U.S. patent application number 11/513172 was filed with the patent office on 2007-08-16 for aqueous two-component organoalkoxysilane composition.
Invention is credited to Wolf-Rudiger Huck, Jolanda Sutter.
Application Number | 20070190345 11/513172 |
Document ID | / |
Family ID | 35695675 |
Filed Date | 2007-08-16 |
United States Patent
Application |
20070190345 |
Kind Code |
A1 |
Sutter; Jolanda ; et
al. |
August 16, 2007 |
Aqueous two-component organoalkoxysilane composition
Abstract
The present invention relates to aqueous two-component adhesion
promoter compositions and also to their use in methods of adhesive
bonding or sealing. Additionally it relates to packaging consisting
of the two-component composition and also a pack having two
chambers. The two-component adhesion promoter composition is
composed of a first component K1 comprising at least one
organoalkoxysilane S and at least one anhydrous surfactant T; and
of a second component K2 comprising at least water and at least one
acid, the acid being present in an amount such that, after
components K1 and K2 have been mixed, the resulting mixture is
acidic.
Inventors: |
Sutter; Jolanda; (Oberwil,
CH) ; Huck; Wolf-Rudiger; (Zurich, CH) |
Correspondence
Address: |
Bingham McCutchen LLP
18th Floor
Three Embarcadero Center
San Francisco
CA
94111
US
|
Family ID: |
35695675 |
Appl. No.: |
11/513172 |
Filed: |
August 31, 2006 |
Current U.S.
Class: |
428/448 ;
206/813; 516/55; 524/858 |
Current CPC
Class: |
C09J 5/02 20130101; C08G
77/04 20130101; C08G 77/04 20130101; C09J 4/00 20130101; C09J 4/00
20130101 |
Class at
Publication: |
428/448 ;
516/055; 524/858; 206/813 |
International
Class: |
B32B 9/04 20060101
B32B009/04; B01F 3/08 20060101 B01F003/08 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 2, 2005 |
EP |
05108072.9 |
Claims
1. Aqueous two-component adhesion promoter composition composed of
a first component K1 comprising at least one organoalkoxysilane S
and at least one anhydrous surfactant T; and of a second component
K2 comprising at least water and at least one acid; and the acid
being present in an amount such that after components K1 and K2
have been mixed the resulting mixture gives an acidic reaction.
2. Aqueous two-component adhesion promoter composition according to
claim 1, characterized in that the acid is an organic acid, in
particular a sulphonic acid or carboxylic acid, especially acetic
acid or formic acid.
3. Aqueous two-component adhesion promoter composition according to
claim 2, characterized in that the acid is preferably an aromatic
sulphonic acid, especially p-toluenesulphonic acid or
dodecylbenzylsulphonic acid.
4. Aqueous two-component adhesion promoter composition according to
claim 1, characterized in that the acid is an inorganic acid,
especially an acid having a sulphur atom or phosphorus atom.
5. Aqueous two-component adhesion promoter composition according to
claim 1, characterized in that the acid is present in an amount
such that, after components K1 or K2 have been mixed, the resulting
mixture has a pH of between 3 and 5.
6. Aqueous two-component adhesion promoter composition according to
claim 1, characterized in that the organoalkoxysilane S is an
aminosilane.
7. Aqueous two-component adhesion promoter composition according to
claim 6, characterized in that the aminosilane is an aminosilane of
the formula (I) or a reaction product of an aminosilane of the
formula (I) with a compound containing at least one functional
group which reacts with primary or secondary amino groups ##STR10##
where R.sup.1 is an alkyl group having 1 to 8 C atoms, preferably a
methyl group or an ethyl group, in particular a methyl group;
R.sup.2 is an alkyl group having 1 to 5 C atoms, preferably a
methyl group or an ethyl group or an isopropyl group, in particular
a methyl group or an ethyl group, R.sup.3 is a linear or branched
alkylene group having 1 to 4 C atoms, in particular a propylene
group, R.sup.4 is H or a linear or branched alkylene group having 1
to 10 C atoms or is a substitutent of the formula (II) ##STR11##
R.sup.5 is H or a linear or branched alkylene group having 1 to 10
C atoms or a linear or branched alkylene group having 1 to 10 C
atoms with further heteroatoms, or is a substitutent of the formula
(II) ##STR12## and a is the value 0, 1 or 2, in particular 0 or 1,
preferably 0.
8. Aqueous two-component adhesion promoter composition according to
claim 7, characterized in that aminosilane is selected from the
group comprising aminosilanes of the formula (III), (IV) and (V)
##STR13##
9. Aqueous two-component adhesion promoter composition according to
claim 7, characterized in that the aminosilane is a reaction
product of an aminosilane of the formula (III) or (IV) as described
in claim 8 with a compound containing epoxy groups.
10. Aqueous two-component adhesion promoter composition according
to claim 9, characterized in that the compound containing epoxy
groups is an epoxysilane, in particular an epoxysilane of the
formula (VI) ##STR14##
11. Aqueous two-component adhesion promoter composition according
to claim 7, characterized in that a=0 and R.sup.2 is methyl and
R.sup.5 is propylene.
12. Aqueous two-component adhesion promoter composition according
to claim 1, characterized in that organoalkoxysilane S is an
organoalkoxysilane of the formula (XIV) ##STR15## where R.sup.1' is
an alkyl group having 1 to 8 C atoms, preferably a methyl group or
an ethyl group, in particular a methyl group; R.sup.6' is an alkyl
group having 1 to 5 C atoms, preferably a methyl group or an ethyl
group or an isopropyl group, in particular a methyl group or an
ethyl group, R.sup.3' is a linear or branched alkyl chain having 1
to 20 C atoms which is optionally substituted by an epoxy, or vinyl
or (meth)acrylate group; and a is the value 0, 1 or 2, in
particular 0 or 1, preferably 0.
13. Aqueous two-component adhesion promoter composition according
to claim 1, characterized in that the weight fraction of
organoalkoxysilane S is .gtoreq.40% by weight, based on the weight
of component K1.
14. Aqueous two-component adhesion promoter composition according
to claim 1, characterized in that the weight ratio of
organoalkoxysilane S to anhydrous surfactant T(S:T) has a value of
20:1 to 1:2, in particular 5:1 to 1:2, preferably 3:1 to 2:3.
15. Aqueous two-component adhesion promoter composition according
to claim 1, characterized in that the weight fraction of water is
.gtoreq.60% by weight, based on the weight of component K2.
16. Packaging (6) consisting of a pack (5) which has two chambers
(1, 2) separated from one another by at least one dividing wall
(3); and an aqueous two-component adhesion promoter composition
according to claim 1, the first component K1 being present in the
first chamber (1) and the second component K2 being present in the
second chamber (2).
17. Packaging (6) according to claim 16, characterized in that the
dividing wall (3) is manufactured from a material which ruptures or
tears as a result of the application of pressure.
18. Aqueous composition obtained by mixing components K1 and K2 of
an aqueous two-component adhesion promoter composition according to
claim 1.
19. Use of an aqueous two-component adhesion promoter composition
according to or of an aqueous composition according to claim 18 as
a pre-treatment agent for improving the adhesion of an adhesive or
sealant applied thereto.
20. Method of substrate surface pre-treatment, comprising the steps
of a) mixing components K1 and K2 of a two-component adhesion
promoter composition according to claim 1 b) applying the resulting
mixture to a substrate surface.
21. Method of adhesive bonding or of sealing, comprising the steps
of i) mixing components K1 and K2 of a two-component adhesion
promoter composition according to claim 1 ii) applying the
resulting mixture to a substrate S1 to be bonded or sealed iii)
applying adhesive or sealant to the flashed-off aqueous adhesion
promoter composition located on the substrate S1 iv) contacting the
adhesive or sealant with a second substrate S2; or i') mixing
components K1 and K2 of a two-component adhesion promoter
composition according to claim 1 ii') applying the resulting
mixture to a substrate S1 to be bonded or sealed iii') applying
adhesive or sealant to the surface of a second substrate S2 iv')
contacting the adhesive or sealant with the flashed-off aqueous
adhesion promoter composition located on the substrate S1; or i'')
mixing components K1 and K2 of a two-component adhesion promoter
composition according to claim 1 ii'') applying the resulting
mixture to a substrate S1 to be bonded or sealed iii'') flashing
off the two-component adhesion promoter composition iv'') applying
adhesive or sealant between the surfaces of the substrates S1 and
S2, the second substrate S2 consisting of the same material as or
different material from the substrate S1.
22. Method according to claim 21, characterized in that step iv) or
iv') or iv'') is followed by a step v) of curing of the adhesive or
sealant.
23. Method according to claim 21, characterized in that the
adhesive is a moisture-curing one-component polyurethane
adhesive.
24. Adhesively bonded or sealed article obtained by a method
according to claim 21.
25. Adhesively bonded or sealed article according to claim 24,
characterized in that the article is a means of transport, in
particular a car, or a component for mounting on a means of
transport, in particular a car.
Description
TECHNICAL FIELD
[0001] The present invention pertains to the field of aqueous
two-component organoalkoxysilane compositions and in particular to
the field of aqueous adhesion promoters for improving the adhesion
of adhesives and sealants.
PRIOR ART
[0002] It is known for adhesives and sealants that the adhesion for
certain substrates is difficult to achieve. Such substrates must
therefore be subjected to pre-treatment. One method frequently used
is that of pre-treatment using primers or adhesion promoter
compositions. The use of organoalkoxysilanes, often called just
silanes, for this purpose has been known for a long time. Primers
or tie coats of this kind, however, typically contain large amounts
of solvent. For environmental and workplace safety reasons,
solvent-based pre-treatment agents of this kind are increasingly
losing their desirability. Attempts have therefore been made to
prepare aqueous organoalkoxysilane compositions as primers or
adhesion promoter compositions.
