CA2114842C - Method and material mixture for manufacture of reactive hotmelts - Google Patents

Abstract

The invention proposes the following method of producing reactive melts which are especially useful as hotmelt adhesives:

a) suitable meltable hydroxy functional or amino functional polymers or polymer mixes (A) which become liquid at temperatures above 40°C are inhomogenously mixed with b) powdered, solid, surface desactivated polyisocyanates (B) or a suspension of such polyisocyanates (B) in a low volatility carrier fluid, c) in approximately stoichiometric proportions at a temperature of at least 40°C in a static mixer so that the resultant mixture of substances exhibits partial areas in which the ratio (1) of polymer (A) to (2) solid isocyanate (B) and desactivating agent (C) is different from the average ratio of these substances or mixtures thereof within the entire mix, d) the inhomogenous mixture is extracted in a form suitable for the intended use and solidified by cooling to below the mixture's softening point.

These preformed or possibly nonformed solid reactive melts are able to be stored at room temperature and retain their latent thermoreactivity.

Description

2I~~~~~.
Dr. Thomas P. Abend, CH-9010 St. Gallen Method and material mixture for manufacture of reactive hotmelts The use of hotmelts for solvent free adhering, sealing and coating of solid or flexible materials is nowadays state of the art and is, for ecological reasons, preferred. In accordance with requirements, various thermoplastic polymers are nowadays used in the formulations, for example, amongst others, polyethylenes, copolymers of ethylene with vinyl acetate, copolymers of ethylene with acrylic esters or . methacrylic esters, polyacrylate or polymethacrylate, polymers or copolymers of the alpha olefins, copolymers of styrene with isoprene or butadiene, polyamides and copolyamides, polyester or copolyester, thermoplastic polyurethane and epoxy resins.
A problem which still remains unsolved is the thermoplasticity of the hotmelts or hotmelt adhesives near the softening point and at temperatures above the softening point, as well as the resistance of the adhesion to solvents.
Near the softening point, the resistance to thermal deformation of the bond reduces greatly, and when the melting point is exceeded, the hotmelt adhesives lose there strength, which can lead to failure of the adhesive bond.
Hotmelt powders or films for textile applications may be mentioned as an example: these should, at the lowest possible application temperatures, result in high bond strength (shortening of application time, elimination of damage to the textile fibre, elimination of bleeding or "off-setting"); the bond shall afterwards, however, withstand the high temperatures associated with subsequent handling and treatment processes (pressing, ironing, shaping, drying on shaped forms or mannekins). The adhesive bonds are here subjected to temperatures which are of the same intensity or many times greater than the softening point of the adhesive ' or the previously applied bonding temperature. The dimensional stability of bonded textile items is threatened by these treatments.
The same undesirable effects, namely, failure of the adhesive bond, will occur if the hotmelt adhesive is subjected to solvents as used in dry cleaning, or excessive washing temperatures.
There has been no lack of experiments concerning the reduction or elimination of thermoplasticity and solubility of the adhesive bonds of hotmelts and hotmelt adhesives.
Thus, moisture reactive isocyanate or silane groups have been introduced into the polymer. Crosslinked, thermoset polymers will ensue as a result of the influence of moisture or water after application of the molten adhesive. A disadvantage is that these systems must be stored under exclusion of moisture up to their point of application. In hot curing systems, crosslinked, thermoset polymers will also arise from functional polymers with heat reactive crosslinkers, with peroxides of hydroxy functional or amino functional polymers with blocked isocyanates, and solid epoxy resins with dicyandiamides etc.. A disadvantage with the outlined reactive hotmelt adhesives is that the crosslinking temperature exceeds 130 to 140°C. Reaction times in practice require still higher temperatures, which forbids the use of various, heat sensitive substrates.
The composition of nonreactive, of moisture reactive or heat reactive hotmelts, their advantages and their disadvantages, are known to the expert and are described in the technical literature and patent specifications, for example in:
"Schmelzklebstoffe", Vol. 4a (1985), 4b (1986), 4c (1987), "Schmeltzhaftklebstoffe, Vol. 6a (1990) of the "Klebstoff-Monographen" by R. Jordan, Publisher: Hinterwaldner Verlag (Munich) .
The purpose of the invention is to avoid the disadvantages as they are known, and in particular therefore to produce hotmelts which:
- are able to be preformed or applied to the surface of substrates, - subsequently solidify, through cooling, - afterwards, after any desired period, can be remelted on the substrate through the application of heat, if necessary j oined, - subsequently, through increasing the temperature further, can be irreversibly crosslinked.
Surprisingly, a method, which does not possess the disadvantages known up to now and considerably extends the area of application of the hotmelts or melting adhesives, of manufacturing reactive hotmelts applied in bulk or preformed as well as a solid mixture of substances at room temperature, has been found.
In accordance with an embodiment of the present invention there is provided a method of manufacturing a room-temperature shelf-stable mixture of reactive substances comprising: (A) at least one thermoplastic polymer having a melting point above 40°C, so that it is solid at room temperature, and which carries functional groups reactive with isocyanate, (B) at least one solid polyisocyanate in powder form, suspended in the solid thermoplastic polymer and having a melting point higher than that of the thermoplastic polymer, (C) at least one deactivating agent for reacting with surface isocyanate groups in the solid polyisocyanate, wherein the polyisocyanate is pre-mixed with the deactivating agent, and is thereby deactivated, the pre-mix of polyisocyanate and deactivating agent is then, at a temperature above the melting point of the polymer but below the melting point of the deactivated polyisocyanate, mixed with the polymer, which has been made liquid through warming, in layers, so that the resulting mixture includes first layers which predominantly comprise the polymer, and, between the first layers, second layers which predominantly comprise the deactivated polyisocyanate and also unbound deactivating agent, and the mixture is then cooled and solidified with the layer structure.
In accordance with another embodiment of the present invention there is provided a room-temperature shelf-stable mixture of reactive substances, comprising: (A) at least one thermoplastic polymer having a melting point above 40°C, so that it is solid at room temperature, and which carries functional groups reactive with isocyanate, (B) at least one solid polyisocyanate in powder form, suspended in the solid thermoplastic polymer and having a melting point higher than that of the thermoplastic polymers (C) at least one deactivating agent for reacting with surface isocyanate groups in the solid polyisocyanate, the mixture including first layers which predominantly comprise the polymer, and, between the first layers, second layers which predominantly comprise the polyisocyanate and the deactivating agent, wherein a first part of the deactivating agent is bound to the surface of the isocyanate particles and a second part of the deactivating - 4a -agent is unbound in the mixture.
These preformed or, if necessary, nonformed, solid reactive hotmelts are shelf stable at room temperature and retain latent thermoreactivity. After any period of time, they can be made liquid again through heating of the multilayer of substrate and preapplied hotmelt or hotmelt adhesive, joined, and then irreversibly crosslinked through raising of the ~,.-.

