Patent Application
20250163307
The invention relates to reactive polyurethane hot-melt adhesives having improved initial strength and to use of the adhesives for bonding of substrates in production of white goods, automotive vehicles, and electronic devices.
Hot-melt adhesives are solvent free adhesives, which are solid at room temperature, and which are applied to the substrate to be bonded in form of a melt. After cooling the adhesive solidifies and forms an adhesive bond with the substrate through physically occurring bonding. Conventional hot-melt adhesives are non-reactive adhesives, which soften again upon heating and are, therefore, not suitable to be used at elevated temperatures. Reactive hot-melt adhesives contain polymers with reactive groups that enable chemical curing of the adhesive, for example, by crosslinking of the polymer chains. Due to the chemically cured polymer matrix reactive hot-melt adhesives do not soften upon heating and these adhesives are, therefore, suitable for use also at elevated temperatures. The chemical curing of the polymers can be initiated, for example, by heating or exposing the adhesive composition to water, such as atmospheric moisture. Moisture curing hot-melt adhesives typically contain polymers functionalized with isocyanate or silane groups, which enables crosslinking of the polymer chains upon contact with atmospheric moisture.
Moisture curing polyurethane hot-melt adhesives (PUR-RHM) consist mainly of isocyanate-functional polyurethane polymers, which have been obtained by reacting suitable polyols, typically polyester and/or polyether polyols, with polyisocyanates, where the reaction is conducted at a molar excess of isocyanate (NCO) groups over hydroxyl (OH) groups. The adhesive composition is cured by reaction of the residual isocyanate groups with water, which results in various chain extension and/or crosslinking reactions of the polymers. A fully cured polyurethane hot-melt adhesive comprises urea and/or urethane bonds and, depending on the starting materials used for providing the isocyanate-functional polymer, ester and/or ether bonds. A crosslinked hot-melt adhesive does not remelt when subjected to heating and therefore, typically has a very good heat-stability. However, some PUR-RHM adhesives exhibit a rather slow build-up of adhesive bonding strength, which can be a significant disadvantage especially in automotive lamination applications.
There is thus a need for a novel type of moisture curable polyurethane hot-melt adhesive having improved initial adhesion strength. Such adhesives are especially suitable for use in automotive interior lamination applications.
The object of the present invention is to provide an adhesive composition, which overcomes or at least mitigates the disadvantages of the prior art moisture curable polyurethane hot-melt adhesives as discussed above.
Particularly, it is an object of the present invention to provide a moisture curable polyurethane hot-melt adhesive composition having improved initial adhesion strength. The cured adhesive composition should also preferably have excellent mechanical properties, particularly a high lap shear strength and low viscosity at typical application temperatures of hot-melt adhesives.
It was surprisingly found out that the objects can be achieved with the features of claim 1.
The core of the present invention is a novel type of moisture curable polyurethane hot-melt adhesive composition comprising at least one isocyanate-functional polyurethane polymer obtained by reacting a polyol composition with a polyisocyanate, wherein the polyol composition comprises a low molecular weight polyether polyol having a high hydroxyl number.
It was surprisingly found out that the addition of a low molecular weight polyether polyol to the adhesive composition significantly improves the initial (green) adhesion strength of the adhesive composition.
Other subjects of the present invention are presented in other independent claims. Preferred aspects of the invention are presented in the dependent claims.
The subject of the present invention is an adhesive composition comprising at least one isocyanate-functional polyurethane polymer P obtained by reacting:
wherein the at least one polyether polyol PO2 has a hydroxyl-number determined according to ISO 4629-2:2016 standard of at least 100 mg KOH/g, preferably at least 150 mg KOH/g.
The prefix “poly” in substance designations such as “polyol” or “polyisocyanate” refers to substances which in formal terms contain two or more per molecule of the functional group that occurs in their designation. A polyol, for example, is a compound having two or more hydroxyl groups, and a polyisocyanate is a compound having two or more isocyanate groups.
The term “polymer” designates a collective of chemically uniform macromolecules produced by a polyreaction (polymerization, polyaddition, polycondensation) where the macromolecules differ with respect to their degree of polymerization, molecular weight, and chain length. The term also comprises derivatives of said collective of macromolecules resulting from polyreactions, that is, compounds which are obtained by reactions such as, for example, additions or substitutions, of functional groups in predetermined macromolecules and which may be chemically uniform or chemically non-uniform.
