US 20090266482A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2009/0266482 A1
Garmann et al. (43) Pub. Date: Oct. 29, 2009
(54) HIGH-STRENGTH POLYURETHANE (30) Foreign Application Priority Data
ADHESIVE
Nov. 15, 2006 (DE) ...................... 10 2006 O54 1977
(76) Inventors: Helga Garmann, Westhausen (DE); Nov. 15, 2006 (DE) ...................... 10 2006 O54 1979
Claus-Heinrich Puck, Ellwangen
(DE); Gerhard Mosshammer, Publication Classification
Bopfingen (DE)
(51) Int. Cl.
Correspondence Address: B32B 37/2 (2006.01)
Henkel Corporation COSL 73/04 (2006.01)
10 Finderne Avenue
Bridgewater, NJ 08807 (US) (52) U.S. Cl. ...................................... 156/275.5; 525/453
(21) Appl. No.: 12/463,680 (57) ABSTRACT
(22) Filed: May 11, 2009 The invention relates to a method for adhesively bonding
Related U.S. Application Data Substrates together that contains irregularities on the Surface
of the substrates. The adhesive is particularly suitable for
(63) Continuation of application No. PCT/EP2007/ adhesively bonding thin flexible substrates onto a rigid sub
059626, filed on Sep. 13, 2007. Strates.
US 2009/0266482 A1 Oct. 29, 2009

HIGH-STRENGTH POLYURETHANE a good adhesion. If the Substrates have distinctly uneven

ADHESIVE surfaces, then the adhesive just cannot fill these spaces. With
rigid Substrates, there remain cavities that weaken the
CROSS REFERENCE TO RELATED strength of the adhesive bond. If a substrate is thin and flex
APPLICATIONS ible, then the uneven surface of such substrates is often
0001. This application is a continuation of PCT/EP2007/ pressed through Such that the unevenness of the Substrate is
059626 filed Sep. 13, 2007, which claims the benefit of DE 10 visible for example on a bonded film. In contrast, if greater
2006 0541979, filed Nov. 15, 2006, the complete disclosures amounts of the adhesive are applied then the problem arises
of which are hereby incorporated by reference in their that the excess adhesive has to be leveled and possibly leaks
out of the sides of the adhesive bond. This causes contami
entirety. nation of the bonded object or of the equipment used. Apart
FIELD OF INVENTION from that, the cohesion of thick adhesive layers particularly
for foamed glued joints—is often poor.
0002 The invention relates to a method for adhesively
bonding wood materials, wherein a 1K polyurethane adhe SUMMARY OF THE INVENTION
sive is applied onto a substrate half and is then adhesively
bonded by pressing against the second Substrate, wherein an 0007 Accordingly, the object of the invention was to pro
activation occurs by increased temperature during the bond vide a method permitting a simple application of a one com
ing. A high initial adhesion is achieved and the adhesive ponent polyurethane adhesive having a long processing time
increases in Volume such that irregularities on the Substrate and that can make up for possible unevenness of the Substrate
sides facing one another are leveled out and a smooth Surface Surface on bonding.
is obtained. 0008 According to the invention, the object is achieved by
BACKGROUND
referring to the claims. It concerns the provision of a method,
in which a moisture curing 1 K polyurethane adhesive is
0003. Two component polyurethane adhesives are applied at a low temperature and which has only a low reac
described in EP 1 366 132 which describe/comprise 10 to tivity during and after its application. The coated Substrate
98% of an oleochemical polyol. 1 to 7.5% of a diol having an can optionally be stored; after the bonding and pressing with
OH number from 400 to 2000, 1 to 7.5% of a polyol having an a second Substrate and a crosslinking at increased tempera
OH number from 200 to 2000 and at least one polyisocyanate. ture, there then results a high-strength adhesive bond. The
Two component polyurethane adhesives for adhesively bond adhesive foams slightly during the crosslinking reaction,
ing wood materials are described in DE 4401 572 A1; said thereby enabling the height differences between the substrate
adhesives are based on an isocyanate component and a polyol Surfaces to be equalized and a Smooth Surface to be obtained.
component that in addition to an oleochemical polyol com 0009. Another subject matter of the invention is moisture
prises 2 to 7 weight percent, based on the oleochemical reactive 1 K polyurethane adhesives that do not foam after
polyol, of at least one di- and/or trihydric alcohol. 2K PU application, after thermal activation adhesively bond with
adhesives of this type require an exact dosing of the ingredi foaming. Here the 1K polyurethane adhesive based on a pre
ents and have only a limited processing time. polymer comprising isocyanate groups consists of the reac
0004 One component polyurethane adhesives for wood tion product of
components are also known. Thus, in DE 44 12759 A1, an 0.010 20 to 50 parts by weight of at least one oleochemi
adhesive is described that is characterized by a content of 50 cal polyol.