[0003] Organoalkoxysilanes, especially hydrophobic
organoalkoxysilanes, are difficult to mix with water. In numerous
instances there are two phases formed, with turbidities and flocs
apparent at their interface. For a practical adhesion promoter,
however, it is necessary for the adhesion promoter to be
homogeneous.
[0004] It is in the nature of organoalkoxysilanes, however, to
react with water. The alkoxysilane groups undergo hydrolysis with
water to form silanols (Si--OH groups). Silanols can then undergo
condensation to siloxanes (Si--O--Si groups). Such siloxanes,
however, are usually no longer soluble, and undergo precipitation,
leading to unwanted turbidities and precipitates. The storage life
of aqueous organoalkoxysilane compositions is therefore very
short.
[0005] U.S. Pat. No. 6,511,752 B2 discloses an aqueous primer which
has been prepared from an aminotitanate, epoxysilane, and water and
which possesses a long shelf life.
[0006] U.S. Pat. No. 6,294,620 B1 shows an aqueous emulsion primer
which is prepared at a neutral pH in a two-step process in a
high-speed mixer from water-insoluble ethoxysilanes in the presence
of an emulsifier.
[0007] With regard to the preparation of these aqueous primers,
however, there are narrow limits in respect of the
organoalkoxysilane compositions, and/or they are very complicated
to prepare.
SUMMARY OF THE INVENTION
[0008] It is an object of the present invention, therefore, to
provide an aqueous adhesion promoter composition which has broad
usefulness and can be prepared by a simple method.
[0009] Surprisingly it has been found that a two-component adhesion
promoter composition according to Claim 1 solves this problem.
[0010] The two components K1 and K2 in unmixed form are extremely
stable on storage. Component K1 is much less sensitive to moisture
than are typical organoalkoxysilane compositions, and so is well
able to tolerate small amounts of moisture, of the kind which may
come about, for example, as a result of poorly sealed containers or
through the use of containers made from plastics which are known to
be pervious to water diffusion.
[0011] The ready-to-use adhesion promoter composition is produced
by simple shaking of the two components. Accordingly, the
two-component adhesion promoter composition constitutes a
pre-treatment system which is reliable in service, is easy to
employ, and can be prepared and used even by untrained users. A
consequent possibility are packaging forms consisting of a
two-component pack having two chambers separated from one another
by at least one dividing wall, into which the two components of the
aqueous adhesion promoter composition have been packed, such
packaging forms representing, also to the non-expert, a simple and
reliable system of application.
[0012] It has been found, moreover, that, even after it has been
mixed, the adhesion promoter composition can be used for a
relatively long time, typically up to several weeks, without
problems occurring with the adhesion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Exemplary embodiments of the invention are illustrated in
more detail below with reference to the drawings. Across the
various figures, elements that are alike are provided with the same
reference symbols. The direction of forces is indicated by
arrows.
[0014] FIG. 1 shows a cross section through an embodiment P1 having
a rupturable dividing wall,
[0015] FIG. 2 shows a cross section through an embodiment P2 having
a bursting assistant, in particular having a cutting means,
[0016] FIG. 3 shows a cross section through an embodiment P3 having
a seal,
[0017] FIG. 4 shows a cross section through an embodiment P4 having
an extractable dividing wall,
[0018] FIGS. 5-9 show a cross section through preferred embodiments
of P1
[0019] FIG. 10 shows a cross section through preferred embodiments
of P2
[0020] FIG. 11 shows a cross section through preferred embodiments
of P4
[0021] Only the elements important for the direct understanding of
the invention have been shown. Movements and pressures are
indicated by arrows.
WAYS OF PERFORMING THE INVENTION
[0022] The present invention relates to an aqueous two-component
adhesion promoter composition composed of a first component K1 and
of a second component K2. The first component K1 in this
composition comprises at least one organoalkoxysilane S and at
least one anhydrous surfactant T. The second component K2 comprises
at least water and at least one acid. It is essential that the
amount of acid be selected such that, after the two components K1
and K2 have been mixed, the resulting mixture is acidic. This means
that the pH of such a mixture is less than 7. The preferred pH of
such a mixture is between 3 and 5, in particular between 3.5 to
4.5.
[0023] The term "anhydrous" in the present document should not be
interpreted to mean "absolutely free of water". Consequently,
compounds and compositions are referred to as "anhydrous" even if
they include slight traces of water, i.e. if they include a
residual water content of not more than 1% by weight, in particular
of not more than 0.5% by weight.
[0024] The term "organoalkoxysilane" or "silane" for short refers
in the present document to compounds in which on the one hand there
is at least one, usually two or three, alkoxy groups attached
directly to the silicon atom (via an Si--O bond) and which, on the
other hand, have at least one organic radical attached directly to
the silicon atom (via an Si--C bond) and which do not have
Si--O--Si bonds. Correspondingly, the term "silane group"
identifies the silicon-containing group that is attached to the
organic radical of the organoalkoxysilane. The organoalkoxysilanes,
respectively their silane groups, have the capacity to undergo
hydrolysis on contact with moisture. This hydrolysis forms
organosilanols, which are organosilicon compounds containing one or
more silanol groups (Si--OH groups) and, as a result of subsequent
condensation reactions, organosiloxanes are formed, which are
organosilicon compounds containing one or more siloxane groups
(Si--O--Si groups).
[0025] Terms such as "aminosilane", "epoxysilane", "alkylsilane",
"(meth)acrylatosilane" and "mercaptosilane" refer to silanes which
contain the corresponding functional group, in this case, in other
words, an aminoalkylalkoxysilane, epoxyalkylalkoxysilane,
alkylalkoxysilane, (meth)acrylatoalkoxysilane and
mercaptoalkylalkoxysilane.
[0026] Organoalkoxysilanes S are, in particular, aminosilanes,
epoxysilanes, mercaptosilanes, (meth)acrylatosilanes and
alkylsilanes.
[0027] Aminosilanes are, in particular, aminosilanes of the formula
(I) or the reaction products of the formula (I) containing at least
one secondary or primary amino group with a compound (ARV) which
contains at least one functional group that is able to react with a
primary or secondary amino group. ##STR1##
[0028] In this formula R.sup.1 is an alkyl group having 1 to 8 C
atoms, preferably a methyl group or an ethyl group. R.sup.1 is
preferably a methyl group.
[0029] Additionally, R.sup.2 is an alkyl group having 1 to 5 C
atoms, preferably a methyl group or an ethyl group or an isopropyl
group. R.sup.2 is preferably a methyl group or an ethyl group.
[0030] Additionally, R.sup.3 is a linear or branched alkylene group
having 1 to 4 C atoms. R.sup.3 is preferably a propylene group.
[0031] Additionally, R.sup.4 is H or a linear or branched alkylene
group having 1 to 10 C atoms or is a substitutent of the formula
(II) ##STR2##
[0032] Additionally, R.sup.5 is H or a linear or branched alkylene
group having 1 to 10 C atoms or a linear or branched alkylene group
having 1 to 10 C atoms with further heteroatoms, or is a
substitutent of the formula (II) ##STR3##
[0033] A particularly advantageous radical of a linear alkylene
group having 1 to 10 C atoms with further heteroatoms, R.sup.5, is
the radical CH.sub.2CH.sub.2NH.sub.2.
[0034] Finally, the index a is a value 0, 1 or 2, in particular 0
or 1. Preferably a is 0.
[0035] Examples of aminosilanes of this kind of the formula (I) are
3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane,
3-amino-2-methylpropyltrimethoxysilane,
4-aminobutyltrimethoxysilane, 4-aminobutyldimethoxymethylsilane,
4-amino-3-methylbutyltrimethoxysilane,
4-amino-3,3-dimethylbutyltrimethoxysilane,
4-amino-3,3-dimethylbutyldimethoxymethylsilane,
2-aminoethyltrimethoxysilane, 2-aminoethyldimethoxymethylsilane,
aminomethyltrimethoxysilane, aminomethyldimethoxymethylsilane,
aminomethylmethoxydimethylsilane,
N-methyl-3-aminopropyltrimethoxysilane,
N-ethyl-3-aminopropyltrimethoxysilane,
N-butyl-3-aminopropyltrimethoxysilane,
N-cyclohexyl-3-aminopropyltrimethoxysilane,
N-phenyl-3-aminopropyltrimethoxysilane,
N-methyl-3-amino-2-methylpropyltrimethoxysilane,
N-ethyl-3-amino-2-methylpropyltrimethoxysilane,
N-ethyl-3-aminopropyldimethoxymethylsilane,
N-phenyl-4-aminobutyltrimethoxysilane,
N-phenylaminomethyldimethoxymethylsilane,
N-cyclohexylaminomethyldimethoxymethylsilane,
N-methylaminomethyldimethoxymethylsilane,
N-ethylaminomethyldimethoxymethylsilane,
N-propylaminomethyldimethoxymethylsilane,
N-butylaminomethyldimethoxymethylsilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
bis(trimethoxysilylpropyl)amine, tris(trimethoxysilylpropyl)amine,
and also their analogues with ethoxy or isopropoxy groups instead
of the methoxy groups on the silicon.
[0036] Preferred aminosilanes of the formula (I) are aminosilanes
which are selected from the group comprising aminosilanes of the
formula (III), (IV) and (V). ##STR4##
[0037] The most preferred aminosilanes of the formula (I) are the
aminosilanes 3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane,
bis(trimethoxysilylpropyl)amine and
tris(trimethoxysilylpropyl)amine.
[0038] In one embodiment the aminosilane is a reaction product of
an aminosilane of the formula (I) as has been described above,
having at least one secondary or primary amino group, with a
compound (ARV) which contains at least one functional group which
is able to react with a primary or secondary amino group.