The term “polyurethane polymer” designates polymers prepared by the so called diisocyanate polyaddition process. These also include those polymers which are virtually or entirely free from urethane groups. Examples of polyurethane polymers are polyether-polyurethanes, polyester-polyurethanes, polyether-polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.
The term “isocyanate-functional polyurethane polymer” designates polyurethane polymers comprising one or more unreacted isocyanate groups. The polyurethane prepolymers can be obtained by reacting excess of polyisocyanates with polyols and they are polyisocyanates themselves. The terms “isocyanate-functional polyurethane polymer” and “polyurethane prepolymer” are used interchangeably.
The term “molecular weight” refers to the molar mass (g/mol) of a molecule or a part of a molecule, also referred to as “moiety”. The term “average molecular weight” refers to number average molecular weight (Mn) or to weight average molecular weight (Mw) of an oligomeric or polymeric mixture of molecules or moieties. The molecular weight may be determined by gel permeation chromatography (GPC) using polystyrene as standard, styrene-divinylbenzene gel with porosity of 100 Angstrom, 1000 Angstrom and 10000 Angstrom as the column and, depending on the molecule, tetrahydrofurane as a solvent, at 35° C., or 1,2,4-trichlorobenzene as a solvent, at 160° C.
The term “average OH-functionality” designates the average number of hydroxyl (OH) groups per molecule. The average OH-functionality of a compound can be calculated based on the number average molecular weight (Mn) and the hydroxyl number of the compound. The hydroxyl number of a compound can be determined by using method as defined in DIN 53 240-2 standard.
The term “open time” designates the length of a time period during which an adhesive applied to a surface of a substrate is still able to form an adhesive bond after being contacted with another substrate.
The “amount of at least one component X” in a composition, for example “the amount of the at least one polyol” refers in the present document to the sum of the individual amounts of all polyols contained in the composition. For example, in case the at least one polyol is a polyester polyol and the composition comprises 20 wt.-% of at least one polyol, the sum of the amounts of all polyester polyols contained in the composition equals 20 wt.-%.
The term “room temperature” refers to a temperature of ca. 23° C.
The adhesive composition is preferably a hot-melt adhesive composition, more preferably a one-component hot-melt adhesive composition. The term “one-component composition” refers in context of the present invention to a composition in which all constituents of the composition are stored in a mixture in the same container or compartment.
The adhesive composition comprises at least one isocyanate-functional polyurethane polymer P obtained by reacting a polyol composition with at least one polyisocyanate PI. The “polyol composition” is understood to comprise all polyols that are used for obtaining the at least one isocyanate-functional polyurethane polymer P.
Preferably, the adhesive composition further comprises:
Adhesive compositions comprising the at least one isocyanate-functional polymer P obtained with a polyol composition comprising the at least one polyether polyol PO2 and the at least one thermoplastic polymer TP have been found out to have improved initial adhesion strength properties compared to polyurethane-based moisture curing hot-melts adhesives of prior art.
The polyol composition comprises the at least one at 25° C. solid polyester polyol PO1 and the at least one polyether polyol PO2.
Suitable polyester polyols for use as the at least one polyester polyol PO1 include crystalline, partially crystalline, and amorphous, polyester polyols. These can be obtained by reacting dihydric and trihydric, preferably dihydric, alcohols, for example, 1,2-ethanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimer fatty alcohol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforesaid alcohols, with organic dicarboxylic acids or tricarboxylic acids, preferably dicarboxylic acids, or their anhydrides or esters, such as succinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedicarboxylic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, dimer fatty acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, or mixtures of the aforesaid acids. Polyester polyols made from lactones such as from ε-caprolactone, also known as polycaprolactones, are also suitable.
Preferred polyester polyols include those obtained by reacting adipic acid, sebacic acid or dodecanedicarboxylic acid as dicarboxylic acid and hexanediol or neopentyl glycol as dihydric alcohol. Further examples of suitable polyester polyols include polyester polyols of oleochemical origin. Polyester polyols of this type may be prepared, for example, by complete ring opening of epoxidized triglycerides of a fat mixture comprising at least partially olefinically unsaturated fatty acids, with one or more alcohols having 1-12 carbon atoms, and by subsequent partial transesterification of the triglyceride derivatives to give alkyl ester polyols having 1-12 carbon atoms in the alkyl radical. Particularly suitable crystalline and partially crystalline polyester polyols include adipic acid/hexanediol polyester and dodecanedicarboxylic acid/hexanediol polyesters.
