EP2414587B1 - Dünnes mattes bedruckbares papier und verfahren für seine herstellung - Google Patents

Dünnes mattes bedruckbares papier und verfahren für seine herstellung Download PDF

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Publication number
EP2414587B1
EP2414587B1 EP10713484.3A EP10713484A EP2414587B1 EP 2414587 B1 EP2414587 B1 EP 2414587B1 EP 10713484 A EP10713484 A EP 10713484A EP 2414587 B1 EP2414587 B1 EP 2414587B1
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EP
European Patent Office
Prior art keywords
paper
range
silica
fine
paper according
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Not-in-force
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EP10713484.3A
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English (en)
French (fr)
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EP2414587B8 (de
EP2414587A1 (de
Inventor
Jean-Marie Baumlin
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Arjo Wiggins Fine Papers Ltd
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Arjo Wiggins Fine Papers Ltd
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Publication of EP2414587B8 publication Critical patent/EP2414587B8/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H21/00—Non-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
    • D21H21/14—Non-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
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H21/00—Non-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
    • D21H21/50—Non-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 form
    • D21H21/52—Additives of definite length or shape
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate

Definitions

  • the present invention relates to a fine matte writing and / or printable paper, in particular by offset printing, also called graphic paper, and to drying time of the writing and / or short printing inks, as well as its method of printing. preparation.
  • This fine paper can be used in many fields such as art publishing, writing, packaging, etc.
  • printer or printing There are several types of printer or printing including desk top inkjet, continuous inkjet, black-white offset (for example for newspaper printing), offset 4 color (four-color), digital offset, thermal offset, electrophotography (photocopier, laser printer), gravure printing, screen printing, and sublimation.
  • inks used for printing a paper depend on the type of printing.
  • Inks for inkjet printing include volatile solvents or water as a vehicle, while inks for offset printing use vegetable oils or petroleum distillates as the vehicle.
  • a coated paper comprises a conventional paper on which is deposited a layer comprising a binder and pigments. The fibers of the paper are then masked by the layer so that they are not more visible.
  • the paper serves only as a support for the layer that is designed to give the coated paper a very good print quality. The coated paper of the coated paper is therefore not visible in the final product and may be of relatively low quality.
  • a coated paper has a low value hand (generally less than 1.04 cm 3 / g, and the pulp used for its manufacture comprises cellulosic fibers of more or less good quality, a binder, and a relatively large quantity of fillers (generally greater than 15% by dry weight relative to the total dry weight of the paper).
  • a coated paper is generally smooth and is usually declined according to different levels of gloss, the glossiest coated papers being obtained by calendering.
  • a coated paper typically has a Bekk smoothness between 100 and 3000s, and a degree of gloss of between 11 and 80% approximately (these measurements being carried out at 75 ° according to the Tappi®T480 standard).
  • the layer is generally deposited on the paper at a rate of 18 to 35 g / m 2 per side and comprises inexpensive pigments such as calcium carbonates.
  • the layer is usually deposited on the paper by a smoothing coating technique such as the blade, which gives the coated paper a dish that masks the imperfections of the paper such as the appearance and roughness provided by the fibrous mat.
  • the production of a coated paper is made at low cost with machines of several meters in width ranging from sheet speeds to winding typically greater than 1000m / min.
  • the paper first receives a primer which is a first generally pigmented coating layer which is deposited in line at a rate of a few g / m 2 , receives the aforementioned pigmented layer defining the printability of the final product, and is calendered into end of line.
  • the pigments used therefore generally have a relatively small particle size (of the order of one micron) and their quantity is on the contrary relatively large in the layer.
  • a fine paper is a precious or quality paper which differs from a conventional paper or support used for the preparation of a coated paper, in particular by its hand, the composition of the paper pulp which is used for its manufacture, and its manufacturing cost which is higher. Fine paper is generally "marked” or “textured” naturally because of the manufacturing process employed and / or by a treatment applied to it, such as graining.
  • a fine paper has a hand generally greater than or equal to 1.10 cm 3 / g, and the paper pulp which is used for its manufacture comprises good quality cellulosic fibers, a binder, and a low proportion of fillers and / or adjuvants, such as starch.
  • a thin paper is considered as matt when its degree of gloss is of the order of 4-8%, and as gloss when its degree of gloss is of the order of 10-20% (these measurements being carried out at 75 ° according to the Tappi®T480 standard).
  • a glossy fine paper has a degree of gloss equivalent to that of a matte coated paper, which is why a thin paper generally appears duller than a coated paper.
  • a thin paper An important characteristic of a thin paper is its printability, and in particular the drying time of the inks used for its printing.
