WO2007138096A1 - Process of high speed laminating - Google Patents

Process of high speed laminating Download PDF

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Publication number
WO2007138096A1
WO2007138096A1 PCT/EP2007/055324 EP2007055324W WO2007138096A1 WO 2007138096 A1 WO2007138096 A1 WO 2007138096A1 EP 2007055324 W EP2007055324 W EP 2007055324W WO 2007138096 A1 WO2007138096 A1 WO 2007138096A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
anyone
linear aliphatic
solvent
range
Prior art date
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.)
Ceased
Application number
PCT/EP2007/055324
Other languages
English (en)
Inventor
Heinz-Peter Pfeiffer
Peter Schreiber
Engin Temeltas
Regina Wittenbruch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bostik SA
Original Assignee
Bostik SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bostik SA filed Critical Bostik SA
Publication of WO2007138096A1 publication Critical patent/WO2007138096A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/14—Velocity, e.g. feed speeds
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives

Definitions

  • the invention is directed to a process for bonding substrates, in particular, for producing foil laminates under high speed, preventing misting effects during laminating.
  • Laminate adhesives are used for large-area bonding of individual foils to form laminates.
  • the properties of the individual foils are combined in such a way that the laminate is suitable for subsequent use as a packaging material for the packaging of goods, such as, for example, foodstuffs, hygiene articles or items which need protection from damage prior to first usage.
  • Laminate adhesives consist as a rule of isocyanate group- containing polyurethane binders, usually manufactured from hydroxyl- group-containing polyesters, polyether or simultaneously ester-and ether- group-containing hydroxy-functional condensation products and polyfunctional isocyanates, described, for example, in WO 99/24486, U.S. 6,503,981 and U.S. 6,914,102.
  • customary coating and laminating machines are used, for example, pressure, laminating and hotmelt machines known by a person skilled in the art, which have a heatable application mechanism, and which are operating, for example, with smooth or patterned rollers or also with suitable wipers. Evaporation zones, IR or hot-air drying or heating ducts can be used.
  • a thin coating application of, for example, 0.5 to 10 g/m2, is sufficient.
  • the coating speed can be in the range of about 50 to 300 m/min or more.
  • U.S. 4,092,202 describes a method for producing foil laminates by coating under high speed using a solvent-free, free NCO or NCS group containing reaction product of hydroxyl-functional polyethers or polyesters with polyisocyanates.
  • Preferred polyethers are aliphatic, straight- or branched-chain polyethers; preferred polyesters are linear or branched products made from aliphatic and/or aromatic polycarboxylic acids and polyols.
  • polyisocyanates aliphatic, aromatic and/or cyclo-aliphatic products may be usable.
  • Unwanted misting effects during the laminating process may require the machine speed to be limited. Such misting effects can lead to a large amount of pollution inside and outside the laminating machine caused by the laminate adhesive product. Misting can also promote the evaporation of monomeric isocyanates which originate from the adhesive composition and which can be injurious to the health of the operators of the machines.
  • the present invention provides a method of producing laminates by applying a solvent-free adhesive composition onto at least one side of the substrates to be joined together at high speed greater than 100 m/min and curing; wherein the solvent-free adhesive composition is comprising :
  • the wt% are based on the adhesive composition.
  • the method according to the invention provides a method which follows the steps of applying the solvent-free adhesive composition according to the invention onto one or both of the foil sides to be joined together at a speed of more than 100 m/min.
  • the solvent-free adhesive composition used for the method according to the invention comprises the polyester of component A), the polyethers of component (B) and the diisocyanates of component (C).
  • the polyesters of component A) are linear aliphatic polyesters based on linear dicarboxylic acids having a carbon number in the range of C3 to C12, preferred in a range of C4 to C8, and diols.