to 95 wt.% of an isocyanate-containing polyurethane pre 001 1 0 to 15 parts by weight of a polyol based on
polymer, 2 to 8 wt.% of a hydrophobic silicon dioxide and 2 polyethers or polyesters,
to 6 wt.% of a powdered molecular sieve as well as by 0012 80 to 40 parts by weight of a polyisocyanate,
optional additional conventional additives and/or accelera
tors. The minimum molding time in order to achieve the 0013 optional additives
initial adhesion is 9 hours. This is very long. In general, the wherein the sum of the fractions should make up 100%.
short molding times of two component adhesives based on 0014) Another subject matter concerns storage stable
PU are not achieved with one component polyurethane adhe adhesive layers on substrates made of wood materials involv
sives. 1 Kreactive PU hot melt adhesives are described in DE ing the use of the abovementioned adhesives. Oleochemical
4429679 which comprise interalia prepolymers of isocyan polyols are understood to mean polyols based on natural oils
ates and polyols, wherein castor oil derivatives can also be and fats, e.g. the reaction products of epoxidized fats with
comprised. The hot melt adhesives set immediately after mono, di or polyhydric alcohols or glycerine esters of long
application at increased temperature. chain fatty acids that are at least partially substituted with
0005. The 1K or 2K polyurethane adhesives from the prior hydroxyl groups. A subgroup of these compounds is the ring
art have various disadvantages. 2K PU adhesives have to be opening products of epoxidized triglycerides, i.e. epoxidized
carefully mixed and thereupon have only a limited processing fatty acid glycerine esters, in which the ring opening has been
time. 1 KPU adhesives often react very slowly and require a carried out with the conservation of the ester bonds. A great
lengthy molding time. Moreover, these adhesives are mois number of epoxidized triglycerides of vegetal or animal ori
ture-sensitive, evento air humidity, and consequently are only gin can be used as starting materials for manufacturing the
storage stable for a short time after application. On extended ring opening products. Thus, for example, epoxidized trig
storage before adhesion they lose their adhesive properties lycerides that contain 2 to 10 weight percent epoxide oxygen
and their reactivity. are suitable. These types of products can be manufactured by
0006. A further disadvantage of the known adhesives is the epoxidation of the double bonds of a series of fats and oils,
that they are generally applied in a thin layer in order to ensure e.g. beef tallow, palm oil, peanut oil, rapeseed oil, cotton seed
US 2009/0266482 A1 Oct. 29, 2009

oil, soya oil, sunflower oil and linseed oil. Particularly pre the triglyceride derivatives to alkyl ester polyols having 1 to
ferred epoxidized triglycerides are epoxidized soya oil and 12 carbon atoms in the alkyl group is particularly preferred.
epoxidized linseed oil. 0022. The di-, tri- or polyhydric alcohols that are conven
tionally employed in the polyurethane chemistry and which
DETAILED DESCRIPTION OF THE INVENTION are known to the person skilled in the art can be employed as
the additional polyol components in an inventively suitable
00.15 Methanol, ethanol, propanol, isopropanol, butanol, polyurethane prepolymer. These concern for example poly
hexanol, 2-ethylhexanol, fatty alcohols containing 6 to 22 alkylene glycols, polyester polyols based on aliphatic or aro
carbon atoms, cyclohexanol, benzyl alcohol. 1.2-ethanol, matic carboxylic acids, OH-functional polycaprolactone
1.2-propane diol. 1,3-propane diol. 1,4-butane diol, 1.6-hex diols, polycarbonate diols obtainable for example by the reac
ane diol, neopentyl glycol, trimethylolpropane, glycerine, tion of low molecular weight diols with diaryl carbonates, or
trimethylolethane, pentaerythritol, sorbitol as well as ether OH group-containing polybutadienes. Such polyols can be
group-containing hydroxy compounds Such as alkyl glycols used singly or in a mixture.
or oligomeric glycols as well as oligomeric glycerines can be 0023 Exemplary suitable polyol components are poly
employed as the alcohols for the ring opening of the epoxi ether polyols known to be based on the reaction products of
dized triglycerides. low molecular polyhydric alcohols with alkylene oxides.
