 150 g/m2 commercialisée par la société ARJOBEX Ltd sous la marque POLYART®, ayant un pouvoir de fluorescence de 8.The coating composition of Test 4o (9% of carrier substance PVA in dry weight relative to dry pigments and 1.5% in dry weight relative to to the dry pigments of the fluorescent whitening agent A (disulfonated stilbene derivative)) with a coating weight of 23 g / m 2 dry per side deposited on a plastic sheet (based on an extruded polyolefin film coated with a pigmented precursor) of 150 g / m 2 marketed by the company ARJOBEX Ltd under the trademark POLYART®, having a fluorescence power of 8.

Le tableau 6 montre qu'on obtient une feuille avec un haut pouvoir de fluorescence. Tableau 6 Essai 6 Pouvoir de fluorescence de la feuille couchée 68 Δa* de l'essai 0,6 Table 6 shows that a sheet with a high fluorescence power is obtained. Table 6 Trial 6 Fluorescence power of the reclining leaf 68 Δa * of the test 0.6

Claims (15)

  1. A coated white sheet, comprising at least one base sheet and a printable and white surface coat having a pigmented composition which comprises:
    • at least some white coating pigments and at least one coating binder;
    • at least one fluorescence whitening agent; and
    • at least one support substance for said whitening agent,
    characterized in that the pigmented composition comprises a total amount of whitening agent of more than 1% dry weight with respect to the dry weight of said pigments, and a total amount of support substance of more than 2% dry weight with respect to the dry weight of said pigments, and in that the sheet has a fluorescence intensity of more than 55, measured in accordance with international standard ISO 11475: 2004, by the difference between the value for the CIE whiteness under D65 illuminant and the value for this same CIE whiteness after interposing a filter that eliminates wavelengths shorter than 420 nm, and is offset-printable with no mottling.
  2. A coated sheet according to claim 1, characterized in that it comprises at least one sub-coat comprising pigments and at least one binder, disposed below said surface coat.
  3. A coated sheet according to any one of the preceding claims, characterized in that the total quantity of dry weight of said fluorescent whitening agent in said surface coat is lower than or equal to 4% with respect to the dry weight of said coating pigments.
  4. A coated sheet according to any one of the preceding claims, characterized in that the total quantity of dry weight of said support substance in said surface coat is 10% or less with respect to the dry weight of said coating pigments.
  5. A coated sheet according to any one of the preceding claims, characterized in that the coating pigments of said surface coat are selected from calcium carbonates, kaolins, tales, titanium dioxide and plastic coating pigments.
  6. A coated sheet according to any one of the preceding claims, characterized in that said fluorescent whitening agent of said surface coat is selected, alone or as a mixture, from stilbene disulphonic acid derivatives containing a total of 2, 4 or 6 sulphonic groups.
  7. A coated sheet according to any one of the preceding claims, characterized in that said support substance is selected, alone or as a mixture, from polyvinyl alcohols, carboxymethylcellulose, polyvinylpyrrolidone and polymers based on N-vinylformamide.
  8. A coated sheet according to the preceding claim, characterized in that the polyvinyl alcohols have a high degree of hydrolysis, in particular more than 98%.
  9. A coated sheet according to one of the preceding claims, characterized in that the weight of said surface coat is at least 5 g/m2 dry weight per face, preferably at least 10 g/m2, more particularly comprised between 15 and 30 g/m2.
  10. A coated sheet according to one of the preceding claims, characterized in that said surface coat comprises a coating binder selected from acrylic polymers, polymers (styrene-butadiene) and mixtures thereof.
  11. A coated sheet according to one of the preceding claims, characterized in that said fluorescence intensity of said coated sheet is more than 60.
  12. A coated sheet according to one of the preceding claims, characterized in that said base sheet, if appropriate coated with sub-coat(s), has fluorescence intensity comprised between 0 and 20.
  13. A process for producing the coated sheet defined in one of claims 1 to 12, characterized in that said surface coat is formed by depositing its said pigmented composition in an aqueous medium by curtain coating onto said base sheet, if appropriate coated with sub-coats.
  14. A process according to the preceding claim, characterized in that the pigmented composition of said surface coat is deposited by curtain coating simultaneously with a pigmented sub-coat.
  15. A process according to claim 13 or claim 14, characterized in that the base sheet is a paper.
EP20080762016 2007-01-31 2008-01-31 Offset-printable coated white paper having a high fluorescence intensity and method for producing same Active EP2118366B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0700676A FR2911884B1 (en) 2007-01-31 2007-01-31 OFFSET-PRINTING WHITE SHEET WHICH HAS A HIGH FLUORESCENCE POWER AND METHOD FOR MANUFACTURING THE SAME
PCT/FR2008/050156 WO2008107617A2 (en) 2007-01-31 2008-01-31 Offset-printable coated white paper having a high fluorescence intensity and method for producing same