  • the polyesters are hydroxy functional and exhibit hydroxyl values in the range of 15 to 150 mg of KOH/g and acid values in the range of 0 to 6 mg of KOH/g.
  • Suitable linear dicarboxylic acids are adipic acid, sebacic acid,fugic acid, succinic acid, derivatives thereof and mixtures thereof.
  • Diols which may be used are, for example, ethylene glycol, diethylene glycol, triethylene glycol, hexanediol, butanediol, propylene glycol, methylpropandiol-1.3, neopentylglycol, and mixtures thereof.
  • the polyesters may be produced in conventional manner by performing an esterification reaction of the acid component with the alcohol component, for example, in a nitrogen atmosphere, for example, at temperatures of between 140 and 260 0 C, with or without use of conventional esterification catalysts.
  • the linear aliphatic polypropylene glycols of component B) are hydroxy-functional preferably exhibiting a hydroxyl value of 50 to 400 mg of KOH/g.
  • Mn number average molecular weight
  • a preferred amount of component B) is 20 to 40 wt%.
  • the diisocyanates used as component C) may be aliphatic diisocyanates, trimerization products thereof and/or aromatic diisocyanates as known by a person skilled in the art.
  • diisocyanates are isophorone diisocyanate (IPDI), or hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate or the trimerization products, for example, aliphatic diisocyanate-based isocyanurates or mixtures thereof.
  • Aromatic diisocyanate compounds may also be present, such as, for example, tolylene diisocyanate (TDI), diphenylalkyl diisocyanates (for example diphenylmethyldiisocyanates or MDI) or mixtures thereof.
  • TDI tolylene diisocyanate
  • MDI diphenylalkyl diisocyanates
  • MDI diphenylmethyldiisocyanates
  • TDI and MDI are used.
  • the diisocyanates can be used also in blocked form. Blocking may proceed with conventional agents, e.g., with ethylene glycol monobutyl ether, butanone oxime, phenol, ethyl acetoacetate, malonic ester, dimethylpyrazole or caprolactam.
  • the solvent-free adhesive composition may be produced with less than 3% chain extenders related to the adhesive composition.
  • the chain extenders may comprise the short-chain diols conventionally used for this purpose, such as, ethylene glycol, 1 ,2- or 1 ,3-propanediol, 1 ,6-hexanediol, di- or tripropyleneglycol.
  • no chain-extenders are used.
  • Components A), B) and C) can be mixed together by techniques known by the art, and can be stored for months. They can also be mixed together directly prior to application onto the substrates to be bonded. Mixing may be performed, for example, in a static mixer or a mixing tube.
  • the viscosity of the finished adhesive composition lies, for example, in a range from 300 to 1 ,000 mPas, particularly preferably, between 400 to 800 mPas, measured at 100 0 C.
  • the adhesive composition according to the invention may contain the additives conventional in polyurethane chemistry, such as, for example, catalysts, accelerators, light stabilizers, extenders, pigments in the amounts conventional in coating chemistry, e.g., from 0.5 to 5 wt.%, relative to the adhesive composition.
  • additives are used.
  • Adhesion promoters may be used in quantities under 2 wt% based on the adhesive composition. Preferably, no adhesive promoters are used.
  • the adhesive composition according to the invention may be used to stick the most varied materials together.
  • These materials may be, for example, web-form materials of plastics, such as, polyethylene, polypropylene, polyamide, PET (polyethylene terephthalate), paper or metal, e.g., metal foils, such as, aluminium foils, or plastics films, such as, metal oxide vapour-deposited or metal vapour-deposited plastics films.
  • the invention also provides use of the adhesive composition of the invention for bonding substrates, in particular, for producing laminates for packaging.
  • the application speed employed in the course of the method according to the invention should be in the range of about 100 to 300 m/min, preferably, more than 150 m/min and more preferably, more than 200 m/min. Basically, however one can also use faster speeds if the machines are designed accordingly.
  • the method according to the invention can be carried out on the most varied types of machinery, for example, pressure, laminating, and hotmelt machines comprising, for example, a heatable application mechanism suitable for thin application at the required machine operating speed.