0016. The ring opening reaction of epoxidized fatty acid Polyether polyols are understood to mean polyols having 2 to
ester or triglyceride with an alcohol can optionally be fol 4 OH groups per molecule; they should have an M. (number
lowed by a transesterification with itself or with other, sub average molecular weightas determined by GPC) from 300 to
sequently added triglycerides, such as for example palm oil, 15,000 g/mol. Thus in particular, the reaction products of low
peanut oil, rapeseed oil, cotton seed oil, Soya oil, Sunflower oil molecular weight polyhydric alcohols with alkylene oxides
and linseed oil. Such oleochemical polyols are described for having up to 4 carbon atoms can be employed. Exemplary
example in the German patent application DE-A 41 28 649. Suitable reaction products are those from ethylene glycol,
0017. Another group of oleochemical polyols are ring propylene glycol, the isomeric butane diols or hexane diols
opening and transesterification products of epoxidized fatty with ethylene oxide, propylene oxide and/or butylene oxide
acid esters of lower alcohols, i.e. of methyl, ethyl, propyl or or mixtures thereof. Furthermore, the reaction products of
butyl esters of epoxidized fatty acids. The ring opening or trihydric alcohols such as glycerine, trimethylolethane and/or
transesterification products with alcohols with a functionality trimethylolpropane or higher hydric alcohols such as for
of 2 to 4 are preferred, especially the transesterification prod example pentaerythritol or Sugar alcohols with the cited alky
ucts with ethylene glycol, propylene glycol, oligomeric eth lene oxides can be employed.
ylene glycols, oligomeric propylene glycols, glycerine, trim 0024 Polyester polyols that can be manufactured by poly
ethylolpropane or pentaerythritol. Such products can be condensation are also suitable. These types of polyester poly
manufactured by known epoxidation processes or ring open ols preferably include the reaction products of polyhydric,
ing processes, wherein the transesterification can be carried preferably dihydric alcohols, optionally together with minor
out during or after the ring opening step by removing the amounts of trihydric alcohols, and polycarboxylic, preferably
lower alcohol from the reaction equilibrium. Ring opening dicarboxylic and/or tricarboxylic acids. Instead of free poly
and transesterification products are preferred, in which a carboxylic acids, the corresponding polycarboxylic acid
molar ratio between epoxidized fatty acid ester and the alco anhydrides or corresponding polycarboxylic acid esters with
hol used for transesterification was from 1:1 to 1:10.
0018 Similarly to the oleochemical polyols, the transes alcohols having preferably 1 to 3 carbon atoms can also be
employed. Hexane diol. 1,4-hydroxymethylcyclohexane,
terification products of epoxidized fatty alcohols with C-Cs 2-methyl-1,3-propane diol, butane-1,2,4-triol, triethylene
alcohols of a functionality 1 to 10, especially 2 to 4, comprise glycol, tetraethylene glycol, ethylene glycol, polyethylene
a molar ratio of epoxy groups to the hydroxyl groups of 1:1 to glycol, dipropylene glycol, polypropylene glycol, dibutylene
1:10. glycol and polybutylene glycol are particularly suitable for
0019. In the context of the invention, the use of oleochemi manufacturing these types of polyester polyols. The polycar
cal polyols that can be obtained from the transesterification of boxylic acids can be aliphatic, cycloaliphatic, or aromatic or
di- or polyhydric alcohols such as e.g. from the addition both. The can be optionally substituted, for example by alkyl
product of ethylene oxide or propylene oxide on glycerine groups, alkenyl groups, ether groups or halides. Succinic
with triglycerides such as palm oil, peanut oil, rapeseed oil, acid, adipic acid, Suberic acid, azelaic acid, sebacic acid,
cotton seed oil, soya oil, Sunflower oil and linseed oil, is also phthalic acid, isophthalic acid, terephthalic acid, trimellitic
possible Likewise polyols can be used that can be obtained acid, phthalic anhydride, tetrahydrophthalic anhydride,
according to the teaching of DE-A 4124 665 by the transes hexahydrophthalic anhydride, tetrachlorophthalic anhydride,
terification of polymerized glycerine with the abovemen endomethylene tetrahydrophthalic anhydride, glutaric anhy
tioned triglycerides. Resin-modified oleochemical polyols dride, maleic acid, maleic anhydride, fumaric acid, dimer
can also be employed. fatty acids or trimer fatty acids or mixtures of two or more
0020. The inventively suitable oleochemical polyols can thereof are suitable exemplary polycarboxylic acids. Minor
have hydroxyl numbers from 50 to 400, preferably 100 to 250 amounts of monocarboxylic fatty acids can optionally be
(mg KOH/g solid). present in the reaction mixture. In the context of the invention,
0021. The use of castor oil or dimerdiols as the oleochemi polyester diols from at least one of the cited dicarboxylic
cal polyols as well as those polyester polyols that are manu acids and diols that possess terminal OH groups are particu
factured by the total ring opening of epoxidized triglycerides larly suitable. Polyesters of this type can be optionally reacted
of a fat mixture comprising at least partially olefinically at their terminal groups with alkylene oxide units. The
unsaturated fatty acids with one or more alcohols having 1 to molecular weight should be between 300 and 5000 g/mol,
12 carbon atoms and Subsequent partial transesterification of especially less than 2500 g/mol.