[0039] This functional group able to react with a primary or
secondary amino group is preferably an epoxy group. Other groups,
however, are also conceivable, such as isocyanate groups or
activated double bonds, for example. Particularly suitable
compounds with epoxy groups are epoxysilanes. Preferred compounds
(ARV) which can react with the aminosilane of the formula (I)
having at least one secondary or primary amino group are
epoxysilanes of the formula (VI) ##STR5##
[0040] R.sup.1' in this formula is an alkyl group having 1 to 8 C
atoms, preferably a methyl group or an ethyl group. R.sup.2' is an
alkyl group having 1 to 5 C atoms. Additionally, R.sup.3' is a
linear or branched alkylene group having 1 to 4 C atoms, and a' is
0, 1 or 2, especially 0 or 1.
[0041] R.sup.1' is in particular a methyl group. R.sup.2' is
preferably a methyl group or an ethyl group or an isopropyl group.
With particular preference R.sup.2' is a methyl group or an ethyl
group. R.sup.3' is preferably propylene. The index a' is preferably
0.
[0042] Examples of epoxysilanes are
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,
3-glycidyloxypropyltriethoxysilane and
3-glycidyloxypropyltrimethoxysilane.
[0043] Preferred epoxysilanes are
3-glycidyloxypropyltriethoxysilane and
3-glycidyloxypropyltrimethoxysilane. The most preferred epoxysilane
is 3-glycidyloxypropyltrimethoxysilane.
[0044] The aminosilane of the formula (I) used for the reaction
product comprises, in addition to
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and
N-(2-aminoethyl)-3-aminopropyltriethoxysilane, preferably
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, in particular,
aminosilanes of the formula (III) or (IV), especially
3-aminopropyltrimethoxysilane, bis(trimethoxysilylpropyl)amine,
3-aminopropyltriethoxysilane and bis(triethoxysilylpropyl)amine.
Preference is given to 3-aminopropyltrimethoxysilane and
bis(trimethoxysilylpropyl)amine.
[0045] In accordance with the stoichiometry of the aminosilane of
the formula (I) and of the amine-reactive compound (ARV) it is
possible for the reaction product still to have primary or
secondary amino groups or not.
[0046] Examples of such reaction products are compounds of the
formula (VII), (VIII), (IX), (X), (XI) and (XII).
[0047] The compounds of the formula (VII), (VIII) and (IX) are
obtained from the reaction of
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and
3-glycidyloxypropyltrimethoxysilane. ##STR6##
[0048] The compounds of the formulae (X) and (XI) are obtained from
the reaction of 3-aminopropyltrimethoxysilane and
3-glycidyloxypropyltrimethoxysilane. ##STR7##
[0049] The compound of the formula (XII) is obtained from the
reaction of bis(trimethoxysilylpropyl)amine and
3-glycidyloxypropyltrimethoxysilane. ##STR8##
[0050] Examples of amine-reactive compounds (ARV) having activated
double bonds are, for example, .alpha.,.beta.-unsaturated
compounds, especially maleic diesters, fumaric diesters, citraconic
diesters, acrylic esters, methacrylic esters, cinnamic esters,
itaconic diesters, vinylphosphonic diesters, vinylsulphonic aryl
esters, vinyl sulphones, vinyl nitriles, 1-nitroethylenes or
Knoevenagel condensation products such as those, for example, of
malonic diesters and aldehydes such as formaldehyde, acetaldehyde
or benzaldehyde. Amine-reactive compounds of this kind form Michael
adducts for which the amine undergoes addition to the double bond.
Examples of reaction products of this kind are Michael adducts of
3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane,
4-amino-3,3-dimethylbutyltrimethoxysilane,
4-amino-3,3-dimethylbutyldimethoxymethylsilane,
aminomethyltrimethoxysilane or aminomethyldimethoxymethylsilane
with dimethyl, diethyl or dibutyl maleate, tetrahydrofurfuryl,
isobornyl, hexyl, lauryl, stearyl, 2-hydroxyethyl or
3-hydroxypropyl acrylate, dimethyl, diethyl or dibutyl phosphonate,
acrylonitrile, 2-pentenenitrile, fumaronitrile or
.beta.-nitrostyrene, and also the analogues of the aforementioned
aminosilanes with ethoxy groups instead of the methoxy groups on
the silicon. Mention should be made in particular of the Michael
adduct diethyl N-(3-trimethoxysilylpropyl)aminosuccinate.
[0051] Examples of amine-reactive compounds (ARV) having isocyanate
groups are isocyanatosilanes or polyisocyanates. Particular
isocyanatosilanes are 3-isocyanatopropyltrimethoxysilane and
3-isocyanatopropyltriethoxysilane. Examples of polyisocyanates are
tolylene 2,4- and 2,6-diisocyanate (TDI) and any desired mixtures
of these isomers, diphenylmethane 4,4'-, 2,4'- and
2,2'-diisocyanate (MDI) and any desired mixtures of these and
further isomers, phenylene 1,3- and 1,4-diisocyanate,
2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, hexamethylene
1,6-diisocyanate (HDI), 2-methylpentamethylene 1,5-diisocyanate,
2,2,4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI),
dodecamethylene 1,12-diisocyanate, cyclohexane 1,3- and
1,4-diisocyanate and any desired mixtures of these isomers,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
(isophorone diisocyanate or IPDI), perhydrodiphenylmethane 2,4'-
and 4,4'-diisocyanate (HMDI),
1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), xylylene m-
and p-diisocyanate (XDI), tetramethylxylylene 1,3- and
1,4-diisocyanate (TMXDI), 1,3- and
1,4-bis(isocyanatomethyl)cyclohexane, oligomers of the
aforementioned polyisocyanates, and also any desired mixtures of
the aforementioned polyisocyanates. Preference is given to MDI,
TDI, HDI and IPDI, and also to their biurets or isocyanurates.
[0052] If the organoalkoxysilane S is an epoxysilane then the
preferred epoxysilanes are those as described above as
amine-reactive compounds (ARV).
[0053] Exemplary mercaptosilanes as organoalkoxysilane S are
3-mercaptopropyltrimethoxysilane and
3-mercaptopropyltriethoxysilane.
[0054] Exemplary (meth)acrylatosilanes as organoalkoxysilane S are
3-methacryloyloxypropyltrimethoxysilane and
3-methacryloyloxypropyltriethoxysilane.
[0055] If the organoalkoxysilane S is an alkylsilane, mention is to
be made in particular of the silanes with C.sub.1-C.sub.6 alkyl
radicals, such as, for example, methyltrimethoxysilane,
ethyltrimethoxysilane and butyltrimethoxysilane.
[0056] As surfactants T it is possible to use natural or synthetic
substances which in solutions lower the surface tension of the
water or other liquids. As surfactants, also called wetting agents,
it is possible to use anionic, cationic, nonionic or ampholytic
surfactants or mixtures thereof.
[0057] Examples of anionic surfactants are surfactants containing
carboxylate, sulphate, phosphate or sulphonate groups, such as, for
example, amine acid derivatives, fatty alcohol ether sulphates,
fatty alcohol sulphates, soaps, alkylphenol ethoxylates, fatty
alcohol ethoxylates, and also alkanesulphonates, olefinsulphonates
or alkyl phosphates.
[0058] The non-ionic surfactants include, for example, ethoxylates,
such as ethoxylated adducts of alcohols, such as polyoxyalkylene
polyols, amines, fatty acids, fatty acid amides, alkylphenols,
ethanolamides, fatty amines, polysiloxanes or fatty acid esters,
and also alkyl or alkylphenyl polyglycol ethers, such as fatty
alcohol polyglycol ethers, or fatty acid amides, alkylglycosides,
sugar esters, sorbitan esters, polysorbates or trialkylamine
oxides, and also esters and amides of poly(meth)acrylic acids with
polyalkylene glycols or aminopolyalkylene glycols, which may be
capped with alkyl groups at no more than one end.
[0059] Examples of cationic surfactants are quaternary ammonium or
phosphonium compounds, such as tetraalkylammonium salts,
N,N-dialkylimidazoline compounds, dimethyldistearylammonium
compounds, or N-alkylpyridine compounds, especially ammonium
chlorides.
[0060] The ampholytic or amphoteric surfactants include amphoteric
electrolytes, known as ampholytes, such as aminocarboxylic acids,
for example, and betaines.
[0061] Surfactants of this kind are widely available
commercially.
[0062] Particularly suitable are nonionic surfactants, especially
alkoxylated alcohols. Compounds which have been found to be
particularly suitable include alkoxylated nonionic
fluorosurfactants, especially Zonyl.RTM. FSO-100, which is
available commercially from ABCR, Germany, and alkoxylated alcohols
or alkoxylated alkylphenols, especially Antarox FM 33, which is
available commercially from Rhodia.
[0063] In order to ensure good stability of component K1 on storage
it is necessary for the surfactant to be anhydrous, since the
introduction of substantial amounts of water by the surfactant can
lead to premature hydrolysis of the silanes and hence to storage
problems. With regard to the understanding of the term "anhydrous",
refer to the definition above.
[0064] In order to maximize the stability of component K1 on
storage it is of advantage if the proportion of organoalkoxysilane
S to surfactant T is maintained within a defined ratio. If the
ratio S:T is greater than 5:1, the sensitivity to water is not
substantially improved. If this ratio is less than 1:2, in
particular less than 2:3, the adhesion of the aqueous adhesion
promoter composition is influenced increasingly negatively.
[0065] In order to ensure effective and rapid mixing of components
K1 and K2 it is also possible to use higher ratios of S:T than 5:1,
in those cases in which an increase in the storage stability of
component K1 is not needed or wanted. In that case ratios of
organoalkoxysilane S to surfactant T (S:T) of between 20:1 to 1:2
are possible.
[0066] Preferably the ratio of organoalkoxysilane S to surfactant T
(S:T) is between 5:1 and 1:2.
