EP2877507A1 - Formulations d'adhésif - Google Patents

Formulations d'adhésif

Info

Publication number
EP2877507A1
EP2877507A1 EP13739730.3A EP13739730A EP2877507A1 EP 2877507 A1 EP2877507 A1 EP 2877507A1 EP 13739730 A EP13739730 A EP 13739730A EP 2877507 A1 EP2877507 A1 EP 2877507A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
uretdione
adhesive formulations
formulations according
groups
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.)
Withdrawn
Application number
EP13739730.3A
Other languages
German (de)
English (en)
Inventor
Dorota Greszta-Franz
Berta VEGA SANCHEZ
Beate Baumbach
Hans-Josef Laas
Mathias Matner
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Priority to EP13739730.3A priority Critical patent/EP2877507A1/fr
Publication of EP2877507A1 publication Critical patent/EP2877507A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
    • 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
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
    • B32B37/182—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only one or more of the layers being plastic
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/027—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing urethodione groups
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • 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
    • C08G18/80—Masked polyisocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
    • C08G18/8016—Masked aliphatic or cycloaliphatic polyisocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]

Definitions

  • the present invention relates to adhesive formulations based on uretdione polyaddition compounds which are free of isocyanate groups and their use for the production of adhesive bonds between substrates, in particular for the production of flexible Folienverbunden.
  • aliphatic polyisocyanates are less sensitive to moisture and form in the reaction with water naturally not primary aromatic amines, but also have, as is well known in polyurethane chemistry, a significantly lower reactivity to polyols as aromatic polyisocyanates. Their curing therefore requires high temperatures, a long curing time or the use of mostly heavy metal-containing catalysts.
  • WO 2006/026670 describes Example, the use of a polyurethane prepolymer based on aliphatic polyisocyanates in an adhesive formulation.
  • the formulation achieved sufficient bond adhesion only after three days at 60 ° C, although the polyurethane prepolymer additionally a heavy metal catalyst (dibutyltin dilaurate, DBTL) was added.
  • DBTL heavy metal catalyst
  • the long cure time at elevated temperature is not only a hindrance to productivity, but can also lead to roller telescoping and wrinkling.
  • these prepolymers still contain residual monomers due to the described production process of the aliphatic polyurethane prepolymers of monomeric diisocyanates. In practice, the use of such adhesives would require control of the monomeric diisocyanate content associated with logistical and financial overhead.
  • Isocyanate group-free adhesives based on uretdiones are also known.
  • EP-A 0601793 describes 1K adhesives containing hydroxyl and uretdione groups which are substantially free of isocyanate groups and cure by thermal cleavage of uretdione rings and subsequent reaction with the hydroxyl groups. Curing by this method, however, requires temperatures of at least 180 ° C, which makes the adhesive unsuitable for use in the field of flexible packaging films.
  • catalysts for lowering the curing temperature of uretdione-containing polyaddition compounds is known in particular in the field of powder coatings.
  • EP-A 0 803 524 compounds containing, for example, ⁇ , ⁇ , ⁇ '-trisubstituted amidine structures in EP-A 1 522 547 ammonium carboxylates, hydroxides, fluorides and also metal alkoxides and hydroxides, have been mentioned as suitable catalysts.
  • the catalysts mentioned in these publications allow a significant lowering of the curing temperature of about 180 ° C to about 130 ° C, but the embodiments can not be deduced that a lowering of the curing temperature to room temperature would be possible.
  • Object of the present invention was therefore to develop new adhesive formulations based on isocyanate-free, aliphatic polyurethanes, which are free of migratory monomeric diisocyanates and can be used at low temperatures, especially at room temperature.
  • free of migratory monomeric diisocyanates means that no monomeric diisocyanates are detectable in the adhesive formulations used above the detection limit or, in the migration test according to ⁇ 35 Foodstuffs and Consumer Goods Act, no migraine above the Detection limit could be determined.
