POLYURETHANE-BASED HUMIDITY AND HEAT-ADHESIVE COMPOSITION COMPRISING LOW ISOMYANATE MONOMER CONTENT

专利摘要:
The present invention relates to a curable adhesive composition with heat and moisture comprising: a) from 40 to 60% by weight of at least one polyurethane obtainable by polyaddition reaction of at least one diisocyanate particularly with at least one polyether diol, in the presence or absence of at least one reaction catalyst, at a reaction temperature T1 below 95 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) leading to an NCO / OH molar ratio ranging from 1.6 to 1.9; b) from 39 to 59% by weight of at least one compatible tackifying resin and c) from 0.01 to 1% by weight of at least one crosslinking catalyst. The present invention also relates to a process for preparing said adhesive composition, a self-adhesive carrier coated with the crosslinked adhesive composition and the use of said carrier for the manufacture of self-adhesive labels and / or tapes.
公开号:FR3015510A1
申请号:FR1362993
申请日:2013-12-19
公开日:2015-06-26
发明作者:Guillaume Michaud；Frederic Simon
申请人:Bostik SA；
IPC主号:

专利说明:

[0001] Polyurethane moisture-curable adhesive composition comprising a low content of isocyanate monomer The technical field in which the subject of the present application is concerned is the field of pressure-sensitive adhesives, crosslinked under the action of moisture and heat. More specifically, the invention relates to an adhesive composition that is crosslinkable to moisture and heat, comprising at least one particular polyurethane comprising two terminal isocyanate groups, at least one phenolic tackifying resin, and at least one crosslinking catalyst, with in particular a particularly low isocyanate monomer content; and a self-adhesive backing coated with a pressure sensitive adhesive consisting of said crosslinked composition. Said self-adhesive support is useful for the manufacture of labels and / or self-adhesive tapes.
[0002] Pressure-sensitive adhesives (also called self-adhesive adhesives or, in English, "Pressure Sensitive Adhesives" or PSA) are substances giving the support which is coated immediate tackiness at room temperature (often referred to as "tack"), which allows its instant adhesion to a substrate under the effect of a light and brief pressure.
[0003] PSAs are widely used for the manufacture of self-adhesive labels which are affixed to articles for the purpose of presenting information (such as bar code, name, price) and / or for decorative purposes. PSAs are also used for the manufacture of self-adhesive tapes of various uses. For example, in addition to the transparent adhesive tape widely used in everyday life, there is the shaping and assembly of cardboard packaging; surface protection for painting work, in construction; the maintenance of electrical cables in the transport industry; carpet bonding by double-sided adhesive tape. For the manufacture of self-adhesive labels and / or tapes, PSAs are often applied by continuous coating processes over the entire surface of a large (possibly printable) backing layer, at a rate (usually expressed in g / m2) and hereinafter referred to as "grammage". The support layer is made of paper or film of a single or multi-layered polymeric material. The adhesive layer which covers the support layer may itself be covered with a protective release layer (often called the "release liner"), for example consisting of a silicone film. The multilayer system obtained is generally packaged in the form of large coils up to two meters in width and one meter in diameter, which can be stored and transported.
[0004] These multilayer systems can be subsequently converted into end-user-applicable self-adhesive labels, by means of transformation methods that include printing the desired informative and / or decorative elements on the printable side of the support layer, and then cutting to the shape and dimensions desired. The protective release layer can be easily removed without modification of the adhesive layer which remains attached to the support layer. After separation of its protective release layer, the label is applied to the article to be coated either manually or using labellers on automated packaging lines. These multilayer systems can also be converted into self-adhesive tapes by cutting and packaging rolls of width and length determined.
[0005] Because of their high tack at room temperature, the PSAs allow a rapid grip or adhesion of the self-adhesive label and / or tape to the substrate (or article) to be coated (for example, in the case of labels , on bottles or, in the case of ribbons, on packaging cartons to be shaped), suitable for obtaining significant industrial production rates.
[0006] As part of the present application, we have been interested in a particular category of PSA: HMPSA or "Hot Melt Pressure Sensitive Adhesive" in English, which are hot melt adhesives and have properties at least comparable to PSA, especially in terms of adhesion strength, tack and self-adhesion. In general, the compositions at the base of these adhesives are solid or quasi-solid at room temperature, and need to be melted before deposition (or coating) on a support. After cooling and optionally crosslinking the applied composition, the support is coated with an adhesive seal having a high tack and tack on various substrates. It is known from the prior art the use of low molecular weight polymers (or pre-polymers) of polyurethane type, crosslinkable to moisture and heat, in the preparation of hot melt pressure sensitive adhesives (HMPSA) . The preparation of these polyurethanes is by reaction of a polyol (generally a diol) with a more or less stoichiometric excess of polyisocyanate (generally a diisocyanate).
[0007] This stoichiometric excess can be expressed by a molar ratio NCO / OH (denoted "NCO / OH ratio") strictly greater than 1, which corresponds to the molar ratio of the number of isocyanate groups (NCO) on the number of hydroxyl groups (OH) carried. by the reactive species carrying such functions, used in the preparation of the polyurethane. By placing itself in a given NCO / OH ratio, it is possible to react all the OH functions of the polyol (s) so as to obtain a polyurethane comprising only isocyanate groups at the ends of the polymeric chain. A polyurethane comprising isocyanate end groups is thus obtained. In the field of adhesives, such polyurethanes are referred to as "reactive polyurethanes" or "NCO-terminated polyurethanes", as opposed to "OH-terminated polyurethanes" which refer to polyurethanes in which the end groups are hydroxyl groups, which are not not sensitive to moisture. These OH-terminated polyurethanes are obtained by using a stoichiometric excess of polyol relative to the amount of polyisocyanate, ie an NCO / OH ratio strictly less than 1, and are not crosslinkable to moisture due to the absence of groups. terminal isocyanates. Within the scope of the present application, it is sought to provide NCO-terminated polyurethane compositions which are crosslinkable with moisture and with heat and, after crosslinking, lead to pressure-sensitive adhesives possessing good adhesive properties. . However, because of the reactivity of these polyurethanes in the presence of atmospheric moisture, or more generally of compounds having a labile hydrogen atom such as amines or alcohols, it is difficult to formulate these polyurethanes in the form of a stable composition. storage, and therefore often used two-component systems (or kit) that can synthesize the polyurethane at the last moment just before use of the composition. In general, these two-component systems make it possible to separately store the reagents necessary for the synthesis of the polyurethane, namely the polyol (s) on the one hand, and the polyisocyanate (s), on the other hand, optionally in the presence of other ingredients, and to mix these reagents, just before use of the composition. The adhesive composition obtained is therefore prepared at the last moment just before being applied to a support. However, this method of preparation requires additional handling efforts and is complicated to implement for the user, particularly when the reagents or the composition to be prepared have a viscosity at room temperature (23 ° C) relatively high.
[0008] Another disadvantage of the reactive polyurethane adhesive compositions is that they often comprise a large amount of low molecular weight diisocyanate compounds from diisocyanate monomers (with a molar mass of less than 300 g / mol) used in excess and having no not reacted during the synthesis of polyurethane. It has been observed that the majority of the crosslinkable hot melt adhesive compositions of the prior art based on NCO-terminated polyurethane are formulated from the polyurethane obtained directly after synthesis, and thus contain all the residual diisocyanate monomers ( unreacted) from the synthesis of polyurethane. Finally, the adhesive composition may comprise greater or lesser amounts of diisocyanate monomers, which can lead to a number of problems, including, inter alia, a risk of toxicity to humans and their environment. In fact, when it is envisaged to use NCO-terminated polyurethane-based reactive glues in the production of adhesive films for sealing flexible packaging intended for food products, it is desirable that these glues contain reduced levels of isocyanate monomers. because they are likely to migrate through the layers of flexible packaging and contaminate the food contained in the package or in contact with it. The presence of a large content of free diisocyanate monomers can generate toxic emissions for man and his environment during the use of the adhesive composition, especially during the hot application thereof. To effectively combat this exposure to monomers, special measures must be taken, such as the establishment of appropriate extraction or ventilation systems, and thermal control. However, this generates additional costs and constraints that run counter to the provision of an economical and economical industrial preparation process. In particular because of the disadvantages mentioned above, most regulations require labeling any product containing a content of certain diisocyanate compounds with a molar mass of less than 300 g / mol, expressed in percent by weight, greater than a certain authorized limit. For aliphatic diisocyanates such as hexamethylene diisocyanate (HDI, with a molar mass equal to about 168 g / mol) or isophorone diisocyanate (IPDI, with a molecular weight of about 222 g / mol), this limiting content has been fixed 0.5% by weight of the product; and for aromatic diisocyanates such as toluene diisocyanate (TDI, with a molar mass of about 174 g / mol) or diphenyl methane diisocyanate (MDI, with a molecular weight of about 250 g / mol), this value has been lowered 0.1% by weight of the product, because these are known to form in contact with moisture aromatic primary amines potentially harmful to health. The amount of these diisocyanates and their corresponding amines can be evaluated in a manner well known to those skilled in the art using tests performed under standard conditions. In fact, it is desirable to provide adhesive compositions comprising a content of diisocyanate, and more precisely of residual diisocyanate monomer, lower than the above-mentioned labeling thresholds, so as to reduce the risks of exposure to these compounds when of their use.