[0067] The optimum ratio of organoalkoxysilane S to surfactant T
amounts, in particular for aminosilanes as organoalkoxysilane S, to
a value of 3:1 to 2:3.
[0068] It is preferred for component K1 to contain not less than
33% by weight, in particular not less than 40% by weight, of
organoalkoxysilane S.
[0069] Component K1 may comprise further constituents. Examples of
such additions are solvents, inorganic fillers, catalysts and
stabilizers, dyes or pigments.
[0070] If further constituents of this kind are used, it is
preferred for component K1 not to contain more than 1% by weight,
in particular not more than 0.5% by weight, of water.
[0071] Preference is given to components K1 which are composed
essentially only of organoalkoxysilane S and surfactant T. By
"essentially" is meant in this context that the weight total of
organoalkoxysilane S and surfactant T is more than 90% by weight,
in particular more than 95% by weight, preferably more than 99% by
weight, based on the weight of component K1.
[0072] Since especially polar organoalkoxysilanes, in particular
those which are water-soluble, are more sensitive to water in terms
of stability on storage, the improvements which can be achieved by
virtue of the present invention are manifested in particular with
regard to polar, especially water-soluble, organoalkoxysilanes S.
This is the reason why very apolar organoalkoxysilanes S, such as
higher alkylalkoxysilanes, for example, such as
dodecyltrimethoxysilane or octadecyltrimethoxysilane, are not
preferred as organoalkoxysilanes S. The improvement in stability on
storage with respect to water is particularly significant in the
case of aminosilanes as organoalkoxysilanes S.
[0073] The components K1, particularly if they contain aminosilanes
as organoalkoxysilanes S, are significantly less sensitive to the
effect of water during the storage period. This is manifested in
particular when water, especially in the form of atmospheric
moisture, may come into contact with component K1. Reasons for such
contact may be, for example, packs which are not impervious. Thus
in practice it may well be the case that original packs, for
example, are not impervious, or that a storage container is poorly
or unimperviously resealed after having been opened for the first
time, or that the said container is completely unsealed and exposed
to the environment for a certain time. Finally, the storage
stability of components K1 can be increased sharply if they are
stored in vessels made of plastic. The plastics typically used for
plastic containers, such as polyethylene or polypropylene, indeed,
frequently exhibit an inadequate water vapour diffusion
imperviousness. Silane compositions of the prior art are therefore
stored not in plastic containers but instead in containers made of
glass, metals or composites. Through the possibility of the use of
plastic containers for storage of the components K1 presented here,
there are therefore enormous cost advantages and weight advantages
arising, and also additional freedoms in the design and form of the
pack or packaging respectively.
[0074] The improved storage properties and/or reduced sensitivity
to water during the storage time are apparent in particular through
the absence, or at least severe retardation, of the formation of
precipitations or turbidities or gels, without adverse affect on
the adhesion promotion properties.
[0075] Component K2 contains besides water at least one acid. The
acid may be organic or inorganic. Organic acids are firstly
carboxylic acids, in particular a carboxylic acid selected from the
group comprising formic, acetic, propionic, trifluoroacetic,
oxalic, malonic, succinic, maleic, fumaric and citric acid and also
amino acids, especially aspartic acid and glutamic acid. Preferred
acids are those having a pK.sub.a of between 4.0 and 5. Acids of
this kind, on account of their pK.sub.a, possess an excellent
buffer effect in the pH range of 3.5 to 4.5 that is optimum for the
present invention and that results when components K1 and K2 are
mixed. By pK.sub.a is meant by the chemist, as is known, the
negative decadic logarithm of the acid dissociation constant
K.sub.a: PK.sub.a=-log.sub.10K.sub.a.
[0076] Acetic acid is a preferred carboxylic acid.
[0077] Organic acids are secondly, in particular, those acids which
contain a sulphur atom or a phosphorus atom. Organic acids of this
kind are, in particular, organic sulphonic acids. By organic
sulphonic acids are meant compounds which contain an organic
radical containing carbon atoms and also contain at least one
functional group --SO.sub.3H.
[0078] The aromatic sulphonic acid may be monocyclic or polycyclic
and there may be one or more sulphonic acid groups present.
Possible examples include 1- or 2-naphthalenesulphonic acid,
1,5-naphthalenedisulphonic acid, benzenesulphonic acid or
alkylbenzenesulphonic acids.
[0079] Preferred aromatic acids are those which have the formula
(XIII) ##STR9##
[0080] R in this formula is an alkyl radical having 1 to 18 atoms.
Preferably R is a methyl or dodecyl group, in particular a dodecyl
group.
[0081] The acid may also be an inorganic acid. Acids which have
been found particularly suitable as inorganic acids are those which
contain a sulphur atom or a phosphorus atom.
[0082] Acids containing phosphorus atoms are, in particular,
phosphoric acid, phosphorous acid, phosphonic acid and phosphonous
acid.
[0083] Acids containing sulphur atoms are, in particular, sulphur
acids, especially sulphuric acid, sulphurous acids, persulphuric
acid, disulphuric acid (pyrosulphuric acid), disulphurous acid,
dithionic acid, dithionous acid, thiosulphuric acid or
thiosulphurous acid.
[0084] It has been found that effective adhesion to paints,
particularly to automotive topcoats, can be achieved if the acid
contains at least one sulphur atom and has a PK.sub.a of less than
2.
[0085] Component K2 may comprise further constituents. Examples of
such additions are solvents, inorganic fillers, catalysts and
stabilizers, dyes or pigments.
[0086] The weight fraction of the water is preferably at least 60%
by weight, based on the weight of component K2.
[0087] It is preferred for component K2 to be composed essentially
of water and acid, in other words for the amount of water and acid
together to be more than 90% by weight, in particular more than 95%
by weight, preferably more than 99% by weight, based on the weight
of component K2.
[0088] The amount of acid in the component is to be such that a
mixture of components K1 and K2 is acidic and that its pH is
preferably between 3 and 5, in particular between 3.5 to 4.5.
[0089] This needs to be borne in mind if component K1 includes
basic constituents, particularly if component K1 includes
aminosilanes.
[0090] Apart from one another, components K1 and K2 can be stored
for a very long time. For the application of the aqueous adhesion
promoter compositions, components K1 and K2 are mixed. It is a
substantial advantage of the present invention that this mixing is
very easy to accomplish.
[0091] If component K1 is added to component K2, the two components
mix spontaneously or after gentle stirring. This is in stark
contrast to those cases, not in accordance with the invention, in
which organoalkoxysilanes without surfactants are added to
component K1. Because of the difference in density, in that case
the majority of organoalkoxysilanes fall to the bottom, producing a
two-phase system which can be homogenized only by means of intense
high-speed mixing or dispersing. In many cases, moreover, in the
course of addition or at the phase boundary, precipitations or
turbidities are produced which lead to an inhomogeneous product and
are unwanted.
[0092] A further observation which has been made is that, owing to
the use of the surfactant as part of component K1, the amount of
acid that need be used in order to achieve effective miscibility of
the silane component with the water component is less. This results
in a lower odour nuisance from the inherent odour of the carboxylic
acid, as compared with the similar component without
surfactant.
[0093] The mixing of the components allows the hydrolysis of the
organoalkoxysilanes S. Application of the mixed components
preferably takes place not immediately after mixing. It is of
advantage to allow a short time to elapse, typically of between one
and ten minutes, before the mixture is applied to a substrate
surface.
[0094] The desire is for the hydrolysis of the organoalkoxysilanes
S to take place as quickly as possible after mixing but for the
condensation to siloxanes to be retarded as much as possible.
[0095] In order to achieve rapid hydrolysis of the
organoalkoxysilanes S, methoxysilanes (R.sup.2 or
R.sup.2'=--CH.sub.3) are preferred over ethoxysilanes (R.sup.2 or
R.sup.2'=--CH.sub.2CH.sub.3).
[0096] There are in principle the three different ways of achieving
an adhesive bond or a seal.
[0097] In a first method, after components K1 and K2 of a
two-component adhesion promoter composition have been mixed, the
mixture thus obtained is applied to a substrate S1 to be bonded or
sealed. Subsequently an adhesive or sealant is applied to the
flashed-off aqueous adhesion promoter composition which is located
on the substrate S1. Thereafter the adhesive or sealant is
contacted with a second substrate S2.
[0098] In a second method, after components K1 and K2 of a
two-component adhesion promoter composition have been mixed, the
mixture thus obtained is applied to a substrate S1 to be bonded or
sealed. Subsequently an adhesive or sealant is applied to the
surface of a second substrate S2. Thereafter the adhesive or
sealant is contacted with the flashed-off aqueous adhesion promoter
composition which is located on the substrate S1.
[0099] In a third method, after components K1 and K2 of a
two-component adhesion promoter composition have been mixed, the
mixture thus obtained is applied to a substrate S1 to be bonded or
sealed. After the two-component adhesion promoter composition has
been flashed-off, the adhesive or sealant is applied between the
surfaces of the substrates S1 and S2.
[0100] In all three of these methods the second substrate S2 may
consist of the same material as or a different material from the
substrate S1.
[0101] The flashing-off of the aqueous adhesion promoter
composition applied to the substrate surface makes it possible on
the one hand for a major part of the water present on the substrate
surface to evaporate and on the other hand for the
organoalkoxysilanes, or their silanols, to undergo crosslinking
with one another and/or with the surface. The flash-off time is
typically about 10 to 15 minutes.
[0102] The application of the mixed aqueous adhesion promoter
composition is accomplished by spraying, spreading, rolling or
dipping. Typically the mixed aqueous adhesion promoter composition
is applied by brush, cloth or felt.
[0103] In order to achieve a bonded or sealed assembly, in all
three of these methods, the last of the specified steps is followed
by a step of curing of the adhesive or sealant.