According to one or more embodiments, the at least one at 25° C. solid polyester polyol PO1 has a softening point determined by Ring and Ball method according to ISO 4625-1:2020 standard of at least 55° C., preferably at least 65° C., more preferably at least 75° C.
According to one or more embodiments, the at least one at 25° C. solid polyester polyol PO1 has:
According to one or more embodiments, the at least one polyester polyol PO1 has a number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using polystyrene as standard of 500-10000 g/mol, preferably 1500-5000 g/mol and/or a hydroxyl number determined according to ISO 4629-2 standard of 10-75 mg KOH/g, preferably 15-55 mg KOH/g.
Suitable at 25° C. solid partially crystalline, crystalline, and amorphous polyester polyols for use as the at least one PO1 are commercially available, for example, under the trade name Dynacoll® 7100- and 7300-series (from Evonik Industries).
According to one or more embodiments, the polyol composition a) comprises at least 35 wt.-%, preferably at least 50 wt.-%, more preferably at least 65 wt.-%, based the total weight of the polyol composition a), of the at least one at 25° C. solid polyester polyol PO1.
The polyol composition a) further comprises the at least one polyether polyol PO2 having a hydroxyl-number determined according to ISO 4629-2:2016 standard of at least 100 mg KOH/g, preferably at least 150 mg KOH/g, more preferably at least 200 mg KOH/g, still more preferably at least 250 mg KOH/g.
According to one or more embodiments, the at least one polyether polyol PO2 has a hydroxyl-number determined according to ISO 4629-2:2016 standard of 150-1000 mg KOH/g, preferably 200-750 mg KOH/g, more preferably 250-500 mg KOH/g, even more preferably 275-500 mg KOH/g.
According to one or more embodiments, the at least one polyether polyol PO2 has:
According to one or more preferred embodiments, the at least one polyether polyol PO2 is a polyether diol, preferably an aromatic polyether diol. Suitable polyether diols are commercially available, for example, under the trade name of Dianol (from Arkema).
According to one or more embodiments, the at least one polyether polyol PO2 is an alkylene oxide adduct of bisphenol A, preferably of a compound of formula (I)
where y and y represent integers which independently from each other are in range of 1 to 5.
Suitable alkylene oxide adduct of bisphenol A of formula (I) are commercially available, for example, under the trade name of Dow Resin 565 (from Dow Chemicals), under the trade name of Dianol (from Arkema), and under the trade name of Synfac Polyols (from Milliken Chemicals).
According to one or more preferred embodiments, the at least one polyether polyol PO2 is a compound of formula (I), where x and y in formula (I) have a value of 1.
According to one or more embodiments, the polyol composition a) comprises 1.5-45 wt.-%, preferably 2.5-35 wt.-%, more preferably 5-25 wt.-%, even more preferably 10-20 wt.-%, based on the total weight of the polyol composition a), of the at least one polyether polyol PO2.
According to one or more embodiments, the polyol composition a) further comprises:
According to one or more embodiments, the at least one at 25° C. liquid polyester polyol PO3 has:
According to one or more embodiments, the polyol composition a) comprises 5-50 wt.-%, preferably 10-40 wt.-%, more preferably 15-45 wt.-%, based on the total weight of the polyol composition a), of the at least one at 25° C. liquid polyester polyol PO3.
Suitable polyisocyanates to be used as the at least one polyisocyanate PI include, for example, aliphatic, cyclo-aliphatic, and aromatic polyisocyanates, especially diisocyanates, particularly monomeric diisocyanates. Non-monomeric diisocyanates such as oligomeric and polymeric products of monomeric diisocyanates, for example adducts of monomeric diisocyanates are also suitable but the use of monomeric diisocyanates is preferred.
The term “monomer” designates a molecule having at least one polymerizable group. A monomeric di- or polyisocyanate contains particularly no urethane groups. In the context of the present invention, oligomers or polymer products of diisocyanate monomers such as adducts of monomeric diisocyanates are not monomeric diisocyanates.
