WO2009052835A2 - Procédé amélioré pour la préparation d'un stratifié et stratifié pouvant être obtenu par ce procédé - Google Patents

Procédé amélioré pour la préparation d'un stratifié et stratifié pouvant être obtenu par ce procédé Download PDF

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Publication number
WO2009052835A2
WO2009052835A2 PCT/DK2008/050262 DK2008050262W WO2009052835A2 WO 2009052835 A2 WO2009052835 A2 WO 2009052835A2 DK 2008050262 W DK2008050262 W DK 2008050262W WO 2009052835 A2 WO2009052835 A2 WO 2009052835A2
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Prior art keywords
film
ink
catalyst
laminate
adhesive
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PCT/DK2008/050262
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English (en)
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WO2009052835A3 (fr
Inventor
Max Otto Henri Rasmussen
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Max Otto Henri Rasmussen
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Publication of WO2009052835A2 publication Critical patent/WO2009052835A2/fr
Publication of WO2009052835A3 publication Critical patent/WO2009052835A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B32B37/1292—Application of adhesive selectively, e.g. in stripes, in patterns

Definitions

  • the present invention relates to a method for the preparation of a laminate comprising a first and a second film, an adhesive, and an ink, in which a catalyst is incorporated, wherein the ratio between the solid content of the catalyst and the solid content of the ink lies in the range of 0.2: 1 to 10: 1.
  • the present invention also relates to the laminate obtained by means of the method and the use of the laminate in the pro- duction of laminated plastic films.
  • Plastic film is a frequently used material for the packaging of numerous articles and products. Within many fields of application, the requirements for such plastic films are of a character that cannot be met by one film alone. Consequently, various laminates of films have been developed with properties that in many respects meet the requirements better.
  • adhesives are used to attach separate films to each other, thus generating a laminate.
  • Various requirements are made for such adhesives, e.g. adherence, heat resistance, transparency etc., and it has been proved that, inter alia, polyurethane-containing adhesives may be used for the adhesion of the separate films of a laminate, thus obtaining the requested properties of the laminate.
  • polyurethane adhesives it is problematic, however, that the curing time is long and that a laminate has to age, possibly at a comparatively high temperature and in a properly ventilated room, to ensure the adhesive curing.
  • the simplest way to accelerate the curing of an adhesive is to add the catalyst directly into the adhesive, immediately before the adhesive is applied to a film that is to be attached to an- other film.
  • this is not efficient, however, since to some extent the adhesive composition will have cured before use. The curing will cause an increased viscosity and a subsequently more difficult application to the film, whereby the application quantity cannot be controlled.
  • a limited space of time is available for the administration of the adhesive composition, the so-called pot-life, and, consequently, production disturbances may cause glue vessels and application devices having to be cleared of cured adhesives.
  • Inks which includes cure promoting lamination inks and cure primers, are often made of inks and cure primers based on vinyl resins, nitrocellulose/polyurethane (NC/PUR) resins, polyvinyl butyral (PVB) resins or acrylic resins. While the vinyl resin based inks are usually diluted with different mixtures of solvents like ethyl acetate, acetone, methyl ethyl ketone (MEK) or mixtures of these with ethyl alcohol or isopropyl alcohol (IPA), the NC/PUR resin or PVB resin based inks are diluted with pure ethanol or IPA or mixtures of ethanol or IPA with ethyl acetate.
  • N/PUR nitrocellulose/polyurethane
  • PVB resin based inks are usually diluted with different mixtures of solvents like ethyl acetate, acetone, methyl ethyl ketone (MEK) or mixtures of
  • NC/PUR and PVB based lamination inks may sometimes contain adhesion promoters in order to ensure good adhesion to a wide selection of printing and lamination films. These adhesion promoters can also cause problems or interaction in various ink formulations and are sometimes avoided or their use is limited or excluded from certain lamination ink formulations.
  • inks which may be applied and used at lower application weights as compared to the inks known today, and which comprise a catalyst in an amount, at which their ability to accelerate the cure of laminating adhesives is not lost.
  • inks are based on water in order to avoid the risk of smell due to insuffi- cient drying.