temperature above the "activation temperature". These hotmelts serve the purpose of bonding, sealing, laminating or coating of wood, plastics, metals, glass, textiles, synthetic non-wovens, cardboard, paper, films, foils and so forth.
Polymer reactive systems, carrying hydroxyl or amino groups, and desactivated, solid, isocyanates in powder form are known from patent specifications EP-062 780, EP-100 507, DE-32 30 757, DE-34 03 499, DE-34 03 500 as well as the technical literature, for example as contained in Blum, R.; Schupp, H., Prog. Org. Coat. 1990, 18(3), S. 275 - 288.
In the method described, a homogeneous mixture of a liquid polyol or polyamine and a solid isocyanate, with surface desactivated by amines, is produced which will not react at room temperatures. On attaining or exceeding the so-called "activation temperature", or reaction temperature, which lies above 55°C, preferably above 80°C, the reaction between solid isocyanates and functional groups of the polymer will commence, if necessary accelerated by catalysts. This reaction will lead to crosslinked, high molecular weight polyurethane or polyurea.
As an "activation temperature", that (minimum) temperature is denoted at which the viscosity of the hotmelt begins to increase through the reaction of the desactivated isocyanate with the hydroxyl, or the polymer which contains hydroxyl or amino groups, under formation of urethane or urea groups.
This temperature can, through commencement of exothermal reactions between the named components, for example be ascertained by using thermoanalytical methods, for example DSC (Differential Scanning Calorimetry).
It has been suggested in, amongst others, DE-32 30 757, that solid polyols with a softening point in the region of 45 to 2iI484~

65°C be mixed with the desactivated, solid isocyanates. After homogenising and degassing of the mixture, the melt is allowed to solidify, and then brought to a granulated condition through a suitable grinding process. At a suitable time, the reactive blend, stable when stored at room temperature, can be transferred to a mold heated to approximately 70 to 100°C. After melting, the viscous melt will solidify at 100 to 120°C, through the impact of heat.
Instructions concerning the continuous method, presented here in accordance with the invention, for creation of an inhomogenous, latent reactive hotmelt and its use for achieving a permanent and heat resistant bond with one or more substrate surfaces, do not arise out of this patent.
In the following, the components will be indicated as follows:
- Polymer A, for thermoplastic polymer with functional, isocyanate reactive groups, - Isocyanate B, for solid di- or polyisocyanate, - Desactivating agent C, to include bound desactivating agent C' and unbound desactivating agent C " , which together form the desactivating potential, - Crosslinking or chain extension components D, for solid or liquid isocyanate reactive compounds with molecular weight up to 500, - Additives E, for isocyanate nonreactive organic or inorganic compounds.

