USOO6790906B2

(12) United States Patent (10) Patent No.: US 6,790,906 B2

Chaignon et al. (45) Date of Patent: Sep. 14, 2004

(54) FIRE-RETARDANT POLYURETHANE (56) References Cited

SYSTEMS
U.S. PATENT DOCUMENTS
(75) Inventors: Jóel Chaignon, Ecos (FR); Francois
Adeleu, Gournay en Bray (FR); 4,876.291 A 10/1989 Dallavia et al.
Jean-Marc Leleu, Gourney en Bray 5,196.455 A 3/1993 Bryant
(FR); Peter Merz, Wollerau (CH);
Ukiwo Obasi Onuoha, Zürich (CH) FOREIGN PATENT DOCUMENTS

(73) Assignee: Sika Schweiz AG, Zurich (CH) EP O2O0801 A1 11/1986

FR 1356972 1/1963
(*) Notice: Subject to any disclaimer, the term of this FR 1496648 10/1966
FR 1505924 12/1966
patent is extended or adjusted under 35 WO WO 94/06886 A1 3/1994
U.S.C. 154(b) by 0 days.
(21) Appl. No.: 10/324,054 Primary Examiner Rachel Gorr
(22) Filed: Dec. 20, 2002 (74) Attorney, Agent, or Firm-Burns, Doane, Swecker &
Mathis, L.L.P.
(65) Prior Publication Data
(57) ABSTRACT
US 2003/0220407 A1 Nov. 27, 2003
A Storage-Stable moisture-curing one-component fire
(Under 37 CFR 1.47) retardant polyurethane System, useful as adhesive, Sealant or
coating material, comprising at least one hydrated mineral
Related U.S. Application Data having a water-content of less than 0.1% and being treated
with a moisture-reactive compound, and at least one binder
(63) Continuation of application No. 08/799.908, filed on Feb. on isocyanate basis. Such PU-Systems preferably further
13, 1997, now abandoned. comprise at least one phosphorus-containing compound,
(30) Foreign Application Priority Data most preferably a phosphorus-containing plasticizer, which
Feb. 14, 1996 (CH) ............................................... 385/96
is preferably halogen-free. The binder on isocyanate basis
has preferably an isocyanate content in the range of from
(51) Int. Cl." ................................................ C08G 18/10 0.01 to 10% by weight referred to the total weight of the
(52) U.S. Cl. ........................ 524/706; 524/710; 524/786 System.
(58) Field of Search ................................. 524/710, 706,
524/786 17 Claims, No Drawings
 US 6,790,906 B2
1 2
FIRE-RETARDANT POLYURETHANE It was Surprisingly found to be possible to formulate a
SYSTEMS flame-retardant and Storage-Stable, moisture-reactive
PU-System containing a considerable amount of hydrated
This application is a continuation of application Ser. No. minerals filler material, Such as aluminium trihydroxy
08/799,908, filed Feb. 13, 1997, now abandoned. hydrate (ATH), even in large amounts, e.g. more than 35%,
BACKGROUND OF THE INVENTION if the hydrated minerals are treated by a particular method
This application claims the priority of Swiss application which is also part of the present invention.
No.385/96, filed on Feb. 14, 1996, the disclosure of which The desired Storage-Stability can be achieved by a specific
is incorporated herein by reference in its entirety. production method for the hydrated mineral wherein a
1O mineral’s Surface activity is reduced and neutralized, thus
The present invention relates to one-component polyure
thane (PU) systems, particularly fire-retardant (FR) systems. preventing undesired increases in Viscosity upon Storage
These Systems are preferably halogen-free. The Systems can (which makes application impossible).
be used as adhesive, Sealant or coating materials. The surface activity of hydrated minerals depends on the
The use of aluminium trihydroxy hydrate (ATH) alone or 15
groups capable of reacting with NCO-groups of the binder.
in combination with a phosphorus or halogen containing It is a further object of the present invention to provide an
compound is known in two-component polyurethane SyS ecological System that moisture-cures to a flame and Smoke
tems. Such a system is described, e.g., in U.S. Pat. No. retardant elastomer, particularly Such a System for use as an
4,876,291. That document describes a method for forming a adhesive, Sealant or coating material.
fire-retardant composition that is added to the polyol com
ponent shortly before mixing with the isocyanate compound This was possible through the use of a specially treated
in order to achieve Superior physical foam properties. This hydrated mineral, preferably with a halogen-free,
fire-retardant composition contains a hydrated filler, Such as phosphorus-containing Substance, preferably a phosphorus
ATH, which is pretreated with 0.25 to 5% polyfunctional containing plasticizer. Such a phosphorus-containing com
isocyanate relative to the amount of ATH, resulting in a pound improves the fire-retardant performance of the
moisture content of about 0.2%. 25 hydrated mineral, preferably ATH, in an unexpected manner.