  • the object of the present invention is to provide an improved method for the preparation of a laminate comprising a first and a second film, an adhesive, and an ink, in which a catalyst is incorporated
  • this is in one aspect achieved by: a) providing an ink mixture comprising an ink and a catalyst, said mixture having a ratio between the solid content of the catalyst and the solid content of the ink in the range of 0.2: 1 to 10: 1, more preferred 2: 1 to 5: 1, and even more preferred 3: 1 to 4: 1; b) applying to a first film one or more completely or partially covering layers of the ink mixture; c) laminating the first film, which has been applied with the ink mixture, to a second film using an adhesive, the curing of which is accelerated by the catalyst.
  • the ratios and percentages indicated according to all aspect of the present invention are on weight basis.
  • the ratio between the solid content of the catalyst and the solid content of the ink is higher when applied to the film during the laminating procedure as compared to the ratio in inks used in well-known pro- cedures.
  • the ink mixture according to the present invention is capable of comprising such a high ratio of catalyst to ink provides a significant advantage over the prior art cure primers, whereby substantially less ink mixture need to be applied to the laminate for achieving the same or an even better catalytic effect. This is of great significance for the speed and consequently the cost of the lamination process.
  • the present invention also relates to the laminate obtainable by this method as well. Furthermore, the invention relates to the use of a laminate according to any of the aspects of the present invention for the production of a laminated plastic film. Thus, the present inventors have surprisingly discovered that an improved lamination is achieved even using the specific ink mixture.
  • the measurable amine migration is comparatively low, and, in addition, a fairly satisfactory mutual adherence of the films is obtained shortly after the preparation of the laminate. Due to the quick curing of the adhesive used as well as the low amine migration, the laminate prepared needs no or only moderate ageing before further treatment. Espe- dally within the food industry a low amine migration is in great demand, and, when in use, the laminate should show no amine migration at all.
  • the fact that the laminate prepared may be exposed to further treatment shortly after its preparation is advantageous from a producer's point of view, inter alia, because this will reduce the need for storage room, and, sales of the laminate prepared can start sooner after production.
  • a laminate according to the invention has a reduced tendency to telescoping, i.e. shear of the films relative to each other.
  • the ink mixture is applied to the first film at an application weight in the range of 0.2 to 0.8 g/m 2 based on dry weight, preferably at 0.3 g/m 2 . Due to the low solid content of the mixture of ink and catalyst it is possible to apply ink at this low application weight range.
  • a method for the preparation of a laminate comprising the steps of: a) providing an ink mix- ture comprising an ink and a catalyst, said mixture having a total solid content in the range of 2 to 20 % based on the weight of the mixture, b) applying to a first film one or more completely or partially covering layers of the ink mixture, c) laminating the first film, which has been applied with the ink mixture, to a second film using an adhesive, the curing of which is accelerated by the catalyst. Due to this low solid content in the ink mixture the mixture may be applied at a lower application weight as compared to prior art mixtures.
  • a method for the preparation of a laminate comprising the steps of: a) providing an ink mixture comprising an ink and a catalyst, said ink being water soluble, for example an polyethylene imine, ethylene ethyl acrylate or polyvi- nylidene chloride, preferably polyethylene imine, b) applying to a first film one or more completely or partially covering layers of the ink mixture, c) laminating the first film, which has been applied with the ink mixture, to a second film using an adhesive, the curing of which is accelerated by the catalyst.
  • the ink mixture is used in a so-called in-line-process where it is applied directly in the laminating machine.
  • in-line and out-of-line are referring to the lamination process. Consequently, in an out-of-line application the ink mixture is added out of context with the lamination, e.g. during the printing process, and in an in-line application the ink mixture is applied in the lamination process. It is also contemplated that some facilities may comprise an integrated printing and laminating station in which case in- line would refer to application in the lamination station.
  • Printing stations are not always availible to apply the ink mixture and it would be too costly to have to apply the ink mixture in an extra operation. Moreover many laminates are unprinted, around 20 - 30%, therefore these would have to be covered by a ink mixture application unit placed on the laminator.
  • a means for converting should be present on the laminator for switching the ink mixture unit on and/or off dependening on how urgent an order for lamination is, thus in this embodiment a ink mixture unit would be supplied together with the laminator. In such situations it is an advantage to use the in-line application.