[0009] Various solutions have been envisaged for reducing the content of diisocyanate monomer after synthesis of the polyurethane. However, these proposed solutions add purification steps which are generally expensive and undesirable. Moreover, the reduction of the diisocyanate monomer content leads to a significant increase in the viscosity of the polyurethane, which can make the formulation or the implementation thereof difficult. International application WO 00/43432 discloses moisture-and heat-curable hot-melt adhesive compositions comprising an NCO-terminated polyurethane obtained from a polyol having an unsaturation level of less than 0.02 milliequivalents per gram, and a polyisocyanate, said polyurethane being combinable with a variety of tackifying resins. However, these compositions are not entirely satisfactory, especially in view of the benefits sought above. Indeed, these compositions comprise relatively high levels of unreacted diisocyanate monomers, and often use a tin-based reaction and crosslinking catalyst such as tin dibutyltin dilaurate (DBTL) which is potentially toxic. In addition, these compositions have compatibility problems between polyurethane and tackifying resins leading firstly to non-homogeneous adhesive compositions before crosslinking and secondly to heterogeneous and poorly performing adhesives after crosslinking in terms of membership. Thus, there is a need to be able to formulate NCO-terminable, moisture and heat-curable polyurethane adhesive compositions which, after coating on a substrate and then cross-linking, lead to a pressure-sensitive adhesive which does not exhibit one or more of the aforementioned disadvantages.
[0010] In particular, there is a need to be able to formulate compositions with a very low content of diisocyanate monomer of low molecular weight, in particular below the statutory labeling thresholds, and which lead to adhesives sensitive to pressure, having an adhesive power and / or or a comparable or even improved tack compared to the adhesives of the prior art. There is also a need to find solvent-free adhesive compositions that are respectful of man and the environment, having a particularly low diisocyanate monomer content, lower than that of the prior art. Furthermore, there is a need to provide ready-to-use (so-called single-component) adhesive compositions which are sufficiently stable on storage so as not to be formulated in the form of a two-component system. It has now been found that the composition that is the subject of the present application makes it possible to meet all or part of these needs. In particular, the adhesive composition according to the invention does not have the disadvantages of the prior art, and in particular does not present any problem of incompatibility between the polyurethane and the tackifying resin used. In particular, it has been found that the particular combination forming the subject of the present application, combining a particular reactive polyurethane, a particular phenolic tackifying resin, and a crosslinking catalyst, in particular contents, led to homogeneous pressure-sensitive adhesives. having improved adhesion and reduced diisocyanate monomer content relative to prior art adhesives, and while maintaining immediate tackiness and satisfactory appearance. The adhesive compositions according to the invention are transparent. Furthermore, it was found that this combination could be prepared using a preparation process requiring no separation or purification step of residual diisocyanate monomers from the polyurethane synthesis reaction, and had a residual content. in diisocyanate monomers particularly weak under the regulations. The present invention therefore relates firstly to an adhesive composition comprising: a) from 40 to 60% by weight of at least one polyurethane obtainable by polyaddition reaction: of at least one chosen aromatic or aliphatic diisocyanate among the following diisocyanates, and their mixture: - isophorone diisocyanate (IPDI), - 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diisocyanate diphenylmethane (2,4'-diisocyanate) MDI), a derivative of hexamethylene diisocyanate allophanate (HDI) of formula (I): ## STR5 ## wherein is an integer ranging from 1 to 2; q is an integer ranging from 0 to 9, and preferably 2 to 5; -R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising 1 to 20 carbon atoms, preferably 6 to 14 carbon atoms; R 3 represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms, and preferably a divalent propylene group; with at least one polyether diol, in the presence or absence of at least one reaction catalyst, at a reaction temperature T1 lower than 95 ° C and preferably from 65 ° C to 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1.9, preferably from 1.65 to 1.85; b) from 39 to 59% by weight of at least one compatible tackifying resin, with a number-average molar mass ranging from 200 Da to 5000 Da, and chosen from resins obtainable by one of the following processes: b1) polymerization of terpene hydrocarbons in the presence of Friedel-Crafts catalysts, followed by reaction with phenols, b2) polymerization of alpha-methyl styrene, followed by reaction with phenols; and c) from 0.01 to 1% by weight of at least one crosslinking catalyst, said percentages being expressed by weight relative to the total weight of the adhesive composition. Other objects and features of the present invention will appear more clearly on reading the description and examples.
[0011] In the present application, in the absence of any indication to the contrary: the amounts expressed in the form of a percentage correspond to weight / weight percentages; the number-average molar masses, expressed in grams per mole (g / mol), are determined by calculation by analysis of the content of end groups (NCO or OH) expressed in milliequivalents per gram (meq / g) and the functionality (number of NCO or OH function per mole) of the considered entity (polyurethane used according to the invention, polyether diol or corresponding polyether block); the number and weight average molar masses, expressed as dalton (Da), are determined by gel permeation chromatography (GPC), the column being calibrated with standards of Polyethylene Glycol (PEG); "cyclic" means that the hydrocarbon chain comprises in its structure one or more hydrocarbon rings, which may be aromatic or aliphatic, such as rings having from 5 to 6 carbon atoms; - "Diisocyanate monomer" means any difunctional isocyanate compound, that is to say comprising two groups (or functions) isocyanate NCO, aliphatic or aromatic, used as a reagent in the synthesis of a polyurethane, and having a molar mass less than 300 g / mol, and especially ranging from 100 to 270 g / mol. Polyurethane a): The polyurethane used according to the invention preferably has a viscosity ranging from 10,000 to 100,000 mPa.s (millipascal second) at 23 ° C, and more preferably a viscosity of less than 50,000 mPa.s. This viscosity can be measured using a Brookfield viscometer according to ISO 2555. Typically, the measurement can be made at 23 ° C, using a Brookfield RVT viscometer, with a number 6 needle at one time. rotation speed of 20 revolutions per minute (rpm).
[0012] The diisocyanate (s) which can be used to prepare the polyurethane used according to the invention can be chosen from the following aliphatic or aromatic diisocyanates, and their mixture: (a) isophorone diisocyanate ( IPDI) (in which the weight percentage of isocyanate group is approximately 38% by weight relative to the weight of IPDI), a2) 2,4-toluene diisocyanate (2,4-TDI) (the percentage by weight isocyanate group is about 48% by weight based on the weight of 2,4-TDI), a3) diphenylmethane 2,4'-diisocyanate (2,4'-MDI) (the percentage by weight of group isocyanate is equal to 34% by weight relative to the weight of 2,4'-MDI), a4) an allophanate derivative of hexamethylene diisocyanate (HDI) of formula (I) as described above, in wherein p, q, R and R3 are selected such that the HDI allophanate derivative of formula (I) comprises an NCO isocyanate group content of from 12 to 14% by weight relative to the weight of said derivative. Preferably, the diisocyanate (s) that can be used to prepare the polyurethane used according to the invention is (are) chosen from among the following diisocyanates, and their mixture: (a) isophorone diisocyanate (IPDI) , A2) 2,4-toluene diisocyanate (2,4-TDI), a4) an allophanate derivative of hexamethylene diisocyanate (HDI) of formula (I) as described above, in which: p is an integer from 1 to 2; q is an integer ranging from 2 to 5; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 6 to 14 carbon atoms; - R3 represents a divalent propylene group; p, q, R and R3 are chosen such that the HDI allophanate derivative of formula (I) comprises an isocyanate group content ranging from 12 to 14% by weight relative to the weight of said derivative. The diisocyanate (s) which can be used to prepare the polyurethane used according to the invention (mentioned in a2, a3 and a4 above) can be used in the form of a mixture containing essentially the said diisocyanate (s) and a low content of residual diisocyanate compound (s) resulting from the synthesis of said diisocyanate (s). The content of the residual diisocyanate compound (s) tolerated (corresponding to the isomers of 2,4-TDI, 2,4'-MDI and HDI respectively) is such that the use of said mixture in the preparation of the polyurethane according to the invention has no impact on the final properties of the polyurethane.
[0013] For example, the diisocyanate (s) which can be used to prepare the polyurethane used according to the invention (mentioned in a2, a3 and a4 above) can be used in the form of a mixture containing at least 99% by weight of diisocyanate (s) and less than 1% by weight of residual diisocyanate compound (s), preferably in the form of a mixture containing at least 99.5 % by weight of diisocyanate (s) and less than 0.5% by weight of residual diisocyanate compound (s), more preferably in the form of a mixture containing at least 99.8% by weight of diisocyanate (s) and less than 0.2% by weight of residual diisocyanate compound (s), based on the weight of said mixture. Preferably, the residual diisocyanate monomer content is such that the weight content of isocyanate group in said mixture remains approximately equal to that indicated above relative to the weight of diisocyanate a2, a3 and a4 alone. Thus, 2,4-TDI as mentioned in a2) can be implemented in the form of a commercially available technical TDI, corresponding to a composition whose 2,4-TDI content is at least 99 % by weight, and preferably at least 99.5% by weight, based on the weight of said composition. The 2,4'-MDI as mentioned in a3) can be implemented in the form of a commercially available technical MDI, corresponding to a composition whose 2,4'-MDI content is at least 99% by weight, and preferably at least 99.5% by weight, relative to the weight of said composition.
[0014] The HDI allophanate derivative of formula (I) as mentioned in a4) may be used in the form of a composition in which it is included at a rate of at least 99.5% by weight, of preferably at least 99.8% by weight, said composition comprising less than 0.5% by weight of HDI, preferably less than 0.2% by weight of HDI, relative to the total weight of said composition. Such a composition may be obtained for example by: - carbamation reaction ranging from 80 to 100 ° C of a saturated or unsaturated, acyclic, linear or branched monohydric alcohol comprising from 1 to 20 carbon atoms, and oxyalkylated, the part of which alkylene is linear or branched and comprises from 1 to 4 carbon atoms, with a first HDI monomer, in an NCO / OH molar ratio greater than 2, advantageously greater than 4, preferably greater than 8, then - allophanation reaction at a temperature ranging from 100 to 180 ° C., preferably around 140 ° C., the carbamate compound obtained with a second HDI monomer, in an NCO / OH molar ratio of from 5 to 20, and - distillation of the HDI monomers unreacted, to obtain a reagent comprising less than 0.5% by weight of HDI, preferably less than 0.2% by weight of HDI. According to a first preferred embodiment, the diisocyanate (s) that can be used to prepare the polyurethane used according to the invention is (are) chosen from the aliphatic or aromatic diisocyanates mentioned in (a1) (a2). and a3) in any of the above paragraphs, alone or in admixture. According to a second preferred embodiment, the diisocyanate (s) which can be used to prepare the polyurethane used according to the invention is (are) chosen from the aliphatic diisocyanates mentioned in a) in any one of the following: paragraphs above, alone or in mixture. The diisocyanates that can be used to prepare the polyurethane used according to the invention are widely available commercially. By way of example, mention may be made of the "Scuranatee T100" marketed by the company Vencorex, corresponding to a 2,4-TDI of purity greater than 99% by weight, the "Desmodure I" marketed by Bayer, corresponding to an IPDI, or those of the "Tolonatee" series marketed by Vencorex, such as "Tolonatee X FLO 100" corresponding to a composition comprising at least 99.5% by weight of HDI allophanate derivative of formula (I) and less than 0.5% by weight HDI based on the weight of said composition. The polyether diol (s) usable according to the invention may be chosen from those whose number-average molar mass ranges from 2000 to 12000 g / mol, preferably from 3500 to 8500 g / mol, and more preferably from 3500 to 6000 g / mol. The use of such polyether diols leads to a polyurethane generally having a number average molecular weight ranging from 3000 to 21000 g / mol, preferably 4600 to 16800 g / mol, and more preferably from 4600 to 14000 g / mol. Such polyether diols are preferably linear.
