EP2038478B1 - Method for finishing paper and paper products - Google Patents
Method for finishing paper and paper products Download PDFInfo
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- EP2038478B1 EP2038478B1 EP07730254A EP07730254A EP2038478B1 EP 2038478 B1 EP2038478 B1 EP 2038478B1 EP 07730254 A EP07730254 A EP 07730254A EP 07730254 A EP07730254 A EP 07730254A EP 2038478 B1 EP2038478 B1 EP 2038478B1
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- EP
- European Patent Office
- Prior art keywords
- paper
- finishing agent
- process according
- finishing
- paper products
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
Definitions
- the invention relates to a process for finishing paper and paper products by treating the surface of paper and paper products with at least one finishing agent and the finished papers and paper products obtainable by the process.
- finishing agents such as hardeners, water repellents, hydrophilicizing agents and / or paper coating slips.
- the finishing agents are always applied over the entire surface of the top and / or bottom of the paper or paper products.
- Suitable reactive materials are, for example, thermally curable binders such as urea-formaldehyde adducts, one- or two-component systems based on epoxy resins, polyacrylates and polymethacrylates. Also in this process, the entire top or bottom of the paper is treated with at least one reactive material.
- the US 2004/013 1842 teaches a method of making tissue papers by printing a hydrophobic composition in places on the surface of a tissue sheet.
- the hydrophobic composition causes softness of the tissue paper with good absorption properties.
- US 3,667,422 discloses an apparatus for applying adhesive materials to a panel.
- the DE 3707480 teaches a paper towel, which is sprayed in places with an oily or greasy agent as a care product.
- an oily or greasy agent as a care product.
- the EP 333 417 describes a method for coating paper products by applying substrates to the surface of the paper products which improve the surface strength and thus the printability.
- the US 4968 534 relates to a method for impregnating paper products by means of a device which applies the impregnating agent in the form of a pattern.
- the invention has for its object to improve the properties of paper and paper products, in particular their stiffness, printability, laminability and biocidal activity against microorganisms to the effect that in comparison with known methods already achieved a sufficient effect with a smaller amount of finishing agents.
- the object is achieved according to the invention with a method for finishing paper and paper products by treating the surface of paper or paper products with at least one finishing agent, if at least one finishing agent in the form of a pattern is applied to the top and / or bottom of paper or paper products and one as a finishing agent at least one agent that increases the stiffness of paper.
- the finishing agent is preferably applied to the top and / or bottom of paper or paper products by means of a printing process applied. Such printing processes belong to the state of the art. They are commonly used to print on sized or coated papers or textiles with printing pastes other than paper finishing equipment.
- the finishing agent can z. B. after the screen printing, ink-jet printing, flexographic printing or offset printing process on the top and / or bottom of paper or paper products to be printed.
- the finishing agent is printed on the top of paper or paper products by the ink-jet printing process.
- the paper may be unsized or a bulk sized paper or paper product.
- Suitable engine sizes are, for example, alkyldiketenes, alkenylsuccinic anhydrides or rosin size.
- the invention also relates to papers and paper products which are each obtainable by the process according to the invention.
- These are essentially writing and printing papers, packaging papers, corrugated cardboard, wallpaper, cardboard, filters and laminates, for example, of a composite of cardboard or paper and at least one film of a thermoplastic material, for example polyethylene, polypropylene, polyamide, polyester or polycarbonate ,
- the finishing agent according to the invention for example, in the form of a grid, a rhombus, spiral, circular, sheet-like, strip-shaped or punctiform printed on the top and / or bottom of paper or paper products, the arrangement of the pattern in an orderly or random (stochastic) can.
- the finishing materials are always applied according to the pattern.
- the finishing agent is applied to the surface of paper that does not coat the entire surface with it is.
- the proportion of the total surface area printed with a finishing agent is 0.1 to 90, preferably 1 to 70%, and most is in the range of 10 to 50%.
- the printed paper or paper product is dried and optionally heated to a temperature at which the finishing agents crosslink, e.g. to temperatures in the range of 35 to 200 ° C.
- the effect achieved with the aid of the method according to the invention depends on a number of factors, in particular on the composition and amount of finishing agent, on the structure of the finishing agent printed on the paper and on the orientation of the paper, ie the stiffness of the paper depends on the orientation of the cellulose fibers from. It is different for a paper sheet in the machine direction than transverse to it.
- the finishing agent is in the form of a pattern and may be printed eg on the top and / or bottom of paper or paper products in the form of a grid, a rhombus, a polygon (eg hexagon, octagon), spiral, circular, sheet, strip or dot.
- the individual strips of a grid or rhombus can have different dimensions, for example a thickness of 0.1 to 100 mm, preferably 1 to 10 mm and a length of 0.1 to 100 mm, preferably 1 to 10 mm.
- the distance between the individual strips of a grid, ie the unprinted areas, may for example have a spacing of 0.1 to 100 mm, preferably 1 to 10 mm.
- the grid can be square, rectangular or rhombic. If you print the paper strip-shaped, so the strips can extend over the entire length or width of the paper.
- the paper can also be punctiform printed with a variety of points or area, which is to be understood by sheet-like that a larger area is provided with a finishing agent, for. B. an area with the dimensions 2 x 2 to 10 cm or 4 x 1 to 10 cm.
- circular areas printed on a paper may have a diameter of 1 mm to 10 cm.
- the method according to the invention can be integrated into the papermaking process.
- the paper products may be similarly printed during or after manufacture with at least one finishing agent.
- paper products are meant, for example, packaging papers, corrugated board, wallpaper, cardboard and laminates, for example, from a composite of cardboard or paper and at least one film of a thermoplastic material.
- cellulose fibers of all kinds both natural and recovered, in particular recycled paper fibers, which are mostly used in admixture with virgin fibers, can be used to make the papers and paper products.
- Fresh fibers or fresh fibers are to be understood as meaning cellulose fibers which have hitherto not yet been processed into a paper product or which have not yet been dried.
- Suitable pulps for the production of the pulps are all qualities customary for this purpose, for example wood pulp, bleached and unbleached pulp and pulps from all annual plants.
- Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).
- pulp for example, sulphate, sulphite and soda pulps come into consideration.
- unbleached pulp also referred to as unbleached kraft pulp
- Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf.
- the paper or paper products according to the invention are printed according to the pattern with a finishing agent.
- a finishing agent at least one agent is used which increases the stiffness of paper. These agents usually also increase the dry and / or wet strength of paper and paper products at the same time.
- Other finishing agents are conventional dry strength agents and / or wet strength agents for paper.
- the invention preferably uses a thermally curable binder from the group of urea-formaldehyde adducts, urea-glyoxal adducts, melamine-formaldehyde adducts, phenol-formaldehyde adducts, one- and two-component systems based on epoxy resins, polyurethanes or isocyanates, polyacrylates, polymethacrylates, styrene- (meth) acrylate copolymer dispersions and / or styrene-butadiene- (meth) acrylic acid copolymer dispersions.
- a thermally curable binder from the group of urea-formaldehyde adducts, urea-glyoxal adducts, melamine-formaldehyde adducts, phenol-formaldehyde adducts, one- and two-component systems based on epoxy
- the use of mixtures of at least two reactive materials of interest e.g. Mixtures of melamine / urea-formaldehyde condensates.
- the reactive materials may be present as an aqueous solution or as an aqueous dispersion. In this case, transitions between solution and dispersion are possible.
- dispersions for example, the average particle diameter of the polymer particles dispersed in water is below 1 ⁇ m, preferably below 500 nm and most in the range of 10 to 100 nm.
- Examples of (i) a reactive substance forming a polymer are urea-glyoxal adducts and derivatives thereof, eg, 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2 (hereinafter called "DMDHEU").
- DMDHEU 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2
- it can be used either alone or together with (ii) at least one C 1-5 -alcohol, a polyol or mixtures thereof.
- 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinon-2 together with an alcohol and / or a polyol as a finishing agent
- mDMDHEU correspondingly modified 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2 arise
- Such compounds are for example from the US-A 4,396,391 and the WO 98/29393 known.
- the compounds of group (ii) include C 1-5 -alcohols, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and n-pentanol, preferably methanol, and polyols, such as Ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, glycerol, trimethylolpropane and polyalkylene glycols such as polyethylene glycol, polypropylene glycol, block copolymers of ethylene glycol and propylene glycol. Preference is given to polyethylene glycols of the formula HO (CH 2 CH 2 O) n H where n is from 3 to 20 and diethylene glycol.