  • Application equipment is available from Ahlbrandt Systems GE or Weko Biel. These examples of units are capable of applying at least 1 gr/m 2 wet mixture, thus being applicable in the methods of the present invention.
  • the in-line application may be used in both solvent based and solvent free systems.
  • the ink mixture application may be placed in different positions on one film and it may be applied on either the first or second film.
  • the ink mixture may be applied before or after drying, preferably before drying and adhesive application.
  • the ink mixture may in preferred embodiments be added in at least two alternative positions, either on a more rigid typically printed film or another film, which is usually more flexible and may be heatsealable/weldable and/or heatsealable/weldable at a lower temperature than the first film.
  • a more rigid typically printed film or another film which is usually more flexible and may be heatsealable/weldable and/or heatsealable/weldable at a lower temperature than the first film.
  • the more and less rigid film respectively.
  • the ink mixture is applied on the less rigid film, which is usually a film more weldable than the first.
  • the less rigid film may comprise a high content of release agent.
  • the film is by means of the ink mixture provided with a high affinity for the lamination adhesive as compared to the film wothout ink mixture.
  • a polyethylene imine (herein after PEI) based ink mixture provides a particularly high affinity to the film and is a preferred primer base according to the present invention. It is a general desire that the more weldable inner film has a high content of release agent. A higher content of release agent allows for a faster operation of the packing machines.
  • a disadvantage of a high content of release agent is however, that the attachment of the laminate may be impaired and additionally that the release agent may react with some adhesives used in the lamination process in an undesired way.
  • applying the ink mixture according to this embodiment provides both a higher affinity of release agent-containing films and increases the curing of the adhesive.
  • the ink mixture will end up between the food contact film and the adhesive. This provides a barrier between the food and the adhesive for the formation of aromatic amines, which are known to be able to migrate into the foodstuff through the film.
  • the ink mixture may be added on top of the more rigid, typically printed, film, for example before adhesive application.
  • the ink mixture may be applied on top of the printing ink.
  • printing inks contain many types of additives as well as remnants of alcohol and/or water all of which may react in an undesired way with the residues, such as isocyante residues, of the lamination adhesive.
  • residues such as isocyante residues
  • the ink mixture used is a waterbased polyethylenimine primer, for example based on a K-1023 formulation available from Mica Corporation, which offers a number of important advantages over solvent based inks.
  • solvent based inks there are always the risk of smell due to insufficient drying of the solvents.
  • water based PEI based primers the risk of odour or smell is less than from solvent based cure primers.
  • Water is furthermore a cost-effective diluent and with a desire to run and apply a formulation at arround 2 % solids for ideal drying speeds, the cost of diluting with water is negligible.
  • ink used in the present description and claims in- eludes cure promoting lamination inks as well as primers and refers to both pigmented and un-pigmented inks and varnishes as well as clear and coloured varnishes.
  • inks e.g. gravure, flexography or offset printing
  • the ink employed may be of any suitable type, e.g. nitrocellulose, PVB or acryl or combinations thereof.
  • the inks may be offset inks, e.g. oil-based or water-based.
  • the ink may have any colour or be uncoloured.
  • the inks may be based on any solvent, in particular, they may be dilutable in ethanol, isopropanol, ethylacetate, methylethylketon, acetone, water or combinations thereof. Furthermore, inks without being based on solvents may be used.
  • the inks used according to the invention may be single- component, dual-component and/or even three-component inks.
  • Single- component inks are immediately employable for printing, possibly after having been diluted by a suitable solvent.
  • Dual-component inks are foreseen to be mixed immediately before use, whereby the first component comprises a standard ink and the second component the catalyst.
  • Water-based inks are, however, preferred, in order to avoid the risk of smell due to insufficient drying.
  • the water-soluble inks based on polyethylene imine, ethylene ethyl acrylate, ethylene acrylic acid copolymers, poly acrylic acid or polyvinylidene chloride are particularly preferred.
  • a major advantage of using polyethylene imine as compared to any other ink is that polyethylene imine adheres to almost any film surface, which typically is employed in the film industry, whereas conventional inks, such as inks based on acrylic, PVB and NC/PU either have to be modified or ink promoters have to be added in order to obtain a satisfactory adhesion.