US 2009/0266482 A1 Oct. 29, 2009

0025 However, polyether polyols with a molecular ethylene glycol, diethylene glycol, glycerine, dimethylolpro
weight of 300-10,000 g/mol, preferably 500-5,000 g/mol are pane, propylene glycol, dipropylene glycolor triethylene gly
particularly Suitable. In this way, depending on the desired col.
molecular weight, addition products of only a few moles of 0030 Aromatic isocyanates with a functionality of ca. 2 to
ethylene oxide and/or propylene oxide per mole or even of 6, e.g. diphenylmethane diisocyanate, either in the form of the
more than a hundred moles of ethylene oxide and/or propy pure isomers, as the isomeric mixture of the 2,4'-/4,4'-isomers
lene oxide on low molecular weight polyhydric alcohols can or even the diphenylmethane diisocyanate (MDI) liquefied
be employed. Diols or triols are particularly preferred. with carbodiimide, as well as the so-called "raw-MDI’, i.e.
Polypropylene glycols or polyethylene glycols are particu the mixture of isomers/oligomers of MDI, are preferably used
larly Suitable. Among the cited polyether polyols, the reaction as the di- or polyisocyanates. Likewise, oligomerized adducts
products of polyhydric low molecular weight alcohols with having terminal NCO groups made from the above cited
propylene oxide are particularly suitable under conditions, in isocyanates can be employed with correspondingly polyfunc
which, at least partially, secondary hydroxyl groups are tional low molecular weight polyols, polyamines or aminoal
formed. cohols. Monomer-free MDI preparations can also be
employed.
0026. The amount of the oleochemical polyols should be 0031. The amount of the isocyanate component is more
between 20 and 50 parts by weight. The amount of the poly than 40 parts by weight up to 80 parts by weight of aromatic
ether polyols or polyester polyols can be between 0 and 15 isocyanate, especially between 50 to 75 parts by weight.
parts by weight, based on the amount of all prepolymeric 0032. The ratio of the isocyanate groups comprised in the
ingredients The duration of the possible storage before bond isocyanate component to the OH groups comprised in the
ing and activation can also be influenced by the amount of the polyol components is chosen such that there remains an NCO
additional polyols. group-containing prepolymer. The resulting prepolymer
0027. In addition, an inventive adhesive can also comprise should comprise between 5 to 30 wt.% NCO groups.
at least one higher functional low molecular weight polyol. 0033. The 1KPU adhesives according to the invention can
“Low molecular weight' should be understood to mean poly further comprise auxiliaries and additives. These are under
ols with a molecular weight between 80 up to 500 g/mol, stood to mean Substances that are generally added in Small
especially up to 300 g/mol, wherein the functionality should quantities so as to modify the properties of the adhesive in the
be between 3 to 10. Polyols in this case are those that provide desired manner, e.g. its processability, shelf life and also to
a higher crosslinking of the polymer. Where required, the match application properties to the practical field of use.
cohesion of the adhesive can be influenced in this manner. Suitable auxiliaries can be: fillers, leveling agent, exhausters,
thixotropic agents, catalysts, antioxidants, dyes, drying
The amount should preferably be less than 5 parts by weight agents, flame retardants, solvents and wetting agents.
and is chosen Such that the prepolymer does not prematurely 0034 Suitable fillers are inorganic compounds that are
gel during production. Examples are glycerine, trimethylole unreactive to isocyanates Such as chalk, coated chalks, lime
thane or trimethylolpropane, pentaerythritol, Sugar alcohols powder, calcium magnesium carbonates, aluminum oxides
or mixtures thereof. and aluminum hydroxides, precipitated silica, Zeolites, ben
0028. The polyisocyanates are polyfunctional. Preferably, tonites, glass, hollow spheres or ground minerals.
the Suitable polyfunctional isocyanates comprise on average 0035. The leveling agent is intended to improve the flow of
2 to maximum 5, preferably up to 4 and especially 2 or 3 NCO the adhesive during application, i.e. its ability on application
groups. Exemplary Suitable isocyanates are phenyl isocyan to level out resulting unevenness, Stripes, bubbles, craters etc.
ate, 1.5-naphthylene diisocyanate, 4,4'-diphenylmethane Suitable leveling agents are unreactive compounds Such as
diisocyanate (MDI), hydrogenated MDI (Hi-MDI), xylene glycol ethers, silicone oils, acrylate copolymers, polyvinyl
diisocyanate (XDI), tetramethylxylene diisocyanate derivatives.