As polymers A, solid at room temperature, with melting or softening point at 4-0°C or higher, the following are suitable for execution of the method according to the invention:
Hydroxy functional or amino functional, aliphatic or aromatic polyester, polycaprolactone, polycarbonate, polyacetale, polyacrylate, polyamide, polyurethane, polyether, polythioether, Copolymers of styrene or alpha-methylstyrene with allylalcohol, low molecular weight copolymers of ethylene or alpha-olefins with hydroxyethyl- or hydroxypropyl-acrylates or -methacrylates, and other monomers inert to the hydroxy-functions such as ethyl-acrylate, butylacrylate, ethylmethacrylate, butylmethacrylate, graft polymers as a result of graft reactions of hydroxyethyl- or hydroxypropyl-acrylate, -methacrylate, allylalcohol, aminoalkyl- and mercaptoalkyl-alkoxysilane on polymers of ethylene, alpha-olefins or copolymers of ethylene, alpha-olefins, or copolymers of ethylene, alpha-olefins with vinyl acetate, ethyl-, butyl-acrylate or -methacrylate, hydrolytic products of copolymers of ethylene with vinylacetate, hydroxy containing derivatives of fatty acids, liquid above 40°C and solid below this temperature, hydroxy functional or amino functional prepolymers obtained through the reaction of low or high molecular weight polyols or diamines with di- or polyisocyanates.
Blends of the previously mentioned polymers can also be used.
The number of functional groups per molecule of the polymer shall lie, on average, between 1.5 and 6, preferably between 1.8 and 4, and the molecular weight in the area between 400 and 25'000.

''.-_ g _ The melting or softening point, respectively the solidification point of the polymers shall lie above 40°C, preferably above 55°C. The uppermost limit for the melting or softening point of the polymer is the "activation or reaction temperature" of the surface desactivated isocyanate.
The proportion of the polymer components A shall with advantage amount to at least 40~ weight of the total binder.
Low molecular weight aliphatic or aromatic, hydroxy functional or amino functional crosslinking or chain extension agents D, with a molecular weight of 62 to 500 and a functionality of between 2 and 4, can be used in the blend.
A condition is that they are either solid at temperatures above 40°C or do not lower the softening point of the polymer in the hotmelt below 40°C.
Low molecular weight polyols or polyamines which can be used in the hotmelt as a crosslinking and chain extension agent or for the production of the hydroxy functional or amino functional prepolymers are, for example: ethandiol, propandiol, propylenglycol, dipropylenglycol, butandiol, hexandiol, decandiol, neopentylglycol, l,4cyclohexandimethanol, hydroquinondi(2hydroxyethyl)ether, 2,2,4trimethy11,3pentandiol, bisphenol Aethoxylate, bisphenol Apropoxylate, trishydroxyethylisocyanurate, pentaerythrite, N,Nbis(2hydroxypropyl)aniline, triethanolamine, N,N'bis(hydroxyethyl)piperazine, 3,5diethy12,4 and 2,6diaminotoluol, 2,4' and 4,4' diphenylmethandiamine, 3,3'dimethy14,4'diaminodiphenylmethane, 4,4' diaminodiphenylether or sulphide, 4,4'diaminodicyclohexylmethane.
As organic isocyanates B, mainly the aliphatic, cycloaliphatic and aromatic, solid at room temperature, poly 21I4~~,2 _ g _ functional isocyanates are considered. In so far as the polyfunctional isocyanates are liquid at room temperature, they are converted by chemical reaction to polyisocyanates which are solid at room temperature. The following may be named as examples of reaction products: di or polyisocyanates containing the following groups: ester, urea, biuret, allophanat, carbodiimid, uretdion, urethan, or isocyanurate groups.
The solid isocyanates shall be insoluble in the functional polymer or in the high boiling solvent of the suspension at temperatures below the activation temperature.
The following have in particular proved themselves for the intended purpose:
dimerized 2,4 and 2,6 diisocyanatotoluene or 2,4' and 4,4' diisocyanatodiphenylmethane, possessing uretdione groups.
l,5naphthalindiisocyanate, bitoluylendiisocyanate or 3,3'dimenthy14,4' diphenyldiisocyanate.
modified di or polyisocyanates containing urethane, urea, uretdion,isocyanurate groups on the basis of l,6hexandiisocyanate, lisocyanato3,3,5trimethyl5isocyanatomethylcyclohexa ne, dimethylxylylen and tetramethylxylylendiisocyanate, 2,4', 4,4'diisocyanatodiphenylmethane, 2,4 and 2,6diisocyanatotolene.
4,4' diisocyanato3,3'demethyldiphenylurea.

Reaction products of diisocyanates with trimethylolpropane or other short chain polyols or polyamines.
Mixtures of solid, powder form isocyanate can also be used.
In order to prevent uncontrolled and spontaneous reaction between the powder form, solid isocyanate and the functional polymers, polyols, polyamines on uniting with the liquid polymer, or afterwards during storage and processing of the hotmelt adhesive, the powder form, solid isocyanates are surface desactivated.
The desactivating agent is so selected that it is bonded to the surface of the isocyanate particles through chemical reaction, and in this way gives rise to separation of phases by means of an inert layer between the polyisocyanate particles and the other reactive components, namely the hydroxy functional and amino functional polymers and low molecular weight functional crosslinkers or chain extension agents.
For the desactivating of the isocyanate groups of the solid isocyanate, 0,1 to 25, in particular 0,2 to 12 equivalent percent of the available isocyanate groups of the solid isocyanate are reacted with the desactivating agent C. In order to obtain stable hotmelts, an excess of desactivating agent is always to be used when working. This "unbound"
desactivating agent C " , together with the surface "bound" or "reacted" desactivating agent C', forms the "desactivation potential". The unbound desactivating agent C " can differ from the bound desactivating agent C' in that the surface desactivation takes place in two stages, commencing with desactivating agent C'. The ratio of unbound desactivating 2~ t~84;~