Hydrated minerals, Such as aluminium trihydroxy hydrate The phosphorus-containing material may be present in the
(ATH) impart both flame and smoke retardancy by evolving formulation in a specific ratio relative to the binder. If the
non-toxic gases, Such as water, to dilute combustion prod phosphorus-containing compound is a phosphorus
ucts and to promote char formation. containing plasticizer, e.g., diphenylcresylphosphate (DPK),
However, it has been found that a pretreated ATH, such as then the ratio of phosphorus-containing plasticizer to binder
that described in U.S. Pat. No. 4,876,291, is not suitable for can be in a range of 0.25 to 5, preferably in a ratio of 0.7 to
one-component adhesive formulations held in a Sealed ves 1.5, and most preferably is about 1.
Sel. There is a lack of Storage Stability leading to a fast
increase in Viscosity. As a result, there is a Substantial loSS DETAILED DESCRIPTION OF THE
of handling properties in a relatively short period of time. 35
PREFERRED EMBODIMENTS
One component polyurethane Systems comprising pre The fire-retardant and Storage-Stable moisture-reactive
dried additives are known in the art. WO 94/06886, for PU-Systems of the invention contain a considerable amount
example, discloses a vitreous filler that is predried using an of hydrated mineral filler material(s) Such as aluminium
isocyanate having a functionality of at least 2. FR-A-1,505, trihydroxy hydrate (ATH), and can be prepared according to
924 and FR-A-1,356,972 both describe PU-systems com 40 the method described below. The thus treated ATH may be
prising predried pigments. The pre-drying is performed present even in large amounts, e.g., more than 35%, without
using water-reactive compounds. adversely influencing the Storage-Stability of the System.
The use of aluminium oxide as a drying agent for In order to enhance the flame and Smoke retardancy it is
PU-Systems (produced by incomplete dewatering of alu preferred to use a specially treated hydrated mineral in
minium oxide trihydrate (aluminium hydroxide) to a water 45
combination with a phosphorus-containing plasticizer. The
content of 0.5 to 0.05 mole per mole aluminium oxide), is phosphorus containing material preferably is halogen-free. It
described in FR-1,496,648. improves the fire retardant performance of the hydrated
An optionally high pigmented mass (5 to 25% pigment) is mineral in an unexpected manner. If the phosphorus
described in EP 0200 801. In addition to the pigment, the containing compound is a phosphorus-containing
mass comprises about 1 to 3% by weight of a moisture 50
plasticizer, e.g., diphenylcresylphosphate (DPK), then the
binding agent. weight ratio of phosphorus containing plasticizer to binder
Since two component Systems are not as easy to use as can be in a range of 0.25 to 5, preferably in a ratio of 0.7 to
one component Systems, it is one object of the invention to 1.5, and most preferably about 1 to 1.
provide a one component, fire-retardant (FR) polyurethane The fire-retardant PU-System also preferably contains a
(PU) system, which, most preferably, is halogen-free. It is a 55
latent hardener, which can be present in amounts of up to
further object of the invention to provide a specific manu 10% by-weight, preferably in an amount of from 1 to 3% by
facturing method to achieve Storage-Stable fire-retardant weight based on the weight of the total System.
adhesives.
Another object of the invention is to provide particulate Additionally, the inventive System may contain other
fillers for imparting flame retardation, which are Suitable for 60 plasticizers, other fillers and other additives. Examples of
use in one-component PU systems. additives include adhesion promoters, catalysts, etc.