  • the adhesive application can be accomplished with smooth or patterned rollers, either coaxially or counter-currently, or also with suitable wipers. This is known to a person skilled in the art.
  • the lamination may be accomplished immediately after the application mechanism. It is possible to connect evaporation zones, IR or hot-air drying or heating ducts or additional devices between the steps, but it is not necessary, even at high machine operating speeds, for example, in excess of 150 m/min.
  • the processing temperature is selected so that the viscosity of the mass, when the application mechanism is correspondingly adjusted, permits the desired application volume, while avoiding that the foil, which is to be coated with the adhesive composition, is damaged by the temperature applied or is unfavourably influenced in terms of its quality and gauge.
  • the temperature of the adhesive composition therefore should not be above 110 0 C, preferably between 60 0 C and 100°C
  • the application is possible in continuous or discontinuous application manner as known to a person skilled in the art.
  • the process according to the invention it is possible to produce laminates with high processing reliability, and the foils are joined immediately after application of the adhesive composition in such a way that, even at high machine speeds, there will be no bubble or crease formation as a result of the foils being shifted with respect to each other, or there will be no shifting of the foil during windup, and a high resistance of the foil laminate results. Furthermore, it is ensured that no substances injurious to the health of the consumer are developed or released, and no misting effect is noticed. A perfect, uniform coating, even in quantities of above 0.5 g/m 2 is possible.
  • the present invention is further defined in the following Examples.
  • Viscosity 2500 to 3000 mPas
  • 750 g of 2.4'-Diphenylmethanediisocyanate and 750 g of 4,4' Diphenylmethanediisocyanate are filled into a 4I reactor with interior thermometer and stirrer and homogenized by heating to 50 0 C.
  • 912 g of the polyester of Example 1 are added and the mixture is heated until the exothermic reaction starts.
  • the batch is kept at 80°C for 1 hour and cooled to 60°C to charge 1508 g of polypropyleneglycol 1100.
  • the batch is heated to 80°C again, stirred for 2 hours at this temperature.
  • 72 g of dipropyleneglycol is added and one hour later the viscosity and the isocyanate content of the resulted composition is measured.
  • Example 1 b On a Labocombi 400 lamination machine a polyester web (thickness 12 ⁇ m / 300 mm width) was bonded with aluminium foil (thickness of 9 ⁇ m / 300 mm width) by use of the adhesive composition of Example 1 b to give a laminate, and cured during a time of 3 days. Dry coating weight was approximately 1.5 g/m 2 .
  • a laminate of the same materials was produced under the use of an adhesive of the prior art based on a linear aromatic polyester with Mn 1000 to 1200.
  • the adhesive of the prior art shows misting effects already at lower application speeds.
  • the values for bond strength according to the 90° Peel Test (DIN 53357, method A) of different laminates were measured. The results are shown in Table 2.
  • the bonding properties of the laminates provided by the invention have similar values as the bonding properties of the laminates provided by the prior art, according to the application standards in this application field.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a method of producing laminates by (a) applying a solvent-free adhesive composition comprising (A) 5 to 40 wt% of at least one linear aliphatic polyester based on linear dicarboxylic acids having a carbon number in the range of C3 to C12 and diols, (B) 20 to 50 wt% of at least one linear aliphatic polypropylene glycol having a molecular weight Mn of 400 to 2000, and (C) 20 to 45 wt% of at least one diisocyanate, the wt% are based on the adhesive composition, onto at least one side of the substrates to be joined together at a high speed greater than 100 m/min, and (b) curing the applied composition to avoid misting effects during coating and laminating under high speed.
PCT/EP2007/055324 2006-05-31 2007-05-31 Process of high speed laminating Ceased WO2007138096A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80965506P 2006-05-31 2006-05-31
US60/809,655 2006-05-31