Publications (2)

Publication Number Publication Date
EP2118366A2 EP2118366A2 (en) 2009-11-18
EP2118366B1 true EP2118366B1 (en) 2010-12-01

Family

ID=38515698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20080762016 Active EP2118366B1 (en) 2007-01-31 2008-01-31 Offset-printable coated white paper having a high fluorescence intensity and method for producing same

Country Status (12)

Country Link
US (1) US8808842B2 (en)
EP (1) EP2118366B1 (en)
CN (1) CN101646823B (en)
AT (1) ATE490370T1 (en)
BR (1) BRPI0806830B1 (en)
CA (1) CA2677013C (en)
DE (1) DE602008003759D1 (en)
ES (1) ES2353072T3 (en)
FR (1) FR2911884B1 (en)
PT (1) PT2118366E (en)
WO (1) WO2008107617A2 (en)
ZA (1) ZA200904909B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7878978B2 (en) 2004-03-18 2011-02-01 University Of Pittsburgh- Of The Commonwealth System Of Higher Education Use of relaxin to increase arterial compliance
US7572065B2 (en) 2007-01-24 2009-08-11 Adc Telecommunications, Inc. Hardened fiber optic connector
CN102154922B (en) * 2010-12-30 2012-09-05 中冶美利纸业股份有限公司 Preparation method of fluorescent colorful offset paper
US9243401B2 (en) * 2014-05-16 2016-01-26 Awi Licensing Company Acoustic ceiling board with improved aesthetics

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4423118A (en) * 1981-08-20 1983-12-27 The Dow Chemical Company Thickened paper coating composition
US6576155B1 (en) * 1998-11-10 2003-06-10 Biocrystal, Ltd. Fluorescent ink compositions comprising functionalized fluorescent nanocrystals
GB9917508D0 (en) * 1999-07-27 1999-09-29 Ciba Spec Chem Water Treat Ltd Coating colour
US6547929B2 (en) * 2000-04-12 2003-04-15 Rohm And Haas Company Paper having improved print quality and method of making the same
DE10044131B4 (en) 2000-09-06 2005-12-01 Zanders Feinpapiere Ag Device and method for separating cut edges of flat parts and for guiding circulating conveyor belts
DE10055592A1 (en) * 2000-11-09 2002-05-23 Basf Ag Paper coating composition, used for paper is used in printing, contains N-vinylformamide polymer or copolymer with water-soluble ionic monomer, e.g. (meth)acrylic acid or salt, as cobinder
DE10144131A1 (en) * 2001-09-07 2003-03-27 Basf Ag Pigment-free mixture for use in coloring applications or in detergents contains an optical brightener and a (co)polymer with N-vinylcarboxamide units or nitrogen-heterocyclic units, e.g. polyvinylformamide
WO2004035931A1 (en) * 2002-10-15 2004-04-29 Dow Global Technologies Inc. Process for making coated paper or paperboard
AU2003292605A1 (en) * 2002-12-25 2004-07-29 Jsr Corporation Copolymer latex for noncontact coating and composition comprising the same, and coated paper and method for production thereof
GB0421685D0 (en) * 2004-09-30 2004-11-03 Arjo Wiggins Fine Papers Ltd Multi-layer coating products and curtain coating process for same
ES2329699T3 (en) * 2004-10-27 2009-11-30 Basf Se COMPOSITIONS OF FLUORESCENT WHITENING AGENTS.

Also Published As

Publication number Publication date
US8808842B2 (en) 2014-08-19
PT2118366E (en) 2010-12-20
ES2353072T3 (en) 2011-02-25
ATE490370T1 (en) 2010-12-15
FR2911884B1 (en) 2010-02-26
CN101646823A (en) 2010-02-10
WO2008107617A2 (en) 2008-09-12
CA2677013C (en) 2015-11-24
BRPI0806830A2 (en) 2014-06-03
US20100035075A1 (en) 2010-02-11
WO2008107617A9 (en) 2009-11-12
FR2911884A1 (en) 2008-08-01
BRPI0806830B1 (en) 2018-10-30
DE602008003759D1 (en) 2011-01-13
WO2008107617A3 (en) 2008-10-30
ZA200904909B (en) 2011-03-30
CN101646823B (en) 2012-07-04
EP2118366A2 (en) 2009-11-18
CA2677013A1 (en) 2008-09-12

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