  • another thin paper when stacked on top of one another, or that same thin paper when it is rolled up on itself.
  • Fine papers used in 4-color offset printing are mostly untreated.
  • the inks are deposited directly on the fibers which are only coated with usual adjuvants.
  • the paper has no pigments on the surface and the fibers of the paper are noticeable and stand out clearly after printing.
  • the visible textured appearance of the fine paper gives a relief to the printed surface and results in a final impression after printing of the very aesthetic fine paper, which is appreciated by the users.
  • Another significant difference between a thin paper and a coated paper is that when a coated paper has a certain surface roughness, it is due to the layer deposited on the paper, while the surface roughness of a paper end is mainly due to its own texture.
  • a thin paper is indeed in general textured or marked, its texture may be natural and / or forced, that is to say in this case obtained by a graining process or marking or a similar process.
  • the graining of a thin paper can be carried out during the manufacture of the paper (for example by means of, for example, an adequate drip cloth of the paper pulp or embossing or marking rolls) or after it.
  • a grained fine paper comprises recessed and / or raised patterns on at least one of its faces, giving for example to the final product after printing textures such as curved lines or geometric figures.
  • a coated paper has a smooth surface which does not show the fibrous mat or a marking of the support by an element of the manufacturing process.
  • the fine paper can be laid and include shepherds made for example by means of a watermarking roll.
  • the fine papers of the current art suffer from a relatively low print quality, in particular because the drying time of the inks used is very long.
  • the fibers of the fine paper do not fix enough printing inks and therefore do not allow the inks to dry quickly.
  • the dishes are not uniform because they depend on the fibrous mat of fine paper which, by its very structure, is not uniform.
  • a treatment layer comprising pigments and a binder is then deposited on one side of the thin paper to improve its printability.
  • the purpose of the present invention is in particular to improve the printability of a thin paper, in particular by offset printing, while preserving its texture, and by reinforcing its mattness so that this fine paper has a lower degree of gloss. about 4% before printing, or less than about 7% after printing.
  • the degree of gloss of a printed fine paper is in fact generally greater than the degree of gloss of the same paper before printing.
  • the invention aims in particular to reduce the drying time of the inks (deposited for example by an offset process) which is about 3 hours for a thin paper not treated in the current technique . It is also intended to improve or control other fine paper printing characteristics, such as mottle, ink density, contrast and dusting.
  • Mottling is the name given to the lack of uniformity of an impression, and is evaluated with the eye or with the aid of a camera by observing a printing with 100% of a flat black and a blue flat.
  • Dusting is the name given to the appearance of a powder at the blanket during offset printing, this defect being linked to poor adhesion of the treatment layer to the paper. If the dusting is too important, the printer has to stop the machine to clean it before resuming printing, which is time consuming and expensive.
  • a thin matte writing and / or printable paper in particular by offset printing, this paper having a hand greater than or equal to 1.10 cm 3 / g and comprising on at least one of its faces a layer comprising pigments and a binder, characterized in that the pigments comprise silica, the average particle diameter of which is between 3 and 20 ⁇ m, and the amount deposited per unit area of the layer is greater than 0.5 g / m 2 and less than 1.5 g / m 2 , said paper having on said face a degree of gloss before printing less than or equal to 4% when measured at 75 ° according to the Tappi®T480 standard.
  • the fine paper thus treated has a drying time of a printing ink of less than 20 minutes, preferably less than 15 minutes.
  • the fine paper according to the invention has a hand greater than or equal to 1.10 cm 3 / g, preferably greater than 1.2 cm 3 / g, and for example greater than 1.25 cm 3 / g. It has a thickness of between 0.1 and 0.5 mm for example, and preferably between 0.15 and 0.35 mm, and / or a grammage of between 100 and 300 g / m 2 , and preferably between 120 and 240 g / m 2 .
  • the hand of a thin paper is obtained by the ratio of its thickness on its grammage.
  • the fine paper according to the invention is matte or even ultra matte because it has a very low degree of gloss, less than or equal to 4% before printing, whereas the fine papers of the prior art generally have at best a degree of gloss of about 4%.
  • the degree of gloss of the fine paper according to the invention may be between 2 and 4% and preferably between 2 and 3%, which corresponds to a degree of gloss of the fine paper after printing of between 3 and 7%, and preferably between 3 and 5%.
  • the degree of gloss of the fine paper after printing is measured at 75 ° according to the standard Tappi®T480, the printing inks used being 100% black ink or four colors at 400% (yellow, red, blue and black at 100% each).
