METHOD AND USE OF A METHOD FOR THE DRY APPLICATION OF BARRIER AND ADHESIVE MATERIELS ON WEBS

Description

[0001] The present invention relates to a method and use of a method for the dry application of barrier and adhesive materials on moving webs of paper or board. The invention particularly relates to dry-application of barrier polymers in the manufacture of packaging materials or laminates.

[0002] Barrier polymers are widely used in packaging materials to avoid or decrease the penetration of water vapour, fat, odours, microbes, etc. through packages. As very few materials stop the penetration of all these media, multilayer structures are often needed. The manufacture of barrier layers is usually performed by extrusion of thermoplastic materials, such as variations of polyethylene and polypropylene, but also by dispersion coating. In the extrusion method, the required polymers are molten and applied onto the web through a slit as a thin film. The hot film adheres to the web mechanically, or in some cases, by means of an adherent material earlier applied to the web. One major disadvantage of this method is that the polymer material has to be heated until it is completely molten and then it is forced through the slit. Both the heat and the mechanical force (shear stress) lead to the breakdown of the polymer structure, causing decrease in mechanical properties, and sometimes decomposition. In the dispersion coating method, solvents or other liquid media are used, which require drying steps and consume energy.

[0003] Same methods used for the application of barrier polymers onto a web are used for introduction of adherents, needed in lamination, onto webs. In the manufacture of multi-layer laminates, after coating with the adherent the webs are forced together by mechanical means with or without subsequent heating.

[0004] Based on the above it can be realised that there exists a need for an improved method for the manufacture of materials, especially packaging materials and laminates comprising one or several layers of barrier polymers.

[0005] The preparation of dry hollow or solid pigments or pigment granulates composed of several different materials used in paper and board coating has been described in WO 01/00713 A1. A water dispersion of pigments or a mixture of pigments and other material used for paper coating was spray-dried to a powder with a dry content of 85 - 100 %.

[0006] The use of such a plastic pigment powder, comprising agglomerates with a particle size of 1 - 500 µm, for dry-application onto paper and board webs, and a method for the dry-application has further been described in WO 01/00713 A1. In this dry-application method the powder is applied to the web by means of an electrostatic field and then fixed to the web by heat. The prerequisite for this application method is that the powder is dry (dry content 85 - 100 %) and fine. A narrow particle size distribution contributes to the even result. The particles become electrically charged by corona treatment and/or by interacting with each other during transportation towards the web. The charged particles stick to the web and stay there until fixation. Paper and board with improved quality are obtained by using this method.

[0007] An object of the invention is a method for the dry-application of barrier and/or adhesive material(s) onto a moving web of paper or board, in particular a method for the manufacture of materials, especially packaging materials and laminates, comprising one or several layers of barrier polymers.

[0008] A further object of the invention is the use of a dry-application method based on ionic blasting for the application of barrier and/or adhesive material(s) onto a moving web of paper or board.

[0009] The characteristic features of the method for the dry-application of barrier and/or adhesive materials onto the moving webs, of the method for the manufacture of materials, especially packaging materials and laminates, comprising one or several layers of barrier polymers, and of the use of a dry-application method based on ionic blasting for the application of barrier and/or adhesive material(s) onto the moving webs are stated in the claims.

[0010] In the present invention it was discovered that moving paper or board webs may be coated by using a dry-application method with barrier and/or adhesive materials applicable in dry form.

[0011] In the dry-application method small particles are applied onto the moving web without contacting it, by means of ionic blasting provided by high voltage, wherein the particles are charged by the ions formed by corona discharge. Thereafter, an electric field transfer the charged particles onto the web or the surface.

[0012] Suitable barrier and adhesive materials are polymeric materials, such as polyethylene, polypropylene, ethyl vinylacetate polymers, polyvinyl alcohol, polyamides, polyesters, ionomers, copolymers of vinylidene chloride and methyl acrylate and the like, which are frequently used in extrusion applications, and thermoplastic biodegradable polymers, such as polylactides, polyglycolides and their copolymers.