(TMXDI), 4,4'-diphenyidimethylmethane diisocyanate, di 0036. The 1K polyurethane adhesives can also comprise
and tetraalkylene diphenylmethane diisocyanate, 4,4'-diben catalysts that accelerate the reaction of the OH group with the
Zyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene NCO groups, mainly organometallic compounds, e.g. lead
diisocyanate, the isomers of toluene diisocyanate (TDI), phenyl-ethyl dithiocarbaminate, di-n-octyltin mercaptide, di
optionally in a mixture, 1-methyl-2,4-diisocyanato cyclohex n-octyltin bis-dodecylmercaptide, di-n-octyltin dichloride,
ane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocy especially tin(II) salts of carboxylic acids, such as dibutyltin
anato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocy maleate, dibutyltin diacetate, dibutyltin dilaurate, tin(II)
anato-1.5.5-trimethylcyclohexane (IPDI), phosphorous acetate, tin(II) ethylhexanoate and tin(II) diethylhexanoate or
containing diisocyanates, tetramethoxybutane-1,4- strong bases such as alkali metal hydroxides, alkali metal
diisocyanate, butane-1,4-diisocyanate, hexane-1,6- alcoholates and alkali metal phenolates.
diisocyanate (HDI), dicyclohexylmethane diisocyanate, 0037 Aliphatic tertiary amines are likewise suitable, par
cyclohexane-1,4-diisocyanate, ethylene diisocyanate, ticularly those with a cyclic structure. Under the tertiary
phthalic acid bis-isocyanatoethyl ester or 1,12-diisocyanato amines, those that are also suitable carry additional groups,
dodecane and dimer fatty acid diisocyanate. particularly hydroxyl and/or amino groups, which are reac
0029. In one embodiment the isocyanate component can at tive towards isocyanates. Examples of these are dimethylmo
least partially comprise dimer fatty acid isocyanate, manu noethanolamine, diethylmonoethanolamine, methylethyl
factured from mixtures of predominantly C36 dicarboxylic monoethanolamine, triethanolamine, trimethanolamine,
acids converted into dimer fatty acid isocyanates. Moreover, tripropanolamine, tributanolamine, trihexanolamine, tripen
low molecular weight reaction products of MDI or TDI with tanolamine, tricyclohexanolamine, diethanolmethylamine,
low molecular weight mono- to tetrahydric alcohols with a diethanolethylamine, diethanolpropylamine, diethanolbuty
molecular weight of less than 300 can be used. Such as e.g. lamine, diethanolpentylamine, diethanolhexylamine, dietha
US 2009/0266482 A1 Oct. 29, 2009

nolicyclohexylamine, diethanolphenylamine as well as their activation at increased temperature. This causes the water/the
ethoxylation and propoxylation products, diaza-bicyclo-oc moisture present in the Surroundings or in the adhesive to
tane (DABCO), triethylamine, dimethylbenzylamine, bis react with the isocyanate groups and the buildup of adhesion
dimethylaminoethyl ether, tetramethylguanidine, bis-dim occurs rapidly. Surprisingly this reaction in thin layers of the
ethylaminomethylphenol, 2,2'-dimorpholinodiethyl ether, adhesive does not take place in the absence of thermal acti
2-(2-dimethylaminoethoxy)ethanol, 2-dimethylaminoethyl Vation even though sufficient atmospheric moisture is
3-dimethylaminopropyl ether, bis(2-dimethylaminoethyl) present.
ether, N,N-dimethylpiperazine, N-(2-hydroxyethoxyethyl)- 0043. The 1K polyurethane adhesives according to the
2-azanorbornane, Texacat DP-914, N.N.N.N-tetramethylbu invention are Suitable for adhesively bonding a great many
tane-1,3-diamine, N.N.N.N-tetramethylpropane-1,3-di Solid or flexible Substrates. Thus, plastics, metals, glass, par
amine and N.N.N.N-tetramethylhexane-1,6-diamine. ticularly wood and wood materials (chipboard, MDF boards)
0038. Such amine catalysts can also be in oligomerized or can be adhesively bonded. In particular, non-flexible sub
polymerized form, e.g. as nitrogen-methylated polyethylene strates can be adhesively bonded to each other or flexible film
imine. Mixtures of the different catalysts can also be used. substrates can be adhesively bonded to such rigid substrates.