  • This low degree of gloss is obtained by the deposition of a treatment layer on a thin paper, the treatment layer comprising silica pigments whose particle size is between 3 and 20 ⁇ m and whose deposited amount is greater than 0. , 5 g / m 2 and less than 1.5 g / m 2 , silica is used for its matifying power so as to reduce the gloss of the fine paper before and after printing, the matifying power of the silica particles being due to their size and / or their alveolar or porous structure diffusing light.
  • the invention defined above with reference to the amount of silica deposited per unit area of the treatment layer may be, alternatively or in combination, defined by reference to the amount of silica contained in the layer determined by dry weight relative to to the total dry weight of the layer.
  • the treatment layer comprises silica pigments whose particle size is between 3 and 20 ⁇ m and whose quantity is greater than 6% and less than 15% (in particular less than 10%) by dry weight relative to total dry weight of the layer.
  • the size of the silica particles is here relatively large, particularly with respect to the pigments used, which are of the order of one micron.
  • the silica particles may have an average diameter greater than 6 .mu.m, and for example less than 15 or 20 .mu.m. These particles have a mean diameter of between 3 and 20 ⁇ m, preferably between 5 and 18 ⁇ m, more preferably between 7 and 15 ⁇ m, and for example of the order of 8-10 ⁇ m.
  • the silica used is, for example, a porous amorphous synthetic silica, such as that marketed by Grace under the trademark Syloid ED5®.
  • the amount of silica in the layer is relatively small but is however sufficient to improve the performance of the fine paper during a printing, especially offset printing.
  • the invention can significantly reduce the drying time of printing inks, this time being less than 20min, and can be less than 15min or even 10min for fine papers treated according to the invention. This is due in particular to the porosity of the silica particles, these particles being capable of absorbing the fatty compounds which serve as a vehicle in the printing inks. Furthermore, because the size of the silica particles is relatively large, these particles help to avoid the mixing of the pigmented layers containing the inks when they are brought into contact with each other during printing. The silica particles then serve as spacers, which reduces the drying time of the inks. In a particular embodiment of the invention, the average diameter of the silica particles is greater than or equal to the thickness of the treatment layer to enhance this property of spacers.
  • silica pigments being relatively expensive, the presence of these pigments in small amounts in the treatment layer generates a small extra cost of fine paper manufacture.
  • the layer deposited on the fine paper may comprise other pigments chosen for example from calcium carbonates, kaolin, titanium dioxide, talc, and mixtures thereof.
  • the calcium carbonates are preferably the majority pigments in the treatment layer.
  • the amount of calcium carbonates in the layer may be between 60 and 90%, and preferably between 70 and 85%, by dry weight relative to the total dry weight of the layer.
  • the calcium carbonates used may for example be those marketed by Imerys under the trade names Carbital 75® and Carbital 95®. These calcium carbonates are mixtures of calcium carbonates, Carbital 75® comprising 75% calcium carbonates with a particle size of less than 2 ⁇ m and Carbital 95® comprising 95% calcium carbonates with particle sizes below 2 .mu.m.
  • the treatment layer is free of aluminum oxide or aluminum hydroxide.
  • the binder of the treatment layer may be chosen from polyvinyl alcohols (PVA), styrene-butadiene or styrene-acrylic copolymers (used in particular in the form of latex), and mixtures thereof.
  • the layer may comprise an amount of PVA and / or latex of between 7 and 13%, preferably between 8 and 12%, and for example of the order of 11-12% by dry weight relative to the total dry weight. of the layer.
  • the treatment layer may further comprise a rheology modifier such as a thickener, a crosslinking agent and / or a surfactant.
  • the layer may comprise a quantity of crosslinking agent of between 0.2 and 0.6%, preferably between 0.3 and 0.5%, and for example of the order of 0.4%, by dry weight relative to total dry weight of the layer. It may comprise an amount of surfactant of between 0.1 and 0.5%, preferably between 0.2 and 0.4%, and for example of the order of 0.3%, by dry weight relative to the weight. total dry of the layer. It may comprise a quantity of thickener of between 0.5 and 1%, and preferably between 0.6 and 0.8% by dry weight relative to the total dry weight of the layer. This thickener may be carboxyl methyl cellulose.
  • the weight of the treatment layer on said face may be between 3 and 18 g / m 2 , preferably between 7 and 13 g / m 2 , and is for example of the order of 10 g / m 2 .
  • the treatment layer may have a thickness of between 2 and 10 ⁇ m, and for example of the order of approximately 5 ⁇ m.
  • the amount of silica in the layer is greater than or equal to 6%, especially 7%, in particular between 6% and 15% or between 6% and 10%, or may be between 7 and 9%, preferably between 7 and 9%. , 5 and 8.5%, and is for example of the order of 8%, by dry weight relative to the total dry weight of the layer.