[0104] A variety of adhesives or sealants can be used. Depending on
the use and location of deployment of the bonded or sealed body,
the adhesive or sealant may be epoxy resin-based, isocyanate-based,
based on (meth)acrylates or on silane-terminated polymers (STPs),
particularly silane-terminated polyurethanes or silicones. The
adhesives or sealants in question may, for example, be
room-temperature-curing adhesives or sealants, hotmelt adhesives,
dispersion adhesives or sealants, or pressure-sensitive
adhesives.
[0105] The adhesive or sealant may be one-component or
multicomponent. Preferably the adhesive or sealant is
one-component.
[0106] With maximum preference the adhesive is a moisture-curing
one-component polyurethane adhesive or sealant, in particular a
moisture-curing one-component polyurethane adhesive of the kind
available commercially, for example, as Sikaflex.RTM. from Sika
Schweiz AG.
[0107] The bonded or sealed articles obtained in this way are of
diverse nature. In particular they come from the field of
industrial manufacture, and are preferably means of transport,
especially cars. They may also be components for mounting. Mounting
components of this kind are, in particular, prefabricated modular
components which are used as modules on the production line and in
particular are attached or installed by adhesive bonding. These
prefabricated components for mounting are preferably employed in
the construction of means of transport.
[0108] Examples of a mounting component of this kind are the
driver's cab of vans or trucks or locomotives, or sliding roofs for
cars.
[0109] Also possible, however, are applications in the construction
of furniture, white goods, such as washing machines, architectural
components such as facings, or lifts.
[0110] Components K1 and K2 may be stored in two spatially separate
containers or are part of a packaging form.
[0111] A packaging form 6 of this kind is composed of a pack 5
which has two chambers 1, 2 separated from one another by at least
one dividing wall 3, and an aqueous two-component adhesion promoter
composition as described above, the first component K1 being
present in the first chamber and the second component K2 being
present in the second chamber 2.
[0112] The possible and preferred embodiments of the chambers and
also of the dividing walls are described schematically below.
[0113] FIG. 1 shows an embodiment P1 of a packaging form 6,
respectively a pack 5 that is used. In this embodiment the dividing
wall 3 is manufactured from a fragile material. FIG. 1a shows a
variant in which the first chamber 1 is not completely surrounded
by the second chamber 2, while FIG. 1b describes a variant in which
the first chamber 1 is completely surrounded by the second chamber
2. The dividing wall 3 between the two chambers ruptures on
application of pressure, as a result of which the two components
K1, K2 can come into contact with one another, mix and/or react.
The pressure is typically generated externally by the action of
force on the outer wall 4, 4' of the chambers. This action of force
is preferably an impact action or bending of the pack. The material
of the dividing wall 3 is typically produced from glass, aluminium,
an aluminium alloy, from a thin plastic or a composite material.
The dividing wall 3 must be manufactured in a thickness such that
it does not rupture simply as a result of the unintended action of
force, of the kind which typically occurs, for example, in the
course of transport. The outer wall 4, 4' must be of a design such
that it does not rupture or tear when the pressure that leads to
the rupture of the dividing wall 3 is applied. The outer wall 4, 4'
is manufactured either from a metal or from an elastic plastic.
[0114] FIG. 2 shows an embodiment P2 of a packaging form 6,
respectively a pack 5 that is used, with bursting means, especially
cutting means 7. In this embodiment the pressure is applied to the
dividing wall 3 by means of a cutting means 7. Either the cutting
means 7 is mobile and is pressed onto the stationary dividing wall
3, or else the cutting means 7 is fixed and the dividing wall 3 is
pressed onto the cutting means 7. As a result of the pressure the
wall 3 tears, so that the two components K1, K2 can come into
contact with another and/or react with one another. In the storage
state of the packaging form, the cutting means 7 is preferably at a
certain distance from the dividing wall 3. Cutting means 7 and
dividing wall 3 can be displaced onto one another. This is
accomplished either by application of pressure and hence by a
deformation of the outer wall 4, 4', or by means of a thread. The
outer wall 4, 4' must be of such a design that it does not rupture
or tear itself when the pressure that leads to the collapse of the
dividing wall 3 by means of cutting means 7 is applied. The outer
wall 4, 4' is manufactured either of a metal foil or of an elastic
plastic. The nature of the cutting means may in principle take very
different forms. Thus FIG. 2a) shows a sharp point as cutting means
7, whereas FIG. 2b shows a ball as a bursting assistant, in
particular cutting means, 7. The cutting means 8 preferably has
either points or edges. Such points or edges facilitate the
severing of the dividing wall 3. Therefore an embodiment according
to FIG. 2a is preferred.
[0115] FIG. 3 shows an embodiment P3 of a packaging form 6,
respectively a pack 5 that is used. In this embodiment the dividing
wall is realised by a seal 3'. In the unopened state of the pack 5,
the seal 3' separates the two chambers 1, 2 from one another. This
is achieved by virtue of the fact that, in the unopened state, the
seal 3' is squeezed by at least two wall sections 8, 8' of the
outer wall 4, 4'. At least one of the wall sections 8, 8' is
designed so that it can be moved by external influence. Such
mobility is achieved in particular by way of a thread 9, 9'. In the
case of desired opening, the wall section 8, 8' is removed from the
squeezed seal 3', which as a result loses its sealing function and
opens a passage, so that the two components K1, K2 can come into
contact and/or react with one another. In one particular variant of
this embodiment, when the packaging form is opened or shaken, the
seal 3' becomes so loose that it falls into one chamber.
[0116] The seal 3' is manufactured from an elastic material of the
kind typically used for the sealing of liquids.
[0117] FIG. 3a) shows a version with a thread 9, whereas FIG. 3b)
has two threads 9, 9'. FIG. 3b) is advantageous over 3a) because in
a first step the first chamber can be filled with a component K1 or
K2, after which the seal 3' can be screwed on via a thread 9 and
hence tightly sealed via the wall section 8, and only at a later
point in time can this part, which has the function of a lid, be
screwed onto the second part of the packaging form, with the other
component, K2 or K1, with the second thread 9', and hence the
second chamber as well can be closed off tightly via the wall
section 8'.
[0118] FIG. 4 shows an embodiment P4 of a packaging form 6,
respectively a pack 5 that is used. In this embodiment the dividing
wall 3 is of extractable design. In this case, between the
chambers, there is a thin dividing wall 3 which is extracted by
means of external intervention, so that the two components K1, K2
can come into contact and/or react with one another. The connecting
points in the region where the dividing wall is connected to the
inside wall of the chambers 1, 2 have predetermined breakage points
for this purpose. Particularly suitable for extraction are
embodiments for which the dividing wall 3 is connected to a tearing
tab 16. FIG. 4a) shows a version in which only the dividing wall 3
is connected to the inside walls of the chambers 1, 2. For this
purpose, the connecting points in the region where the dividing
wall is connected to the inside wall of the chambers 1, 2 has a
predetermined breakage point, in the same way as the region where
the tearing tab 16 is connected to the outer wall. In FIG. 4b),
when the dividing wall is extracted, at the same time the cover 11,
which is connected to the tearing tab 16 and the dividing wall, is
separated from the packaging form as well, thereby producing an
opening 10 through which the two components which have come into
contact with one another can be removed from the pack.
[0119] FIG. 5 shows one preferred embodiment of embodiment P1. In
this embodiment the first chamber 1 containing one component K1 is
composed of a fragile glass or plastic ampoule 3. The second
chamber 2 containing the other component K2 is likewise a fragile
glass or plastic ampoule. The two ampoules are preferably arranged
in a tube-in-tube arrangement or--as depicted--in an
ampoule-in-ampoule arrangement. This ampoule arrangement is
recessed in a receptacle whose outer walls 4 are manufactured from
flexible plastic or cardboard. This plastic receptacle additionally
has an opening 10 which is covered by a porous cover 20, in
particular by a felt strip or a sponge. When the packaging form is
activated, bending of the outer walls 4 or an impact on the outer
walls of the plastic or cardboard receptacle cause the glass
ampoules to break open, so that the components K1, K2 can mix
and/or react. The reaction mixture soaks the felt or foam 20 and
can be applied by contact thereof with a surface. The felt or foam,
additionally, helps to prevent any splinters which may originate
from the broken ampoule from emerging from the packaging form 5, 6.
This embodiment P1 therefore represents a disposable packaging form
for the application of a two-component aqueous adhesion promoter
composition. It is especially suitable for small quantities. This
packaging form is suitable in particular for the pre-treatment of a
sheet of vehicle glazing, in particular a car window or screen.
[0120] FIG. 6 shows a further preferred embodiment of embodiment
P1. In this case a fragile glass or plastic ampoule 3 containing
one component K1 is held in a bottle with a fixing means 14 that
contains the other component K2. FIG. 6a) shows an embodiment with
a horizontal ampoule 3. The ampoule in this case can be broken,
where appropriate, by a rigid means, a metal spatula for example,
so that the components K1, K2 can mix and/or react, or the ampoule
can be made to burst by compression or impact of the bottle. The
rigid means may be introduced through an opening in the bottle.
After the means has been removed, the bottle can where appropriate
be sealed and shaken. FIG. 6b) shows an embodiment with a vertical
ampoule 3. The design of the ampoule is such that it is longer than
the bottle height and protrudes into a fixing means 14 in the lid
12. The lid 12 carries a thread 9 and preferably has a safety tab
13, which prevents the lid 12 being rotated inadvertently. When
activation is desired, the safety tab 13 is removed and the lid 12
is rotated, as a result of which the base of the lid 12 moves
towards the ampoule 3 and places it under pressure for breaking or
tearing, so that the components K1, K2 can mix and/or react. The
lid closure ensures, furthermore, that the bottle is tight and can
be shaken. In both embodiments, according to FIGS. 6a and 6b, it is
preferable to attach a felt or fine net 20 for the application of
the reaction mixture after the components K1, K2 have been mixed,
in order to prevent the emergence from the packaging form of any
splinters which may come from the broken ampoule. It is preferred
to use a felt or a sponge, since a felt or sponge is fully
saturated by the two-component aqueous adhesion promoter
composition and is therefore very suitable for applying said
composition. The felt or sponge is typically connected to a shaped
part which has a thread and can be screwed onto the thread 9 of the
bottle.