[0015] Preferably, the polyether diol (s) usable according to the invention is (are) chosen from polyoxyalkylene diols, the alkylene portion of which, linear or branched, comprises from 2 to 4 carbon atoms. preferably 3 carbon atoms such as polyoxypropylene diol. Preferably, the polyether diol (s) usable according to the invention has a hydroxyl number (OH) ranging from 9 to 56 mg KOH / g, and preferably from 13 to 32 mg KOH. and more preferably 18 to 32 mg KOH / g. The hydroxyl number represents here the number of hydroxyl functions per gram of polyether diol and is expressed in the text of the present application in the form of the equivalent number of milligrams of potassium hydroxide (KOH) used in the determination of the hydroxyl functions. Preferably, the polyether diol (s) used (s) according to the invention has (s) a polymolecularity index (Ip) ranging from 1 to 1.4 and preferably from 1 to 1.2. More preferably, polyoxypropylene diol is used with a polymolecularity index ranging from 1 to 1.4 and preferably from 1 to 1.2. This index corresponds to the ratio of the weight average molar mass to the number-average molar mass of the diol (Ip = Mw / Mn) determined by GPC. Such polyether diols are sold under the name "Acclaim®" by the company Bayer, such as "Acclaim® 12200" of average molar mass in number of about 11335 g / mol and whose hydroxyl number ranges from 9 to 11 mg KOH / g, "Acclaim® 8200" with a number average molar mass of 8057 g / mol and a hydroxyl number ranging from 13 to 15 mg KOH / g, and "Acclaim® 4200" mass molar average in number close to 4020 g / mol, and whose hydroxyl number ranges from 26.5 to 29.5 mg KOH / g.
[0016] Furthermore, the polyether diols that can be used according to the invention can be obtained, in a known manner, by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a double metal-cyanide complex. The polyurethane used according to the invention can be obtained by the preparation method as described above.
[0017] According to a first embodiment, the polyurethane used according to the invention is capable of being obtained by polyaddition of at least one aromatic or aliphatic diisocyanate chosen from those mentioned in al), a2) and a3) in any one of above paragraphs with a polyether diol, preferably as described in any one of the preceding paragraphs, in the presence or absence of at least one reaction catalyst, at a reaction temperature T1 lower than 95 ° C and preferably ranging from from 65 ° C to 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1, 9, preferably 1.65 to 1.85. According to a second embodiment, the polyurethane used according to the invention is capable of being obtained by polyaddition: of at least one aliphatic diisocyanate chosen from those mentioned in a4) in any one of the above paragraphs, put in the form of a composition in which it is at least 99.5% by weight, said composition comprising less than 0.5% by weight of HDI relative to the total weight of said composition; with a polyether diol, preferably as described in any one of the preceding paragraphs, in the presence or absence of at least one reaction catalyst, at a reaction temperature Ti of less than 95 ° C. and preferably of 65 ° C. at 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1.9, preferably from 1.65 to 1.85. Preferably, the polyurethane used according to the invention is obtained by polyaddition of one or two aromatic or aliphatic diisocyanates chosen from those mentioned in al), a2), a3), a4), as described in any one of the paragraphs. with one or two polyether diols, preferably as described in any one of the preceding paragraphs, in the presence or absence of at least one reaction catalyst, at a reaction temperature Ti below 95 ° C and preferably at 65 ° C and 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1, 9, preferably 1.65 to 1.85. More preferably, the polyurethane used according to the invention is obtained by polyaddition of an aromatic or aliphatic diisocyanate chosen from those mentioned in al), a2), a3), a4), as described in any one of the paragraphs. with a polyether diol, preferably as described in any one of the preceding paragraphs, in the presence or absence of at least one reaction catalyst, at a reaction temperature Ti lower than 95 ° C. and preferably ranging from 65 ° C. At 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1.9, preferably from 1.65 to 1.85.
[0018] The reaction between the said diisocyanate (s) and the said polyether diol (s) is preferably carried out at a reaction temperature Ti ranging from 65 ° C. to 80 ° C. to obtain within a reasonable time the desired polyurethane, especially for the transposition of the polyurethane preparation on an industrial scale. The term "NCO / OH molar ratio" means the molar ratio of the number of isocyanate groups to the number of hydroxyl groups of the diisocyanate and diol reactants used for the synthesis of the polyurethane. The set of conditions for obtaining the polyurethane used according to the invention described above makes it possible to obtain a particularly low concentration of unreacted diisocyanate monomer at the end of the reaction and a polyurethane having the physicochemical properties necessary for obtaining, in combination with the other ingredients mentioned in b) and c), a hot-melt adhesive composition heat-and moisture-curable having satisfactory adhesive performance.
[0019] The adhesive composition according to the invention may thus advantageously comprise less than 0.5% by weight, preferably less than 0.3% by weight, of (each) aliphatic diisocyanate monomer (optionally present in the adhesive composition), and / or less than 0.1% by weight, preferably less than 0.06% by weight, of (each) aromatic diisocyanate monomer (optionally present in the adhesive composition), relative to the total weight of the adhesive composition, depending on whether the polyurethane used according to the invention was obtained from (s) diisocyanate (s) aromatic (s) and / or aliphatic (s). The principle of the analytical method for determining the concentration of free diisocyanate monomers is based on the specific reaction of the isocyanate group NCO with an amine (1- (2-methoxyphenyl) piperazine or PPZ) to form stable derivatives of urea . These derivatives are obtained during the preparation of the adhesive sample by dilution / solubilization of this sample with a solution of acetonitrile 0.02 mol / l of PPZ. The PZZ derivatives formed from the isocyanates contained in the sample to be analyzed are then assayed by a C18 reverse phase high performance liquid chromatography (HPLC) system with a mobile phase gradient comprising a mixture of water and water. acetonitrile buffered with an aqueous solution of tetrabutylammonium bisulfate at 0.2% by weight, at a pH ranging from 2 to 3, provided with an ultraviolet detector (UV) operating at 254 nm. These compounds are identified and quantified by comparing their retention time and their surface of chromatographic peaks with those of the standard PPZ derivatives obtained by reaction of a diisocyanate monomer of known nature and concentration.
[0020] The adhesive composition according to the invention may also have an NCO group content (also referred to as "NCO content", denoted% NCO) ranging from 0.15 to 1.7% by weight, preferably from 0.2 to 1.1% by weight, based on the total weight of the adhesive composition. These isocyanate groups correspond to those borne by the NCO-terminated polyurethane and those carried by the other isocyanate compounds present in the adhesive composition, such as unreacted diisocyanate monomers. This NCO content is computable in a manner well known to those skilled in the art and provides as a first approximation an indication of the ability of the polyurethane present in the adhesive composition to crosslink later in contact with moisture.
[0021] When this level is too low, the polyurethane does not crosslink sufficiently to obtain good adhesive properties. When this level is too high, the crosslinked adhesive composition is too rigid and thus once cross-linked to a little or no adhesive adhesive.
[0022] According to a third embodiment, the polyurethane used according to the invention has a number-average molar mass ranging from 3000 to 21000 g / mol, and can be obtained by polyaddition of an aromatic or aliphatic diisocyanate chosen from those cited. in al), a2), a3), a4, as described in any one of the preceding paragraphs, with a polyether diol having a number-average molar mass ranging from 2000 to 12000 g / mol, preferably chosen from polyoxyalkylene diols. , the linear or branched alkylene portion of which comprises from 2 to 4 carbon atoms, preferably 3 carbon atoms, such as polyoxypropylene diol, in the presence or absence of at least one reaction catalyst, at a lower reaction temperature Ti 95 ° C and preferably ranging from 65 ° C to 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) leading to a molar ratio NCO / OH, noted r1, ranging from 1, 6 to 1.9. According to a preferred variant of this third embodiment, the polyurethane used according to the invention has a number-average molar mass ranging from 4600 to 16800 g / mol, and can be obtained by polyaddition of an aromatic or aliphatic diisocyanate. chosen from among those mentioned in al), a2), a3), a4, as described in any one of the preceding paragraphs, with a polyether diol having a number-average molar mass ranging from 3500 to 8500 g / mol, preferably chosen among the polyoxyalkylene diols, the alkylene portion, linear or branched, comprises from 2 to 4 carbon atoms, and more preferably 3 carbon atoms such as polyoxypropylene diol, in the presence or absence of at least one reaction catalyst, to a reaction temperature Ti lower than 95 ° C and preferably ranging from 65 ° C to 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) leading to a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1.9. According to a more preferred variant of this third embodiment, the polyurethane used according to the invention has a number-average molar mass ranging from 4600 to 14000 g / mol, and can be obtained by polyaddition of an aromatic diisocyanate or aliphatic composition as described in any one of the preceding paragraphs, with a polyether diol having a number-average molar mass ranging from 3500 to 6000 g / mol, preferably chosen from polyoxyalkylene diols, the linear or branched alkylene portion of which comprises from 2 to 4 carbon atoms, preferably 3 carbon atoms such as polyoxypropylene diol, in the presence or absence of at least one reaction catalyst, at a reaction temperature Ti of less than 95 ° C. and preferably of 65 ° C. at 80 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in a molar ratio NC 0 / 0H, denoted r1, ranging from 1.6 to 1.9.