0039 Resins of natural or synthetic origin can also be Exemplary suitable flexible substrates are wood veneers,
added as additional additives. The natural resins can be of veneer films or multi-layer films. The water content of the
both vegetal and also animal origin, Such as shellac and colo Substrate is generally not critical; the moisture usually present
phonium, tall resins, balsamic resins or root resins. Not only on the Surface is beneficial for a good adhesion and crosslink
the native natural resins, but also principally their derivatives ing. For porous wood materials the moisture content can
can be used, be they obtained by disproportionation, dimer preferably be in the range 2 to 20 wt.%, especially in the
ization, hydrogenation, polymerization, esterification, salt range 4 to 16 wt.%.
formation or by the addition of unsaturated compounds e.g. 0044) To carry out the method according to the invention,
maleic acid. a suitable 1K PU adhesive according to the invention is
0040. The synthetic resins are generally obtained by poly applied onto a substrate. This can be made by methods of the
merization or polycondensation. Characteristically, they do prior art, for example by coating with a doctor blade, spray
not have sharp melting points or softening points. Exemplary ing, roller coating, extrusion coating or by other methods. The
resins are those based on hydrocarbons, terpenes, coumarone/ viscosity of the adhesive should be selected such that the
indene, furans, alkyds, aldehydes, ketones, phenols, glycer method of application affords a uniform layer. For low vis
ine esters, polyesters, epoxides, ureas, melamines, polya cosities a roller coating is particularly suitable, for high vis
mides and isocyanates. The amount of the additive should be cosities an application by extrusion is more advantageous.
less than 10 parts by weight. The application can optionally be facilitated by heating the
0041) Adhesives according to the invention can be manu adhesive. When required, it is also possible to add inert sol
factured from the abovementioned oleochemically-based vent so as to influence the viscosity; however this technique is
polyols, the additional polyols based on polyethers or poly less preferred. The application temperature should be less
esters and from the appropriate polyisocyanates according to than 50° C., particularly below 40° C., especially at about
methods and techniques knownto the person skilled in the art. room temperature of 15 to 30°C. The coating thickness can be
The polyols are generally provided singly or in a mixture and up to 750 um, especially between 10 to 250 um.
optionally dried. This can be carried out by distillation, for 0045. After the liquid adhesive has been applied onto this
example also under vacuum. Moreover, water can also be Substrate Surface the layer can optionally cool down and if so
removed from the polyols by means of water Scavengers, such can gel. There results a thin coating that at room temperature,
as for example molecular sieves. Minor residual quantities of i.e. attemperatures below 30°C., shows practically neither a
water, less than 500 ppm, do not further interfere, as generally crosslinking reaction nor forms bubbles and is storage stable
an excess of isocyanate is processed. Subsequently, the iso for a period between 30 minutes and 24 hours; in particular
cyanate or a mixture of a plurality of isocyanates is added to this adhesive layer is storage stable for more than 3 hours. The
the thus essentially anhydrously prepared polyol mixture. storage conditions are variable. The relative humidity during
Care should be taken here to ensure a good mixing of the storage can be up to 95% relative humidity. Optionally it can
components. The reaction between the OH groups and the be required, in order to prevent contamination of the adhe
isocyanate groups normally begins spontaneously; optionally sive-coated Surface during storage, to cover it with non-ad
it can be Supported by heating or a minor quantity of catalyst hesive protective film, e.g. based on polymer or with non
can be added. Stick coated paper.
0042. The resulting prepolymer contains NCO. Further 0046. In the work method according to the invention, after
additives can optionally be added to this mixture. In which the Substrate has been coated, a second Substrate, for example
case, care should be taken that these additives do not comprise another rigid wood substrate or preferably a flexible sub
any groups that react with the isocyanate groups. The finished strate, especially a wood film or plastic film, is applied. For
adhesive should have a viscosity between 500 and 150,000 this, the substrate to be adhesively bonded is applied onto the
mPas at the application temperature, for example at 30° C. adhesive-coated Substrate Surface in a compression device.
especially between 1000 and 50,000 mPas (measured with The composite is compressed prior to the application or pref
Brookfield RVT, 30° C. EN ISO 2555). In the absence of erably at the same time as the adhesive is activated. The
water it is storage stable for any length of time. With the activation occurs by heating to a temperature above 50°C.,
adhesive according to the invention it is possible to spread preferably above 70° C., particularly above 80°C. Tempera
thin layers of adhesive onto a substrate, which are storage tures above 250° C. are generally unsuitable as they can
stable for up to 24 hours at room temperature without losing damage the Substrate and require unnecessary energy; in par
their adhesive properties. These thin layers can Subsequently ticular the temperature should be les than 200° C. Pressure
be joined together with other substrates and be crosslinked by and elevated temperature are held between 10 seconds and 30
US 2009/0266482 A1 Oct. 29, 2009

minutes, especially between 1 to 15 minutes. A reaction of the the application device is not contaminated. It is Sufficient to
adhesive layer occurs within this time with the water clean with greater periodic intervals as no gel formation or
absorbed in the adhesive, the moisture of the substrate or protrusions appear in the moisture-curing adhesive. Accord
atmospheric moisture. The pressure and elevated temperature ingly, the inventive method is particularly Suitable for a con
can then be removed, the substrates are firmly bonded and can tinuous application process.