An isocyanate is called “aliphatic” when its isocyanate group is directly bound to an aliphatic, cycloaliphatic or arylaliphatic moiety. The corresponding functional group is therefore called an aliphatic isocyanate group. An isocyanate is called “aromatic” when its isocyanate group is directly bound to an aromatic moiety. The corresponding functional group is therefore called an aromatic isocyanate group.
According to one or more embodiments, the at least one polyisocyanate PI is a diisocyanate, preferably a monomeric diisocyanate, more preferably a monomeric diisocyanate having a number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using polystyrene as standard of not more than 1000 g/mol, preferably not more than 500 g/mol, more preferably not more than 400 g/mol.
Examples of suitable monomeric diisocyanates include, for example, 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene 1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI) and mixtures of these isomers, 1,10 decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine diisocyanate, lysine ester diisocyanate, cyclohexane 1,3-diisocyanate and cyclohexane 1,4-diisocyanate and mixtures of these isomers, 1-methyl-2,4-and-2,6-diisocyanatocyclohexane and mixtures of these isomers (HTDI or H6TDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (=isophoronediisocyanate or IPDI), perhydro-2,4′-and-4,4′-diphenylmethane diisocyanate (HMDI or H12MDI) and mixtures of these isomers, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis(isocyanato-methyl)cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI) and mixtures of these isomers, m- and p-tetramethyl-1,3- and 1,4-xylylene diisocyanate (m- and p-TMXDI) and mixtures of these isomers, bis(1-isocyanato-1-methylethyl) naphthalene, 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers (TDI), 4,4′-, 2,4′- and 2,2′-diphenylmethane diisocyanate and mixtures of these isomers (MDI), 1,3- and 1,4-phenylene diisocyanate and mixtures of these isomers, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (TODI), and dianisidine diisocyanate (DADI).
According to one or more embodiments, the monomeric diisocyanate is selected from the group consisting of 4,4′-, 2,4′-, and 2,2′-diphenylmethane diisocyanate and mixtures of these isomers (MDI), 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers (TDI), 1,6-hexamethylene diisocyanate (HDI), and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI). Furthermore, a person skilled in the art knows that the technical grade products of diisocyanates may frequently contain isomer mixtures or other isomers as impurities. According to one or more embodiments, the monomeric diisocyanate is selected from the group consisting of MDI and IPDI. Suitable monomeric diisocyanates are commercially available, for example, under the trade name of Lupranat® (from BASF) and Desmodur (from Covestro).
Preferably, the at least one isocyanate-functional polyurethane polymer P has an average isocyanate functionality of not more than 3.5, preferably not more than 3.0. The term “average NCO-functionality” designates in the present disclosure the average number of isocyanate (NCO) groups per molecule. The average NCO functionality of a compound can be determined by using the method as defined in ISO 14896-2006 standard method A.
According to one or more embodiments, the at least one isocyanate-functional polyurethane polymer P has an average isocyanate functionality of 1.1-3.5, preferably 1.5-3, more preferably 1.8-2.5.
Preferably, the adhesive composition comprises at least 50 wt.-%, more preferably at least 65 wt.-%, even more preferably at least 75 wt.-%, still more preferably at least 80 wt.-%, based on the total weight of the adhesive composition, of the at least one isocyanate-functional polyurethane polymer P.
According to one or more embodiments, the adhesive composition comprises 50-95 wt.-%, preferably 60-90 wt.-%, more preferably 65-90 wt.-%, even more preferably 70-85 wt.-%, based on the total weight of the adhesive composition, of the at least one isocyanate-functional polyurethane polymer P.
The adhesive composition comprises, in addition to the at least one isocyanate-functional polyurethane polymer P, the at least one thermoplastic polymer TP.
According to one or more embodiments, the adhesive composition comprises 2.5-30 wt.-%, preferably 5-30 wt.-%, more preferably 5-25 wt.-%, even more preferably 10-25 wt.-%, based on the total weight of the hot-melt adhesive composition, of the at least one thermoplastic polymer TP.
According to one or more preferred embodiments, the at least one thermoplastic polymer TP comprises at least one at least one thermoplastic polyurethane TPU.