agent C " to bound desactivating agent C' can amount to 0.1 to 10.
The optmal concentration of desactivator must be experimentally ascertained, corresponding to the intended use of the reactive hotmelt and corresponding to the particle size of the solid isocyanate. The mean particle size will dictate the required concentration of desactivator, particles with smaller particle size and correspondingly more surface area requiring more desactivating amine.
The quoted literature (Blum, R.; Schupp, H., Prog. Org. Coat.
1990, 18(3), 275 288) and the above quoted patents provide instructions as to the determination of the optimal concentration of desactivators.
The solid polyisocyanates B are desactivated, preferably through reaction with primary and secondary aliphatic amines, di or polyamines, derivatives of hydrazine, amidine and guanidine. Further desactivating agents are listed in the above mentioned patent specifications.
The following have been found sound: ethylendiami.ne, l,3propylendiamine, diethylentriamine, triethylentetramine, 2,5dimethylpiperazine, 3,3'dimethy14.4'diaminodicyclohexylmethane, methylonandiamine, isophorondiamine, 4,4'diaminodicyclohexylmethane, diamino and triaminopolypropylenether (Jeffamine ~ Texaco Chem. Co.), polyamidoamine (EuretekR, Shering AG, Berlin), aminoalkylalkoxysilane and mixes of mono,di and polyamine.
The solid, surface desactivated isocyanates are sensitive to mechanical stress arising from high shear action. Through excessive shear, mainly in metering and supply pumps, in the _ 211842 ,...

piping, in the static mixers or under the action of doctor blades, the inert layer separating the reactive phases (comprised mainly of polyureas) can be destroyed, exposing the surface of the solid isocyanate. Premature reaction will be the result. Through the presence of the desactivating agent C " , the system is "selfhealing": as long as the desactivating agent C " is present in the system, the exposed isocyanate surface will react rapidly and preferentially with the desactivating amines, with spontaneous formation of a new inert polyurea layer.
As a desactivating agent C " , low molecular weight amine or polymine, with molecular weights up to 450, has been particularly proven in that these diffuse more rapidly than the higher molecular weight polyamine onto the damaged surface of the solid isocyanate.
The desactivating reaction can also take place in processing of a master batch, in an inert, light solvent. The solvent can be removed after completion of the desactivating reaction, if necessary after introduction of a second desactivating amine which acts as an unbound desactivating agent C " .
Within the entire mixture of substances, the relationship of the isocyanate groups of reactive, solid isocyanate B to the sum of amino and/or hydroxyl groups of the polymer A, of the desactivating agent C, and of the lower molecular weight chain extension agent or crosslinking agent D amounts to 0,5 to 2, preferably 0,8 to 1,5 (data in equivalents) Liquid phase for the preparation of the suspensions of solid isocyanate B can be high boiling solvents, liquid or low melting plasticizers or low melting point, low molecular weight, if necessary functional polymers or resins. The ~1~48~2 mentioned low molecular weight hydroxy functional chain extension agents and crosslinking agents D, which are compatible with the polymers A, are also particularly suitable. In the case of the desactivating reaction, the solid isocyanates react preferentially with the simultaneously present desactivating amines.
The use of low molecular weight and low viscosity solvents or plasticizers for manufacture of the suspension of solid desactivated isocyanate can be advantageous: During metering and pumping, within the piping and during mixing with the polyol components in the static mixer, the viscosity of the suspension and, with that, the associated shear stress to the inert surface of the desactivated isocyanate, is small.
The isocyanate functional groups of the components, which if necessary serve to form the preparation of the suspension or dispersion of the solid, desactivated isocynate, must likewise be considered when calculating the NC=/NH+OH ratios.
If necessary, the following, further additives E can be introduced:
the urethane catalysts known to the expert in the art, mainly based on organometals. Tertiary amines can become volatile during open storage of the reactive hotmelts or react with the carbon dioxide in the air and so loose some of their effectiveness.
Organometals for the intended purpose are organic tin (II), tin {IV), iron, lead, cobalt, bismuthantimon, zinc, and magnesiumcompounds.
Diazabicyclooctane (Dabco) can be used as amine catalysts, as well as diazabicycloundecene (DBU), mainly after partial or complete neutralisation with organic acids or phenols. The catalysts are ~~.~~8~~

employed as a rule in an amount between 0,001 and 3 percent weight, related to the total composition.
Polymers without isocyanate functional groups, small amounts of solvent, plasticizer, diluents and resins, pigments, dyestuffs, fillers, pyrogenic silicic acid, carbon black, short chopped fibers, metal in powder form, metallic oxides, ferrites, light and oxidation stabilisers, fungistatic or bacteriostatic agents, Theological agents, nonsag additives, surfactants, and adhesive additives. The use of such additives in hotmelts is state of the art.
In an initial embodiment of the method according to the invention, as represented in figure 1, the controlled, nonhomogenous mixture of both the components according to the invention, 1 the polymers A
and 2 the suspension of the desactivated, solid isocyanate B in a carrier liquid 2, which still contains excessive desactivating agent C'', can take place in a completely or partially heated two component mixing machine with static mixer 3 as commonly used for processing 2component coatings, sealants and adhesives.
These devices are state of the art, known to the expert in the art and commercially available.
Static mixers 3 for mixing of two or more components are nowadays, as an alternative to dynamic mixing heads, state of the art. For the intended purpose, mainly the static (tube) .a ,...