  • the weight of the silica on said face is between 0.5 and 1.5 g / m 2 , and is preferably between 0.5 and 1.35 g / m 2 ,
  • the fine paper according to the invention is preferably formed of cellulose fibers, a binder, and fillers the amount of which is less than 22%, and preferably less than 15% by dry weight relative to the total dry weight. paper. It can also be textured naturally and / or forced by a method of the aforementioned type, and include patterns in relief and / or recessed, the treatment layer does not change or little texture on said face. These patterns generally have dimensions of at least several tens of microns.
  • the paper according to the invention may have, before its treatment, a Bendtsen roughness of between 100 and 1500 ml / min, and preferably between 200 and 1400 ml / min, and / or a Bendtsen porosity of between 400 and 700 ml / min, and of preferably between 450 and 600ml / min, and / or a Bekk smoothness of between 1 and 30s, and preferably between 2 and 25s.
  • the present invention also relates to a method for preparing a thin matte writing and / or printable paper as described above, characterized in that it comprises a step of depositing the layer defined in the present application on the minus one of the faces of the thin paper by a non-contact type coating process, such as the curtain, the gravure roll or the air knife.
  • a non-contact type coating process such as the curtain, the gravure roll or the air knife.
  • the curtain, gravure roll and air knife coating techniques do not smooth the thin paper but simply deposit the paper. layer on thin paper, this layer following the texture of fine paper.
  • the layer deposited by these techniques has a more uniform thickness and the outer surface of the layer is less flat and therefore more pronounced, which contributes to the dullness of the final product and the final rendering after printing.
  • the fine papers used are for the most part (examples 1 to 5 and 7 to 10) of the fine papers marketed by the applicant under the Conqueror Velin® and Rives tradition® brands. These two fine papers are textured, the first naturally and the second naturally and forcibly.
  • Rives tradition® fine paper has a weight of 240g / m 2 , a Bendtsen roughness of 1370ml / min, a porosity of 460ml / min and a Bekk smoothness of 2s.
  • Bendtsen porosity or Bendtsen air permeability is a measure of the amount of air passing through a sheet of paper under given conditions, the measurement being expressed in ml / min. The more open, ie porous, the paper, the higher the value of the Bendtsen porosity.
  • Bekk smoothness is the measure of the time required for a given volume of air to flow between the paper and a glass surface in contact with the paper (according to ISO 5627). The rougher the paper, the more air passes through the hollows on the surface of the paper (which are related to roughness) and the shorter the air passage time. The smoother the paper, the longer it takes.
  • Conqueror Velin® fine paper has a grammage of 120g / m 2 , a Bendtsen roughness of 200ml / min, a porosity of 580ml / min and a Bekk smoothness of 21s.
  • Conqueror Velin® fine paper is half as thick as Rives tradition® fine paper and has a higher porosity than Rives tradition® fine paper.
  • Conqueror Velin® fine paper has a lower roughness and greater smoothness than Rives tradition® fine paper, which means that Conqueror Velin® fine paper is less textured than Rives tradition® fine paper.
  • Example 6 a textured fine paper having a basis weight of 115 g / m is used.
  • Examples 1 and 2 relate to fine papers, Rives tradition® for the first and Conqueror Velin® for the second, which are untreated, that is to say which are not covered with a treatment layer.
  • the other examples (3 to 12) relate to treated fine papers, that is to say having a treatment layer based on pigments and a binder, on at least one of their faces.
  • the treatment layer comprises as pigments only Kaolin 60% of which has a particle size of less than 2 .mu.m. This treatment layer is therefore devoid of silica.
  • the binder of the layer is acrylic styrene, and the layer further comprises a synthetic thickener.
  • the treatment layer is deposited by the technique of the air knife on the thin paper at a rate of 8 g / m 2 per face.
  • the fine papers of Examples 4 to 12 are all covered with a silica-containing treatment layer which is that marketed by Grace under the trademark Syloid ED5®. These are particles of porous amorphous synthetic silica having a size of between 8.4 and 10.2 ⁇ m and a porosity of 1.8 ml / g.
  • the treatment layers of Examples 4 to 12 all include calcium carbonates, which are the majority pigments in the layer, a binder, a crosslinking agent, and a thickener for Examples 4-5 and 7-12.
  • Example 6 further comprises a surfactant.
  • Calcium carbonates are mixtures of calcium carbonates of two types, the first being calcium carbonates marketed by Imerys under the trademark Carbital 75® and the second being calcium carbonates marketed by the same company under the trademark Carbital 95®. These calcium carbonates are mixed in specific proportions so as to obtain mixtures of calcium carbonates, 80% of which have a size of less than 2 ⁇ m in the case of Examples 4 to 8 and 10, and 90% have a size of less than 2 ⁇ m in the case of example 9.