Subsequently stored. The strength and dimensional stability 0.052 The adhesive bonds according to the inventive
of the composites manufactured in this way is already pro method are characterized by an unusually high strength and
duced at the pressing temperature; a recooling and physical resistance against moisture. Possible unevenness of a Sub
setting to attain adequate strength values is not needed. strate Surface is compensated for by an inventive mode of
0047 Another inventive mode of operation joins a plural operation and a second thin flexible substrate layer can be
ity of different or similar substrate layers together, said sub adhesively bonded onto the first uneven substrate. The adhe
strates having an adhesive layer according to the method on sively bonded substrates from the inventive method possess a
one side, which are then pressed together and adhesively very Smooth Surface. Due to the long open time, no contami
bonded. Laminated wood molded objects can be produced in nants appear on the application device. Moreover, the occur
this way. rence of premature gel is not observed in the adhesive film.
0048. After application onto a substrate surface, the adhe
sive layer according to the invention when stored below 40° EXAMPLES
C., particularly 30°C., neither exhibits crosslinking reactions
nor bubble formation as troublesome side reactions. The Example 1
unactivated adhesive layer does not lose its adhesive action 0053 10 parts of a polyether diol based on propylene
when stored, i.e. the open time of the adhesive up to the final glycol with an M, of ca. 2000 were dried under vacuum. To
adhesive bonding is long.
0049. However, it is inventively required that when heated this diol were added a further 30 parts of an oleochemical
to the activation temperature and in the associated compres polyol with an M. of ca. 1000 and an OH number of ca. 200.
sion step, the adhesive foams during the crosslinking. The To this mixture were added 60 parts of crude MDI (Isonate
foam Volume is only slight and in particular should be less 143 L). The mixture was homogenized and stirred at a tem
than 50 volume 96 of the adhesive. Whereas the density of the perature of 75°C. for 30 minutes. An adhesive was obtained
inventively non-foamed adhesive is normally ca. 1.00 to 1.20 with a NCO content of 16% and a viscosity of 10,000 mPas at
30° C.
g/cm, the density of the crosslinked adhesive can be lower.
The foam volume can be determined from the density of the Example 2
crosslinked adhesive. The density should be between 1.10
down to 0.3 g/cm, especially between 0.5 up to 0.95 g/cm. 0054 39.5 parts of an oleochemical polyol with an M. of
Surprisingly, the slight foaming of an inventively Suitable 1000 and an OH number of 200 were freed from water under
adhesive leads neither to a decrease in cohesion nor in adhe
a vacuum. 0.5 parts of pentaerythritol were added. To this
sion of the adhesive to the substrates. The adhesively bonded mixture were added 60 parts of crude MDI. 0.01% DBTL
Surfaces have a high adhesive strength. were added as catalyst, the mixture was homogenized and
0050. The inventive method is particularly suitable for allowed to react for one hour at 50° C. An adhesive was
adhesively bonding thin flexible substrates onto a rigid sub obtained with a viscosity of 50,000 mPas at 30° C. and an
strate, for example films based on polymers, wood or com isocyanate content of 17%.
posite materials, onto rigid, hard plastic, metal or wood Sub
strates; however, two or more similar Substrates can also be Example 3
adhesively bonded. In this case the surface of the hard sub
strate does not particularly need to be polished or pre-treated. 0055 25 parts of an oleochemical polyol with an M., of ca.
Possible unevenness or cavities in the surface, for example 1000 and an OH number of ca. 200 were dried. To this mixture
with a depth of up to 1 mm, are bridged or filled in with a were added 75 parts of crude MDI (Isonate 143 L). The
suitable adhesive when the inventive method is used. In this mixture was homogenized and stirred at a temperature of 75°
way, a thin, flexible substrate is successfully adhesively C. for 30 minutes. An adhesive was obtained with a NCO
bonded to afford a smooth surface and the foam content in the content of 20% and a viscosity of 20,000 mPas at 30° C.
cured adhesive does not impair the strength.
0051. Another subject matter of the invention is a method Adhesive Bonding:
for applying thin reactive adhesive layers onto Substrates by
means of calendaring, rolling or coating, wherein the appli 0056 1) A beech wood object was cleaned to remove
cation temperature is below 50° C., especially below 40°C. adherent dust constituents. An adhesive according to
1K polyurethane adhesives from the prior art generally have examples 1 to 3 was then applied with a coating layer of ca. 50
a short open time, i.e. the adhesive reacts even at room tem um with a knife blade at room temperature (25° C.). After
perature with atmospheric moisture. By using an inventive cooling the Substrate, a storage stable coating was obtained.