mixer from Sulzer AG (Winterthur, Switzerland), in which the mixing ensues radially and longitudinally within a system of interspaced and overlapping webs, and the KenicsR static mixer system (according to US Patent 3,286,992) or the comparable StatomixR static mixer system from MIXPAC Systems AG (Rotkreuz, Switzerland), with opposed, helical elements arranged in a tube which mix longitudinally, have proved their worth. An element comprises, for example, a lefthand spiralled helical baffle of a half turn. This is followed by an element with a righthand baffle of a half turn.
The static mixers also permit mixing of more than two partial flows, for example a third separate flow of a catalyst solution or a pigment dispersion.
According to this invention, the static mixers permit nonhomogenous mixing of the components and the formation of partial. areas or zones in which use is not made of the number of mixing elements which would otherwise be necessary for complete homogenous mixing: homogenous shall mean here that the concentration of a soluble, compatible, mixable component in a partial area of lmm2 does nor deviate by more than 2~
from the average value within the entire mixture.
An extrudate 4, which is not completely homogenous, results at the end of the static mixer. This extrudate comprises layers or partial areas which are alternately either rich in polymers A, or rich in solid isocyanate B and desactivating amines C.
Through the excess of unbound desactivating agent C " in the isocyanate rich layers, premanufactured hotmelts are attained with excellent shelf stability.

It is known to the expert in the art that, for mixing with a static helical element mixer, 20 to 32 elements, preferably at least 24 elements, must be used, and with the tube mixer from the firm Sulzer at least 12 elements, in order to achieve a homogenous mixture, a condition being that the viscosity of the components must not vary by more than a factor of 100 to 1.
Processing, according to the invention, is such that 10 to 22, and preferably 12 to 18 elements, of a baffle mixer are used in the tube of a static mixer. At a constant flow speed, this number of elements corresponds approximately to 50 to 90~ of the number of elements which would otherwise be necessary to create a homogenous, molecularly dispersed mixture, for example of the desactivating amines C " in the Polymer A. If other types of static mixers are used, likewise only 50 to 80~ of the number of elements are used which would otherwise be necessary to create a homogenous mixture.
The nonhomogenous mixture can be made visible at the end of the static mixer by adding a dye or pigment to one of the components. The resulting partial areas will be visible through the different optical density of the components, and can be measured.
The thickness of the layers, or expansion of the partial areas, which are either rich in polymer A or rich in solid isocyanate B and desactivating amine C, preferably approximately corresponds to the mean particle size of the solid, desactivated isocyanate particles and shall not fundamentally exceed the maximum particle size. The optimal number of mixing elements in the static mixer must be ascertained by means of experiments, and is determined by the viscosity, the rheological characteristics of the components or the blend and the intended application of the hotmelts.