[0013] Other suitable polymeric materials are polymers based on polystyrene, polyacrylate, polymethacrylate, poly(styrene-acrylate)copolymers, plastic pigments based on melamin-formaldehyde and urea-formaldehyde or combinations thereof. If the polymeric materials are supplied as aqueous dispersions, they must be dried before the dry-application. This procedure is described in WO 01/00713 A1.

[0014] The essential features of the polymers in the dry-application method are particle size, glass transition temperature (Tg) and electrostatic properties. The diameter size of the particles, or particle agglomerates, is between 0.01 and 500 µm, preferably between 1 and 50 µm. In the case the material is supplied in the form of pellets, it must be ground, optionally with dry ice, to a powder with suitable particle size. The glass transition temperature (Tg) is preferably
more than 40°, depending on the web material used and on characteristics of the polymer. The polymer shall either be grindable or dryable and often a grinder is used in connection with application.

[0015] The barrier and/or adhesive material i.e. the polymer powder is applied onto the moving web, by using the dry-application method based on ionic blasting. The web is selected from paper or board. The powder layer is covered with a film (polyethylene terephthalate or other non-sticking material) to avoid potential sticking of the polymer material to the surface of the calender rolls during fixing. The fixing is performed at temperatures suitable for the powder material, depending on nip pressure and calender speed.

[0016] The method according to the invention has several advantages over the state of the art. The degrading effect of thermomechanical treatment on the polymeric material is decreased. By using the dry-application method it is possible to introduce materials with good barrier properties but which are too sensitive to thermal degradation or in other ways difficult to be utilised by conventional extrusion coating methods. Such materials are for example thermoplastic biodegradable polymers, such as polylactides, polyglycolides and their copolymers.

[0017] The dry-application method allows the introduction of the adhesive layer in the lamination process without solvents or other liquid media, thus avoiding drying steps and saving energy.

[0018] The dry-application method allows one or more layers of one or different polymers to be applied before fixation. Also the thickness of the applied dry layer can be varied starting from very thin (<1g/m²) layers. The fixing parameters, such as characteristics of the powder material, temperature, nip pressure and calender speed will define the upper limit for each product.

[0019] The invention is illustrated in more detail in the following examples, which, however, are not intended to limit the scope of the invention.

Examples

[0020] The base materials chosen for the experiments were webs of paper (81,4 g/m²) and aluminium foil. The dry-application barrier and/or adhesive materials were chosen among materials used in paper coating and lamination, especially in extrusion applications. These materials are usually provided in the form of pellets with a diameter of 1 - 2 mm, and the material must thus be ground to a powder before application. The tests were made with powders produced with a laboratory grinder. To avoid sticking the pellets were fed into the grinder together with dry ice. This grinder had a 0.25 mm screen, resulting in that the biggest fraction of the polymer powder was 0.25 mm.

[0021] The powders were applied to the webs by a laboratory dry coating device. The feeding was kept constant in all trials (24 g/m²). The calender speed was kept constant in all trials (about 6 rpm, accounting for about 5 m/min web speed). Three temperature ranges were used, 150, 170 and 190°C, and three nip pressures, 50, 100 and 150 bar, corresponding to 12, 25 and 37 kN/m linear load, respectively.

[0022] The produced structures were tested for grammage, thickness and pinholes. For some samples the water vapour transmission rate (WVTR) was measured, too. Additionally the lamination structures were tested for delamination. For all materials the applicability of the material upon the web and the appearance of the produced structure were visually assessed.

Example 1:

Barrier coating of paper with polyethylene.

[0023] Polyethylene powder with a particle size (diameter) below 0.25 mm was applied onto the paper web by using the dry-application technique. The application of the polyethylene powder onto the paper was satisfying, however the coating amount varied much, from 12.1 to 26.0 g/m², the average being 18.2 g/m². The thickness varied between 19.6 and 25.1 µm, average 22.6 µm. The results are presented in Table 2. The variation in coating thickness was caused by unevenness of the powder, which also caused pinholes. All tested nip temperatures and pressures worked, giving good adhesion to paper, and bad adhesion to PET film or aluminium foil. Delamination was very easy. The water vapour transmission rate was best (lowest) for samples prepared at 190°C, approximately 145 g/m²/day.