  • the binder is in Examples 4 to 10 a mixture of styrene-butadiene or acrylic styrene latex and polyvinyl alcohol.
  • the crosslinking agent is an aqueous solution of ammonium zirconium carbonate.
  • the thickener used in Examples 4 to 5 and 7 to 12 is carboxyl methyl cellulose.
  • the surfactant of Example 6 is a nonionic surfactant of the Gemini® type.
  • the treatment layers are deposited on the fine papers at a rate of 8 to 12.5 g / m 2 per side, in Examples 4 to 12, the layers of Examples 4-5 and 7-10 being deposited by air knife and the layer of Example 6 being deposited in the curtain.
  • the amount of silica is less than 6% by dry weight relative to the total dry weight of the layer, that is to say with respect to the cumulative dry weight of all pigments (silica and calcium carbonates) of the layer as well as dry residues of the binder and crosslinking agent, and optionally thickener and surfactant.
  • the amount of silica is greater than 6% by dry weight relative to the total dry weight of the layer.
  • the first test consists in measuring the degree of gloss of each fine paper (treated or untreated) before printing. This degree of gloss is measured at 75 ° according to the Tappi®T480 standard, which is briefly described in the following.
  • the gloss level of a thin paper is measured using a reflectometer that records the amount of light reflected from the surface of the fine paper, the illumination and reflection angles being 75 ° to a normal on this surface.
  • the device (BYK Gardner D-4553) is previously calibrated using a black glass plate.
  • the second test consists in measuring the drying time of the printing inks on each thin paper, after printing this paper by an offset process.
  • this drying time is determined by contacting a 400% printed side (that is to say with 4 colors at 100% each: yellow, red, blue and black) of a thin paper with a non-printed side of another thin paper, using an Erichsen press.
  • the contact area between thin papers is determined by a 25mm diameter disc of the press, which is applied to fine paper with a force of 250N for 1 sec.
  • This test also called "tacky time" consists of measuring the time from which there is no ink transfer from one side to the other of the fine papers.
  • the third and final test is to measure the degree of gloss of each fine paper after printing. This degree of gloss is also measured at 75 ° according to the Tappi®T480 standard. This measurement is made on one side of the thin paper that is uniformly printed at 100% with black ink.
  • the fine papers treated with a layer comprising more than 6% of silica and / or comprising an amount of silica deposited per unit area of the layer greater than 0.4, in particular greater than 0.5 g / m 2 have a degree of gloss of between 2, 6 and 3.6%, which is very low and is therefore particularly interesting.
  • the untreated fine papers (Examples 1 and 2) have a gloss level of 4.6 and 6.8%, respectively.
  • the fine paper treated with a layer containing no silica has a degree of gloss of 7.5%
  • the fine papers treated with a layer comprising a quantity of silica substantially less than 6% or an amount of silica. deposited per unit area of the layer less than 0.4g / m 2 (Examples 4 and 6) have an even higher degree of gloss of 4.5 and 3.9%, respectively.
  • the amount of silica in the layer is 5.2% and the amount of silica deposited per unit area of the layer is 0.47 g / m 2 and makes it possible to give the fine paper a low gloss. 2.8%.
  • the drying time of the printing inks on this paper is still too long (27min), as will be seen in what follows.
  • the gloss of the fine papers after printing is between 3.6 and 6.6% for the fine papers according to the invention of Examples 7 to 12, and between 4.6 and 15.8% for the treated and untreated fine papers. other examples (1 to 6).
  • the drying time of the inks deposited by offset printing on the untreated fine papers is very long because it is greater than 3 hours.
  • the drying times of the printing inks on the fine papers of Examples 3 to 6 are between 27 and 80 minutes and are therefore still too long.
  • the drying time of the inks on the fine papers according to the invention (Examples 7 to 12) are between 4 and 8 minutes, which is significantly less than 10 minutes and is therefore considered as a very short drying time for inks deposited by an offset process.
  • curtain coating has the advantage of allowing to deposit a treatment layer at a higher speed, up to 1000m / min or even beyond.
  • this technique may require the respect of certain coating conditions such as the addition of a surfactant in the treatment layer and the achievement of a minimum flow rate at the coating head in order to maintain the stable fluid curtain.
  • the figure 1 is a graph representing the evolution of the degree of gloss of the treated fine papers (on the ordinate, with a scale of 0 to 20%, measured at 75 ° according to the Tappi®T480 standard) as a function of the quantity of silica deposited per unit of surface of the treatment layer (on the abscissa, with a scale from 0 to 1.5g / m 2 ).