  • isocyanate group-free does not exclude in the context of the present invention that the polyaddition compounds having uretdione groups to be used according to the invention may still have small residual amounts of free isocyanate groups
  • Starting compounds for the polyaddition compound A) containing uretdione groups are any uretdione group-containing polyisocyanates having an average isocyanate functionality of at least 2.0, as obtained in a manner known per se by catalytic dimerization of a polyisocyanate
  • Part of the isocyanate groups of simple diisocyanates can be obtained. If appropriate, monomeric diisocyanates still left over from the excess used are finally removed, usually by distillation, preferably by short-path distillation, more preferably by thin-layer distillation.
  • any diisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups for example those of the molecular weight range 140 to 400, suitable by any method, for example by phosgenation or on phosgene free way, for example by urethane cleavage, can be obtained.
  • Suitable diisocyanates are, for. B.
  • IPDI Isophorone diisocyanate
  • TMDI Trimethylhexamethylene diisocyanate
  • XDI 1,3-bis (isocyanatomethyl) benzene
  • TMXDI 1,3-bis (1-isocyanato-1-methylethyl) benzene (tetramethyl-m-xylylene diisocyanate, TMXDI) 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and any desired mixtures of these isomers
  • TDI diphenylmethane 2,4'- and / or -4,4'-diisocyanate
  • MDI diphenylmethane 2,4'- and / or -4,4'-diisocyanate
  • ND I 5-diisocyanate
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • MPDI 2-methyl pentane diisocyanate
  • TMDI Trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • XDI 1,3-bis (isocyanatomethyl) benzene
  • uretdione polyaddition compounds A) have a content of free isocyanate groups of less than 2% by weight, preferably less than 1 wt .-% and particularly preferably less than 0.5 wt .-%, and a content of as uretdione present isocyanate groups (calculated on solid as NCO, molecular weight 42) of 1 to 20 wt .-%, preferably from 3 to 17 wt .-%, particularly preferably from 5 to 15 wt .-%.
  • the polyaddition compounds A) may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.
  • polyol or polyol formulation B it is possible to use all compounds known to those skilled in the art which have an average OH functionality of at least 1.5. These may be, for example, low molecular weight diols (eg 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (eg glycerol, trimethylolpropane) and tetraols (eg pentaerythritol), but also higher molecular weight Polyhydroxy compounds such as polyether polyols, polyester polyols, polycarbonate polyols and Polythioetherpolyole.
  • diols eg 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol
  • triols eg glycerol, trimethylolpropane
  • tetraols eg pentaerythr
  • Polyester polyols B) can be prepared in a known manner by polycondensation of low molecular weight polycarboxylic acid derivatives, such as, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride,
  • low molecular weight polycarboxylic acid derivatives such as, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride,
  • Glutaric anhydride maleic acid, maleic anhydride, fumaric acid, dimer fatty acid, trimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, citric acid or trimellitic acid, with low molecular weight polyols such as ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol, trimethylolpropane 1, 4-hydroxymethylcyclohexane , 2-methyl-1,3-propanediol, butantrio 1-1, 2,4,
  • Triethylene glycol tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol, or by ring-opening polymerization of cyclic carboxylic acid esters such as ⁇ -caprolactone.
  • hydroxycarboxylic acid derivatives such as, for example, lactic acid, cinnamic acid or ⁇ -hydroxycaproic acid can also be polycondensed to form polyester polyols. But it can also be polyester polyols of oleochemical origin are used.
  • polyester polyols can be obtained, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 C atoms in the alkyl radical getting produced.
  • Polyether polyols B are also known and, for example, according to the in DE-A 2 622 951, column 6, line 65 - column 7, line 47, or EP-A 0 978 523 page 4, line 45 to page 5, line 14th described method, for. B. by alkoxylation of suitable starter molecules with alkylene oxides, accessible.
  • the alkoxylation reaction can be carried out both basic and acid catalyzed.