[0023] The polyurethane used according to the invention which can be obtained according to this third embodiment, can be represented by the following formula (II): OCN R1NH CO 0 C NH R1 NH C 0 OC R1-N CO O OR wherein R 1 represents a divalent group selected from one of the following divalent aliphatic or aromatic groups corresponding respectively to the aliphatic or aromatic diisocyanates mentioned in al), a2), a3) and a4) above: al ') the divalent group derived from isophorone diisocyanate (IPDI): CH C H3 a2 ') the divalent group derived from 2,4-toluene diisocyanate (2,4-TDI): a3') the divalent group derived from 2,4'- diphenylmethane diisocyanate (2,4'-MDI): a4 ') the divalent group derived from a hexamethylene diisocyanate allophanate (HDI) of the following formula (III): R-OR3 c) (CH2) 6 O (CH2) ) P (III) wherein: - p is an integer from 1 to 2; q is an integer ranging from 0 to 9, and preferably from 2 to 5; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 6 to 14 carbon atoms; - R3 represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms; and preferably, a divalent propylene group; - R2 identical or different from R3, represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms; and preferably, a divalent propylene group; n is a non-zero integer such that the number-average molar mass of the polyether block of formula -PRS] ranges from 2000 to 12000 g / mol, and preferably from 3500 to 8500 g / mol, and more preferably from 3500 to 6000 g / mol; m is an integer such that the number average molar mass of the polyurethane ranges from 3000 to 21000 g / mol, preferably 4600 to 16800 g / mol, and more preferably from 4600 to 14000 g / mol. In particular, R 1 may represent a divalent group selected from one of the following divalent aliphatic or aromatic groups: (a ') the divalent group derived from isophorone diisocyanate (IPDI), 25 a2') the divalent group derived from 2,4 toluene diisocyanate (2,4-TDI), a3 ') the divalent group derived from diphenylmethane 2,4'-diisocyanate (2,4'-MDI), a4') the divalent group derived from a hexamethylene allophanate diisocyanate (HDI) of formula (III) in which: p is an integer ranging from 1 to 2; q is an integer ranging from 0 to 9, and preferably from 2 to 5; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 6 to 14 carbon atoms; - R3 represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms; and preferably, a divalent propylene group; - p, q, R and R3 are chosen such that the corresponding HDI allophanate derivative of formula (I) comprises an isocyanate group content ranging from 12 to 14% by weight relative to the total weight of said derivative. Preferably, R 1 represents a divalent group chosen from one of the following divalent aliphatic or aromatic groups: a ') the divalent group derived from isophorone diisocyanate (IPDI), a2') the divalent group derived from 2,4-toluene diisocyanate (2,4-TDI), a3 ') the divalent group derived from diphenylmethane 2,4'-diisocyanate (2,4'-MDI), a4') the divalent group derived from a hexamethylene diisocyanate allophanate ( HDI) of formula (III) in which: p is an integer ranging from 1 to 2; q is an integer ranging from 2 to 5; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 6 to 14 carbon atoms; - R3 represents a divalent propylene group; - p, q, R and R3 are chosen such that the corresponding HDI allophanate derivative of formula (I) comprises an isocyanate group content ranging from 12 to 14% by weight relative to the total weight of said derivative. The reaction catalyst (s) that may be used may be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reacting at least one diisocyanate and at least one polyether. diol, provided that it does not catalyze the reaction between the hydroxyl function of the phenolic tackifying resin and the isocyanate groups of the NCO-terminated polyurethane.
[0024] Preferably, one or more catalysts chosen from catalysts having no or little risk of toxicity are used. In particular, the reaction catalyst (s) are chosen from: - organometallic derivatives of bismuth, such as bismuth neodecanoate sold under the name "Borchikate315" by the company OM Group, the bismuth carboxylate sold under the name "K" -KAT® XC B221 "by King Industries, - organometallic tin derivatives other than tin dibutyl dilaurate, such as, for example, tin dioctyl dilaurate (DOTL) as sold under the name" TM ® KAT 217 "by the company" TIB Chemical ", - organometallic derivatives of zinc, such as zinc carboxylate sold under the name" Borchikat®22 "by the company OM Group, - organometallic derivatives of titanium, such as the titanium tetrabutylate Ti (OCH 2 CH 2 CH 2 CH 3) 4, titanium ethylacetoacetate sold under the name "Tyzore PITA" by Dupont, - organometallic derivatives of zirconium, such as titanium zirconium late sold under the name "K-KATe A209", zirconium acetylacetonate (Zr (acac) 4), and zirconium tetraethanolate Zr (OCH2CH3) 4, and - their mixture. Up to 0.3% by weight of catalyst (s) of reaction may be present in the adhesive composition. In particular, it is preferred to use from 0.02 to 0.3% by weight of reaction catalyst (s) relative to the total weight of the adhesive composition. Tackifying Resin b): The term "tackifying compatible resin" is intended to denote a tackifying resin which, when mixed in the proportions 50% / 50% by weight with the polyurethane used according to the invention, gives a substantially homogeneous mixture. In particular, the mixture remains transparent (in the spectrum of visible light - wavelength ranging from 380 to 780 nm, measured in a vacuum) and no total or partial phase shift or gellation is observed. in the polyurethane / resin mixture. Preferably, the compatible tackifying resin (s) (s) which may be used according to the invention have a softening temperature ranging from 70 ° C. to 150 ° C., preferably from 75 ° C to 130 ° C.
[0025] Preferably, the adhesive composition according to the invention comprises a compatible tackifying resin capable (s) of being obtained (s) by method b1) or b2) as defined above. Tackifying Resin 1) 1): The compatible tackifying resin (s) capable of being obtained by process b1) as defined previously may be presented a glass transition temperature of from 50 ° C to 110 ° C, preferably from 55 ° C to 90 ° C, and more preferably from 60 ° C to 85 ° C. The compatible tackifying resin (s) capable of being obtained by the process (b1) as defined above may have a softening temperature ranging from 100.degree. At 125 ° C, preferably from 110 ° C to 125 ° C, and more preferably from 115 ° C to 120 ° C. The softening temperature (or point) of the resin can be determined in accordance with the ASTM E 28 standard test, the principle of which is as follows. A brass ring about 2 cm in diameter is filled with the resin to be tested in the molten state. After cooling to room temperature, the ring and the solid resin are placed horizontally in a thermostated bath of glycerine whose temperature can vary from 5 ° C per minute. A steel ball with a diameter of about 9.5 mm is centered on the solid resin disc. The softening temperature is, during the temperature rise phase of the bath at a rate of 5 ° C per minute, the temperature at which the resin disc flows 25.4 mm under the weight of the ball. The compatible tackifying resin (s) capable of being obtained by process (b1) as defined above may have a molar mass in number Mn ranging from 470 to 700. Da, preferably from 500 to 600 Da.
[0026] The compatible tackifying resin (s) capable of being obtained by process (b1) as defined above may comprise a hydroxyl number ranging from 40 to 160 mg. KOH / g, preferably ranging from 50 to 155 mg KOH / g, and more preferably from 90 to 150 mg KOH / g. Tackifying Resin b2): A compatible tackifying resin chosen from those obtainable by process b2) is preferably used, when a reaction catalyst, as described above for example, is used to prepare the polyurethane used according to US Pat. 'invention.
[0027] The compatible tackifying resin (s) capable of being obtained by the method (b 2) as defined above preferably comprises (include) a softening temperature ranging from at 120 ° C, more preferably 90 to 110 ° C. This softening temperature can be measured according to the ASTM E 28 standardized test. The compatible tackifying resin (s) capable (s) to be obtained by the method b2) such that defined above can comprise a number-average molar mass ranging from 650 to 1740 Da, preferably from 650 to 1100 Da, more preferably from 750 to 1050 Da, and more preferably from 950 to 1020 Da.
[0028] According to a first variant, the compatible tackifying resin (s) capable of being obtained by the method b2 as defined previously can comprise a hydroxyl number ranging from from 4 to 15 mg KOH / g. According to a second variant, the compatible tackifying resin (s) capable of being obtained by the method (b 2) as defined above may comprise a hydroxyl number ranging from from 25 to 50 mg KOH / g. The compatible tackifying resin (s) capable of being obtained by process b2) as defined above may comprise a polymolecularity index ranging from 1.2 to 1. , 8, preferably ranging from 1.4 to 1.7. The tackifying resins that can be used according to the invention are commercially available and those that can be obtained by one of the methods b1) and b2) defined above, mention may be made of the following products: - process b1): "Dertophene® H150" available from DRT with a molar mass equal to about 630 Da, having a softening temperature of 118 ° C. and a hydroxyl number ranging from 135 to 150 mg KOH / g; method b2): "Sylvarez® 510" available from Arizona Chemical with a molar mass in number of about 1740 Da, a softening temperature of 95 ° C; and "Sylvares® 525" also available from Arizona Chemical with a molar mass of about 1010 Da, a softening temperature of 75 ° C, and a hydroxyl number of about 4 mg KOH / g.
[0029] According to a particularly preferred embodiment, the adhesive composition according to the invention comprises: a) from 40 to 60% by weight of a polyurethane obtainable by polyaddition of 2,4-TDI, with a polyether diol, in the presence or absence of at least one reaction catalyst, at a reaction temperature T1 below 95 ° C. and preferably ranging from 65 ° C. to 80 ° C., under anhydrous conditions, and in amounts of TDI and polyether diol (s) resulting in a molar ratio NCO / OH, denoted r1, ranging from 1.6 to 1.9, preferably from 1.65 to 1.85; b) from 39 to 59% by weight of a compatible tackifying resin, with a number-average molar mass ranging from 200 Da to 5000 Da, and chosen from resins obtainable by method b2); and c) from 0.01 to 1% by weight of at least one crosslinking catalyst, based on the total weight of the adhesive composition.
[0030] According to a variant of this particularly preferred embodiment, the adhesive composition according to the invention comprises: a) from 40 to 60% by weight of a polyurethane of formula (I), in which: R 1 represents the divalent group derived from 2,4-TDI; R2 represents the divalent propylene group; n is a non-zero integer such that the number-average molar mass of the polyether block of formula 40 R21 ranges from 3500 to 8500 g / mol, and better still from 3500 to 6000 g / mol, m is an integer such that the number average molecular weight of the polyurethane ranges from 4600 to 16800 g / mol, and more preferably from 4600 to 14000 g / mol; b) from 39 to 59% by weight of a compatible tackifying resin, with a number-average molar mass ranging from 200 Da to 5000 Da, and chosen from resins obtainable by method b2); and c) from 0.01 to 1% by weight of at least one crosslinking catalyst, based on the total weight of the adhesive composition.
[0031] The adhesive compositions as defined in these particularly preferred embodiments of the invention make it possible, once coated on a support layer, for example a polymer layer, then cross-linked with moisture and by heating, to obtain an adhesive seal which is sensitive to particularly adherent pressure and resistant to breakage. Indeed, when the adhesive seal is bonded to a substrate, then subjected to a detachment force, it detaches without breaking. There is "adhesive break" of the adhesive seal with respect to the substrate. The tensile strength can be evaluated by standard adhesion tests, such as those described in the examples of the present application, on various substrates such as for example glass, metal, etc.