The inventive moisture-reactive halogen-free fire
SUMMARY OF THE INVENTION retardant adhesive, coating or Sealing material preferably
Accordingly, it is a general object of the present invention contains a mixture of:
to provide isocyanate and/or Silane terminated polyurethane 65 a) 10 to 60% of at least one hydrated mineral having a
Systems that are Storage-Stable, moisture-curing and fire water-content of less than 0.1% being further treated
retardant. with a moisture-reactive compound,
 US 6,790,906 B2
3 4
b) 10 to 50% of at least one phosphorus-containing polybutadienes, polycarbonates, polycaprolactones,
plasticizer, polycaprolactams, polyethers (e.g., polyethylene
c) 10 to 40% of at least one binder on isocyanate basis, Oxides, polypropylene oxides, polybutylene oxides,
d) optionally, at least one latent hardener in Such amounts polystyrene oxides, polyepichlorohydrines, and
that the reactive groups of the hardener are present in polytetrahydrofuranes), polyesters, e.g., any condensa
an amount of 10 to 100% of the isocyanate-groups of tion products of:
the prepolymer, and multivalent alcohols (e.g. ethylene-glycol, propylene
e) optionally, those other components known in the art glycol-1,2 and -1,3, butylene-glycol-1,4 and -2,3,
Such as adhesion promoters, catalyst, fillers, other he Xane diol-1, 6, octane diol-1,8, glycerin,
plasticizers, etc., but which do not fall within one of the trimethylolpropane, pentaerythrite, chinite, mannite
above mentioned groups a) to d). and Sorbite, methylglycoside, diethylene glycol, poly
The isocyanate content (NCO) referred to the total weight ethylene glycols, dipropylene glycol, and polypropy
of the adhesive, Sealant or coating material usually is in the lene glycols) with
range of from 0.01 to 10% by weight, preferably below 1% 15
multivalent carboxylic acids and/or carboxylic acid anhy
by weight. drides and/or carboxylic esters, (e.g. Succinic acid,
Examples of components which fall into aforementioned adipic acid, octanedioic acid, azelaic acid, Sebacic acid,
category e) include: phthalic acid, isophthalic acid, trimelitic acid phthalic
plasticizerS Selected from phthalates, Such as dibutyl-, acid anhydride, tetrahydrophthalic acid anhydride, tet
dioctyl-, dicyclohexyl-, diisooctyl-, diisodecyl-, rachlorophthalic acid anhydride, glutaric acid
dibenzyl-, or butylbenzylphthalate, epoxy-containing anhydride, maleic acid anhydride, fumaric acid, tereph
plasticizers, toluene-Sulfonamides, paraffines, adipic thalic acid-dimethylester and terephthalic acid-bis
esters, castor oils, etc.; glycol-ester, each having terminal, primary and/or Sec
fillerS Selected from Silicic acid derivatives, gypsum, ondary OH-groups, Such as e.g. ethylene-glycols, bis
talcum, active charcoal, metal powder, chalk, kaolinite, 25
hexanediol-1,6, propylene glycol, bis-hexapropylene
carbon black, etc.; glycol, diethyle neglycol, and bis-hexaethylene
auxiliary agents or additives Selected from i) latent glycols).
hardeners, Such as enamines, oxazolidines, aldimines A more preferred composition comprises a mixture of:
and ketimines, possibly in the presence of an acid a) 35 to 45% of at least one hydrated mineral having a
Stabilizer or a latent acid Stabilizer, e.g., an anhydride of water-content of less than 0.1% and being further
a dicarboxylic acid, ii) adhesion promoters, particularly treated with the moisture-reactive compound,
Silane-containing compounds, which may additionally b) 20 to 30% of at least one phosphorus containing
contain at least one reactive group, Such as epoxy-, plasticizer,
isocyanate-, amine groups or double bonds, iii) dyes or c) 20 to 30% of at least one binder on isocyanate basis,
pigments, iv) polyurethane catalysts, Such as lead and/ 35 and
or tin compounds, optionally combined with other d) optionally, at least one latent hardener in Such amounts
polyurethane catalysts, especially with tertiary amine that the reactive groups of the hardener are present in
containing catalysts, v) UV-absorbing agents or an amount of 40 to 90%, most preferred of 50 to 80%
Stabilizers, Such as phenolic antioxydants, vi) Surface of the isocyanate-groups of the prepolymer.