- DMDHEU modified 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2
- DMDHEU and the monohydric alcohol and / or the polyol are mixed, the monohydric alcohol and / or the polyol being in an amount of each 0.1 to 2.0 molar equivalents, based on DMDHEU, are used.
- the mixture of DMDHEU, monohydric alcohol and / or polyol is reacted, for example, at temperatures of 20 to 70 ° C and a pH of 1 to 2.5, wherein the pH after the reaction is adjusted to 4 to 8.
- urea-formaldehyde adducts and urea-glyoxal adducts and their derivatives are to be understood.
- the following compounds may be mentioned by way of example: dimethylolurea, bis (methoxymethyl) urea, tetramethylolacetylenediurea, methylolmethylurea and 1,3-dimethyl-4,5-dihydroxyimidazolidinone-2, 1,3-bis (hydroxymethyl) imidazolidinone-2 or mixtures thereof.
- These compounds of group (i) may also be used as finishing agents in the presence of (ii) at least one C 1-5 -alcohol, at least one polyol or mixtures thereof. Suitable alcohols and polyols have already been mentioned above. Preference is given to methanol, diethylene glycol or mixtures thereof.
- the aqueous solution of the finishing agent contains the reactive compounds of group (i) and the compounds of group (ii), for example, in one concentration from 1 to 70 wt .-%, preferably 10 to 60 wt .-% and in particular 20 to 60 wt .-%.
- the impregnating agent preferably contains 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2 (DMDHEU) as a compound of group (i).
- the finishing agent always contains a catalyst (iii) apart from (i) and optionally (ii).
- Suitable catalysts (iii) are, for example, metal salts from the group of metal halides, metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof.
- Specific examples of (iii) are magnesium chloride, magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminum chloride, aluminum sulfate, zinc nitrate and sodium tetrafluoroborate.
- the compounds mentioned can be used either alone or in admixture as a catalyst.
- catalysts (iii) are ammonium salts such as ammonium chloride, ammonium sulfate, ammonium oxalate, diammonium phosphate or mixtures thereof.
- organic and / or inorganic acids can be used as a catalyst. Examples of these are maleic acid, formic acid, acetic acid, propionic acid, citric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, boric acid or mixtures thereof.
- the compounds of group (iii) used are preferably magnesium chloride, zinc chloride, magnesium sulfate, aluminum sulfate or mixtures of these compounds. Particularly preferred is magnesium chloride.
- the catalyst (iii) is, for example, in a concentration of 0.1 to 10 wt .-%, preferably 0.2 to 8 wt .-%, particularly preferably 0.3 to 5 wt .-%, based on the components (i ) - (iii) of the reactive material.
- Low-formaldehyde should be understood in the present context that the reactive materials do not contain significant amounts of free formaldehyde and that no substantial amounts of formaldehyde are released during drying or curing of the cellulose fibers or paper products treated therewith. In general, such reactive materials contain ⁇ 100 ppm formaldehyde.
- Thermally curable binders other than the binders described in the above-mentioned references are all curable binders which are described, for example, for solidifying fibrous webs in the literature and / or which are used for this purpose in practice, such as thermosetting resins based on phenol and formaldehyde, the abovementioned melamine-formaldehyde and urea-formaldehyde resins, urea-glyoxal resins and in particular formaldehyde-free one and two-component systems based on epoxy resins or polyurethanes, polyacrylates, polymethacrylates, polyvinyl acetates, styrene-acrylate copolymer Dispersions, styrene-methacrylate copolymer dispersions, styrene-butadiene (meth) acrylic acid copolymer dispersions and mixtures of said dispersions with a mixture of a polycarboxylic acid and a polyhydr
- Such mixtures are aqueous solutions containing about 40 to 60% by weight of solids and / or dispersions of a copolymer of 80% by weight of acrylic acid and 20% by weight of maleic acid having a molecular weight M w of 15,000 to 900,000 ⁇ m Combination with triethanolamine or aqueous solutions of a copolymer of 55% by weight of acrylic acid and 45% by weight of maleic acid in combination with triethanolamine.
- These binders may optionally contain an esterification catalyst and / or a bound phosphorus-containing compound such as hypophosphorous acid as a reaction accelerator.
- Thermally curable, aqueous compositions containing at least one copolymer (a) and at least one alkanolamine or higher-functional ⁇ -hydroxyalkylamine and / or at least one polyhydric alcohol may optionally additionally contain at least one surfactant.
- Polycarboxylic acids, polyhydric alcohols, alkanolamines and polyhydric amines are preferably used in amounts such that the number of acid function of the total number of alcoholic hydroxyl and amine functions is equivalent, see. EP-A 0 445 578 .
- crosslinkable materials consisting of an aqueous solution of a polycarboxylic acid (homo- or copolymer) preferably having a molecular weight M w of 10,000 or lower and a polyol such as triethanolamine and in which the ratio of equivalents of hydroxyl groups to equivalents of carboxyl groups in the Range from 0.4: 1 to 1.0: 1, cf. EP-A 0 990 727 ,
- reactive materials are used with particular advantage as finishing agents, which are marketed under the trademark Acrodur® by BASF Aktiengesellschaft.
- An example of this is an aqueous styrene-acrylate polymer dispersion modified with a polycarboxylic acid and a polyhydric alcohol crosslinking component. It already cross-links at a temperature of 130 ° C. However, in order to achieve high production rates, the crosslinking is preferably carried out at temperatures of 180 to 200 ° C.
- Another formaldehyde-free binder is commercially available, for example, as a colorless to slightly yellowish, clear, aqueous solution of a modified polycarboxylic acid with a polyhydric alcohol as crosslinking component. It crosslinks e.g. at drying temperatures of about 160 to 180 ° C.
- compositions containing these reactive agents may optionally contain other formaldehyde-free polymers, for example polyacrylates sold under the trademark Acronal® by BASF Aktiengesellschaft.
- the aqueous solutions and / or dispersions of a reactive material used for printing contain the reactive material, for example, in an amount of 1 to 70 wt .-%, preferably 10 to 60 wt .-% and usually 30 to 50 wt .-%.
- the process according to the invention has the advantage that significantly lower amounts of finishing agent are required with approximately comparable properties of the papers and paper products, and thus less expensive manufacture of papers and paper products.
- An A4 sheet was printed according to the invention with a finishing agent, dried and air-conditioned for 24 hours at 25 ° C and 60% humidity. The measurements were made at room temperature under the prevailing air pressure. From the center of the DIN A4 sheet printed with a finishing agent according to the invention, a test piece having the dimensions 100 ⁇ 100 mm was cut. The test piece was then fixed between two blocks of wood so that 50% of the test piece protruded. The part of the test piece protruding from the blocks was then loaded with weights of 1 to 50 g by placing the weights in the middle of the test piece at a distance of 10 mm from the outer edge. As soon as the end of the test piece protruding from the block reached 25 mm or the weight fell off the paper, the required load in g was measured as a measure of the stiffness.
- A4 size sheets were each printed with the amounts of finishing agents shown in the following table using the ink jet printing method with the patterns also shown in the table.
- the sheets printed with finishing agents 1 to 3 were each stored at 140 ° C for 15 minutes to crosslink the polymers. Thereafter, the stiffness of the paper was determined by the method described above. The results are given in the table.
- line (MD) means lines printed on the A4 sheet, which are in the machine direction of the sheet in papermaking, and "line (CD)” lines which are transverse to the machine direction.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Ausrüstung von Papier und Papierprodukten durch Behandeln der Oberfläche von Papier und Papierprodukten mit mindestens einem Ausrüstungsmittel und die nach dem Verfahren erhältlichen ausgerüsteten Papiere und Papierprodukte.The invention relates to a process for finishing paper and paper products by treating the surface of paper and paper products with at least one finishing agent and the finished papers and paper products obtainable by the process.
Um die Eigenschaften von Papier und Papierprodukten zu verbessern, behandelt man beispielsweise die Oberfläche von Papier oder Papierprodukten mit Ausrüstungsmitteln wie Verfestigern, Hydrophobierungsmitteln, Hydrophilierungsmitteln und/oder Papierstreichmassen. Die Ausrüstungsmittel werden dabei immer vollflächig auf die Oberseite und/oder die Unterseite des Papiers oder der Papierprodukte aufgetragen.To improve the properties of paper and paper products, for example, the surface of paper or paper products is treated with finishing agents such as hardeners, water repellents, hydrophilicizing agents and / or paper coating slips. The finishing agents are always applied over the entire surface of the top and / or bottom of the paper or paper products.