[0032] Crosslinking Catalyst c): The crosslinking catalyst (s) used in the adhesive composition according to the invention may be any catalyst known to those skilled in the art for catalyzing the formation of urea by reaction of a diisocyanate in the presence of water (moisture). Preferably, these catalysts are selected from catalysts not containing tin. For example, one or more tertiary amine catalysts can be used such as: - 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) - 1,5-diazabicyclo [4.3.0] non-5- ene (DBN) - diethyl ether-2,2'-morpholine (DMDEE) / o - 1,4-diazabicyclo [2.2.2] octane (DABCO) These crosslinking catalysts have the advantage of not being carcinogenic , mutagenic and reprotoxic (CMR). Among these crosslinking catalysts, DBU is preferably used. An amount of 0.1 to 2% of one or more stabilizers (or antioxidant) may further be included for example in the adhesive composition according to the invention. These compounds are introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat, light or residual catalysts on certain raw materials such as tackifying resins . These compounds may include primary antioxidants that trap free radicals and are generally sterically hindered primary phenolic compounds substituted with NN methyl and / or tert-butyl groups such as BASF's "Irganox 1076" (octadecyl-3- (3, 5-diterbutyl-4-hydroxyphenyl) -propionate), BASF's "Irganoxe1010" (pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), BASF's "Irganoxe245" (Ethylene bis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate.) The primary antioxidants can be used alone or in combination with other antioxidants such as phosphites such as "Irgafos® 168" also from BASF (tris (2,4-di-terbutylphenyl) phosphite), or with UV stabilizers such as amines The adhesive composition according to the invention may also include one or more several additives chosen in an appropriate manner so as not to deteriorate the properties of the adhesive Examples of suitable additives include pigments, dyes and fillers. These additives may be chosen from those usually used in adhesive compositions. In contrast, the adhesive composition according to the invention does not preferably comprise thermoplastic polymers such as ethylene vinyl acetate (EVA) or plasticizer.
[0033] Preferably, the adhesive composition does not comprise an organic solvent with a boiling point of less than 250 ° C. at atmospheric pressure, such as ethyl acetate, xylene, toluene or N-methyl-2-pyrrolidone. (NMP). More particularly, the adhesive composition consists of: a) from 40 to 60% by weight of at least one polyurethane as defined in any one of the preceding paragraphs, b) from 39 to 59% by weight of at least a tackifying compatible resin as defined in any one of the preceding paragraphs, c) up to 0.3% by weight of at least one reaction catalyst, d) from 0.01 to 1% by weight of minus a crosslinking catalyst, e) less than 0.5% by weight of monomer (s) diisocyanate (s) aliphatic (s), f) less than 0.1% by weight of monomer (s) diisocyanate (s) aromatic (s), g) less than 2% by weight of at least one stabilizer or antioxidant, and h) optionally at least one additive selected from pigments, dyes and fillers.
[0034] According to this preferred embodiment, the nature of the compounds a) to h) and their content are as defined in one of the preceding paragraphs. Thus, the weight content of (each) aliphatic diisocyanate monomer (s) possibly present in the composition, namely IPDI and / or HDI, preferably represents less than 0.3%. the weight of the composition, and the weight content of (each) aromatic monomer (s) diisocyanate (s) optionally present in the composition, namely TDI and / or MDI, preferably represents less than 0.06% of the weight of the composition. According to this preferred embodiment, the adhesive composition according to the invention preferably has a viscosity ranging from 1000 to 50,000 mPa.s at 100 ° C., and preferably a viscosity ranging from 4000 to 15,000 mPa.s at 100 ° C. vs. This viscosity can be measured at 100 ° C. using a Brookfield RVT viscometer coupled with a Thermosel type heating module of the Brookfield brand, with a mobile number 27 at a rotation speed of 20 rpm.
[0035] Another subject of the invention relates to a method for preparing an adhesive composition according to the invention, characterized in that the polyurethane (s) used according to the invention is (are) prepared (s). ) beforehand and then mixed with the other compounds of the adhesive composition. According to a preferred variant according to the invention, the process for preparing the adhesive composition according to the invention comprises in the following order: (i) a step of melting the tackifying resins or, if appropriate in a mixture with one or a plurality of thermal stabilizers or antioxidants, at a temperature T2, (ii) a step of incorporating and mixing, in an inert atmosphere, the polyurethane or polyurethanes, (iii) a step of cooling said mixture, at a temperature T3 less than T2, then, (iv) a step of incorporating into said mixture of the crosslinking catalyst or catalysts, and if appropriate, of the other optional compounds. Stage (i) generally takes place at a temperature T2 greater than or equal to the softening temperature of the tackifying resin, and in the case of a resin mixture, at a temperature T2 greater than or equal to the greater of the temperatures softening of the resins used. In particular, the temperature T2 does not exceed 150 ° C, preferably 130 ° C. Preferably, the temperature T2 is greater than or equal to the softening temperature of the tackifying resin, and in the case of a resin mixture, at a temperature T2 greater than or equal to the greater of the softening temperatures of the resins used, and ranges from 70 ° C to 150 ° C, more preferably from 75 ° C to 130 ° C. In step (ii), the addition of the polyurethane (s) can be carried out in a fractional manner. Indeed, the total amount of polyurethane (s) to be introduced can be fractionated in as many portions as necessary so as to prevent a too large drop in the temperature of the mixture due to the introduction of a large volume of polyurethane ( s), freeze the reaction medium. Between each of the preceding steps, it is possible to introduce a dehydration step under vacuum, in particular before and after adding the polyurethane, so as to work under optimal anhydrous conditions. Each dehydration step can be carried out under a reduced pressure of 10 to 50 millibars (mbar), for a period of from one hour thirty to three hours and preferably of at least two hours. Stage (iii) generally takes place at a temperature T3 lower than the softening temperature of the tackifying resin, and in the case of a mixture of tackifying resins, at a temperature T3 less than the greater of the softening temperatures of the resins used. In particular, the temperature T3 is also at least 45 ° C. Preferably, the temperature T3 is lower than the softening temperature of the tackifying resin, and in the case of a mixture of tackifying resins, at a temperature T3 lower than the highest of the softening temperatures of the resins used, and ranges from 45 ° C to 90 ° C, more preferably 70 ° C to 80 ° C. The present invention also relates to a self-adhesive support capable of being obtained by a process comprising the following steps: (i ') preheating to a temperature T4 of the adhesive composition as defined above in order to make it liquid, then ( ii ') coating said adhesive composition on a support layer, then (iii') crosslinking said adhesive composition by heating the support thus coated at a temperature T5 ranging from 70 ° C to 150 ° C, preferably from 75 ° C to 130 ° C, in the presence of atmospheric moisture, and preferably a relative humidity between 40 and 70% at 23 ° C. Step (i ') generally takes place at a temperature T4 ranging from 70 ° C to 150 ° C, more preferably from 75 ° C to 130 ° C. The coating layer (ii ') is carried out by means of known coating devices, such as for example a lip or curtain-type nozzle, a roller or a manual coating device, also known as a film-puller or filmograph. It implements a grammage of adhesive composition ranging from 20 to 100 g / m2.
[0036] The material that can be used for the support layer is, for example, paper or a film of a single or multi-layered polymeric material. By way of example, mention may be made of a Polyethylene terephthalate (PET) support. The time required for the crosslinking of step (iii ') can vary within wide limits, for example between 1 second and 15 minutes. This thermal crosslinking step combined with a subsequent crosslinking step in the presence of atmospheric moisture (and preferably a relative humidity between 40 and 70% at 23 ° C.) has the effect of creating - between the polyurethane polymer chains used according to the invention, and under the action of the atmospheric moisture of urea-type bonds which lead to the formation of a three-dimensional polymeric network. The thus crosslinked adhesive composition is a pressure-sensitive adhesive which provides the coated carrier layer with desirable tack and tack. Thus, a 50g / m 2 coated PET carrier has a permanent adhesion to a stainless steel substrate corresponding to an adhesive power (measured by the 180 ° peel test on stainless steel described below). after) advantageously greater than 2 N / cm, preferably ranging from 2 to 20 N / cm, in cohesive or adhesive breaking, and more preferably in adhesive breaking. The tack of this same support at room temperature (measured by the instantaneous adhesion test of the loop described hereinafter) is advantageously greater than 2 N / cm, preferably ranging from 2 to 35 N / cm, in cohesive or adhesive, and more preferably in adhesive rupture. The terms "cohesive failure" and "adhesive failure" represent the appearance of the failure facies after detachment of the adhesive seal from the substrate or support. By "cohesive failure" is meant that the separation fracture between the loose materials has appeared within the adhesive joint. By "adhesive rupture" is meant that the separation fracture between the loose materials has appeared on the outside of the adhesive joint, so that the adhesive remains adhered to one of the interfaces between the adhesive joint and one of the materials assembled by gluing. Finally, the adhesive seal formed after application to a substrate of the support layer coated with the crosslinked composition ensures the fixing of said support layer in a temperature range of -60 ° C to + 160 ° C. The self-adhesive support according to the invention may also comprise a protective release layer covering the PSA layer, said protective layer being simply glued.
[0037] The present invention also relates to the use of the self-adhesive support defined above for the manufacture of self-adhesive labels and / or tapes. The basis weight of the adhesive composition necessary for the manufacture of self-adhesive labels may range from 20 to 100 g / m 2, preferably around 50 g / m 2. That required for the manufacture of self-adhesive tapes may vary in a much wider range from 2 to 1000 g / m 2, preferably from 15 to 250 g / m 2. The following examples are given purely by way of illustration of the invention and can not be interpreted to limit its scope. Examples 1-7 illustrate the preparation of a polyurethane used according to the invention. Examples 1A to 7A illustrate adhesive compositions according to the invention comprising the polyurethane obtained in Examples 1 to 7 respectively. Examples 8A to 10A correspond to comparative compositions (denoted by the abbreviation comp) comprising the polyurethane obtained in Example 3, but a tackifying resin different from that used according to the invention: - "Kristalex® F100" = polymer hydrogenated alpha-methyl styrene sold by Eastman Chemical having a softening temperature of 99 ° C., "Sylvalite® RE 105 XL" = rosin ester, sold by Arizona Chemical, having a softening point of 105 ° C, 20 - "Acrynax® 4326" = acrylic resin, sold by Franklin Adhesives & Polymers, having a softening temperature ranging from 70 ° C to 80 ° C. Example 11A corresponds to an adhesive composition prepared according to the prior art (example 2 of application WO 0043432). "Kristalex® 3085" = alpha-methyl styrene hydrocarbon resin, sold by Eastman Chemical, having a softening temperature of from 70 ° C to 80 ° C. Examples 1 to 7 Preparation of the Polyurethanes The polyurethanes 1 to 7 of Examples 1 to 7 were prepared in the same way using the various ingredients listed in Table 1. The amounts of diisocyanate and diol used correspond to a ratio molar NCO / OH ranging from about 1.7 to about 1.8. The amounts indicated in Table 1 are expressed in grams. Experimental Protocol: The diisocyanate