active additives, Such as emulsifying agents, vii) other 40 A preferred hydrated mineral is aluminium trihydroxy
flame retardants, Such as phosphates with aryl groups hydrate (ATH).
or with up to 8 C-atoms in the alkyl group, e.g., Preferred phosphorus containing plasticizers are ones that
diphenylcre Sylphosphate, tric resylphosphate, are halogen-free Such as e.g., diphenyl cresyl phosphate
triethylphosphate, trioctylphosphate, etc., dimethyl (DPK), and a preferred binder on isocyanate basis has an
methylphosphonate, and viii) fungistatic-active and/or 45 isocyanate content (NCO) relative to the total weight of the
bacterioStatic-active Substances. preferred composition in the range from 0.01 to 10% by
Preferred binders are isocyanate and/or Silane terminated weight, preferably below 1% by weight.
polyurethane prepolymers, particularly those formed of the The PU-Systems of the invention are preferably produced
following components: by a particular process, itself being a part of the invention.
a) aromatic diisocyanates, Such as, e.g., 4,4'-diphenyl 50 The proceSS comprises preparing the Systems according to
methane -diisocyanate, 2,4-toluene -diisocyanate, the invention under water-free conditions and using dewa
naphthylene-1,5-diisocyanate, 1,3- and 1,4-phenylene tered hydrated minerals, particularly ATH. The dewatered
diisocyanate, and/or hydrated minerals are treated with moisture-reactive com
b) aliphatic or cycloaliphatic diisocyanates, Such as pounds. Thus, in the PU-System possibly also reaction
he Xamethylene -diisocyanate, 1,12-dodecane 55 products of the moisture-reactive compounds with water are
diisocyanate, cyclobutane-1,3-diisocyanate, present.
cyclohexane-1,3-diisocyanate, cyclohexane-1,4- An effective drying of the hydrated mineral is carried out
diisocyanate, 1-isocyanato-3,3,5-trimethyl-3- under vacuum and at a temperature Suitable for partial
isocyana to methylcyclohexane (isophor one dewatering of the hydrated mineral to a water-content of leSS
diisocyanate), 2,4- and 2,6-hexahydrotoluene 60 than 0.1% (but without causing decomposition of the
diisocyanate, hexahydro-1,3-phenyl-diisocyanate and hydrated mineral). For ATH, the temperature can be above
hexahydro-1,4-phenyl-diisocyanate, perhydro-2,4'- 120° C., but well below 200° C.
diphenylmethane-diisocyanate and perhydro-4,4'- A water-content of the hydrated mineral of more than
diphenylmethane-diisocyanate, and 0.1% leads to an insufficient Storage Stability and greasy
c) polyols having a molecular weight in the range of from 65 consistency of the PU-System. Furthermore, if during the
400 to 10,000, preferably in the range of from 1000 to pre-drying of the hydrated mineral the water-content is not
5000, such as the polyols of e.g., linear or branched reduced to lower than 0.1%, exceSS moisture-reactive com
 US 6,790,906 B2
S 6
pounds is required. This may lead to a polyurethane elas EXAMPLES
tomer with inferior polymer end-properties.
Any moisture-reactive compound which has at least one Materials Used in the Examples
moisture-reactive group and which does not adversely affect
the PU-System, can be applied to the predried hydrated
mineral in the amounts needed to provide good Storage
stability of a ATH-containing PU-System. Such compounds MDI (methylene-4,4'-diphenyl diisocyanate): Bayer, GER
are, e.g., monomers having isocyanate-groups, or polyfunc TDI (tolylene diisocyanate): Bayer, GER
tional isocyanates, preferably mono-isocyanates, Desmodur Z 4370 (trimerized IPDI): Bayer, GER
anhydrides, Silanes, titanates. A preferred moisture-reactive IPDI (isophorone diisocyanate): Bayer, GER
compound is paratoluene Sulfonyl isocyanate (PTSI). 1O PTSI (para-toluene-sulfonyl isocyanate): Rahn AG, CH
Polyoxyalkylene ether polyol: Bayer/Dow, GER
Although it is possible to further dry the hydrated mineral Triethylene dimine: Fluka, CH
to much less than 0.1% by, e.g., drying in a drying chamber DPK (diphenylcresyl phosphate/Disflamoll DPK): BASF, GER
with a chemical absorbent Such as diphosphorus pentoxide, Salicylic acid: Fluka, CH
it is more preferred that a specific amount of moisture DBTDL (dibutyl-tin dilaurate catalyst): Air Products, GER
15 latent hardener BJ: :
reactive component is incorporated into the PU-System (dialdimine derived from benzaldehyde and
together with the hydrated mineral, that was predried to a (polyoxypropylene diamine)
water content of at most about 0.1%. Such a compound *Preparation according to EPO 469 751 A1, Temp. 110° C., but without
further contributes to a lower water-content of the whole any catalyst.