  • Certain waterborne polymeric compounds have sufficient adher- ence to a film substrate without use of an ink promoter (pre-priming), therefore providing a useful base for an ink/primer, for example some grades of waterborne polyurethane dispersions.
  • Ink mixture is in the context of the present invention an ink and a catalyst.
  • Cure primer may also be used having the same meaning as “ink mixture”.
  • any adhesive that is capable of curing in the presence of a catalyst may be used.
  • Preferred adhesives are of the polyurethane type, acrylic adhesives and alcohol-based or water-based imine epoxy systems.
  • Polyurethane adhesives may be single-component systems or dual-component systems.
  • a polyurethane adhesive comprises at least one organic polyisocyanate and at least one polyol, the polyisocyanate comprising two or more isocyanate groups, and the polyol two or more hydroxy groups.
  • the polyol may be a polyester polyol, a polyether polyol or a polyetheresterpolyol.
  • the polyisocyanate may be a pre-polymer.
  • diisocyanates for polyurethane adhesives are 1,6-diisocyanate-hexane, 1,10-diisocyanatedecane, 1,3- diisocyanatecylopentane, 1,4-diisocyanatecyclohexane, 1-isocyanate- 3,3,5-trimethyl-3 or -5-isocyanatemethancyclohexane, 4,4'-, 2,4'- and 2,2'-diisocyanate diphenylmethane, 1,5-di-isocyanatenaphtaline, 4,4'- diisocyanate-dicyclohexylmethane, 1,4-diisocyanate-benzene and/or 2,4- or 2,6-diisocyanatetoluene.
  • Pre-polymers of polyisocyanates may e.g. be achieved by reacting the above diisocyanates with a polyvalent alcohol.
  • polyols for polyurethane adhesives are al- kandiols with linear or branched carbon chains, e.g. ethylenglycol, 1,2- dihydroxypropane, 1,3-dihydroxypropane, 1,4-dihydroxybutane, 1,6- dihydroxyhexane and neopentylglycol.
  • ethylenglycol 1,2- dihydroxypropane, 1,3-dihydroxypropane, 1,4-dihydroxybutane, 1,6- dihydroxyhexane and neopentylglycol.
  • the polyol being a polyetherpolyol, this is usually obtained by adding ethylenoxid to a compound comprising two or more active hydrogen atoms in a molar ratio of 30 to 90%.
  • Suitable examples of compounds comprising two or more active hydrogen atoms are ethylenglycol, diethylenglycol, propylenglycol, dipropylenglycol, glycerin, trimethylolpropane, pentaerytritol, sorbitol, saccharose or the like.
  • ethylenoxid e.g. propylenoxid and bu- tylenoxid may be used.
  • polyetherpolyol has a molecular mass in the range from 1,000 to 20,000, especially between 1,000 and 5,000.
  • Polyurethane adhesives used for single-component systems comprise e.g. pre-polymers of polyisocyanates and polyols, the said adhesive curing when reacted with water. Examples of this may be found in German patent No. 2549227 and European patent application No. 0586843 Al.
  • Dual-component systems either consist of pre-polymers with free isocyanate groups curing by means of a hydroxy group bearing crossbinder, or of pre-polymers with free hydroxy groups, curing by means of isocyanate group bearing crossbinders.
  • Examples of the first type of dual-component systems are disclosed in German laid-open publication No. 4021113 and in European patent No. 150444. Examples of the latter type of dual-component systems are listed in European patent No. 176726.
  • No matter the type of polyurethane adhesive, these may comprise a solvent, be free of solvents or water-based.
  • it is preferred to use a dual- component system in which the various components are mixed immediately before their application to the first film.
  • the catalysts accelerating the curing of the polyurethane adhesives are known from the prior art.
  • Various substance groups are proved active catalysts, inter alia Lewis bases and Lewis acids.
  • the most important Lewis bases are tertiary amines, e.g. diazabicyclooctane, triethyl- amine, dimethylbenzylamine, bisdimenthylaminoethylether, tetrame- thylguanidine and bisdimethylaminomethylphenol.
  • the most important catalytically effective Lewis acids are metallo-organic compounds, espe- dally tin organic compounds, like tindiethyl hexanoate, dibutyltindilau- rate, dibutyltin bisdodecyl mercaptide and lead-phenylethyldithio car- baminate.