Aus der älteren
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Der Erfindung liegt die Aufgabe zugrunde, die Eigenschaften von Papier und Papierprodukten, insbesondere deren Steifigkeit, Bedruckbarkeit, Laminierbarkeit und biozide Wirkung gegenüber Mikroorganismen dahingehend zu verbessern, dass man im Vergleich mit bekannten Verfahren eine ausreichende Wirkung bereits mit einer geringeren Menge an Ausrüstungsmitteln erreicht.The invention has for its object to improve the properties of paper and paper products, in particular their stiffness, printability, laminability and biocidal activity against microorganisms to the effect that in comparison with known methods already achieved a sufficient effect with a smaller amount of finishing agents.
Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Ausrüstung von Papier und Papierprodukten durch Behandeln der Oberfläche von Papier oder Papierprodukten mit mindestens einem Ausrüstungsmittel, wenn man auf die Oberseite und/oder Unterseite von Papier oder Papierprodukten mindestens ein Ausrüstungsmittel in Form eines Musters aufbringt und man als Ausrüstungsmittel mindestens ein Mittel einsetzt, das die Steifigkeit von Papier erhöht. Das Ausrüstungsmittel wird vorzugsweise mit Hilfe eines Druckverfahrens auf die Oberseite und/oder Unterseite von Papier oder Papierprodukten aufgebracht. Solche Druckverfahren gehören zum Stand der Technik. Sie werden üblicherweise zum Bedrucken von geleimten oder gestrichenen Papieren oder von Textilien mit Druckpasten, die von Ausrüstungsmitteln für Papier verschieden sind, angewendet. Das Ausrüstungsmittel kann z. B. nach dem Siebdruck-, Ink-Jet-Druck-, Flexodruck- oder Offsetdruck-Verfahren auf die Oberseite und/oder die Unterseite von Papier oder Papierprodukten gedruckt werden.The object is achieved according to the invention with a method for finishing paper and paper products by treating the surface of paper or paper products with at least one finishing agent, if at least one finishing agent in the form of a pattern is applied to the top and / or bottom of paper or paper products and one as a finishing agent at least one agent that increases the stiffness of paper. The finishing agent is preferably applied to the top and / or bottom of paper or paper products by means of a printing process applied. Such printing processes belong to the state of the art. They are commonly used to print on sized or coated papers or textiles with printing pastes other than paper finishing equipment. The finishing agent can z. B. after the screen printing, ink-jet printing, flexographic printing or offset printing process on the top and / or bottom of paper or paper products to be printed.
Vorzugsweise druckt man das Ausrüstungsmittel nach dem Ink-Jet-Druck-Verfahren auf die Oberseite von Papier oder Papierprodukten. Das Papier kann beispielsweise ungeleimt oder ein in der Masse geleimtes Papier oder Papierprodukt sein. Als Masseleimungsmittel kommen beispielsweise Alkyldiketene, Alkenylbernsteinsäureanhydride oder Harzleim in Betracht.Preferably, the finishing agent is printed on the top of paper or paper products by the ink-jet printing process. For example, the paper may be unsized or a bulk sized paper or paper product. Suitable engine sizes are, for example, alkyldiketenes, alkenylsuccinic anhydrides or rosin size.
Gegenstand der Erfindung sind außerdem Papiere und Papierprodukte, die jeweils nach dem erfindungsgemäßen Verfahren erhältlich sind. Es handelt sich dabei im Wesentlichen um Schreib- und Druckpapiere, Verpackungspapiere, Wellpappe, Tapeten, Karton, Filter und Schichtstoffe beispielsweise aus einem Verbund aus Pappe oder Papier und mindestens einer Folie aus einem thermoplastischen Kunststoff, beispielsweise Polyethylen, Polypropylen, Polyamid, Polyester oder Polycarbonat.The invention also relates to papers and paper products which are each obtainable by the process according to the invention. These are essentially writing and printing papers, packaging papers, corrugated cardboard, wallpaper, cardboard, filters and laminates, for example, of a composite of cardboard or paper and at least one film of a thermoplastic material, for example polyethylene, polypropylene, polyamide, polyester or polycarbonate ,
Die Ausrüstungsmittel werden erfindungsgemäß beispielsweise in Form eines Gitters, einer Raute, spiralförmig, kreisförmig, flächenförmig, streifenförmig oder punktförmig auf die Oberseite und/oder Unterseite von Papier oder Papierprodukten gedruckt, wobei die Anordnung des Musters in geordneter oder in zufälliger Form (stochastisch) erfolgen kann. Die Ausrüstungsmittel werden dabei immer mustergemäß aufgetragen. Im Gegensatz zu bekannten Auftragsverfahren von Ausrüstungsmitteln für Papier, bei denen man das Ausrüstungsmittel auf die gesamte Oberseite bzw. Unterseite von Papier appliziert, wird das Ausrüstungsmittel bei dem erfindungsgemäßen Verfahren in der Weise auf die Oberfläche von Papier aufgebracht, dass nicht die gesamte Fläche damit beschichtet ist. Beispielsweise beträgt der Anteil der insgesamt mit einem Ausrüstungsmittel bedruckten Fläche 0,1 bis 90, vorzugsweise 1 bis 70 % und liegt meisten in dem Bereich von 10 bis 50 %. Der andere, nicht mit einem Ausrüstungsmittel behandelte Teil der Oberfläche des Papiers bleibt unbehandelt. Nach dem Drucken wird das bedruckte Papier oder Papierprodukt getrocknet und gegebenenfalls auf eine Temperatur erhitzt, bei der die Ausrüstungsmittel vernetzen, z.B. auf Temperaturen in dem Bereich von 35 bis 200°C.The finishing agent according to the invention, for example, in the form of a grid, a rhombus, spiral, circular, sheet-like, strip-shaped or punctiform printed on the top and / or bottom of paper or paper products, the arrangement of the pattern in an orderly or random (stochastic) can. The finishing materials are always applied according to the pattern. In contrast to known application methods of finishing compositions for paper in which the finishing agent is applied to the entire top or underside of paper, in the method according to the invention the finishing agent is applied to the surface of paper that does not coat the entire surface with it is. For example, the proportion of the total surface area printed with a finishing agent is 0.1 to 90, preferably 1 to 70%, and most is in the range of 10 to 50%. The other part of the surface of the paper not treated with a finishing agent remains untreated. After printing, the printed paper or paper product is dried and optionally heated to a temperature at which the finishing agents crosslink, e.g. to temperatures in the range of 35 to 200 ° C.
Die mit Hilfe des erfindungsgemäßen Verfahrens jeweils erzielte Wirkung, beispielsweise die Steifigkeit eines Papiers ist von mehreren Faktoren abhängig, vor allem von der Zusammensetzung und Menge des Ausrüstungsmittels, von der jeweils auf das Papier aufgedruckten Struktur des Ausrüstungsmittels und der Ausrichtung des Papiers, d.h. die Steifigkeit des Papiers hängt von der Orientierung der Cellulosefasern ab. Sie ist bei einem Papierblatt in Maschinenrichtung anders als quer dazu. Das Ausrüstungsmittel wird in Form eines Musters und kann z.B. in Form eines Gitters, einer Raute, eines Vielecks (z.B. Sechseck, Achteck), spiralförmig, kreisförmig, flächenförmig, streifenförmig oder punktförmig auf die Oberseite und/oder Unterseite von Papier oder Papierprodukten gedruckt werden. Die einzelnen Streifen eines Gitters oder einer Raute können unterschiedliche Abmessungen aufweisen, z.B. eine Stärke von 0,1 bis 100 mm, vorzugsweise 1 bis 10 mm und eine Länge von 0,1 bis 100 mm, vorzugsweise 1 bis 10 mm haben. Der Abstand zwischen den einzelnen Streifen eines Gitters, d.h. die unbedruckten Stellen, können beispielsweise einen Abstand von 0,1 bis 100 mm, vorzugsweise 1 bis 10 mm haben. Das Gitter kann quadratisch, rechteckig oder rautenförmig sein. Wenn man das Papier streifenförmig bedruckt, so können sich die Streifen über die gesamte Länge bzw. Breite des Papiers erstrecken.The effect achieved with the aid of the method according to the invention, for example the rigidity of a paper, depends on a number of factors, in particular on the composition and amount of finishing agent, on the structure of the finishing agent printed on the paper and on the orientation of the paper, ie the stiffness of the paper depends on the orientation of the cellulose fibers from. It is different for a paper sheet in the machine direction than transverse to it. The finishing agent is in the form of a pattern and may be printed eg on the top and / or bottom of paper or paper products in the form of a grid, a rhombus, a polygon (eg hexagon, octagon), spiral, circular, sheet, strip or dot. The individual strips of a grid or rhombus can have different dimensions, for example a thickness of 0.1 to 100 mm, preferably 1 to 10 mm and a length of 0.1 to 100 mm, preferably 1 to 10 mm. The distance between the individual strips of a grid, ie the unprinted areas, may for example have a spacing of 0.1 to 100 mm, preferably 1 to 10 mm. The grid can be square, rectangular or rhombic. If you print the paper strip-shaped, so the strips can extend over the entire length or width of the paper.