formulation. Surprisingly, it was found not to be necessary
to incorporate moisture-reactive groups into the System in an
amount corresponding to the water remaining in the predried The ATH (aluminium trihydroxy hydrate) used as the
hydrated mineral. For most applications about 50-90 mole Starting material in the examples had an average particle size
%, preferably about 65–75 mole %, are sufficient. of 3.5 um and a water content >0.3%. Such a product is, e.g.,
A preferred one component PU-System providing good 25
available as ATH SB 632 from Solem, France.
Storage stability and homogeneous properties (e.g., no Preparation 1: TDI-Prepolymer
agglomerations and lumps) is achieved when dewatered The TDI-prepolymer was prepared by reacting a polyOX
ATH is dispersed in portions under water-free conditions to
a premix consisting of binder and fire retardant plasticizer ypropylene ether polyol of an average molecular weight of
with the binder having an isocyanate content of preferably 4000 and a hydroxyl number of 40 with toluene
less than 1%. It is then treated with a moisture-reactive diisocyanate (TDI).
component. Finally, the additives and the catalyst, e.g., an 2000 g of the polyol with a water-content of 0.03% by
organo tin catalyst, are added. weight was charged into a flask with 198 g of TDI. The
In case a latent hardener is used for bubble-free moisture prepolymer synthesis reaction was catalized with 0.01%
curing of the PU-System, it is believed the best storage 35 triethylene diamine and allowed to react under nitrogen
stability is achieved when dewatered ATH (predried) is purge while stirring at 80 C. for approximately 3 hours.
dispersed in the fire-retardant plasticizer and then treated The reaction was completed after obtaining a final and
with the moisture-reactive component, e.g., polyfunctional constant isocyanate-content of 1.5% by weight. The pre
isocyanate-containing compounds, at elevated temperatures,
prior to the addition of the binder, latent curing agent, polymer was allowed to cool down to a temperature of 60
additives and catalyst. 40 C. and filled into air-tight cans for use in the formulations
shown below.
The fire-retardant adhesive of the invention may be used
for bonding and/or Sealing of one or more materials, of the Final prepolymer isocyanate-content: 1.5%
Same or different origin, to an assembly. It is very well Suited Viscosity after 24 hours at 23° C.: 15 Pas.
for the use in many applications in the construction area, as 45 Preparation 2: MDI-Prepolymer
well as in other industries Such as vehicle production,
marine, etc. The fire-retardant adhesive of the invention may The same procedure used for preparing the TDI
be used to bond or Seal, e.g., the following: prepolymer was employed here except that for the TDI used
construction materials, especially Stones, concrete, in Preparation 1, 324.98 g of methylene-diphenyl
mortar, road pavings, 50
diisocyanate (MDI) was used.
metal which may be varnished, metallized or otherwise The mixture was allowed to react without catalysis at 90
coated and/or pretreated, Such as, e.g., bodies of C. for 3 hours resulting in a final and constant isocyanate
vehicles, content of 2.0%. The temperature was allowed to cool down
metal alloys which may be varnished, metallized or to 60° C. and the prepolymer was filled in air-tight cans for
otherwise coated and/or pretreated, Such as, e.g., bodies 55 use in the formulations shown below.
of vehicles; Final prepolymer isocyanate-content: 2%
glass, especially glass plates for use in automotive
vehicles, composite glass plates, and front walls of Viscosity after 24 hours at 23° C.: 20 Pa.s.
glass,
plastics, Such as, e.g., PU-elastomers, polyesters, 60 Example 1
acrylonitril-butadiene-styrene-copolymers (ABS), (Fire-Retardant Performance of a Halogen-Free Adhesive)
polyamides, polyvinylacetate, polyvinylchloride, etc.;
and The fire-retardant test "UL94” was used to rate the
any wood. fire-retardant performance where the adhesive Specimen is
The following examples are solely intended to further 65 exposed directly to the flame.