Generally, the expression “the at least one component X comprises at least one component XN”, such as “the at least one thermoplastic polymer TP
comprises at least one thermoplastic polyurethane TPU” is understood to mean in the context of the present disclosure that a composition comprises one or more thermoplastic polyurethanes TPU as representatives of the at least one thermoplastic polymer TP.
Thermoplastic polyurethanes (TPU) are polyurethane-based thermoplastic elastomers (TPE) that are linear segmented block copolymers composed of alternating hard and soft segments or domains formed by the reaction of (1) diisocyanates with short-chain diols (so-called chain extenders) and (2) diisocyanates with long-chain diols.
Thermoplastic polyurethanes have been found out to be especially suitable for use as rheology modifiers to improve the thermal resistance of the cured adhesive composition.
According to one or more embodiments, the at least one thermoplastic polyurethane TPU is a polycaprolactone-copolyester polyurethane.
According to one or more embodiments, the at least one thermoplastic polymer TP is composed of the at least one thermoplastic polyurethane TPU.
According to one or more embodiments, the adhesive composition further comprises at least one catalyst CA that catalyzes the reactions of isocyanate groups with water.
Examples of suitable catalysts include metal-based catalysts such as dialkyltin complexes, particularly dibutyltin (IV) or dioctyltin (IV) carboxylates or acetoacetonates, such as dibutyltindilaurate (DBTDL), dibutyltindiacetylacetonate, dioctyltindilaurate (DOTDL), further bismuth (III) complexes such as bismuthoctoate or bismuthneodecanoate, zinc (II) complexes, such as zincoctoate or zincneodecanoate, and zirconium (IV) com-plexes, such as zirconiumoctoate or zirconiumneodecanoate.
Further examples of suitable catalysts include compounds containing amine groups such as, dimorpholinodialkylethers and/or dimorpholino substituted polyalkylene glycols, for example 2,2′-dimorpholinodiethyl ether and 1,4-diazabicyclo[2.2.2]-octane. Combinations of two or more catalysts may also be used, preferred combinations including of one or more metal-catalysts with one or more morpholine amine compounds.
According to one or more embodiments, the adhesive composition comprises 0.005-2.00 wt.-%, preferably 0.05-1.00 wt.-%, based on the total weight of the adhesive composition, of the at least one catalyst CA.
The adhesive composition of the present invention can further comprise auxiliary substances and additives, for example, those selected from the group consisting of fillers, plasticizers, adhesion promoters, UV absorption agents, UV and heat stabilizers, flame retardants, optical brighteners, pigments, dyes, and desiccants.
Examples of suitable UV stabilizers that can be added to the adhesive composition include, for example, sterically hindered phenols, and suitable UV-absorbers include, for example, hydroxybenzophenones, hydroxybenzotriazoles, triazines, anilides, benzoates, cyanoacrylates, phenylformamidines, and mixtures thereof.
Suitable fillers include inorganic and organic fillers, especially natural, ground or precipitated calcium carbonates, optionally coated with fatty acids or fatty acid esters, especially stearic acid, baryte (heavy spar), talcs, quartz flours, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminum silicate), molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicas including finely divided silicas from pyrolysis processes, industrially produced carbon blacks, graphite, metal powders such as aluminum, copper, iron, silver, steel, polyvinylchloride powder, and hollow spheres.
The total amount of such auxiliary substances and additives is preferably not more than 15 wt.-%, more preferably not more than 10 wt.-%, based on the total weight of the adhesive composition.
According to one or more embodiments, the adhesive composition is obtained by a method comprising steps of:
According to one or more embodiments, the NCO/OH ratio in step B) of the method is not greater than 3.5, preferably not greater than 3.0, more preferably not greater than 2.75, particularly 1.3-2.75, preferably 1.5-2.5.
The reaction conducted in step B) will convert substantially all the hydroxyl groups of the polyol composition a), for example at least 95%, preferably at least 99%, of the hydroxyl groups of the polyol a) composition.
Preferably, the starting mixture provided in step A) is dehydrated under vacuum at a temperature of at or above 120° C. before conducting step B).