Publications (1)

Publication Number Publication Date
WO2007138096A1 true WO2007138096A1 (fr) 2007-12-06

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PCT/EP2007/055324 Ceased WO2007138096A1 (fr) 2006-05-31 2007-05-31 Process of high speed laminating

Country Status (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12157841B2 (en) 2018-11-16 2024-12-03 Dow Global Technologies Llc Solventless adhesive composition process and laminate with same
US12398303B2 (en) 2017-12-27 2025-08-26 Arkema France Two-component solventless adhesive compositions for adhesion to metal and/or metallized substrates

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471445A (en) * 1966-06-27 1969-10-07 Allied Chem Curable urethane compositions
EP0022502A1 (fr) * 1979-07-04 1981-01-21 Herberts Gesellschaft mit beschränkter Haftung Stratifié, procédé pour sa fabrication et utilisation de silanes pour cette fabrication
EP0344912A2 (fr) * 1988-06-02 1989-12-06 Minnesota Mining And Manufacturing Company Compositions durcissables par l'humidité, non dégouttantes
EP0354527A2 (fr) * 1988-08-11 1990-02-14 Hüls Aktiengesellschaft Adhésifs à fusion durcissables par l'humidité et à vitesse de liaison élevée
US5100995A (en) * 1989-09-23 1992-03-31 Bayer Aktiengesellschaft Storage stable polyurethane adhesives
US5965662A (en) * 1994-05-25 1999-10-12 Henkel Kommanditgesellschaft Auf Aktien Moisture curing polyurethane hot-melt adhesive
WO2000043433A1 (fr) * 1999-01-20 2000-07-27 H.B. Fuller Licensing & Financing, Inc. Adhesif thermofusible de polyurethanne durcissant a l'humidite, extremement permeable a la vapeur d'eau et resistant a l'hydrolyse
US6503981B2 (en) * 2000-12-22 2003-01-07 E. I. Du Pont De Nemours And Company Polyurethane based thermoreactive hot-melt adhesives
US6914102B2 (en) * 2002-12-16 2005-07-05 E. I. Du Pont De Nemours And Company Thermoreactive hot-melt adhesives
US20060046067A1 (en) * 2004-08-31 2006-03-02 Olaf Kleineberg Adhesive for high-temperature laminate

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471445A (en) * 1966-06-27 1969-10-07 Allied Chem Curable urethane compositions
EP0022502A1 (fr) * 1979-07-04 1981-01-21 Herberts Gesellschaft mit beschränkter Haftung Stratifié, procédé pour sa fabrication et utilisation de silanes pour cette fabrication
EP0344912A2 (fr) * 1988-06-02 1989-12-06 Minnesota Mining And Manufacturing Company Compositions durcissables par l'humidité, non dégouttantes
EP0354527A2 (fr) * 1988-08-11 1990-02-14 Hüls Aktiengesellschaft Adhésifs à fusion durcissables par l'humidité et à vitesse de liaison élevée
US5100995A (en) * 1989-09-23 1992-03-31 Bayer Aktiengesellschaft Storage stable polyurethane adhesives
US5965662A (en) * 1994-05-25 1999-10-12 Henkel Kommanditgesellschaft Auf Aktien Moisture curing polyurethane hot-melt adhesive
WO2000043433A1 (fr) * 1999-01-20 2000-07-27 H.B. Fuller Licensing & Financing, Inc. Adhesif thermofusible de polyurethanne durcissant a l'humidite, extremement permeable a la vapeur d'eau et resistant a l'hydrolyse
US6503981B2 (en) * 2000-12-22 2003-01-07 E. I. Du Pont De Nemours And Company Polyurethane based thermoreactive hot-melt adhesives
US6914102B2 (en) * 2002-12-16 2005-07-05 E. I. Du Pont De Nemours And Company Thermoreactive hot-melt adhesives
US20060046067A1 (en) * 2004-08-31 2006-03-02 Olaf Kleineberg Adhesive for high-temperature laminate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12398303B2 (en) 2017-12-27 2025-08-26 Arkema France Two-component solventless adhesive compositions for adhesion to metal and/or metallized substrates
US12157841B2 (en) 2018-11-16 2024-12-03 Dow Global Technologies Llc Solventless adhesive composition process and laminate with same

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