illustrate the invention. They are not intended to in any way ATH (without dewatering treatment of invention) was
limit the Scope of the invention. introduced to a premix of binder and DPK. Then 0.05 parts
 US 6,790,906 B2
7 8
by weight (pbw) catalyst (DBTDL) was mixed into the
PU-mass. -continued
amounts test 7 test 8 test 9

Components test 1 test 2

viscosity (mPa s)
initial 115 115 119
binder 26 pbw 26 pbw after 7 df2O. C. 223 132 160
Disflamo DPK 23 pbw 26 pbw after 14 df2O. C. 381 157 254
ATH (SB 632) 35 pbw 42 pbw after 28 df2O. C. inhomo- 250 inhomo
ratio DPK/binder O.83 1.
NFP 925O1 M2 bad good geneous geneous
greasy greasy
pbw= parts by weight for binder see Example 1
NFP 925O1= radiation test

1) Binder=10 pbw TDI-Prepolymer and 16 pbw MDI In an isocyanate-group containing System the treatment of
Prepolymer 15 non-dewatered ATH with a water-Scavenger (compound
(for preparation of the isocyanate-prepolymer See above) reactive with water) according to U.S. Pat. No. 4,876,291 is
not Sufficient and does not result in Suitable Storage Stability
The investigation shows that the best fire-retardant per (see tests 5 and 6).
formance is achieved when the ratio of the fire-retardant
ATH needs to be dewatered below 0.1% and additionally
plasticizer, DPK, to binder is near one and the ATH content treated with a water scavenger, preferably with PTSI (see
is more than 40%. test 8) at elevated temperature.
The adhesive of the invention exhibits improved fire
retardant performance on an ecologically optimized poly Example 3
urethane material:
Classification M2 according to radiation test NFP 92501 25 This example demonstrates the influence of drying of
ATH and the use of an isocyanate compound as a treating
Classification V-O according to inflammation test UL 94 agent on the Storage Stability of moisture-reactive
Classification F2 according to Smoke density flaming test PU-Systems with a latent hardener.
NFX 10702 and NFX 701OO.
After pretreatment of the premix (ATH and Disflamoll
Example 2 DPK) with Desmodur Z 4370 or IPDI at 70° C., the binder,
latent hardener and additives were added.
This example demonstrates the influence of drying of
ATH and the use of an isocyanate compound as a treating
agent on the Storage Stability of moisture-reactive amounts test 10 test 11
PU-System without latent hardener. 35
ATH was introduced to a premix (binder and Disflamoll Components
DPK) being pretreated with PTSI and/or Desmodur Z 4370. ATH (not dried) 40 X
Then 0.05 pbw catalyst (DBTDL) was mixed into the ATH (dried) 40 X
PU-mass. binder 26 X X
40 Disflamo DPK 26 X X
1) ATH SB 632 (Not Dried): Moisture-Content>0.3% latent hardener BJ 18 X X
salicylic acid O and 0.1 X X
Desmodur Z 4370 or 0.5 0.5 0.5
IPDI
Components amounts test 3 test 4 test 5 test 6 extrusion rate (g/min)
45
ATH (not dried) 40 X X X X after 7 df2O. C. 92 92
binder 26 X X X X after 28 df2O. C. 43 88
Disflamo DPK 26 X X X X after 3 months/20 C. greasy, 40
PTSI O6 X X X inhomo
Desmodur Z 4370 1. X X geneous/
viscosity (mPa.s.) 50
15

after production 127 119 121 96 *salicylic acid, up to an amount of 0.1 pbw does not show any influence
after 7 df2O. C. cured cured cured cured
after 14 df2O. C. cured cured cured cured In a one-component PU-System with a latent hardener,
after 28 df2O. C. cured cured cured cured
ATH has to be dewatered below 0.1% and additionally
55 pretreated with a moisture-reactive compound, e.g., Desmo
2) ATH SB 632 (Dried): Moisture-Content<0.1% dur Z4370, at elevated temperatures of, e.g., 70° C.