  • Suitable basic catalysts are, for example, alkali metal hydroxides, e.g. Sodium or potassium hydroxide, or alkali alcoholates, e.g. Sodium methylate.
  • Suitable acid catalysts are, for example, Lewis acids, such as. As antimony pentachloride and boron trifluoride etherate or double metal cyanide (DMC) catalysts, such as. B. zinc hexacyanocobaltate. These catalysts are usually removed following the synthesis by neutralization, distillation and / or filtration.
  • Suitable starter molecules for the preparation of the polyether polyols B) used according to the invention are any compounds of the molecular weight range 60 to 200 which are free of aromatic structures and carry 3 to 6, preferably up to 4, reactive hydrogen atoms. These are, for example, simple aliphatic alcohols having 3 to 6 carbon atoms, such as. B. 1,2,3-propanetriol, 1, 1, 1-trimethylolethane, 1,2,6-hexanetriol, 1, 1, 1-trimethylolpropane, 2,2-bis (hydroxymethyl) -1, 3-propanediol, 1 , 2,4- and 1,3,5-trihydroxycyclohexane or sorbitol to give aliphatic diamines, such as.
  • Polyamines such as. B diethylenetriamine and triethylenetetramine.
  • Another class of suitable starter molecules are also alkanolamines, e.g. Ethanolamine, dialkanolamines, e.g. Diethanolamine, and trialkanolamines, e.g. Triethanolamine.
  • Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be reacted either alone or in any desired sequence successively or in the form of any desired mixtures with one another with the starter molecules mentioned.
  • Particularly preferred polyether polyols B) are addition products of ethylene oxide and / or propylene oxide onto 1,2,3-propanetriol, 1,1,1-trimethylolpropane, ethylenediamine and / or pentaerythritol.
  • Very particularly preferred polyether polyols B) are those in the production of which only propylene oxide is used as alkylene oxide.
  • simple low molecular weight, at least trifunctional alcohols for example those having a molecular weight range of from 92 to 182, may also be used in minor amounts in the polyol formulation B). These are used, if at all, in amounts of not more than 10% by weight, preferably up to 5% by weight, based on the amount of polyol or polyol formulation B).
  • the uretdione group-containing polyaddition compound A) reacts with the polyol or with the polyol formulation B) while maintaining an equivalent ratio of uretdione groups to hydroxyl groups of 0.5: 1 to 2 , 0: 1, preferably from 0.7: 1 to 1.3: 1, more preferably from 0.8: 1 to 1: 1. Any remaining in the uretdione polyaddition compound remaining residual free isocyanate groups remain in the adjustment of the equivalent ratio unconsidered.
  • these are l, 8-diazabicyclo-5,4,0-undecene-7 (DBU), 1,5-diazabicyclo-4.3.0-nonene-5 (DBN), 7-methyl-l, 5,7-triazabicyclo -4,4.0-decene-5, 1,4,5,6-tetrahydro-l, 2-dimethylpyrimidine, 1, 2,4-sodium triazolate, and 2-tert-butyl-l, 1,3,3-tetramethylguanidine.
  • DBU 8-diazabicyclo-5,4,0-undecene-7
  • DBN 1,5-diazabicyclo-4.3.0-nonene-5
  • 7-methyl-l 5,7-triazabicyclo -4,4.0-decene-5, 1,4,5,6-tetrahydro-l, 2-dimethylpyrimidine, 1, 2,4-sodium triazolate, and 2-tert-butyl-l, 1,3,3-tetramethylguanidine.
  • tetraalkylammonium carboxylates disclosed in EP-A 1 522 547, for example tetrabutylammonium acetate or tetrabutylammonium benzoate; Hydroxides, such as benzyltrimethylammonium hydroxide; Fluorides, such as tetrabutylammonium fluoride, and metal alkoxides and hydroxides, such as sodium or potassium tert-butylalkoholat.
  • organometallic catalysts known from powder coatings, such as the zinc and tin carboxylates, alcoholates and acetylacetonates described in WO 2000/034355, optionally in combination with an epoxide acting as acid scavenger and an activator in the form of an ammonium - or phosphonium salt, as well as those described in US-B 8,088,846 as catalysts Reaction products of zinc carboxylates or zinc acetylacetonates with substituted amidines, such as, for example, zinc (1-methylimidazole) 2 (acetate) 2.
  • substituted amidines such as, for example, zinc (1-methylimidazole) 2 (acetate) 2.
  • the exemplified catalysts can be used individually or in the form of any mixtures with each other and come, if at all, in amounts of from 0.01 to 5.0 wt .-%, preferably from 0.1 to 3 wt .-%, particularly preferably from 0.2 to 1 wt .-%, calculated as the total amount of catalysts used based on the total amount of the starting compounds used, for use.
  • the adhesive formulation may additionally contain additives known from adhesive technology as formulation auxiliaries in addition to the abovementioned components.
  • additives include, for example, the customary plasticizers, fillers, pigments, light stabilizers, antioxidants, thixotropic agents, adhesion promoters and optionally further auxiliaries and additives.