If blending is carried out with a "paucity" of mixing elements, an added advantage will be a low pressure drop in the static mixer.
In the mixing device (figure 1), the static mixer 3, the piping 5, and metering devices 6 and pump 7 are heated, the temperature of the heated piping, metering devices, pumps and mixer being of necessity below the activaction temperature of the isocyanate.
The resulting stream of the product 4, namely the liquid hotmelt, exits through dies 8 at the end of the static mixer 3, the cross section of the die determining the cross section of the solid, uncrosslinked hotmelt. The liquid hotmelt can be deposited onto the substrate, for example as a coating, if necessary one or double sided on a carrier or reinforcing material, as a bead, as a profile; in stripform and as a powder point coating, through selection of the die and the method of application. After exiting the die, the adhesive is cooled, either through ambient air, through the cooling effect of the item to which the adhesive is applied, or through a supply of cooled air, gas or inert liquids.
Unsupported reactive hotmelts, for example in the form of a film, a bead, a net, a granulate or in various forms are obtained through application of the liquid, uncrosslinked adhesive onto a belt which supports a nonsticking surface or a surface provided with a releasing agent. After cooling of the adhesive, this can be separated from the carrier surface and immediately, or during application, be applied to the surface to be adhered, sealed or coated.
Reactive hotmelts in powder form are obtained through extruding the liquid mixture onto a conveyor belt with a nonstick surface and cooling it there to a temperature below its melting point. After solidification, the hotmelt adhesive can be released from the belt and in a known way, for example by means of cryogenic grinding, reduced to a granulate or a powder and if necessary passed through a sieve to produce the required fractions. The powders according to the invention serve as reactive hotmelts in powder form for textile fabrics, in accordance with known methods of application, for example scatter coating, powder point coating or paste point coating. They can, however, be used as reactive hotmelt powder for the adhesion of plastic film, veneer, paper, metal foil, sheet metal and similar, either with themselves or with carrier materials, and for coating purposes, such as powder coating, for example.
In another embodiment of the method according to the invention, as represented in figures 2 and 3, a moveable belt is used, primarily a metal belt with a nonsticking surface, which can be heated, and which moves at a constant speed beneath the "application heads" for the individual layers. The mixture according to the invention is created in such a way that a) the molten polymer A 1 is applied with a doctor blade 11 in a layer thickness of 3~ to 200 onto a moveable conveyor belt coated with adhesive, b) the solid, surface desactivated isocyanate B, in powder form 12, is scattered by means of a scattering device 13, or as a suspension 2 of the desactivated powder in a carrier liquid with excess desactivating amine, indeed with said sprinkling device 13 or doctor blades 11, which can control and meter the weight or proportion of the applied isocyanate in relation to the weight of the polymer, c) the steps a) and b) are repeated for sufficiently long until the desired thicknesses of the multilayer coating 14, comprising polymer rich and isocyanate rich layers, is attained.
Alternatively, the liquid flows of (a) Polymer A, and the (b) suspension of solid, desactivated isocyanate B in a carrier liquid are simultaneously extruded in a defined ratio through the separate openings of a multiple die.
The still liquid or pasty multilayer can be shaped, pressed, compressed or stretched prior to solidification.
d) The multilayer 14, whose thickness amounts to between 10~ and several millimeters, can be released from the carrier either in liquid form or after cooling, and subsequently reduced by a known method to a granulate or to a powder with a grain size of up to 500 and if necessary passed through a sieve to produce the desired fractions. The multilayer can also be further processed in film, bead or strip form for adhesive purposes or as a coating material, if necessary being reinforced by a carrier material applied to the one side, or in the form of a reinforcement material held within the multilayer.
Slotted dies 15 or doctor blades 11, which can be heated, can serve as the "application head" or application device for layering of the polymer A and the suspension of the isocyanate B. The doctor blades 11 are able to be adjusted in such a way that a defined gap can be maintained in relation 21148 ~

to the surface of the preceding layer. The liquid polymer A
or the suspension B is metered by the pumps 7, fed to the slotted die 15 and extruded onto the strip. When using the doctor blades, the polymer A and the suspension of desactivated isocyanate B is fed via heated pumps and piping in such a way that a rotating bead 16 arises im front of the doctor blade. The surface of the polymer of the previously applied layer must still be liquid or tacky when applying the subsequent layer (suspension of the solid isocyanate) or scattering of the solid isocyanate.
The adhesion of the various layers in this multilayer shall be the same or greater that the cohesion within the layers.
As mentioned, hotmelts according to the invention can be applied to a carrier or reinforcing material, if necessary applied,single or double sided, as a sealant bead, a profile, in.strips, as powder points, as a carrier free film, as a net, as sealant beads or as a powder onto the adhesing, sealing or coating substrates. On reaching the melting or softening temperature of the polymer, they become liquid. In this condition, they can wet the surface of the substrates or the adhering surfaces. On reaching the activation temperature of the solid desactivated isocyanate, which should be higher than the melting or softening temperature of the polymers, they will irreversibly crosslink to high molecular weight, thermoset polyurethanes or polyureas.
The heat transfer into the system of hotmelts and/or substrates) can ensue by conventional means such as heated air, heated gases, through heat or infrared radiation, contact heat or the exploitation of the residual heat of the substrates, or inductively with microwaves, electrical heating, friction or ultrasonics.

For crosslinking by means of heat produced by induction, microwaves or electrical heating, it has been proven advantageous if a metallic filler, carbon black, graphite, metal oxides or ferrites are added to the hotmelt.
Examples Materials used:
Polymers Softening Hydroxyl Equival Spec.
Point°C value ent g weight Polycaprolactone 55 37 1500 1,07 Capa 231 (a) Polycaprolactone 58 28 2000 1,07 Capa 240 (a) Dynacoll 7350 (b) 65 30 1866 1,19 Isocyanate ~ NCO Equival Melting Function ent g point°C ality Isonate M 143 (c) 29.4 143 < 15 2.1 2.2 Desmodur TT (d) 24.1 174 > 150 2.0 2.1 Amine Laromin C 260 (e) 119.2 < 0 2.0 Catalyst UL29 (f) Tin (IV)organic compound Plasticizer BBP Butylbenzylphthalate (g), liquid (a) Linear Polycaprolactone, Interox chemicals Ltd.
(b) Linear Polyester, Hiils AG
(c) Diphenylmethandiisocyanate, The Dow Chemical Co.