Table 1. Grammage and thickness of raw materials

Webs	Grammage, g/m2		Thickness, µm
	Average	St dev*	Average	St dev*
Paper web	81,4	0,2	95,8	0,2

*Standard deviation

Table 2. Grammage and thickness of coatings and laminate layers

Coatings	Example no	Grammage, g/m2		Thickness, µm
		Average	St dev	Average	St dev
Polyethylene	1	18,2	6,3	22,6	2,7
Saran MA 119	2	20,0	4,4	16,4	3,3

Saran MA 119 is a copolymer of vinylidene chloride and methylacrylate.

Example 2:

Barrier coating/lamination of paper with polylactide.

[0024] The polylactide sample was a non-commercial sample of poly(L-lactide) with a molecular weight of about 90 000 g/mole. The material was applied to the paper web using the dry-application technique. Uneven ground powder polylactide led to an uneven application result. The adhesion to the paper web was, however, good.

Claims

1. A method for the dry-application of barrier and/or adhesive materials onto a moving paper or board web, characterised in that powdery polymeric material with particle or particle agglomerate size between 0.01 and 500 µm, preferably between 1 and 50 µm, is dry-applied by ionic blasting onto the paper or board web, wherein the surface of the applied layer is covered with a film which is non-sticking material, before fixation with a calender.

2. The method according to claim 1, characterised in that as cover film polyethyleneterephtalate is used.

3. Method according to claim 1, characterised in that the polymeric material is selected from the group consisting of polyethylene, polypropylene, ethyl vinylacetate polymers polyvinyl alcohol, polyamides, polyesters, ionomers, polystyrene, polyacrylate, polymethacrylate, poly(styrene-acrylate)copolymers, thermoplastic biodegradable polymers such as polylactides, polyglycolides and their copolymers, plastic pigments based on melamin-formaldehyde and ureaformaldehyde or combinations thereof.

4. Method according to claim 1 for the manufacture of packaging materials or laminates with barrier polymers.

5. Method for the manufacture of packaging materials or laminates with barrier polymers according to claim 4, characterised in that the polymeric material is selected from the group consisting of polyethylene, polypropylene, ethyl vinylacetate polymers, polyvinyl alcohol, polyamides, polyesters, ionomers, polystyrene, polyacrylate, polymethacrylate, poly (styrene-acrylate)copolymers, thermoplastic biodegradable polymers, such as polylactides, polyglycolides and their copolymers, plastic pigments based on melamin-formaldehyde and ureaformaldehyde or combinations thereof.

6. Method for the manufacture of packaging materials or laminates with barrier polymers according to claim 4 or 5, characterised in that more than one layer comprising same or different polymers are applied on the web before fixation with a calender.

7. Use of a dry-application method based on ionic blasting for the application of barrier and/or adhesive material(s) onto a moving paper or board web, characterised in that powdery polymeric material with particle size between 0.1 and 500 µm, preferably between 1 and 50 µm, is dry-applied by ionic blasting onto the paper or board web, wherein the surface of the applied layer is covered with a film which is non-sticking material, before fixation with a calender.

8. Use according to claim 7, characterised in that the polymeric material is selected from the group consisting of polyethylene, polypropylene, ethyl vinylacetate polymers, polyvinyl alcohol, polyamides polyesters, ionomers, polystyrene, polyacrylate, polymethacrylate, poly(styrene-acrylate)copolymers, thermoplastic biodegradable polymers, such as polylactides, polyglycolides and their copolymers, plastic pigments based on melamin-formaldehyde and ureaformaldehyde or combinations thereof.

9. Use according to claim 7 or 8, characterised in that more than one layer comprising same or different polymers are applied on the web before fixation.

