NOVEL POLYCARBONATE-POLYORGANOSILOXANE- AND/OR
POLYURETHANE-POLYORGANOSILOXANE COMPOUNDS
The present invention relates to novel polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds, methods for their production, their use,
functional formulations containing them, precursors for their production, as well as
reactive compositions containing the aforementioned precursors.
Siloxane block copolymers containing quaternary ammonium structures are widely
known. On the one hand, they may be diblock copolymers of the type
siloxane/quaternary ammonium unit (DE 3340708, EP 282720, US 6,240,929, US
6,730,766). On the other hand, triblock copolymers have been developed that are
based on the combination siloxane/quaternary ammonium/polyether block unit (WO
02/10256, WO 02/10257, WO 02/10259, WO 2004/090007, WO 03/078504, WO
2004/041912, WO 2004/042136). The most important advantage of these triblock
copolymers is that their structure is flexible and can be adapted, within very large
ranges, to the concrete product requirements.
Quaternary ammonium compounds containing urea and urethane groups are known
from GB 1128642. The reaction of amino or hydroxy-terminated siloxanes with
diisocyanates leads to isocyanate-terminated intermediate stages, which then react, for
example, with primary-tertiary di or triamines, whereupon the tertiary amino group is
quaternized. It is possible to use, for example, oligoethylene glycols as chain
extenders, which, however, directly leads to a decrease of the amount of quaternary
ammonium groups due to the consumption of isocyanate groups. Thus, this solution is
disadvantageous in that a flexible structural adaptation to the concrete product
requirements that encompasses large ranges cannot be carried out.
The use of an asymmetrically substituted carbonate as a linker group for the synthesis
of siloxane-modified diquaternary compounds containing urethane groups has also
been proposed (WO 2005/058863).
The use of this asymmetrically substituted carbonate linker in the synthesis of
polyurethane block copolymers containing siloxane units with incorporated amine salt
units was also described (C.Novi, A.Mourran, H.Keul, M.Moller, Macromol. Chem.
Phys. 2006, 207, 273-286). The drawback of these concrete block copolymers is that
they only possess pH-sensitive charges in the form of amine salts, which results in
reduced substantivity. A general drawback of this carbonate linker-based approach is
the occurrence of free phenol as a leaving group, or the very difficult bonding of the
carbonate structure to suitable precursors while completely avoiding phenol.
Moreover, it is known to react carbonate-functionalized siloxanes with hydrocarbons
containing primary and secondary amino groups or hydroxyl groups into silicones or
corresponding ethers containing urethane groups. The carbonate-functionalized
siloxanes are either obtained from olefinically unsaturated carbonates by
hydrosilylation with SiH siloxanes (US 5,672,338, US 5,686,547), or by insertion of
CO2 into the epoxy group of epoxy siloxanes (DE 195 05 892). These publications do
not contain any references to the synthesis of materials containing quaternary
ammonium units.
It is thus the object of the invention to provide novel polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds which, on
the one hand, permit a flexible structural adaptation to the concrete product
requirements that encompasses large ranges, and in which, on the other hand,
important product properties can be influenced under the influence of donor-acceptor
interactions, e.g. by means of the urethane groups. Another object is to show that the
aforementioned drawbacks of the prior art, such as the final product containing phenol
and the difficulty in accessing suitable precursors for quaternized block copolymers,
can be avoided.
The novel polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds can be produced simply, safely and specifically, and
possess novel interesting properties.
The present invention relates to novel polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds, containing at least one structural
element of the formula (1):

wherein
R is respectively selected from hydrogen, alkyl, or a bond to the residue ST1,
with cyclic structures forming if R represents a bond to the residue ST1,
R1 is respectively selected from hydrogen, alkyl, or a bond to the residue
ST1 , with cyclic structures forming if R1 represents a bond to the residue
ST1,
R2 is respectively selected from hydrogen, alkyl, or a bond to the residue
ST1 , with cyclic structures forming if R1 represents a bond to the residue
ST1,
ST is a di- or polyvalent, straight-chained, cyclic or branched, saturated,
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue
with up to 1000 carbon atoms, which may contain one or more groups
selected from:
-O-,
-C(O)-, and
a polyorganosiloxane unit with 2 to 1000 silicon atoms,
wherein
ST1 contains no groups of the formula -O-C(O)-O- and no groups of the
formula -O-C(O)-NH-,
wherein, if a plurality of residues ST1 is present, they may be the same or
different,
Y is selected independently from one another from: -O-, -S- and
-NR6-, wherein
R6 is hydrogen or a straight-chained, cyclic or branched, saturated,
unsaturated or aromatic hydrocarbon residue with up to 40 carbon
atoms, which may contain one or more groups selected from -O-, -
C(O)-, -NH- and -NR3-, wherein R3 is defined as above,
R6 represents a bond to the residue ST2 while forming cyclic
structures,
ST2 is a di- or polyvalent, straight-chained, cyclic or branched, saturated,
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue
with up to 1000 carbon atoms, which may contain one or more groups
selected from:

a polyorganosiloxane unit with 2 to 1000 silicon atoms,
wherein
R3 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 40 carbon atoms, which may
contain one or more groups selected from -O-, -C(O)- and -NH-, and
may optionally be substituted by a silyl group, such as an alkoxysilyl
group (for example, a trialkoxysilylgroup), and
R5 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 100 carbon atoms, which may
contain one or more groups selected from -O-, -C(O)- and -NH-, and
may optionally be substituted by a silyl group, such as an alkoxysilyl
group (for example, a trialkoxysilylgroup), or two residues R5 form,
with the nitrogen atom to which they are bonded, a 5 to 7-membered
ring, which may optionally contain one or two further hetero atoms, or
R5, together with R6, forms a divalent alkylene residue which leads to
the formation of a cyclic structure including Y and ST2 ,
wherein, if a plurality of residues ST2 is present, they may be the same or
different,
provided that at least one of the residues ST1 and/or ST2 comprises a
polyorganosiloxane residue,
or acid addition compounds and/or salts thereof.
Preferably, Y represents -O- and -NR6-, wherein
R6 preferably is hydrogen or a straight-chained, cyclic or branched, saturated,
unsaturated or aromatic hydrocarbon residue with up to 20 carbon atoms,
which may contain one or more groups selected from -O-, -C(O)-, -NH-
and -NR3-, wherein R3 is defined as below, and/or
R6 forms a bond to the residue ST2, whereby cyclic structures form. In the
process, the bond from R6 to the residue ST2 preferably takes place via a
residue R5.
ST1 preferably is a di- or polyvalent, straight-chained, cyclic or branched, saturated,
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue with up to
400 carbon atoms, which may contain one or more groups selected from:
-O-,
-C(O)-, and
a polyorganosiloxane unit with 2 to 500 silicon atoms,
ST2 preferably is a di- or polyvalent, straight-chained, cyclic or branched, saturated,
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue with up to
400 carbon atoms, which may contain one or more groups selected from:

a polyorganosiloxane unit with 2 to 500 silicon atoms,
wherein
R3 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 20 carbon atoms, which may
contain one or more groups selected from -O-, -C(O)- and -NH-, and
R5 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 20 carbon atoms, which may
contain one or more groups selected from -O-, -C(O)- and -NH-, or
two residues R5 form, with the nitrogen atom to which they are
bonded, a 5 to 7-membered ring, which may optionally contain one or
two further hetero atoms, or R5, together with R6, forms a divalent
alkylene residue which leads to the formation of a cyclic structure
including Y and ST2.
The case in which R5, together with R6, forms a divalent alkylene residue which leads
to the formation of a cyclic structure including Y and ST2 arises, for example, when -
as will be shown in more detail below - methylpiperazine, for example, is used as the
starting compound HY-ST3-NR52 for preparing the compounds according to the
invention, wherein Y = -NR6 and R6, together with R5, forms an alkylene residue.
Acid addition compound are such compounds which are created by optionally partial
neutralization of amino-containing compounds according to the invention with
inorganic or organic proton acids, such as hydrochloric acid, sulfuric acid, phosphoric
acid, Cl to C22 carboxylic acids, such as acetic acid etc.
Salts of the compounds according to the invention in particular result from the
presence of quaternary ammonium groups which require an anion for the
neutralization of the positive charge. Such anion particularly include: carboxylate
anions such as acetate, stearate, oleate, undecanoate, dodecanoate etc., halogen
anions, such as, in particular, chloride, bromide, iodide, sulfate, hydrogensulfate,
phosphate,
In the compounds according to the invention, protonated ammonium groups (H-N+)
and quaternized ammonium groups (NR4+) may be present at the same time.
In a preferred embodiment of the compounds according to the invention, at least one
of the residues R, R1 and R2 represents hydrogen. Preferably, residues R, R1 and R2
represent hydrogen, so that compounds of the formula (Ia)