  • the metallo-organic compounds are activating the isocyanate groups thus making these electrophile, whereas the bases first and foremost increase the nucleophile properties of the OH group.
  • catalysts are alkaline salts of organic acids and phenols, like phenol-Mannich-bases, phosphine and phospholinoxide.
  • ⁇ -caprolactam and polyethylene glycol have catalytic properties, and in the present invention the use of ⁇ -caprolactam, which is available as a powder, flakes or in a fluid form, is preferred as a catalyst.
  • the catalyst itself may be an appropriate mixture of several different catalysts so as to obtain an optimal curing in relation to various types of adhesive
  • the catalyst content of ink is up to 20%.
  • a catalyst content of more than approximately 66% is employed.
  • the preferred ratio between the solid content of the catalyst and the solid content of the ink lies in the range of 0.2: 1 to 10: 1, more preferred 2: 1 to 5: 1, and even more preferred 3: 1 to 4: 1.
  • the mixture comprising ink and catalyst has preferably a total solid content in the range of 2 to 20% based on the weight of the mixture, when applied to the film. This low content in the mixture makes it possible to apply the mixture of ink and catalyst to a film at an application weight, which lies in the range of 0.2 to 0.8 g/m 2 based on dry weight. An application weight of 0.3 g/m 2 is most preferred.
  • the catalyst per se, may be added to the ink immediately or, as a pre-solution, possibly by use of a surfactant to obtain a homogenous distribution in the ink.
  • the catalyst preferred, ⁇ -caprolactam is preferen- tially added to the ink as a pre-solution.
  • the pre-solution comprises equal parts of ⁇ -caprolactam and isopropanol and/or water.
  • first film should be understood as the film to which the "ink mixture” or “cure primer” is applied.
  • the first film may be the printed film and/or the more rigid film, while in other embodiments the first film is the film without printing ink and/or the less rigid film.
  • the first film may partially or entirely be made of a plastic material, preferably chosen from polyesters, in particular oriented polyesters; polyolefines, e.g. polyethylenes and oriented polypropylenes or cast polypropylenes; polyamides, in particular cast polyamides or oriented polyamides; and cellophane.
  • the first film may also consist entirely or partially of aluminum-containing materials, metalized plastics, paper, or metalized paper.
  • the second film may be of the same type as the first film.
  • the second film consists entirely or partially of alu- minium-containing materials, metallized plastics, paper, metallized paper, or plastic materials, in particular polyethylene and polypropylene.
  • Both the first and the second film and/or less rigid film may be weldable, in a typical embodiment the second film and/or less rigid film is weldable at a lower temperature than the first film.
  • Both films may contain a release agent. It is preferred that the second film and/pr the less rigid film comprises the release agent. Examples of release agents are silicones and Teflon ® , the choice of release agent is within the skill of the art.
  • Both the first and the second film may incorporate a catalyst for an adhesive. Using a film with an incorporated catalyst is particularly recommendable in case of only partial application of ink to the film. In this way, a catalyzed curing also takes place outside the areas of the film covered with catalyst-containing ink. In cases where a film without an incorporated catalyst is used along with partial application of catalyst-containing coloured ink it is recommendable to apply a completely covering layer of clear varnish or un- pigmented catalyst-containing ink to the first film. In this way, a catalyzed curing is ensured outside the areas of the film originally covered with ink as well.
  • Multi-colour printing is well-known in the prior art, i.e. applying several layers of different inks consecutively or on top of each other. All applied inks may contain a catalyst, so that catalyzed curing is taking place within all areas of the laminate. If at last a completely covering ink is applied, a so-called background colour, only that ink needs to contain a catalyst to ensure a catalyzed curing within all areas of the laminate. If desired, a catalyst-containing ink may be used.
  • the first and/or the second film may be a laminate, per se.
  • it may be advan- tageous to coat the metallized film with a plastic film prior to applying the ink.
  • the adhesive may either be applied to the first or the second film, prior to them being attached to- gether or be added simultaneously.
  • the adhesive is applied to the first ink covered film because this first film is more rigid.