and the diol, and if appropriate the reaction catalyst, are mixed in a reactor maintained under constant stirring and under nitrogen, at a temperature T1 ranging from 72 to 80 ° C. The temperature is controlled so as not to exceed 80 ° C. The rate of progress of the reaction is monitored by measuring the NCO content by a dibutylamine assay in return, using hydrochloric acid according to standard NF T52-132. The reaction is stopped when the measured "NCO level" is approximately equal to the desired NCO level. Table 1 Ingredients of polyurethane 1 2 3 4 5 6 7 Acclaim®8200 - 750 - - - - - Acclaimed 4200 929 - 929 912 912 929 412 Scuranatee T100 71 28 71 - - 71 - TolonateeX FLO 100 - - - - - - 118 IPDI - - - 88 88 - - Borchikate315 - - 0.1 0.1 0.1 - 0.05 TM Kate217 - - - - - 0.1 - Characterization: For each of the polyurethanes of Examples 1 to 7 obtained: NCO content in the polyurethane synthesis medium is determined according to standard NF T52-132. The measured values are expressed as a percentage by weight relative to a 100 g sample, are then reported on the total weight of the adhesive composition and are recorded in Table 4. - The weight content of unreacted diisocyanate monomer present in the medium of polyurethane synthesis is measured by an HPLC method equipped with a UV detector as described previously (reverse phase C18, mobile phase: aqueous acetonitrile solution, buffered with an aqueous solution at 0.2% by weight of tetrabutylammonium bisulfate pH 2.5, detection wavelength: 254nm). The measured values are expressed in percentage by weight and are then reported on the total weight of the adhesive composition and are recorded in Table 4. The viscosity of the polyurethane is estimated by measuring at 23 ° C. the viscosity of the polyurethane synthesis medium. at the end of the reaction. This measurement is carried out 24 hours after the end of reaction (D + 1) at 23 ° C., using a Brookfield RVT viscometer, with a number 6 needle at a speed of rotation of 20 rpm (tr min). The measured value is expressed in millipascal seconds (mPa. $) And is recorded in Table 2. Table 2 Characterization of polyurethane 1 2 3 4 5 6 7 Viscosity at 23 ° C (mPa $) 8710 10800 19500 25920 25920 18400 83400 Examples 1A to 10A: Preparation of the adhesive compositions The compositions 1A to 10A were prepared in the same way using the various ingredients listed in Table 3. In particular, these compositions were made from the polyurethanes of Examples 1 to 7 obtained without undergoing a purification step or separation of the residual diisocyanate, not consumed by the polyurethane synthesis reaction. In other words, these compositions were made from the polyurethanes of Examples (denoted 1 to 7) comprising the corresponding unreacted diisocyanate monomer, which represents less than 0.1% of the weight of the polyurethane (for Examples 1-3 and 6) and less than 0.5% by weight of the polyurethane (for Examples 4-5 and 7). The unreacted diisocyanate monomer concentrations were measured according to the method described above in the description. The amounts shown in Table 3 are in grams. Experimental Protocol: The composition IA is prepared by first introducing the tackifying resin and the antioxidants in a vacuum glass reactor and heated to a temperature T2 greater than or equal to the softening temperature of the tackifier resin and less than or equal to 130 ° C. Then, once the resin melts, the vacuum is cut and is introduced under nitrogen half of the polyurethane composition obtained in Example 1 above. The mixture is maintained at a temperature T2 as defined above, with constant stirring. After addition, the mixture is left stirring under vacuum for at least 2 hours, then the vacuum is again cut and the other half of the polyurethane composition 1 is introduced under nitrogen while keeping the mixture under stirring at a temperature T2 such that than previously defined. The medium is then cooled to a temperature T3, at about 80 ° C., the vacuum is then reduced and the catalyst is introduced under a nitrogen atmosphere with vigorous stirring. After addition, the vacuum is restored and the mixture is stirred for a further 10 minutes.
[0038] The composition obtained is stored in an aluminum cartridge previously oven-dried at 100 ° C. and sealed to moisture.
[0039] The experimental protocol applied for Example 1A is reproduced in the same way for Examples 2A to 10A taking into account Table 3. Table 3 Ingredients of IAA 2A 3A 4A 5A 6A 7A 8A 9A 10A adhesive composition (comp) (comp ) (comp) Polyurethane 1 52.0 - - - - - - - - - Polyurethane 2 - 52.1 - - - - - - - - Polyurethane 3 - - 52.1 - - - - 52.1 52.1 52 , 1 Polyurethane 4 - - - 52,1 - - - - - - Polyurethane 5 - - - - 52,0 - - - - - Polyurethane 6 - - - - - 52,0 - - - - Polyurethane 7 - - - - - - 52.1 Dertophene®H150 46.8 47.1 - - - 46.8 - - - - Sylvarese525 - - 47.1 47.1 46.8 - 47.1 - - - KristalexeF100 - - - - - - - - - 47,1 SylvaliteeRE105XL - - - - - - - 47,1 - - Acrynaxe4326 - - - - - - - - 47,1 - DBU 0,5 0,1 0,1 0,1 0,5 0, 5 0.1 0.1 0.1 0.1 Antioxidants 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Characterizations: Measurements The following are carried out in the same manner on the various adhesive compositions 1A to 10A obtained: the viscosity of the The composition is measured at 100 ° C using a Brookfield RVT viscometer coupled with a Brookfield brand Thermosel heater module, with a number 27 mobile at a rotation speed of 20 rpm. This viscosity is expressed in millipascal.second. In addition, the general appearance of each composition (visible light) was visually evaluated. Compositions IA-7A are all transparent. For Comparative Examples 9A and 10A, gelation of the composition was observed, presumably resulting from incompatibility between the tackifying resin and the polyurethane used. The measured values are grouped together in Table 4.
[0040] Table 4 Characterizations of the Adhesive Compositions 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A (comp) (comp) (comp) Viscosity at 100 ° C (mPa.s) 8350 6000 7000 3000 3700 9025 7000 6100 gel% NCO gel (% in 0.77 0.38 0.77 0.74 0.77 0.77 0.66 0.77 0.77 0.77 weight of the adhesive composition) 0.04 0.05 0.04 0, 49 0.49 0.04 0.3 0.04 0.04 0.04 free monomer (% by weight of the adhesive composition) Preparation of a PET carrier layer coated with the crosslinked adhesive composition, at a rate of 50 g m2: The support layer used is a rectangular sheet of polyethylene terephthalate (PET) 50 μm thick and 20 cm by 40 cm in size. The composition LA obtained at a temperature T4 ranging from 70 ° C. to 150 ° C. and preferably from 100 ° C. to 120 ° C. is preheated and introduced into a cartridge from which a bead which is deposited is extruded. near the edge of the leaf parallel to its width.
[0041] The composition enclosed in this bead is then distributed over the entire surface of the sheet, so as to obtain a uniform layer of substantially constant thickness. For this purpose, a film puller (also known as a filmograph) is used which is moved from the edge of the sheet to the opposite edge. A layer of composition corresponding to a basis weight of 50 g / m 2 is thus deposited, which represents a thickness of the order of 50 μm. The PET sheet thus coated is then placed in an oven at a temperature T5 ranging from 70 ° C to 150 ° C and preferably from 100 to 120 ° C for about 15 minutes, then at 23 ° C for 7 days at a rate of relative humidity of 50%, for crosslinking of the composition.
[0042] The sheet is then laminated on a protective release layer consisting of a sheet of silicone film, rectangular and of the same dimensions. The PET support layer thus obtained is subjected to the tests described below. The experimental protocol applied and the tests carried out for the multilayer system obtained with the composition 1A are reproduced in the same manner for Examples 1A to 7A. 180 ° peel test on a stainless steel plate: The adhesive power is evaluated by the 180 ° peel test on a stainless steel plate as described in the FINAT method n ° 1, published in the FINAT Technical Handbook 6th edition, 2001. FINAT is the international federation of self-adhesive label manufacturers and processors. The principle of this test is as follows. A test piece in the form of a rectangular strip (25 mm × 150 mm) is cut in the PET support layer coated with the crosslinked composition obtained previously. This specimen is fixed on 2/3 of its length (after removal of the corresponding protective release layer portion), on a substrate consisting of a defatted stainless steel plate, by applying two passages of a roll of 1 kilo The resulting assembly is left for 15 minutes at room temperature. It is then placed in a traction device capable, from the free end of the rectangular strip, of peeling or detaching the strip at an angle of 180 ° and with a separation speed of 300 mm. minute. The device measures the force required to take off the band under these conditions. The results are expressed in Newton per centimeter (N / cm) and are shown in the following Table 5. In addition, the fracture facies are measured visually, according to the state of the surfaces removed. "RA" is noted for adhesive failure, when it is observed that the entire adhesive seal has remained stuck to the PET support layer. "RC" is noted for cohesive failure, when it is observed that the adhesive joint has been broken and remained for a part adhered to the PET support layer and for the other part bonded to the substrate. The results are shown in Table 5. Instant adhesion test (also called loop test): The immediate tack or tack is evaluated by the instantaneous adhesion test called the loop, described in FINAT method no. 9, whose principle is as follows. A test piece in the form of a rectangular strip (25 mm × 150 mm) is cut in the PET support layer coated with the crosslinked composition obtained previously. After removing all of the protective release layer, the ends of this strip are joined to form a loop with the adhesive layer facing outward. The two joined ends are placed in the movable jaw of a traction device capable of imposing a movement speed of 300 mm / minute along a vertical axis with the possibility of going back and forth. The lower part of the loop placed in the vertical position is first brought into contact with a 25 mm by 30 mm horizontal glass plate over a square zone of about 25 mm side. As soon as this contact is made, the direction of movement of the jaw is reversed. The immediate tackiness is the maximum value of the force required for the loop to come off the plate completely. The results are expressed in Newton per square centimeter (N / cm 2) and are indicated in Table 5. Moreover, the fracture facies are measured visually, according to the state of the surfaces removed. "RA" is noted for adhesive failure: in particular, it is observed that the entire adhesive seal has remained stuck to the PET support layer. "RC" is noted for cohesive failure: it is observed that the adhesive joint was broken and remained for a part adhered to the PET support layer and for the other part bonded to the substrate. The results are shown in Table 5. Table 4 Tests of lA 2A 3A 4A 5A 6A 7A 8A 9A 10A crosslinked adhesive composition on support (comp) (comp) (comp) Peel 180 ° on steel 11.81 RC 3.26 RC 9,45 RA 18,50 RC 10,24 RC 10,24 RC 6,30 RC 0,55 stainless steel (N / cm) RC Instant adhesion of the loop on glass (N / cm2) 12 40 RC 4 82 RC 6 05 RA 2 12 11.94 RC 12.87 RC 7.44 RC 1.24 RC RC na na: not applicable Thus, all the adhesives obtained from Examples 1A to 7A according to the invention, lead to adhesive performance satisfactory in terms of adhesion strength and tack. In addition, the values obtained at the end of the peel test and at the conclusion of the instantaneous adhesion test of the loop are strictly greater than 2N / cm and 2N / cm 2 respectively, which are the minimum values desired for obtaining a self-adhesive power. For comparative example 8A, these cumulative conditions are not fulfilled, and in fact the adhesive obtained is not very efficient and is not suitable as a self-adhesive. For Examples 9A and 10A, the adhesion strength and instant adhesive strength could not be measured because the composition gelled.