result.
In a preferred embodiment of the invention, the compounds according to the invention
have a linear structure. In this case, a linear structure means that the polymer main
chain formed from the units of the formular (I) is substantially linear, i.e. has no
branchings. However, this does permit cyclic structural elements being contained in
the linear polymeric main chain.
In a preferred embodiment of the invention, the residues ST1 and ST2 are each
divalent residues. This means that the compounds according to the invention are
linear compounds and that there are no cyclic structures including R1 and ST1.
Branched polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds are included in the compounds according to the invention, in particular
those in which the branching of the polymeric main chain takes place via at least one
of the residues ST1 or ST2 , which in this case must naturally be more than divalent.
Linear compounds are obtained, in particular, starting from starting compounds of the
formulae

wherein ST1, R, ST2 and Y are defined as above, and wherein p and q are each 2.
Branched compounds according to the invention are obtained, in particular, by using
the aforementioned starting compounds, in which q and/or p >2.
However, branched compounds according to the invention can also be obtained by
later reacting or cross-linking reactive groups in the polymeric main chain.
For example, by reacting

wherein p = 2,
and
ST2-(Y-H)q, which is, for example, a compound of the formula
NH2CH2CH2N(CH3)CH2CH2NH2, NH2CH2CH2CH2N(CH3)CH2CH2CH2NH2 or
aminoethylpiperazine, compounds of the formula (lb):

(1c)
can be obtained, wherein the tertiary amino groups in ST2 can be reacted or cross-
linked, for example, by polyfunctional quaternating agents, such as ST4V(-Q)t.
Moreover, it is also possible to cross-link the compounds according to the invention
later by means of the hydroxyl groups present using polyisocyanates, polycarboxylic
acids or derivatives thereof, such as acid chlorides, or polyepoxides.
The polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention contain at least one polyorganosiloxane
residue, which preferably has the formula (2):
wherein
R4 is a straight-chained, cyclic or branched, saturated, unsaturated or aromatic
hydrocarbon residue with up to 20 carbon atoms, and/or R4 is an alkoxy residue, the
alkyl part of which is a straight-chained, cyclic or branched, saturated alkyl residue
with up to 20 carbon atoms, which may contain one or more oxygen atoms (such as,
for example, in the case of polyalkyleneoxyalkoxy residues), and

Preferred are
R4 Cl to C20, preferably Cl to C9, straight-chained or cyclic or branched,
saturated or unsaturated or aromatic hydrocarbon residue, particularly
preferably methyl and phenyl and
s 1 to 199, especially 1 to 99.
In a particularly preferred case, the siloxane unit (2) has the structure

wherein s is as specified above.
The following compound, for example, constitutes a compound ST2 -(Y-H)q
corresponding to the alternative R4 = alkoxy and/or alkyl:

In an embodiment that is particularly suitable for the use of the compounds according
to the invention in the field of cosmetics, such as in the field of hair care, s is
preferably > 199.
In an embodiment that is particularly preferred for the use of the compounds
according to the invention as softeners, in particular for textiles, s is preferably 20 to
200, particularly preferably 20 to 120.
Particularly preferably, the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention contain at least two
polyorganosiloxane residues of the formula (2).
Preferably, the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention contain at least two
structural elements of the formula (1), more preferably at least 3 structural elements of
the formula (1).
However, it is also included in the scope of the invention that the compounds
according to the invention have only one structural element of the formula (1), which
sometimes are also referred to as "butterfly" compounds. Examples for such
compounds include:

A more complex butterfly structure is formed by stepped reaction of ST -(Y-H)2 with

The above reaction also illustrates a possibility of forming terminal groups of the
compounds according to the invention. The terminal groups can result from either the
non-reacted terminal groups of the polyfunctional monomers used, or reactive
monofunctional compounds, such as, for example, CH-acid compounds, such as
alcohols, amines, or water, or acids, are added for chain termination.
In the polyurethane-polyorganosiloxane compounds according to the invention, Y -
preferably -NR6-, wherein R6 is defined as above. Particularly preferably Y =
-NH-.
The polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds preferably comprise amino groups, protonated amino groups, quaternary
ammonium groups and/or polyether groups. Particularly preferably, they comprise
quaternary ammonium groups and/or polyether groups, because they impart sufficient
hydrophilicity to the compounds according to the invention with good substantivity.
In the polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention, ST1 is preferably unequal to ST2.
In a preferred embodiment of the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds, ST1 and/or ST2 are selected from the
group consisting of polyorganosiloxane-containing residues, polyether-containing
residues, polyorganosiloxane and polyether-containing residues, monocyclic or
polycyclic hydrocarbon residues, acyclic, optionally oxygen-containing hydrocarbon
residues and optionally oxygen-containing hydrocarbon residues comprising aromatic
groups. Preferably, at least one of the residues ST1 and/or ST2 contains a
polyalkyleneoxy group.
In a further preferred embodiment of the invention the polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds containing
ST1 and/or ST2 contain a structural element of the following formula:

wherein s is defined as above, and
r=1 to 12.
The polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention are in particular prepared by reacting a
compound of the formula (6)

wherein R, R1, R2 and ST1 are defined as above, and p > 2, preferably p = 2,
with at least one compound of the formula (7)

wherein ST2 and Y are defined as above, and wherein q > 2, preferably q =2. In this
case, Y = NR6 wherein R6 is as defined above, preferably hydrogen.
In a further preferred embodiment of the invention, the polycarbonate-
polyorganosiloxane and/or polyurethane-polysiloxane compounds have at least one
residue ST2 of the formula (5):

wherein R is defined as above,
ST3 is a straight-chained or cyclic or branched, saturated or unsaturated or aromatic,
substituted or unsubstituted hydrocarbon residue with 2 to 100 carbon atoms, which
may contain -O-, -C(O)-, -NH- and/or -NR3-, wherein R3 is defined as above, and
ST4 is a straight-chained or cyclic or branched, saturated or unsaturated or aromatic,
substituted or unsubstituted hydrocarbon residue with 2 to 200 carbon atoms, which
may contain -O-, -C(O)-, -NH- and/or -NR3- , and/or a polyorganosiloxane unit
with 2 to 500, preferably 2 to 200 silicon atoms, wherein R is defined as above, and
A" represents an organic or inorganic anion.
Substituents of the hydrocarbon residues for ST3 and ST4 include one or more,
preferably one to three substituents, which are preferably selected from the group
consisting of: hydroxy, halogen, such as fluorine or chlorine, and cyano. In this case,
hydroxy is particularly preferred, in particular in ST4.
Including the formula (2), formula (3) preferably results for the quaternized
polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention:

wherein
R, R1, R2, ST1, ST3, ST4, R6 and R5 are defined as above, and
A- is an organic or inorganic anion,
provided that at least one of the residues ST1, ST3 and ST4 contains a
polyorganosiloxane residue.
The above-described compounds according to the invention are preferably prepared
by a method comprising the reaction of a compound of the formula

wherein R, R1, R2 and ST1 are defined as above, and p > 2, preferably p = 2,
with a compound of the formula (8)
HY-ST3-NR52 (8),
wherein ST3, Y and R5 are defined as above,
and a compound of the formula (9)
ST4V(-Q)t (9),
wherein
Q is a residue capable of alkylating an amino group, ST4V , together with the
molecule part arising from Q after the quaternating reaction, forms the
residue ST4, and t > 2, preferably t = 2.
Preferably, Y = NR6, wherein R6 is as defined above, preferably hydrogen.
The reaction partners HY-ST3-NR52 introducing ST3 are substances having primary-
tertiary or secondary-tertiary diamino-structures, such as, for example, N,N-
dimethylpropylenediamine. The use of N-methypiperazine, which is also preferred,
includes the possibility that was treated above, namely of cyclic structures that
comprise Y and ST2 being able to form. Thus, using N-methylpiperazine as HY-ST3-

-CH2-CH2-, R5 = -CH3 and R5 and R6 form -CH2-CH2-) compounds of the formula
(3a) form, for example
The use of primary-secondary diamines for introducing ST3 is also possible in
principle. Remaining amino groups can subsequently be quaternized to the chain
structure. The use of ST3 precursors with primary or secondary amino groups leads to
the formation of polyurethanes.
Alternatively, tertiary amino-functionalized alcohols, such as HOCH2CH2N(CH3)2
can also be used for introducing ST3. In this case, polycarbonates (carbonic acid
esters) are formed.
It lies within the scope of the invention to use higher-functional amines with at least
two tertiary amine functions for producing branched ST3 structures. Examples
include:
N,N,N',N'-tetramethyldipropylenetriamine (Jeffcat ZR50B Huntsman) and
N,N,N',N'-tetramethyldiethylenetriamine.
The reaction partners ST4V(-Q)t containing ST4 are polyfunctional, in particular
difunctional alkylating agents which preferably possess epoxy groups, halocarboxylic
acid ester groups and haloalkyl groups.
More preferably, the hydrocarbon-based epoxide derivatives are
- hydrocarbon diepoxides, e.g. vinylcyclohexenediepoxide
- epichlorohydrin
- epoxy-terminated polyethers, preferably ethyleneoxide- and propyleneoxide-based
polyethers, for example glycidyl-terminated polyethers
- epoxy-terminated polyesters,
- epoxy-terminated polycarbonates
The halogen-functionalized hydrocarbon derivatives, preferably chlorides and
bromides, preferably are
- Hydrocarbon dihalides, optionally interrupted by polyorgano-
siloxane units,
- halogen-terminated polyethers, preferably ethyleneoxide- and propyleneoxide-based
- polyethers
- Halocarboxylic acid esters of hydrocarbon diols and polyethers, preferably
ethyleneoxide- and propyleneoxide-based polyethers, especially chloroacetic acid
esters, chloropropionic acid esters and chlorobutanoic acid esters of hydrocarbon diols
and polyethers.
It also lies within the scope of the invention to transfer difunctional acid alkoxylates
into corresponding glycidyl, halogen or halocarboxylic acid esters derivatives and use
them according to the invention. They are derived, for example, from succinic acid.
Examples for such compounds include:

wherein D is an aliphatic or aromatic, optionally substituted hydrocarbon residue,
such as, for example:

The synthesis of the particularly preferred chlorocarboxylic acids is carried out in the
known manner (Organikum, Organisch-Chemisches Grundpraktikum, 17. edition,
VEB Deutscher Verlag der Wissenschaften, Berlin 1988, pp. 402-408) by reaction of
the diol component with the corresponding halocarboxylic acid anhydrides or
halocarboxylic acid chlorides.
In another embodiment, the hydrocarbon residues ST4 are more complex a,?-epoxy-
or halogen-terminates structures derived from a,?-hydroxyl-functionalized
prepolymers.
Preferably, these a,?-hydroxyl-functionalized prepolymers are the reaction products
of
- diols with diisocyanates
- OH-terminated polyethers, preferably ethyleneoxide- and
propyleneoxide-based
- polyethers with diisocyanates,
- OH-terminated polyesters
- OH-terminated polycarbonates.
In a preferred embodiment, these a,?-hydroxyl-functionalized prepolymers are
transferred into the corresponding a,?-halocarboxylic acid esters, especially
chloroacetic acid esters, chloropropionic acid esters and chlorobutanoic acid esters.
The introduction according to the invention of siloxane blocks into ST4 preferably
takes place via
- a,?-epoxy-terminated siloxanes, preferably a,?-glycidyl- and epoxycyclo-
hexyl-terminated siloxanes,
- a,?-halogenalkyl-terminated siloxanes, preferably chloropropyl- and
chloropropenyl-terminated siloxanes,
- a,?-halocarboxylic-acid-ester-terminated siloxanes, preferably esters of
chloroacetic acid, chloropropionic acid and chlorobutanoic acid,
- a,?-halocarboxylic-acid-ester-terrninated polyethersiloxanes, preferably esters
of chloroacetic acid, chloropropionic acid and chlorobutanoic acid.
The preparation of the a,?-epoxy-terminated siloxanes and a,?-halogenalkyl-
terminated siloxanes introduced into ST4 is described in the prior art (Silicone,
Chemie und Technologie, Vulkan Verlag Essen 1989, pp. 85-90 and 120).
The preparation of a,?-halocarboxylic-acid-ester-terminated siloxanes can be carried
out in analogy to the procedure according to WO 02/10256, Example 1. In this case,
SiH siloxanes are reacted with halocarboxylic acid esters of olefinically or
acetylenically unsaturated alcohols.
The preparation of a,?-halocarboxylic-acid-ester-terminated polyethersiloxanes can
be carried out in analogy to WO 02/10257, Example 1. In this case, SiH siloxanes are
reacted with halocarboxylic acid esters of olefinically or acetylenically unsaturated
polyethers. Alternatively, it is possible to react polyethersiloxanes with
halocarboxylic acids, their anhydrides or acid chlorides (US 5,153,294, US
5,166,297).
In another embodiment, the introduction of siloxane blocks into ST4 is carried out via
a,?-epoxy- or halogen-functionalized siloxane prepolymers, which can preferably be
obtained from the corresponding a,?-hydroxyalkyl or a,?-hydroxypolyether-
terminated siloxane prepolymers.
These OH-terminated siloxane-containing prepolymers are preferably obtained by
reaction of
- a,?-hydroxyalkyl-terminated siloxanes with diisocyanates,
- a,?-polyether-terminated siloxanes with diisocyanates,
and then transferred into the epoxy and halogen derivatives. The a,?-halocarboxylic-
acid-functionalized siloxane prepolymers, which are available by esterification with,
for example, the anhydrides or acid chlorides, constitute a preferred embodiment.
In a special embodiment, hydrocarbon- and siloxane-based prepolymers for ST4 can
be obtained by a,?-epoxy- or halogen-functionalized precursors being made to react
with a stoichiometric deficit of bis-secondary amines, e.g. piperazine, or bis-
secondary aminofunctional siloxanes, for example:

In another special embodiment, hydrocarbon- and siloxane-based prepolymers for ST4
can be obtained by alpha,omega-epoxy-functionalized precursors being made to react
with a stoichiometric deficit of primary amines, e.g. ethanolamine,
NH2CH2CH2CH2Si(CH3)2OSi(CH3)3 or NH2CH2CH2CH2Si[OCH(CH3)2]3. For
example, this opens up the possibility of introducing specifically siloxane, silane or
even reactive alkoxysilane structures into ST4' for instance:
Moreover, it lies within the scope of the invention to use higher-functional
hydrocarbon- or siloxane-based substances for forming the residue ST4. These
materials contain more than two of the epoxy or halogen functions treated above.
Examples for higher-functional hydrocarbon-based substances include the glycidyl or
chloroacetic acid ester derivatives of glycerol, pentaerythrol, sorbitol and of their
ethoxylates/propoxylates. It also lies within the scope of the invention to transfer
higher-functional acid alkoxylates into corresponding glycidyl or chloroacetic acid
ester derivatives and use them according to the invention. They are derived, for
example, from trimellitic acid or pyromellitic acid.
Suitable higher-functional siloxane-based substances with a,?- and/or comb-like
epoxy- or halogen-, preferably halocarboxylic acid ester substitution can be obtained,
for example, from hydroxy-functional precursors which are available by addition of
allylalcohol, butynediol and the alkoxylates of allylalcohol or butynediol to
corresponding SiH-siloxanes. Alternatively, unsaturated epoxy- or halocarboxylic
acid ester-functional precursors, for example, can be added to corresponding SiH
siloxanes.
What is important is that the functionality of these higher-functional hydrocarbon-
based or siloxane-based substances is greater than 2.
Moreover, it lies within the scope of the invention to use monofunctional
hydrocarbon-based or siloxane-based substances for forming the residue ST4. These
materials contain one of the epoxy or halogen functions treated above.
Examples of monofunctional hydrocarbon-based substances are the glycidyl or
chloroacetic acid ester derivatives of alkanols, for example ethanol, 2-propanol,
dodecanol and octadecanol, alkenols, for example allylalcohols, hexenol, oleylalcohol
and alkinols, for example propinol and the alkoxylates, especially
ethoxylates/propoxylates of the aforementioned monofunctional alcohols. It also lies
within the scope of the invention to transfer fatty acid alkoxylates into corresponding
glycidyl or chloroacetic acid ester derivatives and use them according to the
invention.
Suitable monofunctional siloxane-based substances with epoxy- or halogen-,
preferably halocarboxylic acid ester substitution are known, for example, from WO
02/10256. They can be obtained, for example, from unsaturated epoxy- or
halocarboxylic-acid-ester-functional precursors, which are added to corresponding
SiH siloxanes.
If epoxy-containing substances are used for introducing ST4, acid is added in
stoichiometric amounts in the manner known from the prior art. The anions A" are
inorganic anions, such as halogenides, especially chloride, and organic anions, such as
carboxylate, especially C2 to C18-carboxylate, alkylpolyethercarboxylate,
alkylsulfate, especially methosulfate, sulfonate, especially alkylsulfonate and
alkylarylsulfonate, in particular tolylsulfonate.
The molecules for introducing ST1 are poly-, in particular difunctional cyclocarbonate
precursors. They are derived from hydrocarbon- or siloxane-based structures.
In a preferred embodiment, the hydrocarbon- or siloxane-based cyclocarbonate
precursors are derived from epoxy-functionalized derivatives. They can be transferred
into the corresponding cyclocarbonates by base-catalyzed insertion of CO2 into the
epoxide ring (DE 195 05 892). Thus, the above-described compounds of the formula
(10), for example, are also suitable as epoxy-functionalized derivatives for reaction
with CO2