Das Papier kann auch punktförmig mit einer Vielzahl von Punkten oder flächenförmig bedruckt werden, wobei unter flächenförmig verstanden werden soll, dass eine größere Fläche mit einem Ausrüstungsmittel versehen ist, z. B. eine Fläche mit den Abmessungen 2 x 2 bis 10 cm oder 4 x 1 bis 10 cm. Kreisförmige Flächen, die auf ein Papier gedruckt sind, können beispielsweise einen Durchmesser von 1 mm bis 10 cm haben.The paper can also be punctiform printed with a variety of points or area, which is to be understood by sheet-like that a larger area is provided with a finishing agent, for. B. an area with the dimensions 2 x 2 to 10 cm or 4 x 1 to 10 cm. For example, circular areas printed on a paper may have a diameter of 1 mm to 10 cm.
Das erfindungsgemäße Verfahren kann in den Papierherstellungsprozess integriert werden. So ist es beispielsweise möglich, das noch feuchte Papier mit einem Ausrüstungsmittel zu bedrucken und das so behandelte Papier anschließend zu trocknen und gegebenenfalls auf eine höhere Temperatur (170 bis 200°C) zu erhitzen, um das aufgedruckte Ausrüstungsmittel zu vernetzen. Man kann das Papier jedoch auch während des Trockenvorgangs oder danach mit einem Ausrüstungsmittel bedrucken, das bedruckte Material trocknen und gegebenenfalls vernetzen. Die Papierprodukte können in entsprechender Weise während oder nach der Herstellung mit mindestens einem Ausrüstungsmittel bedruckt werden.The method according to the invention can be integrated into the papermaking process. Thus, for example, it is possible to print the still wet paper with a finishing agent and then dry the paper thus treated and optionally heat it to a higher temperature (170 to 200 ° C) to crosslink the printed finishing agent. However, it is also possible to print on the paper during the drying process or afterwards with a finishing agent, to dry the printed material and, if necessary, to crosslink it. The paper products may be similarly printed during or after manufacture with at least one finishing agent.
Als Papiere, die erfindungsgemäß ausgerüstet werden, kommen vorzugsweise sämtliche Papiersorten, insbesondere Rohpapiere in Betracht. Unter Papierprodukten sollen beispielsweise Verpackungspapiere, Wellpappe, Tapeten, Karton und Schichtstoffe beispielsweise aus einem Verbund aus Pappe oder Papier und mindestens einer Folie aus einem thermoplastischen Kunststoff verstanden werden. Beispielsweise kann man zur Herstellung der Papiere und der Papierprodukte von Cellulosefasern aller Art ausgehen, sowohl von natürlichen wie auch von zurückgewonnenen Fasern, insbesondere von Fasern aus Altpapier, die meistens in Mischung mit frischen Fasern (virgin fibers) eingesetzt werden. Unter frischen Fasern bzw. Frischfasern sollen Cellulosefasern verstanden werden, die bisher noch nicht zu einem Papierprodukt verarbeitet worden sind oder die noch nicht getrocknet wurden. Als Faserstoffe zur Herstellung der Pulpen kommen sämtliche dafür gebräuchlichen Qualitäten in Betracht, z.B. Holzstoff, gebleichter und ungebleichter Zellstoff sowie Papierstoffe aus allen Einjahrespflanzen.As papers which are equipped according to the invention, preferably all types of paper, in particular base papers into consideration. By paper products are meant, for example, packaging papers, corrugated board, wallpaper, cardboard and laminates, for example, from a composite of cardboard or paper and at least one film of a thermoplastic material. For example, cellulose fibers of all kinds, both natural and recovered, in particular recycled paper fibers, which are mostly used in admixture with virgin fibers, can be used to make the papers and paper products. Fresh fibers or fresh fibers are to be understood as meaning cellulose fibers which have hitherto not yet been processed into a paper product or which have not yet been dried. Suitable pulps for the production of the pulps are all qualities customary for this purpose, for example wood pulp, bleached and unbleached pulp and pulps from all annual plants.
Zu Holzstoff gehören beispielsweise Holzschliff, thermomechanischer Stoff (TMP), chemo-thermomechanischer Stoff (CTMP), Druckschliff, Halbzellstoff, Hochausbeute-Zellstoff und Refiner Mechanical Pulp (RMP). Als Zellstoff kommen beispielsweise Sulfat-, Sulfit- und Natronzellstoffe in Betracht. Vorzugsweise verwendet man ungebleichten Zellstoff, der auch als ungebleichter Kraftzellstoff bezeichnet wird. Geeignete Einjahrespflanzen zur Herstellung von Papierstoffen sind beispielsweise Reis, Weizen, Zuckerrohr und Kenaf.Wood pulp includes, for example, groundwood, thermomechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure groundwood, semi-pulp, high yield pulp, and refiner mechanical pulp (RMP). As pulp, for example, sulphate, sulphite and soda pulps come into consideration. Preferably, unbleached pulp, also referred to as unbleached kraft pulp, is used. Suitable annual plants for the production of pulps are, for example, rice, wheat, sugar cane and kenaf.
Das Papier bzw. die Papierprodukte werden erfindungsgemäß mustergemäß mit einem Ausrüstungsmittel bedruckt. Als Ausrüstungsmittel setzt man mindestens ein Mittel ein, das die Steifigkeit von Papier erhöht. Diese Mittel erhöhen meistens auch gleichzeitig die Trocken- und/oder Nassfestigkeit von Papier und Papierprodukten. Weitere Ausrüstungsmittel sind übliche Trockenfestmittel und/oder Nassfestmittel für Papier.The paper or paper products according to the invention are printed according to the pattern with a finishing agent. As a finishing agent, at least one agent is used which increases the stiffness of paper. These agents usually also increase the dry and / or wet strength of paper and paper products at the same time. Other finishing agents are conventional dry strength agents and / or wet strength agents for paper.
Um die Steifigkeit von Papier und Papierprodukten zu erhöhen verwendet man gemäß Erfindung vorzugsweise ein thermisch härtbares Bindemittel aus der Gruppe der Harnstoff-Formaldehyd-Addukte, Harnstoff-Glyoxal-Addukte, Melamin-Formaldehyd-Addukte, Phenol-Formaldehyd-Addukte, Ein- und Zweikomponentensysteme auf Basis von Epoxidharzen, Polyurethanen oder Isocyanaten, Polyacrylate, Polymethacrylate, Styrol-(Meth)Acrylat-Copolymerisat-Dispersionen und/oder Styrol-Butadien-(Meth)Acrylsäure-Copolymerisat-Dispersionen. In manchen Fällen ist der Einsatz von Mischungen aus mindestens zwei reaktiven Materialien von Interesse z.B. Mischungen von Melamin/Harnstoff-Formaldehyd-Kondensaten. Die reaktiven Materialien können als wässrige Lösung oder als wässrige Dispersion vorliegen. Hierbei sind Übergänge zwischen Lösung und Dispersion möglich. Wenn man Dispersionen einsetzt, so liegt beispielsweise der mittlere Teilchendurchmesser der in Wasser dispergierten Polymerteilchen unterhalb von 1 µm, vorzugsweise unterhalb von 500 nm und meisten in dem Bereich von 10 bis 100 nm.In order to increase the rigidity of paper and paper products, the invention preferably uses a thermally curable binder from the group of urea-formaldehyde adducts, urea-glyoxal adducts, melamine-formaldehyde adducts, phenol-formaldehyde adducts, one- and two-component systems based on epoxy resins, polyurethanes or isocyanates, polyacrylates, polymethacrylates, styrene- (meth) acrylate copolymer dispersions and / or styrene-butadiene- (meth) acrylic acid copolymer dispersions. In some cases, the use of mixtures of at least two reactive materials of interest e.g. Mixtures of melamine / urea-formaldehyde condensates. The reactive materials may be present as an aqueous solution or as an aqueous dispersion. In this case, transitions between solution and dispersion are possible. When using dispersions, for example, the average particle diameter of the polymer particles dispersed in water is below 1 μm, preferably below 500 nm and most in the range of 10 to 100 nm.