  • suitable fillers are carbon black, precipitated silicas, pyrogenic silicic acids, mineral chalks and precipitation precipitates.
  • plasticizers examples include phthalic acid esters, adipic acid esters, alkylsulfonic acid esters of phenol or phosphoric acid esters.
  • thixotropic agents examples include fumed silicas, polyamides, hydrogenated castor oil derivatives or else polyvinyl chloride.
  • the known alkoxysilyl compounds e.g. Vinyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, i-butyltrimethoxysilane, i-butyltriethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, hexadecyltrimethoxysilane, and also functional silanes, such as, for example, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyl- dimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-glyoxypropyltrimethoxysilane, 3-glyoxypropyltrimethoxys
  • Propyltrimethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane, phenyltriethoxysilane, phenyl trimethoxysilane, polyether functional trimethoxysilanes and 3-methacryloxypropyl trimethoxysilane can be used.
  • the adhesive formulation can be used solvent-free or in a suitable solvent or solvent mixture.
  • Suitable solvents E) are those which have a sufficient solubility of the polyol component and the polyaddition component containing uretdione groups. te have. Examples of such solvents are benzene, toluene, ethyl acetate, butyl acetates, propylene acetates, methyl ethyl ketone, methyl isobutyl ketone, 2-methoxypropyl acetate. Particularly preferred are ethyl acetate and methyl ethyl ketone.
  • the exemplified solvents can be used individually or in the form of any mixtures with each other.
  • the solids content of the adhesive formulations calculated from the total amount of the starting compounds used in relation to the total amount of adhesive formulation including solvent - to values of 20-60 wt .-%, preferably from 25 to 50 wt .-% and particularly preferably from 30 - Adjusted 40 wt .-%.
  • the preparation of the adhesive formulation from the component A) carrying the uretdione groups and the polyol or the polyol mixture B) takes place according to the methods known to the person skilled in the art from polyurethane chemistry.
  • the catalyst C) and the additives D) can be added to the polyol or the polyol formulation B) or to the uretdione group-indicating component A) or both.
  • the catalyst C) and the additives D) are preferably added to the polyol or the polyol formulation B).
  • the adhesive formulation according to the invention can be applied to the substrates to be bonded by any conventional application method, for example by spraying, knife coating or roller applicators.
  • the adhesive formulation according to the invention is used as a solvent-free or solvent-containing laminating adhesive.
  • the adhesive formulation is preferably used for bonding plastic films, aluminum foils, other metal foils, metal-evaporated plastic foils and metal oxide vapor-deposited plastic foils.
  • Another object of the present invention is therefore also a process for the production of film composites which are obtainable by the partial or full-area bonding of at least two identical or different plastic and / or metal foils using the adhesive composition of the invention.
  • the application of the adhesive formulation of the binder system according to the invention to the films to be bonded can also be carried out with machines usually used for such purposes, for example with conventional laminating machines.
  • the two components A) and B) of the adhesive formulation are mixed together immediately prior to the production of the film composite and introduced into the laminating machine or the commissioned work.
  • the mixing of the components A) and B) in the laminating machine itself can be done directly before or in the commissioned work.
  • the so-called carrier film is coated with the adhesive formulation with an average dry coating weight of 1 to 9 g / m 2 and laminated by bringing into contact with a second film to form the resulting film composite.
  • Optionally employed solvents or solvent mixtures are completely removed in a drying tunnel or other suitable device prior to contacting the carrier film with the second film.
  • the material layer should first be free of grease before further cleaning with other pretreatment methods. To ensure this cleaning steps are possible, for example with solvents or predrying in the oven.