The epoxy derivatives that lead to the cyclocarbonates yielding ST1 preferably are
- hydrocarbon diepoxides, e.g. vinylcyclohexenediepoxide
epoxy-terminated polyethers, preferably ethyleneoxide- and propyleneoxide-
based polyethers, for example glycidyl-terminated polyethers
- epoxy-terminated polyesters,
- epoxy-terminated polycarbonates
It also lies within the scope of the invention to transfer difunctional acid alkoxylates
into corresponding glycidyl derivatives and use them according to the invention. They
are derived, for example, from succinic acid.
In another embodiment, the hydrocarbon residues ST1 are structures derived from
more complex a,?-epoxide prepolymers.
They in turn are derived from a,?-hydroxy-functionalized prepolymers, for example
from the reaction products of
- diols with diisocyanates
- OH-terminated polyethers, preferably ethyleneoxide- and propyleneoxide-based
polyethers with diisocyanates,
- OH-terminated polyesters,
- OH-terminated polycarbonates,
which can be transferred into epoxides, for example by reaction with epichlorohydrin.
The siloxane-based epoxy derivatives that lead to the cyclocarbonates yielding ST1
preferably are
- a,?-epoxy-terminated siloxanes, preferably a,?-glycidyl- and epoxycyclohexyl-
terminated siloxanes, the synthesis of which was already discussed in connection with
ST4 precursors.
In another embodiment, the siloxane-based epoxy precursors may be a,?-epoxy
derivatives of a,?-hydroxypolyether-terminated siloxane prepolymers.
In another preferred embodiment, the hydrocarbon- or siloxane-based cyclocarbonate
precursors are derived from corresponding bis-1,2-diol-functionalized derivatives.
They can be transferred into the corresponding cyclocarbonates by reaction with
phosgene or catalyzed transesterification with dialkylcarbonates, for example
dimethylcarbonate (DE 195 05 892).
The bis-1,2-diol derivatives leading to the ST'-yielding cyclocarbonates preferably
are diglycerin, higher oligoglycerins, or bis-glycerol-terminated ethers or polyether
structures. It also lies within the scope of the invention to transfer difunctional acids
into corresponding bis-1,2-diol derivatives. Examples for this include corresponding
bis-glycerol exters of dicarboxylic acids, e.g. of succinic acid.
The siloxane-based bis-1,2-diol derivatives leading to the ST1-yielding
cyclocarbonates preferably are
- a,?-1,2-diol-terminated siloxanes, preferably synthesized from SiH
siloxanes
and glycerolmonoallylether or trimethylolpropanemonoallylether.
In another preferred embodiment, the siloxane-based a,?-cyclocarbonates leading to
ST1 are derived from corresponding SiH siloxanes. They are directly transferred into
the cyclocarbonate-terminated structures by addition to olefinically or acetylenically
unsaturated cyclocarbonates (US 5,672,338,
US 5,686,547). Glycerolcarbonateallylether is an example for a preferred olefinically
unsaturated cyclocarbonate. In turn, this can preferably be obtained from allylglycide
ether by CO2 insertion, or from glycerolmonoallyl ether by reaction with phosgene or
transesterification with, for example, dimethlycarbonate.
In another preferred embodiment the cyclocarbonates leading to ST1 are derived from
dicarboxylic acid ester structures, preferably hydrocarbon-based dicarboxylic acid
ester structures. For example, the corresponding dicarboxylic acids or the acid halides
are directly esterified with glycerolcarbonate for this purpose. Succinic acid is an
example for a suitable dicarboxylic acid.
Moreover, it lies within the scope of the invention to use higher-functional
hydrocarbon-based or siloxane-based substances for forming the residue ST1. These
materials contain more than two of the cyclocarbonate functions treated above.
Examples for higher-functional hydrocarbon-based substances include the
cyclocarbonate derivatives of glycerol, pentaerythrol, sorbitol and of their
ethoxylates/propoxylates, which in turn preferably derive from the glycidyl
derivatives. It also lies within the scope of the invention to transfer higher-functional
acid alkoxylates into corresponding glycidyl derivatives and subsequently
cyclocarbonate derivatives and use them according to the invention. They are derived,
for example, from trimellitic acid or pyromellitic acid.
Higher-functional cyclocarbonate esters are derived from such higher-functional
acids, such as trimellitic acid or pyromellitic acid, by reaction with, for example,
glycerolcarbonate.
Suitable higher-functional siloxane-based substances with a,?- and/or comb-like
cyclocarbonate substitution are preferably derived from SiH-, epoxy- or 1,2-diol-
functionalized materials. As was already described above, they can be transferred into
corresponding higher-functional cyclocarbonates by respectively suitable reactions.
What is important is that the functionality of these higher-functional hydrocarbon-
based or siloxane-based substances is greater than 2.
Moreover, it lies within the scope of the invention to use partially monofunctional
hydrocarbon-based or siloxane-based substances for forming the residue ST1. These
materials contain a cyclocarbon function as a terminal group.
Examples of monofunctional hydrocarbon-based substances are ethylenecarbonate,
propylenecarbonate, glycerolcarbonate, the carbonate ether derivatives of alkanols,
for example ethanol, 2-propanol, dodecanol and octadecanol, alkenols, for example
allylalcohols, hexenol, oleylalcohol and alkinols, for example propinol and the
alkoxylates, especially ethoxylates/propoxylates of the aforementioned
monofunctional alcohols. It also lies within the scope of the invention to transfer fatty
acid alkoxylates into corresponding carbonate ether derivatives and use them
according to the invention.
Moreover, it lies within the scope of the invention to use monofunctional carbonate
ester derivatives, starting from saturated and unsaturated carboxylic acids, such as
acetic acid, dodecanoic acid, stearic acid, undecenoic acid, oleic acid. As was already
explained, they are preferably synthesized by reaction of the acid halides with, for
example glycerolcarbonate.
Suitable siloxane-based monofunctional cyclocarbonates are derived from SiH-,
epoxy- or 1,2-diol-functionalized materials. As was already described above, they can
be transferred into corresponding monofunctional cyclocarbonates by respectively
suitable reactions.
Essentially, monofunctional and/or higher-functional ST1 and ST2 or ST4 precursors
are used for molecular weight control and, in the case of higher-functional
compounds, in order to accomplish a specific deviation from the linear structure
predetermined by difunctional ST1 and ST2 or ST4 precursors, and to influence the
molecular weight and their degree of branching in a specific manner in the process.
Moreover, the use of monofunctional and/or higher-functional ST1 and ST2 or ST4
precursors can serve for shifting the internal ratio ST1 : ST2 or ST4 in a specific
manner. The combination of, for example, di- and trifunctional ST2 precursors with
mono- and difunctional ST1 precursors leads to a molar excess of ST1 segments in
relation to ST2 or ST4 segments.
As a result of the complete reaction sequence shown, polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane-polyammonium
compounds are obtained which comprise siloxane units in at least one of the structural
elements ST1 and/or ST , in particular if the quaternating compounds ST4V(-Q)t are
applied. Naturally, the introduction of quaternized nitrogen atoms can also take place
after the preparation of a polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane-polyamino compound and subsequent quaternating reaction with
mono- or polyfunctional quaternating agents of the type ST4V(-Q)t, wherein t < 1.
The polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention are in particular also prepared by reacting a
compound of the formula (6)