[0121] FIG. 7 shows a further preferred embodiment of the
embodiment P1. In this case, in a chamber 1, there is at least one
metal ball as a mixing assistant 17. As a result of shaking, the
dividing wall 3 present between the two chambers is broken or torn
by the ball 17, so that the components K1, K2 can mix and/or react.
As and when required, the ball 17 can be provided with points or
edges in order to facilitate tearing of the dividing wall 3. The
thickness and nature of the dividing wall 3 and also the amount and
surface design of the balls 17 that are used are to be selected
such that the dividing wall 3 can be destroyed by simple shaking of
the packaging form 6, but not unintentionally, such as in the event
of small vibrations as may occur in the course of transport.
Besides the variant shown in FIG. 7a) with dividing wall 3
stretching between the outer walls 4, 4' between the chambers, in
FIG. 7b) a modification of the ampoule 3 shown in FIG. 6 is
depicted, which contains one component.
[0122] FIG. 8 shows a further preferred embodiment of the
embodiment P1. In this embodiment one component K1 is packed in a
chamber 1 which forms a bubble 21. In FIG. 8a the design of the
bubble 21 is such that at its base it is connected to the dividing
wall 3 and at that point has a predetermined breakage point. By
removal of the safety tab 13 it is possible for the lid 12 to be
rotated shut via the thread 9, as a result of which the base of the
lid 12 moves towards the bubble. This squeezes the bubble 21 until
the pressure produced is sufficiently great to rupture the
predetermined breakage point, so that the components K1, K2 can mix
and/or react. This embodiment is suitable in particular for
low-viscosity components K1, K2. However, after the safety tab 13
has been removed, it is also possible to screw off the lid 12 and
to squeeze the bubble 1, 2 manually by hand to press out the
component contained in it. In FIG. 8b) the bubble 21 has a clamp
closure 18. As a result of the squeezing of the wall of the passage
between the chambers 1 and 2, that wall forms the dividing wall 3
which separates the two chambers 1, 2 from one another in the
unopened state. On opening, the lid 12 is first screwed off by
means of thread 9. Subsequently the clamp closure 18 is removed,
thereby opening the passage between the chambers 1 and 2, so that
components K1, K2 can mix and/or react. This may be assisted by the
pressing-out of the bubble 21. In both embodiments, preferably, the
bubble is designed such that it is connected to the wall 8 of the
other chamber 2 in such a way that it can be easily removed in
order to allow, subsequently, the affixing of a felt or a sponge,
in particular by means of the thread 9, to the opening 10 for the
purpose of applying the adhesion promoter composition.
[0123] FIG. 9 shows another preferred embodiment of the embodiment
P1. In this case it takes the form of a bottle 5 or a double-hose
pouch 5, which has two chambers 1, 2, which are separated from one
another by a dividing wall 3 disposed in the lengthwise direction
of the bottle or pouch. The outer walls 4, 4' of the bottle 5 or
pouch 5 are manufactured from a highly elastic material, while the
dividing wall 3 is manufactured either from a rigid material or in
a very thin form. As a result of axial twisting of the bottle 5 or
of the double pouch 5, the dividing wall is very severely stretched
or loaded, so that the dividing wall 3 tears--depicted in FIG.
9'--so that the components K1, K2 can mix and/or react. At its end
the pouch or bottle preferably has a thread 9 with a tightly
closing lid 12. After mixing or shaking has been carried out, this
lid 12 can be opened and the reaction mixture can be applied to a
surface. In addition, with preference, it is possible to screw a
felt onto this thread 9.
[0124] FIG. 10 shows a preferred embodiment of embodiment P2. In
this case one chamber 1 forms a part of the lid 12 of a bottle 5.
FIGS. 10a)-f) show different preferred arrangements in this
context.
[0125] In FIG. 10a) the cutting means 7 are connected to the wall 8
or lie on it, in the form for example of a ring, and are directed
towards the dividing wall 3 of the chamber 1, 2. By removal of the
safety tab 13 it is possible for the lid 12 and hence the chambers
1, 2 to be moved by way of the thread 9', by rotation, towards the
cutting means 7. When the cutting means 7 make contact with the
dividing wall 3, which is manufactured from a severable material,
the wall 3 is cut through, so that the components K1, K2 can mix
and/or react. If the cutting means 7 are arranged excentrically in
relation to the axis of rotation of the lid 12--as shown in FIG.
10a)--then further rotation of the lid produces an incision in the
form of a curve in the dividing wall 3, so that the dividing wall
can be folded away or even cut out, which is very advantageous for
the mixing of components K1, K2.
[0126] In FIG. 10b) a plurality of cutting means 7 are arranged in
distribution over the opening of the bottle. Between the cutting
means there are passages for the component K1, K2 in the chamber 1,
2. This type is typically achieved by means of a perforated plate
or net with points which is directed against the dividing wall, and
which lies on or is connected to the wall 8. By removal of the
safety tab 13 it is possible for the lid 12 and hence the chamber
1, 2 to be moved by way of the thread 9', by means of rotation,
towards the cutting means 7. When the cutting means 7 make contact
with the dividing wall 3, which is manufactured from a severable
material, the wall 3 is cut through, so that the components K1, K2
can mix and/or react. The presence of a plurality of cutting means
7 arranged in this way has the advantage that at the same time the
dividing wall 3 is perforated at a number of locations
simultaneously and hence the dividing wall is efficiently
destroyed.
[0127] In FIG. 10c) the component K1 is packed in different
chambers 1, 1', 1'' which form a part of the lid 12. These chambers
1, 1', 1'' may be filled balls or pouches manufactured from a
severable or rupturable material. Furthermore it is possible in
principle for these chambers 1, 1', 1'' to be able to contain
different components K1, K1', K1''. Thus, for example, it would be
possible to realise three-component or multicomponent adhesion
promoter compositions in such a way, which would not be suitable
for storage with one another or would lead to relatively poor
adhesion promoter properties. A plurality of cutting means 7 are
arranged in distribution over the opening of the bottle. Between
the cutting means there are passages for component K1 in chamber 1.
Typically this kind is achieved by means of a perforated plate or
net which has points and is directed against the dividing wall, and
which lies on or is connected to the wall 8. By removal of the
safety tab 13 it is possible for the lid 12 and hence the chamber 1
to be moved by way of the thread 9', by means of rotation, towards
the cutting means 7. When the cutting means 7 make contact with the
dividing wall 3 the wall 3 is cut through or ruptured, so that the
components K1, K2 can mix and/or react.
[0128] In FIG. 10d) the component K1 is stored in a chamber 1,
which is manufactured from a severable film and forms a part of the
lid 12. The other chamber 2 is sealed with a dividing wall 3'. In
both chambers cutting means 7 are mounted close to the two dividing
walls 3, 3'. By removal of the safety tab 13 it is possible for the
lid 12 to be rotated by way of the thread 9', as a result of which
the cutting means 7 move towards one another and in this case cut
through the dividing walls 3, 3', so that the components K1, K2 can
mix and/or react. This embodiment possesses the advantage that both
chambers 1 and 2 can be filled with the respective component K1, K2
and can be stored imperviously separately from one another.
[0129] In FIG. 10e) an embodiment is shown in which one chamber 1
forms part of the lid 12, which is typically connected to the
bottle with a thread 9, and where the lid has a protective cover 19
which can be folded open. Situated beneath this protective cover is
one chamber 1. This chamber is manufactured from a deformable and
severable material, a polymeric film, a metal foil or a composite
sheet, for example. Mounted on the inside of the chamber, on the
side facing the protective cover, is a cutting means 7. This part
of the chamber typically has a convexity towards the outside. When
mixing is desired, the protective cover 19 is folded open--depicted
in FIG. 10e')--and pressure is subsequently applied to the
convexity, as a result of which the cutting means 7 is pressed onto
the dividing walls 3, 3', so that these walls tear and the
components K1, K2 can mix and/or react.
[0130] The embodiment described in FIG. 10f) is very similar to
that of FIG. 10e) with the cover. In this case one chamber 1 is
part of the lid 12. The chamber is manufactured from a severable
material. The other chamber 2 is closed off by a dividing wall 3,
which is likewise manufactured from a severable material. In the
unopened state the two walls 3, 3' which delimit the two chambers
1, 2 are arranged very close, preferably in contact with one
another. By removal of the safety tab 13 and rotation of the lid 12
it is possible for the said lid, together with the chamber 1, 2 and
also the cutting means 7, by way of the thread 9', to be moved
towards the dividing wall 3. When cutting means 7 come into contact
with the dividing walls 3, these walls are cut through, so that the
components K1, K2 can mix and/or react. This embodiment as well
possesses the advantage that both chambers 1 and 2 can be filled
with the respective component K1, K2 and stored imperviously
separately from one another.
[0131] FIG. 11 shows a preferred embodiment of embodiment P4. In
this case the two chambers 1, 2 are separated from one another by
an extractable dividing wall. In FIG. 11a) this dividing wall 3 is
connected, additionally, to wall 8 and 8', respectively, of the
respective chamber 1, 2, and so forms a cover 11 to the opening 10.
On extraction, first of all the cover 11 is opened by means of a
tab 16. Thereafter the dividing wall 3 is extracted by means of the
predetermined breakage points, which are located at the points
where the dividing wall is connected to the inside wall of the
chambers 1, 2, so that the components K1, K2 can mix and/or react.