  • pretreatment methods for high performance bonding, there are other methods such as flaming, low pressure plasma or normal pressure plasma treatment and the corona discharge technology.
  • a pretreatment with adhesion promoters is possible.
  • a pretreatment of the material layer takes place before the coating of the adhesive layer.
  • the adhesive layer in the liquid state to the material layer to be bonded, preferably a film, such as a film of plastic or metal.
  • a film such as a film of plastic or metal.
  • These cure according to the invention already at temperatures below 100 ° C, in a preferred embodiment of the invention, the curing at temperatures between 20 and 100 ° C, preferably to 75 ° C, more preferably to 40 ° C in the production of flexible packaging films, optionally at pressures between 1 and 50 bar.
  • the method described can be repeated several times, so that film composites can be produced which consist of more than two bonded material layers.
  • Another object of the invention is a composite film prepared by the process according to the invention using the adhesive formulation according to the invention.
  • the determination of the content of free isocyanate groups was carried out titrimetrically according to DIN EN ISO 11909.
  • the determination of the total isocyanate content i.e., the sum of the content of free and uretdione present isocyanate groups
  • the determination of the total isocyanate content was carried out after the so-called hot titration, such. in EP 0 601 793, Synthesis Comparative Example 1, described in detail. From the difference between the total isocyanate content and the content of free isocyanate groups, the content of isocyanate groups present in the form of uretdione structures was calculated.
  • the hydroxyl content was determined by titrimetry according to DIN 53240 T.2.
  • the residual monomer contents were measured according to DIN EN ISO 10283 by gas chromatography with an internal standard.
  • the determination of the gel time of an adhesive formulation was carried out manually on a 100 g batch.
  • the batch is stirred in a beaker at room temperature (23 ° C) with a wooden stick.
  • the gelling time was taken as the time at which the approach no longer pulls threads when pulling up the wooden stick, but tears off rubbery.
  • the determination of the coating weight was carried out as described below: A 1 dm 2 -sized circle was cut out of the previously laminated composite film with a circle cutter and weighed. Subsequently, the films were separated from each other, cleaned with acetone, dried and weighed again. The difference of these two weights multiplied by 100 gives the order weight in g / m 2 .
  • the bond strength or the peel strength of a previously laminated film composite was determined according to DIN 53357-A by the 180 ° peel test on a tearing machine (Zwick I, manufacturer Zwick
  • Roell determined.
  • the test strips were clamped in the holders of the tearing machine so that they were pulled apart in the determination at a 180 ° angle to each other (the individual strips formed a 90 ° angle to the adhesive layer).
  • the speed at which the film composites were pulled apart was 100 mm / min.
  • the bond adhesion value was the mean applied force needed to separate the test strips.
  • a strip approximately 15 cm wide was cut out transversely to the running direction of the composite. This was folded in the direction of the film composite in the middle in such a way that the sealing medium (LDPE) lies inside one another.
  • LDPE sealing medium
  • the sealed seam was sealed at 120 ° C for 2 seconds. After cooling the sealed foil piece to room temperature, 3 15 mm wide strips were cut out transversely to the sealed seam.
  • the seal strength of the test strips was determined on the above-described tearing machine. For this purpose, the test strips were clamped in the holders of the tearing machine and then pulled apart at a speed of 100 mm / min. As the value of the seal strength of the maximum applied force was specified. In addition, the tear pattern was judged.
  • Crelan EF ® 403 a solid, uretdion phenomenon braves, cycloaliphatic at room temperature on polyurethane with a content of monomeric IPDI of ⁇ 0.1%, a free isocyanate group content of 0.4% and a total isocyanate content of 13.5 %; available from Bayer MaterialScience AG.
  • Desmodur ® XP 2730 a uretdion phenomenon braves HDI polyisocyanate with a content of monomeric HDI of 0.18%), a free isocyanate group content of 22.7% and a viscosity at 23 ° C of 90 mPa-s, available from Bayer Material Science AG.
  • the hot titration of the product and the subsequent calculation according to the method explained above gave a content of uretdione present isocyanate groups of 18.4%.