权利要求:
Claims (8)
[0001]
REVENDICATIONS1. Crosslinkable adhesive composition comprising: a) from 40 to 60% by weight of at least one polyurethane obtainable by polyaddition reaction: of at least one aromatic or aliphatic diisocyanate chosen from the following diisocyanates, and their mixture: isophorone diisocyanate, 2,4-toluene diisocyanate, 2,4'-diisocyanate diphenylmethane, a derivative of hexamethylene diisocyanate allophanate of formula (I): R-OCN OR3- °° (CH2 wherein: p is an integer from 1 to 2; q is an integer ranging from 0 to 9; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms; - R3 represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms; with at least one polyether diol, in the presence or absence of at least one reaction catalyst, at a reaction temperature T1 below 95 ° C, under anhydrous conditions, and in amounts of diisocyanate (s) and polyether diol (s) resulting in an NCO / OH molar ratio, denoted r1, ranging from 1.6 to 1.9; b) from 39 to 59% by weight of at least one compatible tackifying resin, with a number-average molar mass ranging from from 200 Da to 5000 Da, and chosen from resins obtainable by one of the following processes: b1) polymerization of terpene hydrocarbons in the presence of Friedel-Crafts catalysts, followed by a reaction with phenols, b2) polymerization of alpha-methyl styrene followed by reaction with phenols; and c) from 0.01 to 1% by weight of at least one crosslinking catalyst, said percentages being expressed by weight relative to the total weight of the adhesive composition.
[0002]
2. Adhesive composition according to claim 1, characterized in that the (s) diisocyanate (s) aromatic (s) or aliphatic (s) is (are) chosen (s) from the following diisocyanates, and their mixture: al) l isophorone diisocyanate (IPDI), a2) 2,4-toluene diisocyanate (2,4-TDI), a4) an allophanate derivative of hexamethylene diisocyanate (HDI) of formula (I) as described above wherein: - p is an integer from 1 to 2; q is an integer ranging from 2 to 5; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 6 to 14 carbon atoms; - R3 represents a divalent propylene group; - p, q, R and R3 are chosen such that the HDI allophanate derivative of formula (I) comprises an NCO isocyanate group content ranging from 12 to 14% by weight relative to the weight of said derivative.
[0003]
3. Adhesive composition according to claim 1 or 2, characterized in that the HDI allophanate derivative of formula (I) defined in claim 1 or 2 is in the form of a composition in which it is included at the rate of at least 99.5% by weight, said composition comprising less than 0.5% by weight of HDI relative to the total weight of said composition.
[0004]
4. Adhesive composition according to any one of the preceding claims, characterized in that the (s) polyether diol (s) has (have) a number average molar mass ranging from 2000 to 12000 g / mol.
[0005]
5. Adhesive composition according to any one of the preceding claims, characterized in that the (s) polyether diol (s) is (are) chosen from polyoxyalkylene diols, the alkylene portion, linear or branched, comprises 2 to 4 carbon atoms.
[0006]
6. Adhesive composition according to any one of the preceding claims, characterized in that the (s) polyether diol (s) is (are) chosen from polyoxypropylene diols with a polymolecularity index ranging from 1 to 1.4 .
[0007]
7. Adhesive composition according to any one of the preceding claims characterized in that the (s) polyurethane (s) has (s) a number average molar mass ranging from 3000 to 21000 g / mol.
[0008]
8. Adhesive composition according to any one of the preceding claims, characterized in that the (s) polyurethane (s) meets (ent) the following formula (II): OCN R1NH CO 0 C NH R1 NH C 0 0 OC NH Where: R 1 represents a divalent group chosen from one of the following divalent aliphatic or aromatic groups: a ') the divalent group derived from isophorone diisocyanate: CH CH3 a2') the divalent group derived from 2,4-toluene diisocyanate: a3 ') the divalent group derived from diphenylmethane 2,4'-diisocyanate: a4') the divalent group derived from a hexamethylene diisocyanate allophanate (HDI) of the following formula ( Wherein: p is an integer from 1 to 2; q is an integer ranging from 0 to 9; R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms; - R3 represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms; - R2 identical or different from R3, represents a divalent alkylene group, linear or branched, having 2 to 4 carbon atoms; n is a non-zero integer such that the number-average molar mass of the polyether block of formula -PRI is from 2000 to 12000 g / mol; m is an integer such that the number-average molar mass of the polyurethane ranges from 3000 to 21000 g / mol. 10. Adhesive composition according to the preceding claim, characterized in that it comprises: a) from 40 to 60% by weight of a polyurethane of formula (I) as defined in the preceding claim, wherein: - Ri represents the divalent group derived from 2,4-TDI, - R2 represents the divalent propylene group, - n is a non-zero integer such that the number-average molar mass of the polyether block of formula - [OR 2] - ranges from 3500 to 8500 g / mol, m is an integer such that the number average molar mass of the polyurethane ranges from 4600 to 16800 g / mol; b) from 39 to 59% by weight of a compatible tackifying resin, with a number-average molar mass ranging from 200 Da to 5000 Da, and chosen from resins obtainable by method b2); and c) from 0.01 to 1% by weight of at least one crosslinking catalyst, based on the total weight of the adhesive composition. 11. Adhesive composition according to any one of the preceding claims, characterized in that it comprises less than 0.5% by weight of (each) aliphatic diisocyanate monomer (optionally present), and / or less than 0.1% by weight. weight of (each) aromatic diisocyanate monomer (optionally present), based on the total weight of the adhesive composition. 12. Adhesive composition according to any one of the preceding claims, characterized in that it has an NCO group content ranging from 0.15 to 1.7% by weight relative to the total weight of the adhesive composition. 13. Process for the preparation of a composition as defined in one of claims 1 to 10, characterized in that the polyurethane (s) is (are) prepared beforehand and then mixed with other compounds of the adhesive composition. 14. Self-adhesive support obtainable by a process comprising the following steps: (i ') preheating to a temperature T4 of the adhesive composition as defined in any one of claims 1 to 12, in order to render it liquid then (ii ') coating said adhesive composition on a support layer, and (iii') crosslinking said adhesive composition by heating the support thus coated at a temperature T5 ranging from 70 ° C to 150 ° C, in the presence of atmospheric humidity. 15. Use of the self-adhesive support as defined in the preceding claim for the manufacture of self-adhesive labels and / or tapes.