The lid can then be screwed on again and shaking, for example, can
take place. Furthermore, for the purpose of application, a felt or
sponge can be mounted on the opening 10; in particular it can be
screwed on by means of the thread 9.
[0132] In FIG. 11b) the extractable dividing wall 3 is designed in
such a way that it has a tearing tab 16 at the base of the chambers
1, 2. This tearing tab 16 is connected, furthermore, to the cover
11 which closes the opening 10 of the bottle. After the lid 12 has
been removed the cover 11 can be removed and then it is possible to
pull on the tearing tab 16 or directly on the tab 16, so that the
dividing wall 3 detaches from the bottom, by peeling, from the
inside walls of the chambers, at the predetermined breakage points,
so that the components K1, K2 can mix and/or react. The dividing
wall can be produced, for example, by lightly welding a film tape
to the inside wall of a bottle. The tearing tab 16 is typically the
rest of this film tape.
[0133] In all of the figures the first component K1 can be present
in the first chamber 1 and the second component K2 can be present
in the second chamber 2 or else the first component K1 can be
present in the second chamber 2 and the second component K2 can be
present in the first chamber 1.
[0134] The size of the chambers is preferably such that at least
one chamber 1, 2 has a greater volume than the volume of the
component K1, K2 present within it. With particular preference the
volume not occupied by the said component corresponds at least to
the volume of the other component.
[0135] Moreover, the volume ratio K1/K2 of the first component K1
to the second component K2 is between 1000/1 and 1/1000, in
particular between 200/1 to 10/1 or between 1/200 to 1/10. With
preference the volume ratio K1/K2 is between 200/1 to 20/1 or
between 1/200 to 1/20.
[0136] Although component K1 exhibits improved storage stability,
the walls of the chambers may be composed of one or more materials
which are impervious to diffusion of water in liquid or gaseous
state or at least so impermeable that the desired storage stability
is not adversely affected. Particularly suitable for this purpose
are aluminium or glass or composites. Thus it is possible, for
example, to store component 1 in an aluminium pouch or in a plastic
pouch coated with aluminium. This kind of chamber has the advantage
that the wall can be severed at any point and so does not require
precise positioning of the pouch. Pouches of this kind are suitable
in particular for the embodiments according to FIG. 10.
[0137] The packaging form 6 is produced by filling of the chambers
1 and 2 with the components K1, K2, followed where appropriate by
the assembly of the pack. The packaging form has a good storage
stability, typically of at least 6 months, in particular of at
least 9 months. If the packaging form 6 is to be used to apply an
adhesion promoter, it can be activated specifically. For this
purpose the dividing wall 3 must be removed or severed so that the
components K1, K2 can make contact, mix and/or react. Mixing may be
assisted by shaking. Subsequently the adhesion promoter composition
prepared in this way is removed from the packaging form 6 and
applied to a surface to be bonded or sealed. Depending on the
nature of the selected constituents in components K1 and K2 it may
be necessary to allow a short time, typically less than half an
hour, to elapse between contacting of the two components and
application, in order to achieve an optimum adhesion promoter
effect. Preferably, however, the adhesion promoter composition is
applied immediately. The surface may be composed of very different
material, particular preference being given to glass, glass
ceramics, metals, paints and plastics. Where appropriate it may be
necessary for the surface to be pretreated, prior to application of
the adhesion promoter, by further chemical, physical or
physicochemical methods. For application it is preferred to mount a
porous cover 20, in particular a felt or a sponge, on a packaging
form 6 with opening 10. A porous cover 20 of this kind is typically
affixed to a shaped part which ensures, in the edge region, a
connection with the pack. This connection is achieved preferably by
way of a screw connection via a thread 9. The two-component
adhesion promoter composition is applied in a film thickness of
less than 1 millimetre, typically in a film thickness of less than
100 micrometres. If the adhesion promoter composition comprises
fillers and/or binders, a film thickness between 1 and 100
micrometres, in particular between 1 and 20 micrometres, is
preferred. If the adhesion promoter composition contains no fillers
and no binder, a film thickness is preferred which is between one
molecular monolayer of the compound A and 50 micrometres, in
particular between 2 nanometres and 10 micrometres, in particular
between 10 nanometres and 1 micrometre.
LIST OF REFERENCE SYMBOLS
[0138] K1 first component [0139] K2 second component [0140] 1 first
chamber [0141] 2 second chamber [0142] 3 dividing wall [0143] 3'
seal [0144] 4 outer wall [0145] 4' outer wall [0146] 5 pack [0147]
6 packaging form [0148] 7 cutting means [0149] 8 wall section
[0150] 8' wall section [0151] 9 thread [0152] 9' thread [0153] 10
opening [0154] 11 cover [0155] 12 lid [0156] 13 safety tab [0157]
14 fixing means [0158] 15 mixing assistants [0159] 16 tearing tab
[0160] 17 mixing assistants [0161] 18 clamp closure [0162] 19
protective cover [0163] 20 porous cover [0164] 21 bubble
EXAMPLES
[0165] TABLE-US-00001 TABLE 1 Organoalkoxysilane used. Abbreviation
Organoalkoxysilane A1110 3-aminopropyltrimethoxysilane A1120
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane A1130
3-[2-(2-aminoethylamino)ethylamino]propyl- trimethoxysilane A1170
bis(trimethoxysilylpropyl)amine Dy1122
bis(triethoxysilylpropyl)amine A187
3-glycidyloxypropyltrimethoxysilane GLYEO
3-glycidyloxypropyltriethoxysilane A189
3-mercaptopropyltrimethoxysilane A174
3-methacryloyloxypropyltrimethoxysilane MTMS
methyltrimethoxysilane
[0166] Furthermore, the reaction product RP1 was prepared from
3-glycidyloxypropyltrimethoxysilane and
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, by mixing 1 mol of
A1120 with 3 mol of A187. Immediately after mixing it was possible
to check the conversion by IR. The band at about 910 cm.sup.-1
which is characteristic of the epoxy group can in fact still be
detected immediately after mixing, but rapidly disappears.
TABLE-US-00002 TABLE 2 Surfactants used. Abbreviation Surfactant
Supplier Surfynol Surfynol .RTM. 61 Air Products Soprophor
Soprophor BSU Rhodia, Germany FM33 Antarox FM33 Rhodia, Germany AE
01 EnviroGem .RTM. AE 01 Air Products AE 02 EnviroGem .RTM. AE 02
Air Products Hydropalat 120 Hydropalat .RTM. 120 Cognis, Germany
FSO-100 Zonyl .RTM. FSO-100 ABCR, Germany Byk 333 BYK .RTM.-333
Byk-Chemie GmbH, Germany
[0167] In Table 3 the ratio of organoalkoxysilane to surfactant was
varied. The organoalkoxysilane used was the reaction product RP1
and it was combined with different surfactants.
[0168] In the first reference series Ref.S1 no surfactant was used,
i.e. pure organoalkoxysilane was used.
[0169] The respective surfactant was added to 2.5 g of reaction
product RP1 in a glass vessel (diameter 12 mm, 4 cm high, volume
about 4.5 ml, with plastic screw lid), which beforehand had been
dried in an oven at 200.degree. C. for one day and cooled to room
temperature at 25.degree. C./50% relative humidity. Subsequently
the vessels thus filled were closed with lids and stored in an oven
(Ehret, TK/L 4061) with circulating air at 50.degree. C. Over 30
days the samples were visually inspected daily. Table 2 reports the
stability, specifically by reporting the number of days until the
sample was observed to gel. If the sample was still perfect after
day 30, the value >30 was reported. TABLE-US-00003 TABLE 3
Stability (number of days to gel) of organoalkoxysilane/surfactant
mixtures at 50.degree. C. in a closed vessel. RP1:surfactant [g:g]
1:0 20:1 10:1 5:1 2:1 1:1 1:2 Surfactant Ref. S1 BS1 BS2 BS3 BS4
BS5 BS6 Surfynol 1 1 1 2 >30 >30 >30 Soprophor 1 1 1 1
>10 >30 >30 AE 01 1 1 3 3 10 >30 >30 Hydropalat 120
1 1 1 2 >30 >30 >30 Proportion of S 100 95 91 83 66 50 33
in composition [% by wt.]
[0170] In Table 4, different silanes and different surfactants, in
a mixing ratio S:T of 2.125:1, corresponding to an
organoalkoxysilane S fraction of 68% by weight as a proportion of
the total weight of the overall composition, were mixed as
described above.
[0171] In this series of tests, however, a drill was used to drill
a hole of 1 mm in the lid. The storage and determination of
stability took place as for the experiments of Table 3. The
comparative experimental series Ref.S2 took place without addition
of surfactants, i.e. as pure organoalkoxysilanes. TABLE-US-00004
TABLE 4 Stability (number of days to gel) of organoalkoxysilane/
surfactant mixtures at 50.degree. C. in a vessel with a hole in the
lid. BS7 BS8 E89 Ref. S2 Surfynol AE 01 Hydropalat 120 -- A1130 7 1
6 1 A1170 1 4 1 1 MTMS >30 >30 10 1
[0172] In a further experimental series the storage stabilities of
compositions containing reaction products of aminosilanes and
epoxysilanes with different surfactants were compared.
[0173] In this case the reaction product RP1 already described was
used. In addition a reaction product RP2 was prepared from
3-glycidyloxypropyltrimethoxysilane and
3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, by
mixing 1 mol of A1130 with 6.6 mol of A187.
[0174] In Table 5 RP1 or RP2 was mixed with different surfactants
in a mixing ratio S:T of 2.125:1, corresponding to an
organoalkoxysilane S fraction of 68% by weight as a proportion of
the total weight of the overall composition, as described above. In
this experimental series the vessel with a sealed lid (without a
hole as for Table 4) was stored at 50.degree. C. as already
described in the oven, or at 23.degree. C./50% relative humidity.