Die wässrige Lösung und/oder Dispersion enthält somit beispielsweise eine Gruppe eines reaktiven, vernetzbaren Materials, das aus
- (i) mindestens einer reaktiven Substanz, die ein Polymer bildet,
- (ii) gegebenenfalls mindestens einem C1-5-Alkohol, mindestens einem Polyol oder deren Gemischen und
- (iii) mindestens einem Katalysator
- (i) at least one reactive substance which forms a polymer,
- (ii) optionally at least one C 1-5 -alcohol, at least one polyol or mixtures thereof and
- (iii) at least one catalyst
Beispiele für (i) eine reaktive Substanz, die ein Polymer bildet, sind Harnstoff-Glyoxal-Addukte und deren Derivate, z.B. 1,3- Bis(hydroxymethyl)-4,5-dihydroxyimidazolidinon-2 (nachstehend "DMDHEU" genannt). Beim Bedrucken von Papier bzw. Papierprodukten kann es entweder allein oder zusammen mit (ii) mindestens einem C1-5-Alkohol, einem Polyol oder deren Gemischen eingesetzt werden. Falls man 1,3-Bis(hydroxymethyl)-4,5-dihydroxyimidazolidinon-2 zusammen mit einem Alkohol und/oder einem Polyol als Ausrüstungsmittel einsetzt, entstehen entsprechend modifizierte 1,3- Bis(hydroxymethyl)-4,5-dihydroxyimidazolidinone-2 (nachstehend "mDMDHEU" genannt). Solche Verbindungen sind beispielsweise aus der
Zu den Verbindungen der Gruppe (ii) gehören C1-5-Alkohole beispielsweise Methanol, Ethanol, n-Propanol, iso-Propanol, n-Butanol, Isobutanol, tert.-Butanol und n-Pentanol, bevorzugt ist Methanol, sowie Polyole wie Ethylenglykol, Diethylenglykol, 1,2- und 1,3-Propylenglykol, 1,2-, 1,3-, und 1,4-Butylenglykol, Glycerin, Trimethylolpropan und Polyalkylenglykole wie Polyethylenglykol, Polypropylenglykol, Blockcopolymerisate aus Ethylenglykol und Propylenglykol. Bevorzugt sind Polyethylenglykole der Formel HO(CH2CH2O)nH mit n von 3 bis 20 und Diethylenglykol.The compounds of group (ii) include C 1-5 -alcohols, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and n-pentanol, preferably methanol, and polyols, such as Ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, glycerol, trimethylolpropane and polyalkylene glycols such as polyethylene glycol, polypropylene glycol, block copolymers of ethylene glycol and propylene glycol. Preference is given to polyethylene glycols of the formula HO (CH 2 CH 2 O) n H where n is from 3 to 20 and diethylene glycol.
Um modifiziertes 1,3-Bis(hydroxymethyl)-4,5-dihydroxyimidazolidinon-2 (DMDHEU) herzustellen, werden DMDHEU und der einwertige Alkohol und/oder das Polyol gemischt, wobei der einwertige Alkohol und/oder das Polyol in einer Menge von je 0,1 bis 2,0 Moläquivalenten, bezogen auf DMDHEU, eingesetzt werden. Die Mischung aus DMDHEU, einwertigem Alkohol und/oder Polyol wird beispielsweise bei Temperaturen von 20 bis 70°C und einem pH-Wert von 1 bis 2,5 umgesetzt, wobei der pH-Wert nach der Umsetzung auf 4 bis 8 eingestellt wird.To prepare modified 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2 (DMDHEU), DMDHEU and the monohydric alcohol and / or the polyol are mixed, the monohydric alcohol and / or the polyol being in an amount of each 0.1 to 2.0 molar equivalents, based on DMDHEU, are used. The mixture of DMDHEU, monohydric alcohol and / or polyol is reacted, for example, at temperatures of 20 to 70 ° C and a pH of 1 to 2.5, wherein the pH after the reaction is adjusted to 4 to 8.
Unter (i) einer reaktiven Substanz, die ein Polymer bildet, sind sowohl Harnstoff-Formaldehyd-Addukte als auch Harnstoff-Glyoxal-Addukte sowie jeweils deren Derivate zu verstehen. Folgende Verbindungen seien beispielhaft genannt: Dimethylolharnstoff, Bis(methoxymethyl)harnstoff, Tetramethylolacetylendiharnstoff, Methylolmethylharnstoff sowie 1,3-Dimethyl-4,5-dihydroxyimidazolidinon-2, 1,3-Bis(hydroxymethyl)imidazolidinon-2 oder deren Gemische. Auch diese Verbindungen der Gruppe (i) können gegebenenfalls in Gegenwart von (ii) mindestens einem C1-5-Alkohol, mindestens einem Polyol oder deren Gemischen als Ausrüstungsmittel eingesetzt werden. Geeignete Alkohole und Polyole wurden oben bereits genannt. Bevorzugt sind Methanol, Diethylenglykol oder deren Gemische.Under (i) a reactive substance which forms a polymer, both urea-formaldehyde adducts and urea-glyoxal adducts and their derivatives are to be understood. The following compounds may be mentioned by way of example: dimethylolurea, bis (methoxymethyl) urea, tetramethylolacetylenediurea, methylolmethylurea and 1,3-dimethyl-4,5-dihydroxyimidazolidinone-2, 1,3-bis (hydroxymethyl) imidazolidinone-2 or mixtures thereof. These compounds of group (i) may also be used as finishing agents in the presence of (ii) at least one C 1-5 -alcohol, at least one polyol or mixtures thereof. Suitable alcohols and polyols have already been mentioned above. Preference is given to methanol, diethylene glycol or mixtures thereof.
Die wässrige Lösung des Ausrüstungsmittels enthält die reaktiven Verbindungen der Gruppe (i) und die Verbindungen der Gruppe (ii) beispielsweise in einer Konzentration von 1 bis 70 Gew.-%, vorzugsweise 10 bis 60 Gew.-% und insbesondere 20 bis 60 Gew.-%. Das Imprägniermittel enthält vorzugsweise 1,3- Bis(hydroxymethyl)-4,5-dihydroxyimidazolidinon-2 (DMDHEU) als Verbindung der Gruppe (i).The aqueous solution of the finishing agent contains the reactive compounds of group (i) and the compounds of group (ii), for example, in one concentration from 1 to 70 wt .-%, preferably 10 to 60 wt .-% and in particular 20 to 60 wt .-%. The impregnating agent preferably contains 1,3-bis (hydroxymethyl) -4,5-dihydroxyimidazolidinone-2 (DMDHEU) as a compound of group (i).
Das Ausrüstungsmittel enthält außer (i) und gegebenenfalls (ii) immer einen Katalysator (iii). Geeignete Katalysatoren (iii) sind beispielsweise Metallsalze aus der Gruppe Metallhalogenide, Metallsulfate, Metallnitrate, Metalltetrafluoroborate, Metallphosphate oder deren Gemische. Einzelne Beispiele für (iii) sind Magnesiumchlorid, Magnesiumsulfat, Zinkchlorid, Lithiumchlorid, Lithiumbromid, Bortrifluorid, Aluminiumchlorid, Aluminiumsulfat, Zinknitrat und Natriumtetrafluoroborat. Die genannten Verbindungen können entweder allein oder in Mischung als Katalysator eingesetzt werden.The finishing agent always contains a catalyst (iii) apart from (i) and optionally (ii). Suitable catalysts (iii) are, for example, metal salts from the group of metal halides, metal sulfates, metal nitrates, metal tetrafluoroborates, metal phosphates or mixtures thereof. Specific examples of (iii) are magnesium chloride, magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminum chloride, aluminum sulfate, zinc nitrate and sodium tetrafluoroborate. The compounds mentioned can be used either alone or in admixture as a catalyst.