  • the laminates prepared may be used for the wrapping and packaging of food, i.e. they get in immediate contact to food. Therefore, it must be ensured that no noxious substances are transferred to the food, or at least the extent of the transfer must be non-toxic, ⁇ - caprolactam is a comparatively non-toxic compound, which is released for use in materials getting into contact with food. Since the catalyst is placed between the two films of the laminate, it will not get into immediate contact with the food. As the ⁇ -caprolactam content in the ink mix- ture is used up in the curing process with the laminating adhesive, for example the polyurethane laminating adhesive, there are none or only negligible amounts of traces of ⁇ -caprolactam left in the final laminate.
  • the laminating adhesive for example the polyurethane laminating adhesive
  • polyethylene imine based primers can contain rather high content of ⁇ -caprolactam without loosing the adhe- sion properties to either the base-film or the adhesion to the laminating adhesive.
  • R 5258 which is a 5 % solids polyethylene imine based primer supplied by Flevo Chemie (Nederland) BV, Havendijk 8a, 3846 AD Harderwijk, the Netherlands.
  • Flevo Chemie is an agent and toll-manufacturer for Elm
  • CER 1 R 5258 is a water-based primer, and it is therefore possible to mix ⁇ -caprolactam, which is water-soluble, into NOVACER 1 R 5258 by ob- serving general good laboratory practice.
  • ⁇ -caprolactam which is water-soluble
  • NOVACER 1 R 5258 by ob- serving general good laboratory practice.
  • NOVACER 1 R 5258 contains 50 grams polyethylene imine resin.
  • ⁇ -caprolactam and polyethylene imine 150 grams and 200 grams, respectively, of ⁇ - caprolactam was each added to 1 kg sample of NOVACER 1 R 5258.
  • the 2 primers were coated onto 30 pes. of 2 mm glass plates, which had a size of 15 cm x 20 cm. The coatings were applied with a wire rod roller, which by calculation of the 2 % solids content gave a sufficient wet application weight to achieve approximately 0.3 grams per m 2 DRY.
  • the coated glass plates were placed in a hot air oven at 60 0 C for 30 minutes. 5 of the glass plates coated with X 14 were coated again with X 14 in order to examine the effect of a double coating. For testing purpose there was now a stock of 30 coated glasses + 10 uncoated glass plates to be used as a blind reference:
  • OPP film Resinos standard lamination
  • OPP film Exxon/Mobil 35 ⁇ m MB 400
  • BOPP film Film Y
  • Lamination Adhesive Morfree 406 + catalyst C78 Solvent free laminating adhesive from Rohm & Haas, Bremen
  • OK - FILM-TEAR AFTER 2 HOURS 2a Glass coated with X 14/2 Laminated to PE film Z
  • MICA A-131- X was an obvious trial- candidate, as MICA A-131- X can be delivered with a solid content of 5 % as a standard product - similar to the solids content of 5 % of PEI primer Novacer 1 R5258 from Flevo Chemie.
  • content of ⁇ - caprolactam in the first trial was between 3: 1 and 4: 1, for practical and rational reasons a mixing ratio between ⁇ -caprolactam and MICA A-131- X based on dry solids was chosen to be 3.3 : 1 for MICA A-131- X.
  • MICA A-131- X is manufactured by MICA CORPORATION, 9, Mountain View Drive, Shelton, CT 06484-6404, USA .
  • MICA Corporation we asked MICA Corporation to mix 165 gram ⁇ -caprolactam into 1 kg MICA A-131- X, which with a solids-content of 5 % for MICA A-131- X gives a mixing ratio of 3.3 : 1 between ⁇ -caprolactam and the solids content of 50 grams per 1 kg sample of MICA A-131- X.
  • Such a PEI based cure primer may be used both IN-LINE or OUT-OF-LINE.
  • Mica Corporation has made lab-tests confirming that when dried correctly there is no blocking to the opposite film when applied in an out-of-line process for subsequence lamination in a laminating machine.
  • PEI-based cure primer in a so called IN-LINE PROCESS where the cure primer can be applied directly on the laminating machine.
  • K-1023 cure primer with an application weigth of 0.3 g/m 2 dry is relatively easy to dry - it can be applied on the laminating machine - either on the printed film - and when dried well prior to the laminating adhesive unit or alternatively - on the secondary PE-laminating film - if in both cases the K-1023 cure primer coating is dried well.
  • a waterbased PEI primer based on a K-1023 formulation would offer a number of important advantages over solvent based inks. With solvent based inks there are always the risk of smell due to insufficient drying of the solvents.