~~.~84 (d) Toluoldiisocyanateuretdion, "Dimeres TDI", Bayer AG, mean particle size 12~
(e) 3,3' Dimethyl4.4'diamodocyclohexymethane, BASF AG, (f) Witco Chem., Corp.
(g) Bayer AG
Example 1:
Component 1:
The hydroxy functional Polymer A was manufactured as follows:
(1) Dynapol 7350 3732 g (2 Equiv.) (2) Isonate 143 143 g (1 Equiv.) (3) UL29solution, 10~ in BBP 4 g was, during 12 hours at 80°C, converted to (4) 3879 g Polymer A (1 Equiv.) Component 2 Suspension of the solid, desactivated isocyanate (5) Laromin C 260 6.6 g (0.055 Equiv.) (6) Benzylbutylphthalate 374.4 g (7) Desmodur TT 200.0 g (1.15 Equiv.) (8) Total suspension B 581.0 g (1.095 Equiv.) Both the components were metered in a two component mixing unit at a mixing ratio of 1.00 parts/component A to 15 parts/component B by means of heated gear pumps at a temperature of 70°C and fed in separate, heated piping to a thermally insulated static spiral element mixer (diameter 10 mm) from Mixpac AG, Rotkreuz, (Switzerland), which was equipped with 16 elements, namely with opposed spiral elements arranged within one tube. (Inside tube diamater lOmm, length of one element lOmm) .
The continuously mixed hotmelt was applied as a bead to the surface of a right angled profile of glass reinforced plastic (UP). The hotmelt solidified as a result of cooling through the profile and the ambient air. The latent reactive hotmelt was capable of being stored for a period in excess of 4 weeks at room temperature, which means that after 4 weeks storage at 70°C, the hotmelt was still meltable and exhibited a tacky surface .
The latent reactive hotmelt, after 7 days storage, was made liquid through heating at a temperature of 80°C in an oven, and pressed against another UP profile. The temperature of the "sandwich" was increased to 115°C. Within 5 minutes the adhesive joint became firm, and was allowed to remain at this temperature for a further 30 minutes.
The adhesive joint was able to be separated at room temperature only through destruction of the joined "sandwich". The joint withstood temperatures of 140°C, undamaged.
Example 2:
Component 1 The hydroxy functional polymer was manufactured as follows:
(1) Capa 240 4500 g (2.25 Equiv.) (2) Isonate 143 179 g (1.25 Equiv.) (3) UL29solution, 10~ in BBP 5 g was, during 2 hours at 80°C, converted to (4) 4684 g Polymer A (1 Equiv.) melting temperature 58°C.

Component 2 Suspension of a solid, desactivated isocyanate:
(5) Benzylbutylphthalate 341.4 g (6) Laromin C 260 8.6 g (0.072 Equiv.) were mixed and (7) Desmodur TT 200.0 g (1.15 Equiv.) was introduced and homogenously distributed.
(8) suspension of the solid isocyanate B 550.0 g (1.078 Equiv.) Both the components were metered in a two component mixing unit at a mixing ratio of 100 parts/component A to 12 parts/component B by means of heated gear pumps at a temperature of 65°C and fed in separate, heated piping to a thermally insulated static spiral element mixer from Mixpac AG, Rotkreuz, (Switzerland), which was equipped with 16 elements opposed arranged within one tube. (Inside tube diamater 13 mm, length of one element 13mm).
The continuously mixed hotmelt was extruded through a slotted die onto a steel conveyor belt at a layer thickness of 3 mm, separated from the band after passing through a cooling section and reduced to centimenter sized pieces. After complete cooling, the pieces were ground in a powder grinder, cooled by dry ice. Grain sizes above 500 were recycled through the grinder. The powder possessed a melting point of 56°C, the activation temperature was determined as being 98°C.
Example 3:
A hydroxy functional prepolymer was manufactured as follows:
(1) Capa 240 4500 g (2.25 Equiv.) w..

(2) Isonate 143 179 g (1.25 Equiv.) (3) UL29solution, 10~ in BBP 5 g was, during 2 hours at 80°C, converted to (4) 4684 g Polymer A (1 Equiv.) Suspension of a solid, desactivated isocyanate:
(5) Capa 231 500 g (0.33 Equiv.) and (6) Laromin C 260 8 g (0.067 Equiv.) were mixed at 65°C and (7) Desmodur TT 260 g (1.49 Equiv.) was introduced and homogenously distributed.
(8) suspension of the solid isocyanate B 768 g (1.097 Equiv.), melting temperature above 50°C.
The hydroxy functional prepolymer was applied to a nonstick steel belt at 70°C, in 8 layers of 100 or 106 g/m2, total 800 or 848 g/m2, using heated doctor blades at a temperature of 70°C. The liquid surfaces of the individual polymer layers were in each case immediately layered over with 7 layers of 18,7 or 19,86 g/m2 of suspension 8, total quantity 139 g/m2.
The layers of the suspension were applied from 7 application heads, likewise comprising doctor blades heated.to 70°C. The uppermost layer was not coated with the suspension.
At the end of the belt the "multilayer" was separated from the belt after passing through a cooling section and reduced to centimeter sized pieces. After complete cooling the pieces were ground in a powder grinder, cooled by dry ice. Grain sizes above 500 were recycled through the grinder.
For experiments with powder coating on fabrics, a grain size range of 80 to 300 was used with the powder examples 2 and 3. The powders were scattered with a coating weight of 2I~~8~~