  • Desmodur ® E XP 2747 a monomer and solvent-free prepolymer based on HDI with a free isocyanate group content of 16.9% and a viscosity at 23 ° C of 2,600 mPa-s, available from Bayer Material Science AG.
  • Desmodur ® E 23 a monomer-solvent-free prepolymer based on diphenylmethane diisocyanate (MDI) with a free isocyanate group content of 15.4% and a viscosity at 23 ° C of 1,800 mPa-s, available from Bayer Material Science AG.
  • MDI diphenylmethane diisocyanate
  • Desmophen ® 670 a weakly branched, solvent-free, hydroxyl-bearing polyester with a hydroxyl content of 4.3%, available from Bayer MaterialScience AG.
  • Desmophen ® 1380 BT a polyether-based polyol, having a hydroxyl content of 11.5% and a viscosity at 25 ° C of 600 mPa-s, available from Bayer Material Science AG.
  • Baycoll ® AD 2047 a linear, solvent-free, hydroxyl-containing polyesters, with a hydroxyl content of 1.7% and a viscosity at 75 ° C of 7,000 mPa-s, available from Bayer Material Science AG.
  • Baycoll CD ® 2084 a linear, solvent-free, hydroxyl and polyether phenomenon inconveniencer polyester having a viscosity at 75 ° C of 120 mPa-s and a hydroxyl content of 2.5%>, available from Bayer Material Science AG.
  • Catalyst Cl Addocat ® 1872 Rheinchemie (l, 2-dimethyl-l, 4,5,6-tetrahydropyrimidine) catalyst C2).:. Lupragen ® N 700, BASF (l, 8-diazabicyclo-5, 4,0-undecene-7) polyaddition compound AI) having uretdione groups:
  • uretdione polyaddition compound AI As uretdione polyaddition compound AI), a 60%> solution of Crelan ® EF 403 was used in ethyl acetate. The solution had a viscosity at 23 ° C of 3500 mPa ⁇ s. The content of isocyanate groups present in the form of uretdione structures was 8.1%>.
  • a uretdione group-containing IPDI polyisocyanate was prepared as described in Example 3 of EP-A 0 896 973. After removal of the excess monomer, a bright, viscous liquid was obtained which had a content of free NCO groups of about 17.7%. The calculated content of uretdione group isocyanate groups was 20.1%.
  • Examples 1-12 were carried out according to the same pattern. The following description is therefore exemplary of the entire series.
  • room temperature about 23 ° C
  • 100 g of the adhesive formulation were prepared.
  • the polyaddition compound containing the uretdione groups or the polyisocyanate component was initially charged and stirred homogeneously with the polyol component. Subsequently, if necessary, the addition of the solvent and the catalyst and a new homogenization.
  • Examples 1 to 8 according to the invention show that the polyaddition compounds containing isocyanate-group-free uretdione groups in combination with polyols are suitable as adhesive formulations for the production of film composites and thereby provide equivalent composites such as the aromatic 2K polyurethane systems (Examples 11 and 12).
  • the optional co-use of suitable catalysts provides an additional improvement in adhesive properties (Examples 2-4 and 6-8).
  • the corresponding formulations are characterized by achieving acceptable peel and seal strength after one day of storage, which indicates a higher reactivity compared to the conventional aliphatic 2K polyurethane systems from Examples 9 and 10 not according to the invention.
  • Examples 13 to 16 were carried out according to the same pattern. The following description is therefore exemplary of the entire series. Since the adhesive formulations naturally have a limited storage life, they were prepared immediately prior to the production of the film composite. At room temperature (about 23 ° C) 100 g of the adhesive formulation were prepared. For this purpose, the polyaddition compound containing the uretdione groups or the polyisocyanate component was initially charged and stirred homogeneously with the polyol component. Then followed if necessary, the addition of the solvent and the catalyst and a new homogenization. Thus prepared adhesive formulation was used immediately after homogenization for the production of a flexible film composite.
  • the web speed was 2 m / min, the dryer temperature at a supply air of about 100 m 3 / h was 60 ° C. It was laminated with 4.0 bar pressure.
  • the length of the film composite produced with the adhesive formulation was at least 20 m.
  • the dry layer thickness of the adhesive formulation was between 5 and 10 ⁇ .
  • the wound films were stored for 3 and 17 days at 23 ° C and 50% relative humidity. After storage, the peel strength and the seal seam strength of the film composite were determined.