  • the figure 2 is a graph representing the evolution of the drying time of the printing inks of treated fine papers (ordinate, with a scale of 0 to 90 min, measured according to the above method) as a function of the amount of silica deposited per unit area of the treatment layer (on the abscissa, with a scale ranging from 0 to 1.5 g / m 2 ).
  • the fine papers tested to obtain these figures are Rives tradition® and Conqueror Velin® papers which are each treated on at least one side with a treatment layer including silica pigments whose particle size is greater than or equal to at 3 ⁇ m. These figures are examples in the same way as the above and are not intended to limit it.
  • the curves are Conqueror Velin® thin papers with low textures, ie fine papers that are naturally textured and have not been subjected to marking, or Rives tradition® textured fine papers, ie fine papers that have a natural, forced texture (ie, are marked by an appropriate process).
  • the figure 1 shows that, beyond 0.3 g / m 2 of silica deposited, the gloss of the fine paper remains less than 4% before printing. This is true for textured fine papers (Rives tradition®) as for thin textured papers (Conqueror Velin®). This means that, beyond this threshold of 0.3 g / m 2 , the addition of silica changes the gloss of the fine paper favorably and up to about 1.5 g / m 2 . It is important to note that these gloss values correspond to degrees of gloss before printing fine papers, and for example around 2.5 to 3%.
  • the figure 1 shows therefore that a quantity of silica greater than 0.4 g / m 2 (and whose particle size is greater than or equal to 3 ⁇ m) in the treatment layer of the fine paper tested makes it possible to give this fine paper a degree of gloss very low (less than 6% in the case of a degree of gloss after printing).
  • the other printing characteristics are not modified by the addition of this amount of silica in the thin paper treatment layer.
  • the curve for Conqueror Velin® paper from the figure 2 shows that up to 1.5 g / m 2 of silica (whose particle size is greater than or equal to 3 ⁇ m), the greater the amount of silica deposited via the thin textured paper treatment layer is significant from 0.4g / m 2 plus the drying time of the printing inks decreases.
  • the drying time of the inks on the textured fine papers differs slightly from that of the fine textured papers.
  • the curve for Rives tradition® paper from the figure 2 shows that a deposited amount of less than 0.25 g / m 2 of silica pigments whose particle size is greater than or equal to 3 ⁇ m in the textured fine paper treatment layer has no significant influence on the reaction time. drying of the inks. This can be explained by the fact that the silica particles are distributed inhomogeneous in the hollows and bumps of the surface (irregular) of the textured fine paper, and that, when these particles are few, the drying time of the inks is not constant over this whole surface and can be longer in certain places.
  • the deposition of silica through this layer decreases the gloss of the fine paper. Beyond a threshold of approximately 0.4 g / m 2 , the greater the quantity of silica deposited, the longer the drying time of the inks decreases to a plateau which is less than 10 min, and is reached for an amount of silica deposited greater than or equal to 0.6 g / m 2 .
  • the thin paper of Example 5 is a textured paper which must therefore be compared with the curves for the Rives tradition® paper.
  • Figures 1 and 2 This fine paper is covered with a treatment layer such that the amount of silica deposited is 0.47 g / m 2 .
  • this amount of silica makes it possible to impart to the paper a degree of gloss after printing of less than 6%, that is to say a degree of gloss before printing of less than 3.5%, which corresponds substantially to the results of the Example 5 (paper gloss before printing 2.8% and after printing 4.6%).
  • the amount of silica deposited per unit area (0.47 g / m 2 ) while being in the range suitable for the invention does not, however, make it possible to decrease the drying time of the printing inks sufficiently, this time being 27min).
  • the figure 2 clearly shows that for a paper of this quality, a quantity of silica deposited per unit area of greater than or equal to 0.5 g / m 2 (and whose particle size is greater than or equal to 3 ⁇ m) is necessary for the time to drying printing inks on this paper is less than 20min.
  • the fine textured papers (Conqueror Velin® type) tested here which are coated on at least one side of a layer having an amount of silica per unit area greater than 0.4g / m 2 and whose particles is greater than or equal to 3 ⁇ m, have a degree of gloss after printing less than 7% (which corresponds substantially to a degree of gloss before printing less than 4%), and the drying time of the printing inks on these papers is less than 20min.
  • the fine textured papers (Rives tradition® type) tested here which are covered on at least one side of a layer having a quantity of silica deposited per unit area greater than 0.4g / m 2 and whose particle size is greater or equal to 3 ⁇ m, have a degree of gloss after printing less than 6% (which corresponds substantially to a degree of gloss before printing less than 3.5%).
  • the amount of silica deposited is greater than or equal to about 0.5g / m 2 .