approximately 30 g/m2 onto a cotton fabric. The powders were sintered onto the surface of the fabric in a hot air oven at 140°C for a duration of 90 seconds. These coated fabrics can be stored at room temperature for at least 4 weeks.
The fabrics coated with powder were laminated with untreated fabric at a temperature of 170°C for 20 seconds in a press with a pressure of 2 bar, and then further treated at 160°C
for 3 minutes in an air circulation oven.
After 7 days, the samples were washed in boiling water for one hour, dried, and the resistance to peeling was determined:
Sample size Peel strength in g per 2.5 cm according to DIN 54310 before/after after boiling dry cleaning Powder according to Example 2 1170 910 1157 Powder according to example 3 950 810 835 The experiments demonstrated that a thermostable crosslink - took place: the reactive powder, with a melting point of 56°C, was transformed into a thermoset, chemically stable polyurethane after the activation temperature was exceeded.
Inasmuch as the invention is subject to modifications and variations, the foregoing description and accompanying drawings should not be regarded as limiting the invention, which is defined by the following claims and various combinations thereof:

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of manufacturing a room-temperature shelf-stable mixture of reactive substances comprising:
(A) at least one thermoplastic polymer having a melting point above 40°C, so that it is solid at room temperature, and which carries functional groups reactive with isocyanate, (B) at least one solid polyisocyanate in powder form suspended in the solid thermoplastic polymer and having a melting point higher than that of the thermoplastic polymer, (C) at least one deactivating agent for reacting with surface isocyanate groups in the solid polyisocyanate, wherein the polyisocyanate is pre-mixed with said deactivating agent, and is thereby deactivated by a then bound deactivating agent, the pre-mix of polyisocyanate and deactivating agent is then, at a temperature above the melting point of the polymer but below the melting point of the deactivated polyisocyanate, mixed with the polymer, which has been made liquid through warming, in layers, so that the resulting mixture includes first layers which predominantly comprise said polymer, and, between said first layers, second layers which predominantly comprise said deactivated polyisocyanate and also unbound deactivating agent, and the mixture is then cooled and solidified with the said layer structure.

2. The method according to claim 1, which the polyisocyanate is pre-mixed with a deactivating agent, which is different from the unbound deactivating agent.

3. The method according to claim 2, wherein the bound deactivating agent is a high molecular weight amine with a molecular weight above 450, and the unbound deactivating agent is an amine with a molecular weight below 450.

4. The method according to any one of claims 1 to 3, wherein a primary or secondary amine is used as the deactivating agent.

5. The method according to claim 1, wherein the deactivating agent reacts with the surface of the polyisocyanate particles, and unbound deactivating agent is added to the deactivated polyisocyanate.

6. The method according to any one of claims 1 to 5, in which said pre-mix and said liquefied polymer are applied onto a carrier material in layers and are solidified by cooling on said material.

7. A room-temperature shelf-stable mixture of reactive substances, comprising:
(A) at least one thermoplastic polymer having a melting point above 40°C, so that it is solid at room temperature, and which carries functional groups reactive with isocyanate, (B) at least one solid polyisocyanate in powder form, suspended in the solid thermoplastic polymer and having a melting point higher than that of the thermoplastic polymer, (C) at least one deactivating agent for reacting with surface isocyanate groups in the solid polyisocyanate, said mixture including first layers which predominantly comprise said polymer, and, between said first layers, second layers which predominantly comprise said polyisocyanate and said deactivating agent, wherein a first amount of the deactivating agent is bound to the surface of the isocyanate particles and a second amount of the deactivating agent is unbound in the mixture.

8. The mixture according to claim 7 comprising 0.1% to 25%
isocyanate groups, bound to the deactivating agent, wherein the unbound deactivating agent and the bound deactivating agent are present in a ratio between 0.1 to 10.

9. The mixture according to claim 7 or 8, wherein the bound deactivating agent is different from the unbound deactivating agent.

10. Mixture according to claim 9, wherein the bound deactivating agent is a high molecular weight amine with a molecular weight above 450, and the unbound deactivating agent is an amine with a molecular weight below 450.

11. The mixture according to any one of claims 7 to 10, wherein the thickness of said layers corresponds substantially to the particle size of the polyisocyanate powder.

12. The mixture of substances according to claim 11, wherein the thickness of said layers does not exceed the maximum particle size of the polyisocyanate powder.

13. The mixture according to any one of claims 7 to 9, wherein the deactivating agent is a primary or secondary amine.

14. The mixture according to any one of claims 7 to 13, wherein the ratio of thermoplastic polymer to isocyanate and deactivating agent in said first layers is at least 10% greater than their average ratio throughout the mixture.

15. A bonding material comprising a mixture according to any one of claims 7 to 14, said mixture of substances being heat cured at a temperature above the melting point of the thermoplastic polymer and above the melting point of the solid polyisocyanate.