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同族专利:

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公开号 | 公开日

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US20150175850A1|2015-06-25|

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US10428245B2|2019-10-01|

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EP2886571B1|2019-01-30|

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FR3015510B1|2017-05-12|

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CN104726051A|2015-06-24|

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EP2886571A1|2015-06-24|

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CN104726051B|2019-09-03|

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ES2727513T3|2019-10-16|

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FR3018816B1|2014-03-19|2017-07-28|Bostik Sa|POLYURETHANE PREPOLYMER WITH LOW VISCOSITY CYCLOCARBONATE TERMINATIONS AND USE THEREOF IN THE MANUFACTURE OF A MULTICOMPONENT ADHESIVE COMPOSITION|JP6256648B1|2017-06-12|2018-01-10|東洋インキＳｃホールディングス株式会社|Adhesive and pressure-sensitive adhesive sheet, laminate and display device using the same|

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JP6969515B2|2017-07-24|2021-11-24|荒川化学工業株式会社|UV curable adhesive, cured product, adhesive sheet|

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FR3075213B1|2017-12-20|2020-08-28|Bostik Sa|PROCESS FOR PREPARING A COMPOSITION CONTAINING A POLYURETHANE WITH NCO TERMINATIONS|

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FR3097869B1|2019-06-27|2021-11-26|Bostik Sa|Polyurethane-acrylic pressure sensitive hot melt adhesive composition|

法律状态:
2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |

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2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |

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2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |

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2019-11-14| PLFP| Fee payment|Year of fee payment: 7 |

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2020-02-28| CA| Change of address|Effective date: 20200122 |

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2020-11-12| PLFP| Fee payment|Year of fee payment: 8 |

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2021-11-15| PLFP| Fee payment|Year of fee payment: 9 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1362993A|FR3015510B1|2013-12-19|2013-12-19|POLYURETHANE-BASED HUMIDITY AND HEAT-ADHESIVE COMPOSITION COMPRISING LOW ISOMYANATE MONOMER CONTENT|FR1362993A| FR3015510B1|2013-12-19|2013-12-19|POLYURETHANE-BASED HUMIDITY AND HEAT-ADHESIVE COMPOSITION COMPRISING LOW ISOMYANATE MONOMER CONTENT|

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EP14196750.5A| EP2886571B1|2013-12-19|2014-12-08|Moisture- and heat-crosslinkable polyurethane-based adhesive composition comprising a low content of isocyanate monomer|

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ES14196750T| ES2727513T3|2013-12-19|2014-12-08|Adhesive composition, crosslinkable by moisture and heat, based on polyurethane and comprising a low content of isocyanate monomer|

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US14/574,620| US10428245B2|2013-12-19|2014-12-18|Moisture- and heat-crosslinkable polyurethane-based adhesive composition comprising a low content of isocyanate monomer|

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CN201410858526.3A| CN104726051B|2013-12-19|2014-12-19|Comprising low isocyanate-monomer content can moisture-and heat-crosslinking urethane based adhesives composition|