Weitere geeignete Katalysatoren (iii) sind Ammoniumsalze wie Ammoniumchlorid, Ammoniumsulfat, Ammoniumoxalat, Diammoniumphosphat oder deren Gemische. Außerdem können als Katalysator organische und/oder anorganische Säuren eingesetzt werden. Beispiele hierfür sind Maleinsäure, Ameisensäure, Essigsäure, Propionsäure, Zitronensäure, Weinsäure, Oxalsäure, p-Toluolsulfonsäure, Salzsäure, Schwefelsäure, Borsäure oder deren Gemische.Further suitable catalysts (iii) are ammonium salts such as ammonium chloride, ammonium sulfate, ammonium oxalate, diammonium phosphate or mixtures thereof. In addition, as a catalyst organic and / or inorganic acids can be used. Examples of these are maleic acid, formic acid, acetic acid, propionic acid, citric acid, tartaric acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, boric acid or mixtures thereof.
Bevorzugt werden als Verbindungen der Gruppe (iii) Magnesiumchlorid, Zinkchlorid, Magnesiumsulfat, Aluminiumsulfat oder Mischungen dieser Verbindungen verwendet. Besonders bevorzugt ist Magnesiumchlorid.The compounds of group (iii) used are preferably magnesium chloride, zinc chloride, magnesium sulfate, aluminum sulfate or mixtures of these compounds. Particularly preferred is magnesium chloride.
Der Katalysator (iii) ist beispielsweise in einer Konzentration von 0,1 bis 10 Gew.-%, bevorzugt 0,2 bis 8 Gew.-%, besonders bevorzugt 0,3 bis 5 Gew.-% , bezogen auf die Komponenten (i) - (iii) des reaktiven Materials, enthalten.The catalyst (iii) is, for example, in a concentration of 0.1 to 10 wt .-%, preferably 0.2 to 8 wt .-%, particularly preferably 0.3 to 5 wt .-%, based on the components (i ) - (iii) of the reactive material.
Von den oben beschriebenen Produkten, die Formaldehyd einkondensiert enthalten, werden insbesondere formaldehydarme Kondensationsprodukte eingesetzt. Unter formaldehydarm soll im vorliegenden Zusammenhang verstanden werden, dass die reaktiven Materialien keine wesentlichen Mengen an freiem Formaldehyd enthalten und dass auch beim Trocknen bzw. Härten der damit behandelten Cellulosefasern oder Papierprodukte keine wesentlichen Mengen an Formaldehyd freigesetzt werden. Im Allgemeinen enthalten solche reaktiven Materialien < 100 ppm Formaldehyd.Of the products described above, which contain condensed formaldehyde, in particular low-formaldehyde condensation products are used. Low-formaldehyde should be understood in the present context that the reactive materials do not contain significant amounts of free formaldehyde and that no substantial amounts of formaldehyde are released during drying or curing of the cellulose fibers or paper products treated therewith. In general, such reactive materials contain <100 ppm formaldehyde.
Weitere reaktive Materialien, die mit sich selbst und/oder Cellulosefasern unter Vernetzung reagieren, sind formaldehydfreie, thermisch härtbare Bindemittel in Betracht. Solche Bindemittel werden z.B. in den folgenden Druckschriften beschrieben, nämlich
Als thermisch härtbare Bindemittel kommen außer den Bindemitteln, die in den obengenannten Druckschriften beschrieben sind, sämtliche härtbaren Bindemittel in Betracht, die beispielsweise zur Verfestigung von Faservliesen in der Literatur beschrieben sind und/oder die für diesen Zweck in der Praxis verwendet werden wie thermisch härtbare Harze auf Basis von Phenol und Formaldehyd, die obengenannten Melamin-Formaldehyd- und Harnstoff-Formaldehyd-Harze, Harnstoff-Glyoxal-Harze sowie insbesondere formaldehydfreie Ein- und Zweikomponentensysteme auf Basis von Epoxidharzen oder Polyurethanen, Polyacrylate, Polymethacrylate, Polyvinylacetate, Styrol-Acrylat-Copolymerisat-Dispersionen, Styrol-Methacrylat-Copolymerisat-Dispersionen, Styrol-Butadien-(Meth)Acrylsäure-Copolymerisat-Dispersionen sowie Mischungen aus den genannten Dispersionen mit einer Mischung aus einer Polycarbonsäure und einem mehrwertigen Alkohol als Vernetzungskomponente.Thermally curable binders other than the binders described in the above-mentioned references are all curable binders which are described, for example, for solidifying fibrous webs in the literature and / or which are used for this purpose in practice, such as thermosetting resins based on phenol and formaldehyde, the abovementioned melamine-formaldehyde and urea-formaldehyde resins, urea-glyoxal resins and in particular formaldehyde-free one and two-component systems based on epoxy resins or polyurethanes, polyacrylates, polymethacrylates, polyvinyl acetates, styrene-acrylate copolymer Dispersions, styrene-methacrylate copolymer dispersions, styrene-butadiene (meth) acrylic acid copolymer dispersions and mixtures of said dispersions with a mixture of a polycarboxylic acid and a polyhydric alcohol as a crosslinking component.
Beispiele für bevorzugt in Betracht kommende Ausrüstungsmittel sind thermisch härtbare Bindemittel in Form von Mischungen aus
- (a) einem Polymerisat, das durch radikalische Polymerisation erhältlich ist und das zu 5 bis 100 Gew.-% eines ethylenisch ungesättigten Carbonsäureanhydrids oder einer ethylenisch ungesättigten Dicarbonsäure, deren Carbonsäuregruppen eine Anhydridgruppe bilden können, einpolymerisiert enthält und
- (b) mindestens einem Alkanolamin, das mindestens zwei Hydroxylgruppen im Molekül und/oder mindestens einem mehrwertigen Alkohol enthält.
- (A) a polymer which is obtainable by free-radical polymerization and which contains from 5 to 100 wt .-% of an ethylenically unsaturated carboxylic acid anhydride or an ethylenically unsaturated dicarboxylic acid whose carboxylic acid groups can form an anhydride group, in copolymerized form, and
- (B) at least one alkanolamine containing at least two hydroxyl groups in the molecule and / or at least one polyhydric alcohol.
Spezifische Beispiele für solche Mischungen sind ca. 40 bis 60 Gew.-% Feststoffe enthaltende wässrige Lösungen und/oder Dispersionen eines Copolymerisates aus 80 Gew.-% Acrylsäure und 20 Gew.-% Maleinsäure einer Molmasse Mw von 15 000 bis 900 000 in Kombination mit Triethanolamin oder wässrige Lösungen eines Copolymerisates aus 55 Gew.-% Acrylsäure und 45 Gew.-% Maleinsäure in Kombination mit Triethanolamin. Diese Bindemittel können gegebenenfalls einen Veresterungskatalysator und/oder eine gebundenen Phosphor enthaltende Verbindung wie hypophosphorige Säure als Reaktionsbeschleuniger.Specific examples of such mixtures are aqueous solutions containing about 40 to 60% by weight of solids and / or dispersions of a copolymer of 80% by weight of acrylic acid and 20% by weight of maleic acid having a molecular weight M w of 15,000 to 900,000 μm Combination with triethanolamine or aqueous solutions of a copolymer of 55% by weight of acrylic acid and 45% by weight of maleic acid in combination with triethanolamine. These binders may optionally contain an esterification catalyst and / or a bound phosphorus-containing compound such as hypophosphorous acid as a reaction accelerator.
Das oben beschriebene Copolymerisat (a) kann beispielsweise auch aufgebaut sein aus
- 50 bis 99,5 Gew.-% mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure,
- 0,5 bis 50 Gew.-% wenigstens einer ethylenisch ungesättigten Verbindung aus der Gruppe der Ester von ethylenisch ungesättigten Monocarbonsäuren und den Monoestern und den Diestern ethylenisch ungesättigter Dicarbonsäuren mit einem mindestens eine Hydroxylgruppe aufweisenden Amin und
- bis zu 20 Gew.-% eines anderen Monomeren.