  • K-1023 formulated PEI-based inks can be carried out on usual Flexo or Gravure printing presses, og on so-called "satelite printing-stations" on Flexo presses from printing-press manufacturers like Rotomec and Schiavi or on special applications units from special low-coating weigth spray-on application unit manufacturers like Ahlbrandt System GmbH, Altebergstra ⁇ e 23 - 27, 36341 Lauter- bach/Hessen, Germany, BC-Egan - Black Clawson Converting Machinery, 46 North First Street Fulton, NY 13069, USA or WEKO Biel AG, Joh. Renferstrasse 58, CH-2552 Biel.
  • This example demonstrates usefulness of different ink/primer polymeric bases/vehicles for preparation of laminates and for providing adhesive cure acceleration.
  • Primer 1 MICA A-131-X, PEI-based film primer available from Mica Corporation, Shelton, CT
  • Primer 2 MICA M-1164 (a proprietary formula containing acrylic acid copolymer) available from Mica Corporation, Shelton, CT
  • Primer 3 Neores R-600, a polyurethane dispersion, available from DSM Neoresins, Wilmington, MA
  • the bond strength was measured on the peel tester (Thwing- Albert Instrument Company, Friction/Peel Tester Model 225-1) at 12 in/min separation rate (average values were recorded).
  • the following table shows the adhesive bond strength development over time, which reflects the cure rate of the adhesive.

Abstract

L'invention concerne un procédé de préparation d'un stratifié qui comprend un premier et un second film, un adhésif et une encre, dans laquelle un catalyseur est incorporé. Selon l'invention, la teneur en solides du mélange d'encre est plus faible lors de l'application sur le film pendant la procédure de stratification en comparaison de la teneur présente dans les encres utilisées dans les procédures de stratification connues.
PCT/DK2008/050262 2007-10-26 2008-10-27 Procédé amélioré pour la préparation d'un stratifié et stratifié pouvant être obtenu par ce procédé WO2009052835A2 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN106795282A (zh) * 2014-10-17 2017-05-31 株式会社日本触媒 乙撑亚胺聚合物及其制造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0611146A2 (fr) * 1993-02-09 1994-08-17 Toyo Seikan Kaisha Limited Stratifié pour emballage flexible et un procédé pour sa préparation
CA2257963A1 (fr) * 1996-07-15 1998-01-22 Max Otto Henri Rasmussen Procede de preparation d'un produit lamine et produit resultant
WO1998002303A1 (fr) * 1996-07-15 1998-01-22 Max Otto Henri Rasmussen Procede de preparation d'un produit lamine et produit resultant
US20060052523A1 (en) * 2004-09-03 2006-03-09 Paula Bushendorf Laminating adhesive, laminate including the same, and method of making a laminate
EP1647588A2 (fr) * 2004-10-13 2006-04-19 Rohm and Haas Company Compositions durcissables par réaction d'addition du type Michael activé à la surface

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0611146A2 (fr) * 1993-02-09 1994-08-17 Toyo Seikan Kaisha Limited Stratifié pour emballage flexible et un procédé pour sa préparation
CA2257963A1 (fr) * 1996-07-15 1998-01-22 Max Otto Henri Rasmussen Procede de preparation d'un produit lamine et produit resultant
WO1998002303A1 (fr) * 1996-07-15 1998-01-22 Max Otto Henri Rasmussen Procede de preparation d'un produit lamine et produit resultant
US20060052523A1 (en) * 2004-09-03 2006-03-09 Paula Bushendorf Laminating adhesive, laminate including the same, and method of making a laminate
EP1647588A2 (fr) * 2004-10-13 2006-04-19 Rohm and Haas Company Compositions durcissables par réaction d'addition du type Michael activé à la surface

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106795282A (zh) * 2014-10-17 2017-05-31 株式会社日本触媒 乙撑亚胺聚合物及其制造方法
CN106795282B (zh) * 2014-10-17 2019-01-22 株式会社日本触媒 乙撑亚胺聚合物及其制造方法
US10370494B2 (en) * 2014-10-17 2019-08-06 Nippon Shokubai Co., Ltd Ethleneimine polymer and method for producing same

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