The reaction in step B) may be carried out according conventional methods used for preparation of isocyanate-functional polyurethane polymers. The reaction may, for example, be carried out at temperatures in the range of 50-160° C., preferably 60-120° C., optionally in the presence of a catalyst. The reaction time depends on the temperature employed, but may, for example, be in the range of from 30 minutes to 6 hours, particularly from 30 minutes to 3 hours, preferably from 30 minutes to 1.5 hours. Suitable catalysts used in the reaction of step B) include, for example, metal catalysts, such as Coscat®83 (from Vertellus Performance Materials Inc.), and tin catalysts.
The adhesive composition of the present invention is a moisture-curing adhesive composition, i.e., the adhesive composition can be cured by contacting the composition with water, especially with atmospheric moisture.
Furthermore, the adhesive composition of the present invention has good workability under typical application conditions of hot-melt adhesives, particularly at temperatures in the range of 95-200° C., meaning that at the application temperature the adhesive has sufficiently low viscosity to enable application to a substrate in a molten state. The adhesive composition also develops a high initial strength immediately after the application to a substrate upon cooling even before the initiation of the crosslinking reaction with water, particularly with atmospheric moisture.
According to one or more embodiments, the adhesive composition has a viscosity at a temperature of 130° C. of not more than 100′000 mPas, preferably not more than 75′000 mPas. The viscosity at temperature of 130° C. can be measured using a conventional viscometer at 5 revolutions per minute, for example by using a Brookfield DV-2 viscometer with a spindle No. 27, preferably with a Thermosel System for temperature control.
According to one or more embodiments, the adhesive composition has a softening point measured by Ring and Ball method according to 4625-1:2020 standard in the range of 45-115° C., preferably 50-105° C., more preferably 55-95° C.
The preferences given above for the isocyanate-functional polyurethane polymer P, the polyol composition, the polyester polyol PO1, the polyether polyol PO2, the polyester polyol PO3, the thermoplastic polymer TP, and the catalyst CA apply equally to all subjects of the present invention unless stated otherwise.
Another subject of the present invention is use of the adhesive composition of the present invention as an assembly adhesive, a laminating adhesive, or as an adhesive for the building of sandwich elements, particularly as an interior laminating adhesive in automotive industry.
Another subject of the present invention is a method for adhesively bonding a first substrate to a second substrate, the method comprising steps of:
The first and second substrates can be sheet-like articles having first and second major surfaces defined by peripheral edges and defining a thickness there between or three-dimensional shaped articles.
In the method for adhesively bonding a first substrate to a second substrate, the adhesive composition is heated to a temperature above the softening point of the adhesive composition and applied to the surface of the first substrate in molten state using any conventional technique, for example, by using slot die coating, roller coating, extrusion coating, calendar coating, or spray coating. The adhesive composition can be applied to the surface of the first substrate with a coating weight of, for example, 25-750 g/m2, preferably 35-500 g/m2, more preferably 45-350 g/m2, even more preferably 50-250 g/m2.
After the adhesive film has been contacted with the surface of the second substrate, the adhesive composition develops a certain initial adhesive strength by physical curing, i.e., upon cooling. Depending on the application temperature and on the embodiment of the adhesive composition, particularly on the reactivity of the adhesive, the chemical curing reactions may begin already during the application of the adhesive composition on the surface of the first substrate. Typically, however, majority of the chemical curing occurs after the application of adhesive, particularly, after the applied adhesive film has been contacted with the surface of the second substrate.
The first and second substrates can be composed of any conventional material including polymeric material, metal, painted metal, glass, wood, wood derived materials such as natural fiber polypropylene (NFPP), and fiber materials. Suitable polymeric materials include, for example, polyethylene (PE), in particular high density polyethylene (HDPE), polypropylene (PP), glass-fiber reinforced polypropylene (GFPP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polystyrene (PS), polycarbonate (PC), polymethylmethacrylate (PMMA), acrylonitrile butadiene styrene (ABS), polyamide (PA), and combinations thereof. The first and second substrates can be composed of a single layer or of multiple layers of different types of materials. The layer(s) composed of polymeric materials can further contain additives such as fillers, plasticizers, flame retardants, thermal stabilizers, antioxidants, pigments, dyes, and biocides.
Still another subject of the present invention is a composite element obtainable by using the method for adhesively bonding a first substrate to a second substrate of the present invention.
The followings compounds and products shown in Table 1 were used in the examples.