- From 50 to 99.5% by weight of at least one ethylenically unsaturated mono- or dicarboxylic acid,
- 0.5 to 50 wt .-% of at least one ethylenically unsaturated compound from the group of esters of ethylenically unsaturated monocarboxylic acids and the monoesters and the diesters of ethylenically unsaturated dicarboxylic acids having at least one hydroxyl-containing amine and
- up to 20% by weight of another monomer.
Thermisch härtbare, wässrige Zusammensetzungen, die mindestens ein Copolymerisat (a) und mindestens ein Alkanolamin bzw. höherfunktionelles β-Hydroxyalkylamin und/oder mindestens einen mehrwertigen Alkohol enthalten, können gegebenenfalls noch zusätzlich mindestens ein Tensid enthalten.Thermally curable, aqueous compositions containing at least one copolymer (a) and at least one alkanolamine or higher-functional β-hydroxyalkylamine and / or at least one polyhydric alcohol may optionally additionally contain at least one surfactant.
Weitere, als Ausrüstungsmittel verwendbare thermisch härtbare Bindemittel basieren auf wässrigen Mischungen von
- Polycarbonsäuren wie Polyacrylsäure, Polymethacrylsäure, Copolymerisaten aus Acrylsäure und Maleinsäure, Copoylmerisaten aus Methacrylsäure und Maleinsäure, Copolymerisaten aus Ethylen und Maleinsäure, Styrol und Maleinsäure, oder Copolymerisaten aus Acrylsäure oder Methacrylsäure und Estern von Acryl- oder Methacrylsäure mit vorzugsweise einwertigen 1 bis 24 C-Atome enthaltenden Alkoholen, wobei die Polycarbonsäuren einen K-Wert von 50 bis 100 (gemessen in nicht neutralisierter Form der Polycarbonsäuren nach H. Fikentscher in Dimethylformamid bei 25°C und einer Polymerkonzentration von 0,1 Gew.-%) und
- mehrwertigen Alkoholen wie Trimethylolpropan, Glycerin, 2-Hydroxymethylbutandiol-1,4 oder Polyvinylalkohol und/oder mehrwertigen Aminen und/oder Alkanolaminen.
- Polycarboxylic acids such as polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and maleic acid, copolymers of ethylene and maleic acid, styrene and maleic acid, or copolymers of acrylic acid or methacrylic acid and esters of acrylic or methacrylic acid with preferably monovalent 1 to 24 carbon atoms containing alcohols, wherein the polycarboxylic acids have a K value of 50 to 100 (measured in unneutralized form of the polycarboxylic acids according to H. Fikentscher in dimethylformamide at 25 ° C and a polymer concentration of 0.1 wt .-%) and
- polyhydric alcohols such as trimethylolpropane, glycerol, 2-hydroxymethylbutanediol-1,4 or polyvinyl alcohol and / or polyhydric amines and / or alkanolamines.
Polycarbonsäuren, mehrwertige Alkohole, Alkanolamine und mehrwertige Amine werden bevorzugt in solchen Mengen eingesetzt, dass die Anzahl der Säurefunktion der Gesamtzahl aus alkoholischen Hydroxyl- und Aminfunktionen äquivalent ist, vgl.
Bei dem erfindungsgemäßen Verfahren werden als Ausrüstungsmittel mit besonderem Vorteil reaktive Materialien eingesetzt, die unter dem Warenzeichen Acrodur® von BASF Aktiengesellschaft vertrieben werden. Ein Beispiel hierfür ist eine wässrige Styrol-Acrylat-Polymerdispersion, die mit einer Polycarbonsäure und einem mehrwertigen Alkohol als Vernetzungskomponente modifiziert ist. Es vernetzt bereits bei einer Temperatur von 130°C. Um jedoch hohe Produktionsgeschwindigkeiten zu erzielen, führt man die Vernetzung bevorzugt bei Temperaturen von 180 bis 200°C durch. Ein weiteres formaldehydfreies Bindemittel ist beispielsweise als farblose bis leicht gelbliche, klare, wässrige Lösung einer modifizierten Polycarbonsäure mit einem mehrwertigen Alkohol als Vernetzungskomponente im Handel erhältlich. Es vernetzt z.B. bei Trocknungstemperaturen von ca. 160 bis 180°C.In the process according to the invention reactive materials are used with particular advantage as finishing agents, which are marketed under the trademark Acrodur® by BASF Aktiengesellschaft. An example of this is an aqueous styrene-acrylate polymer dispersion modified with a polycarboxylic acid and a polyhydric alcohol crosslinking component. It already cross-links at a temperature of 130 ° C. However, in order to achieve high production rates, the crosslinking is preferably carried out at temperatures of 180 to 200 ° C. Another formaldehyde-free binder is commercially available, for example, as a colorless to slightly yellowish, clear, aqueous solution of a modified polycarboxylic acid with a polyhydric alcohol as crosslinking component. It crosslinks e.g. at drying temperatures of about 160 to 180 ° C.
Besonders bevorzugt sind formaldehydfreie reaktive Materialien, die mindestens eine Polycarbonsäure und mindestens einen mehrwertigen Alkohol und/oder Alkanolamin oder mehrwertiges Amin enthalten. Zusammensetzungen, die diese reaktiven Mittel enthalten, können gegebenenfalls noch weitere formaldehydfreie Polymere enthalten, z.B. Polyacrylate, die unter dem Warenzeichen Acronal® von BASF Aktiengesellschaft vertrieben werden. Die zum Bedrucken eingesetzten wässrigen Lösungen und/oder Dispersionen eines reaktiven Materials enthalten das reaktive Material beispielsweise in einer Menge von 1 bis 70 Gew.-%, vorzugsweise 10 bis 60 Gew.-% und meistens 30 bis 50 Gew.-%.Particularly preferred are formaldehyde-free reactive materials containing at least one polycarboxylic acid and at least one polyhydric alcohol and / or alkanolamine or polyhydric amine. Compositions containing these reactive agents may optionally contain other formaldehyde-free polymers, for example polyacrylates sold under the trademark Acronal® by BASF Aktiengesellschaft. The aqueous solutions and / or dispersions of a reactive material used for printing contain the reactive material, for example, in an amount of 1 to 70 wt .-%, preferably 10 to 60 wt .-% and usually 30 to 50 wt .-%.
Das erfindungsgemäße Verfahren hat gegenüber den bekannten Imprägnierverfahren den Vorteil, dass man bei etwa vergleichbaren Eigenschaften der Papiere und Papierprodukte deutlich geringere Mengen an Ausrüstungsmittel benötigt und somit Papiere und Papierprodukte kostengünstiger herstellen kann.Compared with the known impregnation processes, the process according to the invention has the advantage that significantly lower amounts of finishing agent are required with approximately comparable properties of the papers and paper products, and thus less expensive manufacture of papers and paper products.
Sofern aus dem Zusammenhang nichts anderes hervorgeht, bedeuten die Prozentangaben in Beispielen Gewichtsprozent.Unless otherwise indicated in the context, the percentages in examples represent percent by weight.
Ein DIN A4 Blatt wurde erfindungsgemäß mit einem Ausrüstungsmittel bedruckt, getrocknet und 24 Stunden bei 25°C und 60% Luftfeuchtigkeit klimatisiert. Die Messungen wurden bei Raumtemperatur unter dem jeweils herrschenden Luftdruck vorgenommen. Aus dem Zentrum des mit einem Ausrüstungsmittel erfindungsgemäß bedruckten DIN A4 Blatts schnitt man ein Teststück mit den Abmessungen 100 x 100 mm. Das Teststück wurde dann zwischen zwei Blöcken aus Holz so fixiert, dass 50% des Teststücks herausragten. Der aus den Blöcken herausragende Teil des Teststücks wurde anschließend mit Gewichten von 1 bis 50 g belastet, indem man die Gewichte in der Mitte des Teststücks in einer Entfernung von 10 mm vom äußeren Rand aufsetzte. Sobald das Ende des aus dem Block hervorstehenden Teststücks 25 mm erreichte oder das Gewicht vom Papier fiel, wurde die dafür notwendige Belastung in g als Maß für die Steifigkeit gemessen.An A4 sheet was printed according to the invention with a finishing agent, dried and air-conditioned for 24 hours at 25 ° C and 60% humidity. The measurements were made at room temperature under the prevailing air pressure. From the center of the DIN A4 sheet printed with a finishing agent according to the invention, a test piece having the dimensions 100 × 100 mm was cut. The test piece was then fixed between two blocks of wood so that 50% of the test piece protruded. The part of the test piece protruding from the blocks was then loaded with weights of 1 to 50 g by placing the weights in the middle of the test piece at a distance of 10 mm from the outer edge. As soon as the end of the test piece protruding from the block reached 25 mm or the weight fell off the paper, the required load in g was measured as a measure of the stiffness.