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

Abstract

La présente invention concerne des formulations d'adhésif à base de composés de polyaddition présentant des groupes uretdione, qui sont exemptes de groupes isocyanate et de polyisocyanates monomères, et leur utilisation pour la production de liaisons adhésives entre substrats, en particulier pour la production de feuilles composites flexibles.
EP13739730.3A 2012-07-27 2013-07-24 Formulations d'adhésif Withdrawn EP2877507A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13739730.3A EP2877507A1 (fr) 2012-07-27 2013-07-24 Formulations d'adhésif

Applications Claiming Priority (3)

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EP12178178 2012-07-27
PCT/EP2013/065571 WO2014016325A1 (fr) 2012-07-27 2013-07-24 Formulations d'adhésif
EP13739730.3A EP2877507A1 (fr) 2012-07-27 2013-07-24 Formulations d'adhésif

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EP2877507A1 true EP2877507A1 (fr) 2015-06-03

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KR20170137852A (ko) * 2015-06-10 2017-12-13 쇼와 덴코 가부시키가이샤 금속박과 수지 필름의 라미네이트용 접착제, 적층체, 전지 외장용 포장재와 전지 케이스 및 그 제조 방법
KR20200050954A (ko) 2017-09-07 2020-05-12 쓰리엠 이노베이티브 프로퍼티즈 캄파니 우레트다이온-함유 물질을 포함하는 중합체 재료, 2-파트 조성물, 및 방법
US20210017432A1 (en) * 2018-03-16 2021-01-21 3M Innovative Properties Company Compositions, method of bonding, and bonded assembly
EP3572446A1 (fr) * 2018-05-24 2019-11-27 Evonik Degussa GmbH Mélange réactif d'uretdiones et de catalyseurs
WO2020060893A1 (fr) 2018-09-20 2020-03-26 3M Innovative Properties Company Matériau polymère comprenant un matériau contenant de l'uretdione et un composant époxy, compositions en deux parties et procédés
WO2023057830A1 (fr) * 2021-10-04 2023-04-13 3M Innovative Properties Company Articles en polyuréthane extrudables et compositions et procédés de fabrication et d'impression de ceux-ci
WO2023106186A1 (fr) * 2021-12-09 2023-06-15 Dic株式会社 Adhésif, corps multicouche et matériau d'emballage

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CA2879922A1 (fr) 2014-01-30
US9657206B2 (en) 2017-05-23
US20150175859A1 (en) 2015-06-25

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