  • the Figures 3 and 4 are images obtained by scanning electron microscopy (SEM) of the surface of the treated fine paper obtained in Example 7 above.
  • the microscope is equipped with a chemical surface analysis system (EDX) that can identify silica particles on the surface of thin paper. These particles appear in color under the microscope and have been marked here with circles for clarity. The particles are regularly distributed on the surface of the fine paper and are covered with smaller pigments of calcium carbonate, which is better visible in figure 4 .
  • EDX chemical surface analysis system
  • the dimensions (for example greater than 50 ⁇ m) of the patterns defined by the texture of the paper are generally greater than those (less than or equal to 20 ⁇ m) of the abovementioned bumps of the treatment layer, and therefore that the treatment layer does not modify the texture of the fine paper by little or no.
  • the uneven relief of the treatment layer contributes to the diffusion of light and thus the reduction of the gloss of the treated fine paper. It also helps reduce the drying time of printing inks by reducing the contact surface used during the measurement of this parameter.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Claims (15)

  1. Dünnes mattes Papier zum Beschreiben und/oder Bedrucken, insbesondere durch Offsetdruck, wobei dieses Papier ein spezifisches Volumen größer oder gleich 1,10 cm3/g aufweist und auf mindestens einer Seite eine Schicht trägt, die Pigmente und ein Bindemittel umfasst, dadurch gekennzeichnet, dass die Pigmente Siliciumoxid umfassen, wobei der mittlere Durchmesser der Partikel zwischen 3 und 20 µm beträgt und wobei die pro Flächeneinheit aufgetragene Menge der Schicht mehr als 0,5 g/m2 und weniger als 1,5 g/m2 beträgt, wobei das Papier auf der genannten Seite vor einem Bedrucken einen Glanzgrad kleiner oder gleich 4 % aufweist, gemessen nach der Norm von Tappi®T480 bei 75°.
  2. Papier nach Anspruch 1, dadurch gekennzeichnet, dass die Schicht weitere Pigmente umfasst, die ausgewählt sind aus Calciumcarbonaten, Kaolinen, Titandioxid, Talk und Mischungen davon.
  3. Papier nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Bindemittel ausgewählt ist aus Polyvinylalkoholen, Styrol-Butadien-Copolymeren, Styrol-Acrylat-Copolymeren und Mischungen davon.
  4. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Siliciumoxid ein poröses amorphes synthetisches Siliciumoxid ist.
  5. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Gewicht der Schicht auf der genannten Seite zwischen 3 und 18 g/m2, bevorzugt zwischen 7 und 13 g/m2, und beispielsweise in der Größenordnung von 10 g/m2 beträgt.
  6. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schicht eine Dicke zwischen 2 und 10 µm, und beispielsweise in der Größenordnung von ungefähr 5 µm aufweist.
  7. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schicht ein Verdickungsmittel, ein Vernetzungsmittel und/oder eine oberflächenaktive Substanz umfasst.
  8. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Siliciumoxidpartikel einen mittleren Durchmesser von mehr als 6 µm aufweisen.
  9. Papier nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Siliciumoxidpartikel einen mittleren Durchmesser zwischen 5 und 18 µm, bevorzugt zwischen 7 und 15 µm, und beispielsweise in der Größenordnung von 8 bis 10 µm aufweisen.
  10. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der mittlere Durchmesser der Siliciumoxidpartikel größer oder gleich der Dicke der Schicht auf der genannten Seite ist.
  11. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Menge an Siliciumoxid in der Schicht zwischen 6 und 15 Gewichts-%, insbesondere zwischen 7 und 9 Trockengewichts-%, bevorzugt zwischen 7,5 und 8,5 Trockengewichts-%, und beispielsweise in der Größenordnung von 8 Trockengewichts-%, bezogen auf das gesamte Trockengewicht der Schicht beträgt.
  12. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Gewicht des Siliciumoxids auf der genannten Seite zwischen 0,5 und 1,2 g/m2 beträgt.
  13. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es aus Cellulosefasern und Füllstoffen gebildet ist, deren Menge weniger als 22 Trockengewichts-%, und bevorzugt weniger als 15 Trockengewichts-%, bezogen auf das gesamte Trockengewicht des Papiers beträgt.
  14. Papier nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es eine Rauheit nach Bendtsen zwischen 100 und 1500 ml/min, und bevorzugt zwischen 200 und 1400 ml/min, und/oder eine Porosität nach Bendtsen zwischen 400 und 700 ml/min, und bevorzugt zwischen 450 und 600 ml/min, und/oder eine Glätte nach Bekk zwischen 1 und 30 s, und bevorzugt zwischen 2 und 25 s aufweist.