The adhesive compositions presented in Table 2 were prepared according to the procedures as presented below.
Solid polyester polyols (PO1), polyether polyol (PO2), liquid polyester polyol (PO3), and thermoplastic polymer (TP) were charged into a stainless-steel reactor.
The mixture was kept under vacuum with stirring at 140° C. for 120 minutes to dewater the components and to obtain a homogeneously mixed mixture. The polyisocyanate (PI) was then added to the mixture under a nitrogen blanket. The thus obtained starting mixture was reacted with stirring for 60 minutes under vacuum at a temperature of 140° C. to obtain a reaction product containing the isocyanate-functional polyurethane polymer. The obtained adhesive composition was stored at room temperature under exclusion of moisture.
The adhesive compositions were characterized using the following measurement methods.
The sample adhesive composition provided in a sealed tube was preheated in an oven at a temperature of 130° C. for a time period of 30 minutes. After the heating, a sample of 12.3 g of the adhesive composition was weighted and placed in a disposable sleeve to a viscometer. The viscosity was measured at temperature of 130° C. at 5 revolutions per minute using a Brookfield DV-2 viscometer with a spindle No. 27 equipped with a Thermosel system. The values obtained with 20 minutes of tempering at the measurement temperature and five minutes of measurement were recorded as representative viscosities.
The sample adhesive composition provided in a sealed tube was first preheated in an oven to at temperature of 110° C. for a time period of 30 minutes. After the heating, a sample of 20 g of the molten adhesive was applied with a doctor blade to surface of a silicone paper strip (B700 white, Laufenberg & Sohn KG) placed on a heating plate. The silicone paper strip had dimensions of 30 cm×10 cm and the adhesive was applied as a film having a thickness of 500 μm and dimensions of 30 cm×6 cm. Before applying the adhesive film, the silicone paper strip and the doctor blade were heated to a temperature of 110° C. with the heating plate.
Immediately after application of the adhesive, the silicone paper strip was removed from the heating plate and placed (with the adhesive film facing upwards) on a sheet of plywood at room temperature (23° C.) and the time was recorded as the starting point of the measurement. Every 10 seconds a short strip of silicone coated paper having dimensions of 10 cm×1 cm and formed in a roll (non-siliconized surface facing outwards) was placed on the adhesive film and then slowly removed to separate the strip from the adhesive film. The procedure was repeated until the paper strip could not be removed from the adhesive film without damaging the paper strip or the adhesive film. The time interval between the starting point of the measurement and the last sampling point was recorded as the open time (in seconds) of the adhesive composition
The values of open time presented in Table 2 have been obtained as an average of three measurements conducted with the same adhesive composition.
The adhesive was kept in an oven at 130° C. for more than 30 min to ensure the adhesive was provided in a molten state. After the heating, a sample of the molten adhesive was applied on the surface of a wood substrate having dimensions of 9 cm×2 cm×5 mm. The adhesive was applied as a coating film having dimensions of 2.5 cm×1 cm and a thickness of 1 mm.
Immediately after the application of the adhesive, a second wood substrate having same dimensions as the first wood substrate was positioned over the first wood substrate along the edge of the adhesive film to form a test composite element. The second wood substrate was pressed firmly against the first wood substrate to remove air from adhesive bond. A weigh of 150 g was placed on the top surface of the second wood substrate. Any adhesive squeezed out from the joint was trimmed off with a knife. Lap shear strength (LSS) of the test composite element was measured according to EN 1465 standard using a material testing apparatus (Zwick Z 020) and a test speed 10 mm/min. The lap shear strengths were measure with test composite elements, which had been stored for 3/6/10/20/30 minutes after the bonding of the first wood substrate with the second substrate to investigate the green (initial) adhesive bond strength obtained with the tested adhesive composition.
The adhesive was kept in an oven at 130° C. for more than 30 min to ensure the adhesive was provided in a molten state. An adhesive film having a thickness of 100 μm was coated with doctor knife directly on a PVC film having dimensions of 5 cm×20 cm (width, length). Test specimens were prepared by laminating the PVC film to an ABS board having dimensions of 5 cm×15 cm (width, length) by using a press roll. After 30 minutes, the PVC film was peeled off by hand from the surface of the ABS board and the peel strength was recorded.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/079899 | 3/9/2022 | WO |