The stability was determined as for the experiments of Table 3. The
comparative experimental series Ref.S3 took place without the
addition of surfactants, i.e., as pure organoalkoxysilanes.
TABLE-US-00005 TABLE 5 Stability (number of days to gel) of
organoalkoxysilane/surfactant mixtures at 50.degree. C. and
23.degree. C. in a sealed vessel. RP1 RP2 Surfactant 23.degree. C.
50.degree. C. 23.degree. C. 50.degree. C. BS10 Surfynol >90
>90 >90 >90 BS11 Soprophor 84 >90 84 >90 BS12 FM33
25 >90 74 74 ES13 AE 01 >90 29 >90 1 BS14 AE 02 >90 1
>90 >90 BS15 Hydropalat 120 >40 >40 >40 >40 Ref.
S3 No surfactant 9 1 32 8
[0175] In Table 6 the miscibility of component K1 in component K2
was determined. In this case 0.5 g of the respective mixture of
surfactant/reaction product RP1 was added as component K1 to 25 g
of 1% by weight acetic acid, as component K2 using a pipette. The
assessment reported in Table 6 is made in accordance with the
following code:
"-" formation of drops on the base of the vessel (phase
separation)
"+" the droplets formed initially quickly dissolve (<1
minute)
[0176] "++" spontaneous dissolution during addition TABLE-US-00006
TABLE 6 Miscibility of component K1 and K2. RP1:surfactant [g:g]
1:0 20:1 10:1 5:1 2:1 1:1 1:2 Surfactant Ref. S4 BS16 BS17 BS18
BS19 B820 BS21 Surfynol - - - ++ ++ ++ ++ Soprophor - ++ ++ ++ ++
++ ++ AE 01 - + + + + + + Hydropalat 120 - - - + ++ ++ ++
[0177] Table 7 reports the behaviour of different
organoalkoxysilanes. The evaluation figures are reported
correspondingly to those in Table 6. TABLE-US-00007 TABLE 7
Compositions of aqueous adhesion promoter compositions. Ref. 1 Ref.
2 B1 Ref. 3 Ref. 4 B2 Ref. 5 Ref. 6 B3 Ref. 7 B4 K1 A187 [g] 0.5
0.5 0.33 A189 [g] 0.5 0.5 0.33 A174 [g] 0.5 0.5 0.33 A1170 [g] 0.5
0.33 Surfynol [g] 0.17 0.17 0.17 0.17 K2 H.sub.2O [g] 25.0 24.75
24.75 25.0 24.75 24.75 25.0 24.75 24.75 25.0 24.75 HAc* [g] 0.25
0.25 0.25 0.25 0.25 0.25 0.25 K1 + K2 [g] 25.5 25.5 25.5 25.5 25.5
25.5 25.5 25.5 25.5 25.5 25.5 Solubility - - ++ - - ++ - - ++ - ++
*HAc = acetic acid (100%)
[0178] TABLE-US-00008 TABLE 8 Compositions of aqueous adhesion
promoter compositions. B5 B6 B7 B8 Ref. 8 Ref. 9 K1 A1170 [g] 0.75
Dy1122 [g] 0.75 A187 [g] 0.75 0.75 GLYEO [g] 0.75 0.75 Byk 333 [g]
0.25 0.25 0.25 0.25 0.25 0.25 FSO-100 [g] 0.05 0.05 0.05 0.05 0.05
0.05 K2 HAc* [g] 0.25 0.25 0.25 0.25 Water [g] 48.7 48.7 48.7 48.7
48.95 48.95 K1 + K2 [g] 50 50 50 50 50 50 Solubility ++ ++ ++ ++ -
- *HAc = acetic acid (100%)
[0179] The aqueous adhesion promoter compositions prepared in Table
8 were applied, after the time indicated in Tables 9 and 10 as
hydrolysis time after the mixing of the components K1 and K2, by
means of a cellulose cloth impregnated with them (Tela.RTM. cloth,
Tela-Kimberly Switzerland GmbH), application taking place to float
glass (tin side, Rocholl GmbH, Germany), or to the ceramic edge of
an ESG BMW rear screen from Saint-Gobain Sekurit ("ceramic"). After
a flash-off time of 10 minutes the one-component moisture-curing
polyurethane adhesive Sikaflex.RTM.-250 DM-2 ("DM2") or
SikaTack.RTM.-Move Goes Cool ("MGC"), which both contain
polyurethane prepolymers with isocyanate groups and are available
commercially from Sika Schweiz AG, was applied as a flat triangular
bead using a cartridge press and a nozzle, and cured at 23.degree.
C. and 50% relative humidity (climatic storage "KL") for 7 days.
Thereafter the samples were stored in water at 23.degree. C. for 7
further days (water storage, "WL"), and finally were stored for a
further 7 days at 70.degree. C. and 100% relative humidity (hot wet
storage "CP").
[0180] The adhesion was assessed by means of the bead test.
Adhesion Test ("Bead Test")
[0181] The adhesion of the adhesive was tested by means of the
`bead test`. In this test an incision is made at the end just above
the adhesion face. The incised end of the bead is held with round
pliers and pulled from the substrate. This is done by carefully
rolling up the bead on the tip of the pliers, and placing a cut
vertical to the bead pulling direction down to the bare substrate.
The rate of bead removal is selected so that a cut has to be made
about every 3 seconds. The test length must amount to at least 8
cm. An assessment is made of the adhesive which remains on the
substrate after the bead has been pulled off (cohesive fracture).
The adhesion properties are evaluated by estimation of the cohesive
fracture of the adhesion face: [0182] 1=>95% cohesive fracture
[0183] 2=75-95% cohesive fracture [0184] 3=25-75% cohesive fracture
[0185] 4=<25% cohesive fracture [0186] 5=0% cohesive fracture
(purely adhesive fracture)
[0187] Test results with evaluations of 4 or 5 are considered
inadequate. TABLE-US-00009 TABLE 9 Adhesion of adhesives to aqueous
adhesion promoter compositions after different hydrolysis times on
float glass. Hydrolysis time: 10 min Hydrolysis time: 1 h
Hydrolysis time: 2 h DM-2 MGC DM2 MGC DM-2 MGC KL WL CP KL WL CP KL
WL CP KL WL CP KL WL CP KL WL CP B5 1 1 1 1 2 1 2 2 2 2 2 1 2 1 1 3
3 1 B6 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 B7 2 2 1 2 3 1 2 3 1 2 4
1 1 2 2 1 4 1 B8 2 3 2 3 4 1 1 2 1 3 4 2 1 3 1 1 3 1 Ref. 8 4 4 4 5
5 4 2 2 2 5 5 4 1 1 2 4 5 4 Ref. 9 5 4 4 5 5 4 5 5 4 5 5 4 3 4 4 5
5 4
[0188] TABLE-US-00010 TABLE 10 Adhesion of adhesives to aqueous
adhesion promoter compositions after different hydrolysis times on
ceramic. Hydrolysis time: 10 min Hydrolysis time: 1 h Hydrolysis
time: 2 h DM-2 MGC DM2 MGC DM-2 MGC KL WL CP KL WL CP KL WL CP KL
WL CP KL WL CP KL WL CP B5 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 1 B6 1
1 1 1 1 1 1 1 2 1 1 1 1 1 2 1 1 1 B7 1 1 1 2 2 1 1 1 1 2 2 1 1 1 2
2 2 1 B8 1 2 2 2 2 1 1 1 2 1 2 1 1 1 2 1 1 1 Ref. 8 5 5 5 5 5 4 4 4
5 5 5 4 2 2 2 5 5 3 Ref. 9 5 5 5 5 5 5 5 5 5 5 5 5 5 4 5 5 5 5
[0189] Organoalkoxysilane compositions prepared from A1110 and
different surfactants, in the ratios indicated in Table 11, were
prepared and used as a first component K1 of an aqueous primer. The
second component K2 consisted of water and 1% by weight acetic
acid. 1.05 g of component K1 were introduced into 49 g of component
K2 and the mixture was shaken. This mixture was subsequently
applied to the ceramic edge of a VSG front screen of a Mitsubishi
Space Wagon from Splintex, by means of a cellulose cloth soaked
with the mixture (Tela.RTM. cloth, Tela-Kimberly Switzerland GmbH).
After a flash-off time of 10 minutes the one-component
moisture-curing polyurethane adhesive Sikaflex.RTM.-250 DM-2 or
Sikaflex.RTM.-250 HMV-2+, which both contain polyurethane
prepolymers with isocyanate groups and are available commercially
from Sika Schweiz AG, were applied as a circular bead using a
cartridge press and a nozzle and were cured at 23.degree. C. and
50% relative humidity for 4 days. The adhesion was assessed by
means of the bead test already described. TABLE-US-00011 TABLE 11
Aqueous primers with silane/surfactant mixture in component K1.
Adhesion of Sikaflex .RTM. 250 DM-2 Sikaflex .RTM. 250 DM-2
A1110:surfactant [g:g] 1:0 2:1 1:1 1:2 1:10 Surfactant Ref. S5 BS22
BS23 BS24 Ref. S6 Surfynol 2 1 2 3 3 Soprophor 2 1 2 2 3 Hydropalat
120 2 1 2 2 3 Proportion of S 100 66 50 33 9 in comp. K1 [% by
wt.]
[0190] TABLE-US-00012 TABLE 12 Aqueous primers with
silane/surfactant mixture in component K1. Adhesion of Sikaflex
.RTM. 250 HMV-2+ Sikaflex .RTM. 250 HMV-2+ A1110:surfactant [g:g]
1:0 2:1 1:1 1:2 1:10 Surfactant Ref. S7 BS25 BS26 BS27 Ref. S8
Surfynol 4 4 4 3 5 Soprophor 4 1 2 4 4 Hydropalat 120 4 3 3 4 4
Proportion of S 100 66 50 33 9 in comp. K1 [% by wt.]
* * * * *