1KPU adhesive having along open time, it is possible that the An aluminum test piece was coated in the same way.
application tooling, for example a coating cylinder, can be 0057 The coated substrates were adhesively bonded with
continuously operated for a longer length of time without the a corresponding substrate. The adhesively bonded substrates
need for cleaning. According to this mode of operation the were then subjected to a pressure of 10-100 kg/m in a press,
application device under normal conditions can come into the work piece being simultaneously heated to 150° C. The
contact with the inventive adhesive for longer periods, e.g. up pressure and temperature were maintained for 10 minutes.
to 24 hours. The adhesive does not react with atmospheric 0058. The tensile shear strength of the adhesively bonded
moisture, premature crosslinking reactions do not occur and products was greater than 6 N/mm. Similar values were
US 2009/0266482 A1 Oct. 29, 2009

obtained when the test pieces had been stored for 5 hours at 7. The process according to claim 6, wherein the surface of
room temperature before bonding. In that case the adhesive the substrate is uneven.
Surface was not foamed. 8. The process according to claim 1, wherein an adhesive is
0059 2) The abovementioned wood specimens were applied at room temperature and air humidity of up to 95%.
coated in the same way. A paper film or CPL film was applied 9. The process according to claim 1, wherein the adhesive,
and the adhesively bonded specimen was pressed and heated after curing, has a density between 0.3 g/cm up to 1.10
for 5 minutes at 100° C. g/cm.
0060. The resulting product exhibited a smooth surface 10. The process according to claim 1, wherein stepb occurs
and unevenness of the Substrate was not displayed. for a period of 0.5 to 24 hours at a temperature below 30°C.
0061. In a comparative experiment, a commercial adhe 11. The process according to claim 1 wherein the curing is
sive of the type Macromelt UR 7221 (Henkel KgaA) based on conducted with a heatable cylinder.
an isocyanate-crosslinking polyurethane was applied. The 12. The process according to claim 10, wherein the curing
coating thickness on the wood specimen was also 50 um. conducted with a heatable press.
0062. After storage for 2 hours, the exposed surfaces 13. The process according to claim 1, wherein in step b, the
exhibited foam formation on the surface. applied adhesive has an open time greater than 3 hours at
0063. After storage, the substrate was adhesively bonded room temperature.
with a wood object for 10 minutes at 150° C.; the tensile shear 14. A liquid, moisture-curable one component polyure
strength was less than 4.0 N/mm. An appropriate paper film thane adhesive comprising:
or CPL film was adhesively bonded, compressed and heated. a) a reaction product of 20 to 50 parts by weight of an
The Surface defects became apparent. oleochemical polyol.
1. A process for bonding flat substrates with a moisture b) 0 to 15 parts by weight of a polyether polyol or polyester
crosslinkable one component polyurethane-based adhesive polyol with an M. between 300 and 15000; and
comprising: c) 80 to 40 parts by weight of a polyisocyanate;
a) applying the adhesive onto a first Substrate at tempera wherein the adhesive can be stored in thin layers at room
ture below 50° C.; temperature for 1 to 24 hours and Subsequently crosslink at a
b) optionally, storing the coated Substrate; temperature of 70 to 200° C.
c) bringing a second Substrate in contact with the adhesive 15. The adhesive according to claim 14, which after
coated on the first substrate; crosslinking, has a density between 0.30 g/cm to 1.10 g/cm.
d) curing the adhesive attemperature of 50° C. and 250° C.; 16. The adhesive according to claim 14, wherein and the
wherein the adhesive foams during curing. polyisocyanate is 50 to 75 parts by weight.
2. The process according to claim 1, wherein the adhesive 17. The adhesive according to one of claim 14, wherein the
has a viscosity between 500 and 150,000 mPas at 30° C. polyol is a castor oil or polypropylene glycol and the poly
3. The process according to claim 1, wherein the adhesive isocyanate is aromatic isocyanate.
is applied at a temperature of 15° C. to 40°C. 18. The adhesive according to claim 14, wherein the adhe
4. The process according to claim 1, wherein the curing of sive comprises a polyol with a functionality of 3 to 10, and a
the adhesive is at a temperature of 70° C. to 200° C. catalyst.
5. The process according to claim 1, wherein step d is 19. The adhesive according to 14, wherein the open time of
conducted from 10 seconds to 30 minutes. the adhesive is greater than 3 hours at a temperature below 50°
6. The process according to claim 1, wherein the Substrates C.
are selected from the group consisting of plastic film, wood
and composites.