10. Use according to any of claims 7 - 9, characterised in that the cover film is polyethylene terephthalate.

Ansprüche

1. Verfahren für die Trockenaufbringung von Sperr-und/oder Klebematerialien auf eine sich bewegende Papier- oder Pappebahn, dadurch gekennzeichnet, dass pulverförmiges, polymerisches Material mit Partikel- oder Partikelagglomeratgröße zwischen 0,01 und 500 µm, vorzugsweise zwischen 1 und 50 µm, durch Ionenstrahlen auf die Papier- oder Pappebahn aufgebracht wird, wobei die Oberfläche der aufgebrachten Schicht vor der Fixierung mittels eines Kalanders mit einem Film aus einem nicht haftenden Material abgedeckt wird.

2. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass als Abdeckfilm Polyethylenterephtalat verwendet wird.

3. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass das polymerische Material aus der Gruppe ausgewählt ist, welche aus Polyethylen, Polypropylen, Ethylvinylacetatpolymeren, Polyvinylalkohol, Polyamiden, Polyester, Ionomeren, Polysteren, Polyacrylat, Polymethacrylat, Poly(styren-Acrylat)-Kopolymeren, thermoplastischen biologisch abbaubaren Polymeren, wie zum Beispiel Polyactiden, Polyglykoliden und ihre Kopolymere, auf MelaminFormaldehyd und Ureaformaldehyd basierende Kunststoffpigmente oder Kombinationen davon besteht.

4. Verfahren nach Anspruch 1 zur Herstellung von Verpackungsmaterialien oder Laminaten mit Sperrschichtpolymeren.

5. Verfahren zur Herstellung von Verpackungsmaterialien oder Laminaten mit Sperrschichtpolymeren nach Anspruch 4,
dadurch gekennzeichnet, dass das polymerische Material aus der Gruppe ausgewählt wird, welche aus Polyethylen, Polypropylen, Ethylvinylacetatpolymeren, Polyvinylalkohol, Polyamiden, Polyester, Ionomeren, Polysteren, Polyacrylat, Polymethacrylat, Poly(styren-Acrylat)-Kopolymeren, thermoplastischen biologisch abbaubaren Polymeren, wie zum Beispiel Polyactiden, Polyglykoliden und ihre Kopolymere, auf MelaminFormaldehyd und Ureaformaldehyd basierende Kunststoffpigmente oder Kombinationen davon besteht.

6. Verfahren zur Herstellung von Verpackungsmaterialien oder Laminaten mit Sperrschichtpolymeren nach Anspruch 4 oder 5,
dadurch gekennzeichnet, dass mehr als eine Schicht, welche dieselben oder unterschiedliche Polymere aufweist, vor der Fixierung mit einem Kalander auf die Bahn aufgebracht werden.

7. Verwendung eines Verfahrens zur Trockenaufbringung basierend auf Ionenstrahlung für die Aufbringung von Sperr- und/oder Klebematerial(ien) auf eine sich bewegende Papier- oder Pappebahn,
dadurch gekennzeichnet, dass pulverförmiges, polymerisches Material mit Partikelgröße zwischen 0,1 und 500 µm, vorzugsweise zwischen 1 und 50 µm, durch Ionenstrahlen auf die Papier- oder Pappebahn aufgebracht wird, wobei die Oberfläche der aufgebrachten Schicht vor der Fixierung mittels eines Kalanders mit einem Film aus einem nicht haftenden Material abgedeckt wird.

8. Verwendung nach Anspruch 7,
dadurch gekennzeichnet, dass das polymerische Material aus der Gruppe ausgewählt wird, welche aus Polyethylen, Polypropylen, Ethylvinylacetatpolymeren, Polyvinylalkohol, Polyamiden, Polyester, Ionomeren, Polysteren, Polyacrylat, Polymethacrylat, Poly(styren-Acrylat)-Kopolymeren, thermoplastischen biologisch abbaubaren Polymeren, wie zum Beispiel Polyactiden, Polyglykoliden und ihre Kopolymere, auf MelaminFormaldehyd und Ureaformaldehyd basierende Kunststoffpigmente oder Kombinationen davon besteht.

9. Verwendung nach Anspruch 7 oder 8,
dadurch gekennzeichnet, dass mehr als eine Schicht, welche dieselben oder unterschiedliche Polymere aufweist, vor der Fixierung auf die Bahn aufgebracht werden.