  15. Verfahren zur Herstellung eines dünnen matten Papiers zum Beschreiben und/oder Bedrucken nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es einen Schritt umfasst zum Auftragen einer Schicht auf mindestens eine Seite des dünnen Papiers durch ein kontaktloses Beschichtungsverfahren, wie durch Vorhangbeschichtung mit Helio-Druckzylinder oder durch Luftrakel.
EP10713484.3A 2009-04-01 2010-03-23 Dünnes mattes bedruckbares papier und verfahren für seine herstellung Not-in-force EP2414587B8 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0901598A FR2944034B1 (fr) 2009-04-01 2009-04-01 Papier fin mat imprimable et son procede de preparation
PCT/FR2010/000246 WO2010112688A1 (fr) 2009-04-01 2010-03-23 Papier fin mat imprimable et son procédé de préparation

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EP2414587A1 EP2414587A1 (de) 2012-02-08
EP2414587B1 true EP2414587B1 (de) 2014-04-02
EP2414587B8 EP2414587B8 (de) 2014-06-11

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JP (1) JP5615901B2 (de)
KR (1) KR20110134434A (de)
CN (1) CN102378841A (de)
BR (1) BRPI1014055A2 (de)
CA (1) CA2757155A1 (de)
FR (1) FR2944034B1 (de)
WO (1) WO2010112688A1 (de)

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DE102011076720A1 (de) * 2011-05-30 2012-12-06 Metso Paper, Inc. Verfahren zum herstellen eines gestrichenen produkts zum bedrucken
FR2979358B1 (fr) * 2011-08-31 2013-09-27 Arjowiggins Security Support d'information destine a l'impression sur presses a toner liquide.
FR2999617A1 (fr) * 2012-12-18 2014-06-20 Arjowiggins Security Support d'information destine a l'impression sur presses offset.
TWI677435B (zh) * 2018-10-19 2019-11-21 南亞塑膠工業股份有限公司 一種霧面合成紙

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JPH05269941A (ja) * 1992-01-27 1993-10-19 Mitsubishi Paper Mills Ltd 樹脂被覆紙
US5804293A (en) * 1995-12-08 1998-09-08 Ppg Industries, Inc. Coating composition for recording paper
JPH09268495A (ja) * 1996-03-29 1997-10-14 Oji Paper Co Ltd 非塗工紙風合いを有する艶消し塗工紙
US6391155B1 (en) * 1997-10-11 2002-05-21 Haindl Papier Gmbh Coated web printing paper suitable for cold-set offset printing
JP3788000B2 (ja) * 1997-12-22 2006-06-21 王子製紙株式会社 オフセット印刷用新聞用紙
JPH11286894A (ja) * 1998-03-31 1999-10-19 Nippon Paper Industries Co Ltd 新聞印刷用紙
JP4333026B2 (ja) * 2000-12-20 2009-09-16 日本製紙株式会社 オフセット印刷用艶消し塗工紙
EP1522629A1 (de) * 2003-10-08 2005-04-13 M-real Oyj Beschichtetes Papier als Druckstoff
JP2005232626A (ja) * 2004-02-20 2005-09-02 Daio Paper Corp マット調微塗工紙及びその製造方法
FR2872180A1 (fr) * 2004-06-24 2005-12-30 Arjowiggins Papiers Couches So Papier revetu d'une composition pigmentee comportant de la silice imprimable par offset
EP1809710A1 (de) * 2004-11-08 2007-07-25 Akzo Nobel N.V. Pigmentzusammensetzung in form einer wässrigen dispersion
EP1743976A1 (de) * 2005-07-13 2007-01-17 SAPPI Netherlands Services B.V. Beschichtetes Papier für Offsetdruck
US8003176B2 (en) * 2006-10-04 2011-08-23 3M Innovative Properties Company Ink receptive article
EP2053163A1 (de) * 2007-10-26 2009-04-29 SAPPI Netherlands Services B.V. Beschichtungsformulierung für Offsetpapier und damit beschichtetes Papier

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WO2010112688A1 (fr) 2010-10-07
EP2414587B8 (de) 2014-06-11
JP5615901B2 (ja) 2014-10-29
FR2944034B1 (fr) 2011-06-03
JP2012522905A (ja) 2012-09-27
CA2757155A1 (fr) 2010-10-07
BRPI1014055A2 (pt) 2019-09-24
KR20110134434A (ko) 2011-12-14
US20120076961A1 (en) 2012-03-29
CN102378841A (zh) 2012-03-14
EP2414587A1 (de) 2012-02-08
FR2944034A1 (fr) 2010-10-08

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