A higher amount of Desmodur Z 4370 or IPDI (>0.5%) is
not recommended because the mechanical properties may
become inferior.
amounts test 7 test 8 test 9 60
Components Example 4
ATH (dried) 40 X X X This example demonstrates the Influence of the grain size
binder 26 X X X of ATH on mechanical behaviour.
Disflamo DPK 26 X X X
PTSI O.6 X 65 The mechanical properties were determined according to
Desmodur ZA370 1. X NF P 85 507. Aluminium was used as the Substrate pre
treated with SikaPrimer-215.
 US 6,790,906 B2
10
b) 10 to 50% by weight of said at least one phosphorus
containing plasticizer, and
ATH from Solem, F modulus elongation c) 10 to 40% by weight of said at least one polyurethane
prepolymer.
SB 632 (3.5 m)* O.85 MPa. 220% C* * 8. The PU-System according to claim 7, comprising:
SB 434 (9 m)* O.75 MPa. 110%, C* *
a) 35 to 45% by weight of at least one of said hydrated
*= average particle sizes minerals,
**= cohesive failure
b) 20 to 30% by weight of at least one of said phosphorus
A particle size of about 3.5 um facilitates best perfor containing plasticizers,
mance in connection with modulus and elongation at break. c) 20 to 30% by weight of at least one of said polyurethane
What is claimed is: prepolymer.
1. A one component polyurethane (PU) system compris 9. The PU-System according to claim 7, further compris
ing: ing up to 10% by weight of at least one latent hardener
15 wherein reactive groups of the hardener are present in an
a) at least one polyurethane prepolymer having isocyanate
and/or Silane terminal groups, amount of 10-100% of the isocyanate and/or silane groups
b) at least one hydrated mineral which has been pre-dried of the prepolymer.
prior to addition to the System and has a moisture 10. The PU-System according to claim 9, comprising 1 to
content less than 0.1% by weight; 3% by weight of at least one hardener.
c) at least one phosphorus-containing plasticizer; and 11. The PU-System according to claim 9, wherein the
reactive groups of the hardener are present in an amount of
d) at least one moisture-reactive compound comprising at 40-90% of the isocyanate and/or silane groups of the pre
least one water-reactive group and/or the reaction prod polymer.
uct thereof with water; 12. A PU-System according to claim 11, wherein the
wherein the molar Sum of the water-reactive groupS and/or 25 reactive groups of the curing agent are present in an amount
the reaction products thereof with water does at most of 50-60% of the isocyanate and/or silane groups.
correspond to the at most 0.1% by weight of water in the 13. The PU-System according to claim 7, wherein the
hydrated mineral. polyurethane prepolymer has an isocyanate content referred
2. The PU system according to claim 1, wherein the to the total of the PU-System in the range of from 0.01 to
moisture-reactive compound is Selected from the group 10% by weight.
consisting of monomers having isocyanate groups, poly 14. A PU-System according to claim 13, wherein the
functional isocyanates, mono-isocyanates, anhydrides, isocyanate content is less than 1% by weight.
Silanes and titanates. 15. The PU-System according to claim 7, wherein the ratio
3. The PU-System according to claim 1, wherein the of Said phosphorus-containing plasticizer to Said polyure
hydrated mineral is alumina trihydrate (ATH). 35 thane prepolymer is about 1:1.
4. The PU system according to claim 2, wherein the 16. A method for producing a binder-containing one
moisture-reactive compound comprises paratoluene Sulfo component PU-System according to claim 1, Said method
nyl isocyanate. comprising, pre-drying at elevated temperatures the
5. The PU-System according to claim 1, wherein the hydrated mineral to a water-content below 0.1% by weight,
phosphorus-containing plasticizer is halogen free. 40 and adding Said pre-dried mineral under water-free condi
6. The PU-System according to claim 5, wherein the tions to the prepolymer or composition comprising Said
phosphorus-containing plasticizer is diphenyl cresyl phoS prepolymer either together with or after, a Said moisture
phate. reactive compound comprising at least one water reactive
7. The PU-System according to claim 1, comprising: grOup.
a) 10 to 60% by weight of said at least one hydrated 45 17. A method according to claim 16, wherein drying is
mineral having a water-content of less than 0.1% by carried out under Vacuum.
weight and treated with Said at least one moisture
reactive compound,