Folgende Ausrüstungsmittel wurden eingesetzt:
- Ausrüstungsmittel 1: Mischung aus einer Polycarbonsäure und einem mehrwertigen Amin in Form einer 35%igen wässrigen Lösung (Acrodur® 950L)
- Ausrüstungsmittel 2: Mischung aus einer Polycarbonsäure und einem mehrwertigen Amin in Form einer 35%igen wässrigen Dispersion (Acrodur® D3515)
- Ausrüstungsmittel 3: 70%ige wässrige Lösung eines wärmehärtbaren Harnstoff-Formaldehyd-Harzes (Fixapret® ECO)
- Finishing Agent 1: Mixture of a polycarboxylic acid and a polyvalent amine in the form of a 35% aqueous solution (Acrodur® 950L)
- Finishing Agent 2: Mixture of a polycarboxylic acid and a polyvalent amine in the form of a 35% aqueous dispersion (Acrodur® D3515)
- Finishing Agent 3: 70% aqueous solution of a thermosetting urea-formaldehyde resin (Fixapret® ECO)
DIN A4 Blätter wurden jeweils mit den in der folgenden Tabelle angegebenen Mengen an Ausrüstungsmitteln mit Hilfe des Ink-Jet-Druck-Verfahrens mit den ebenfalls in der Tabelle angegebenen Mustern bedruckt. Die mit den Ausrüstungsmitteln 1 bis 3 bedruckten Blätter wurden jeweils 15 Minuten bei 140°C gelagert, um die Polymeren zu vernetzen. Danach bestimmte man jeweils nach der oben beschriebenen Methode die Steifigkeit des Papiers. Die Ergebnisse sind in der Tabelle angegeben.A4 size sheets were each printed with the amounts of finishing agents shown in the following table using the ink jet printing method with the patterns also shown in the table. The sheets printed with finishing agents 1 to 3 were each stored at 140 ° C for 15 minutes to crosslink the polymers. Thereafter, the stiffness of the paper was determined by the method described above. The results are given in the table.
In der Tabelle bedeutet "Linie (MD)" auf das DIN A4 Blatt gedruckte Linien, die in Maschinenrichtung des Blattes bei der Papierherstellung verlaufen und "Linie (CD)" aufgedruckte Linien, die quer zur Maschinenrichtung verlaufen.In the table, "line (MD)" means lines printed on the A4 sheet, which are in the machine direction of the sheet in papermaking, and "line (CD)" lines which are transverse to the machine direction.
In den Vergleichsbeispielen 1 bis 6 wurde Wasser in den in der Tabelle angegebenen Druckmustern auf das Blatt gedruckt und das so behandelte Blatt vor der Bestimmung der Steifigkeit jeweils getrocknet.
Claims (12)
- A process for finishing paper and paper products by treating the surface of paper or paper products with at least one finishing agent, wherein at least one finishing agent is applied in the form of a pattern to the top and/or bottom of paper or paper products, and wherein the finishing agent used is at least one agent which increases the stiffness of paper.
- The process according to claim 1, wherein the finishing agent is applied with the aid of a printing process to the top and/or bottom of paper or paper products.
- The process according to claim 1 or 2, wherein the finishing agent is printed on the top and/or the bottom of paper or paper products by the screen printing, inkjet printing, flexographic printing or offset printing process.
- The process according to any of claims 1 to 3, wherein the finishing agent is printed on the top of paper or paper products by the inkjet printing process.
- The process according to any of claims 1 to 4, wherein an engine-sized paper or paper product is used.
- The process according to any of claims 1 to 5, wherein the finishing agents are printed in the form of a grid or of a rhombus or in spiral, circular, two-dimensional, strip or dot form on the top and/or bottom of paper or paper products, the pattern printed on being present in each case in ordered or in random form.
- The process according to any of claims 1 to 6, wherein the finishing agent used is a strength agent.
- The process according to any of claims 1 to 7, wherein the finishing agent used is a dry strength agent and/or a wet strength agent for paper.
- The process according to any of claims 1 to 8, wherein the finishing agent used is at least one heat-curable binder from the group consisting of the urea-formaldehyde adducts, urea-glyoxal adducts, melamine-formaldehyde adducts, phenolformaldehyde adducts, one- and two-component systems based on epoxy resins, polyurethanes or isocyanates, polyacrylates, polymethacrylates, styrene/(meth)acrylate copolymer dispersions and/or styrene/butadiene/(meth)acrylic acid copolymer dispersions.
- The process according to any of claims 1 to 8, wherein the finishing agent used is at least one heat-curable binder comprising a mixture of(a) a polymer which is obtainable by free radical polymerization and which comprises from 5 to 100% by weight of an ethylenically unsaturated carboxylic anhydride or of an ethylenically unsaturated dicarboxylic acid whose carboxyl groups can form anhydride groups, incorporated in the form of polymerized units, and(b) at least one alkanolamine which comprises at least two hydroxyl groups in the molecule and/or at least one polyhydric alcohol.
- The process according to any of claims 1 to 8, wherein the finishing agent used is at least one heat-curable binder comprising an aqueous mixture with at least one polycarboxylic acid and at least one polyhydric alcohol and/or at least one polyfunctional amine and/or an alkanolamine.
- A paper or paper product which in each case is obtainable by the process of claims 1 to 11.
Priority Applications (2)
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EP07730254A EP2038478B1 (en) | 2006-06-27 | 2007-06-20 | Method for finishing paper and paper products |
PL07730254T PL2038478T3 (en) | 2006-06-27 | 2007-06-20 | Method for finishing paper and paper products |
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EP06116165 | 2006-06-27 | ||
PCT/EP2007/056104 WO2008000665A2 (en) | 2006-06-27 | 2007-06-20 | Method for finishing paper and paper products |
EP07730254A EP2038478B1 (en) | 2006-06-27 | 2007-06-20 | Method for finishing paper and paper products |
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EP2038478B1 true EP2038478B1 (en) | 2012-04-11 |
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EP07730254A Not-in-force EP2038478B1 (en) | 2006-06-27 | 2007-06-20 | Method for finishing paper and paper products |
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US (1) | US20090272505A1 (en) |
EP (1) | EP2038478B1 (en) |
JP (1) | JP5409356B2 (en) |
CN (1) | CN101479428B (en) |
AT (1) | ATE553252T1 (en) |
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PL (1) | PL2038478T3 (en) |
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2007
- 2007-06-20 PL PL07730254T patent/PL2038478T3/en unknown
- 2007-06-20 US US12/305,108 patent/US20090272505A1/en not_active Abandoned
- 2007-06-20 AT AT07730254T patent/ATE553252T1/en active
- 2007-06-20 JP JP2009517119A patent/JP5409356B2/en not_active Expired - Fee Related
- 2007-06-20 CN CN2007800239398A patent/CN101479428B/en not_active Expired - Fee Related
- 2007-06-20 WO PCT/EP2007/056104 patent/WO2008000665A2/en active Application Filing
- 2007-06-20 EP EP07730254A patent/EP2038478B1/en not_active Not-in-force
- 2007-06-20 ES ES07730254T patent/ES2381999T3/en active Active
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CN101479428B (en) | 2012-11-28 |
JP2009541609A (en) | 2009-11-26 |
JP5409356B2 (en) | 2014-02-05 |
ES2381999T3 (en) | 2012-06-04 |
WO2008000665A3 (en) | 2008-03-27 |
ATE553252T1 (en) | 2012-04-15 |
WO2008000665A2 (en) | 2008-01-03 |
CN101479428A (en) | 2009-07-08 |
US20090272505A1 (en) | 2009-11-05 |
PL2038478T3 (en) | 2012-09-28 |
EP2038478A2 (en) | 2009-03-25 |
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