10. Verwendung nach einem der Ansprüche 7 bis 9,
dadurch gekennzeichnet, dass der Abdeckfilm Polyethylenterephthalat ist.

Revendications

1. Procédé d'application à sec de matières barrières et/ou adhésives sur une bande de papier ou de carton en mouvement, caractérisé en ce que de la matière polymère pulvérulente possédant une dimension de particules ou d'agglomérats de particules comprise entre 0,01 et 500 m, de préférence entre 1 et 50 µm, est appliquée à sec par soufflage ionique sur la bande de papier ou de carton, et dans lequel la surface de la couche appliquée est recouverte d'un film qui est fait d'une matière non collante, avant la fixation exécutée au moyen d'une calandre.

2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise du polytéréphtalate d'éthylène comme film de recouvrement.

3. Procédé selon la revendication 1, caractérisé en ce que la matière polymère est choisie dans le groupe composé des substances suivantes : polyéthylène, polypropylène, polymères d'acétate d'éthyle vinyle, alcool polyvinylique, polyamides, polyesters, polystyrène, polyacrylate, polyméthacrylate, copolymères de poly(styrène-acrylate), polymères thermoplastiques biodégradables tels que les polylactides, les polyglycolides et leurs copolymères, pigments plastiques à base de mélamine-formaldéhyde et d'urée-formaldéhyde ou des combinaisons de ces substances.

4. Procédé selon la revendication 1 pour la fabrication de matériaux d'emballage ou de stratifiés comprenant des polymères barrières.

5. Procédé de fabrication de matériaux d'emballage ou de stratifiés comprenant des polymères barrières selon la revendication 4, caractérisé en ce que la matière polymère est choisie dans le groupe composé des substances suivantes : polyéthylène, polypropylène, polymères d'acétate d'éthyle vinyle, alcool polyvinylique, polyamides, polyesters, ionomères, polystyrène, polyacrylate, polyméthacrylate, copolymères de poly(styrène-acrylate), polymères thermoplastiques biodégradables tels que les polyactides, les polyglycolides et leurs copolymères, pigments plastiques à base de mélamine- formaldéhyde et d'urée-formaldéhyde ou des combinaisons de ces substances.

6. Procédé de fabrication de matériaux d'emballage ou de stratifiés comprenant des polymères barrières selon la revendication 4 ou 5, caractérisé en ce que plusieurs couches comprenant les mêmes polymères ou des polymères différents sont appliquées sur la bande avant la fixation exécutée avec une calandre.

7. Utilisation d'un procédé d'application à sec basé sur le soufflage ionique pour l'application de matières barrières et/ou adhésives sur une bande de papier ou de carton en mouvement, caractérisée en ce que de la matière polymère pulvérulente possédant une dimension de particules ou d'agglomérats de particules comprise entre 0,1 et 500 µm, de préférence entre 1 et 50 µm, est appliquée à sec par soufflage ionique sur la bande de papier ou de carton, et dans lequel la surface de la couche appliquée est recouverte d'un film qui est fait d'une matière non collante, avant la fixation exécutée au moyen d'une calandre.

8. Utilisation selon la revendication 7, caractérisée en ce que la matière polymère est choisie dans le groupe composé des substances suivantes : polyéthylène, polypropylène, polymères d'acétate d'éthyle vinyle, alcool polyvinylique, polyamides, polyesters, ionomères, polystyrène, polyacrylate, polyméthacrylate, copolymères de poly(styrène-acrylate), polymères thermoplastiques biodégradables, tels que les polyacides, les polyglycolides et leurs copolymères, pigments plastiques à base de mélamine- formaldéhyde et d'urée-formaldéhyde ou des combinaisons de ces substances.

9. Utilisation selon la revendication 7 ou 8, caractérisée en ce que plusieurs couches comprenant les mêmes polymères ou des polymères différents sont appliquées sur la bande avant la fixation.

10. Utilisation selon l'une quelconque des revendications 7 à 9, caractérisée en ce que le film de recouvrement est du polytéréphtalate d'éthylène.