wherein R, R1, R2 and ST1 are defined as above, and p > 2,
and at least one compound of the formula (7)

wherein ST2 and Y are defined as above, and wherein q > 2.
In this case, Y = NR6, wherein R6 is as defined above, more preferably hydrogen.
Compounds of the formula (4)

are used particularly preferably.
The reactions for preparing the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention are
preferably carried out in the range of from room temperature to 160°C, preferably to
140°C. The reaction times are a few minutes to some hours. In this case, the amino-
functional precursors are generally more active than the hydroxy-functional
precursors.
Reaction times, reaction temperatures and the conversion achieved are particularly
dependent on the type of the amino groups on the HY precursors. It generally applies
that primary amino groups react more easily than secondary amino groups.
Reaction times, reaction temperatures and the conversion achieved moreover are
particularly dependent on the type of the quaternization-capable or alkylation-capable
group Q on ST4. It generally applies that, for example, halocarboxylic acid ester
groups react more easily than comparable haloalkyl groups.
It lies within the scope of the invention to carry out the entire reaction sequence or
individual partial steps without any solvents or, however, in the presence of solvents.
Preferred solvents are typical lacquer solvents, such as methoxypropylacetate, butyl
acetate, toluene. The reaction in protic solvents, such as alcohols, for example
ethanol, 2-propanol, 1-butanol, 2-butanol, 1-methoxy-
2-propanol or higher ethyleneoxide- or propyleneoxide derivatives may also be
advantageous.
As a result of the total reaction sequence shown using the quaternating reagents,
polycarbonate-polyorganosiloxane and/or polyurethan-polyorganosiloxane
compounds with amino and or ammonium groups are obtained which comprise
polysiloxane units in at least one of the structural elements ST or ST .
The invention further relates to the use of the polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compounds according to the invention for
the production of coatings, agents for surface modification, elastomers, duromers,
adhesives, primers for metal or plastic surfaces, polymer additives, laundry detergent
additives, rheological agents, cosmetic agents, fiber modification agents.
In cosmetic formulations for hair, the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention can, in
particular, fulfill the function of so-called conditioners, i.e. have, in particular, a
favorable effect on the property of hair, such as softness, gloss, volume, ease of
combing etc., wherein they may also be used, in particular, in combination with other
common conditioners, such as, for example, poly-alpha-olefins, fluorinated oils,
fluorinatedwaxes, fluorinated rubbers, carboxylic acid esters with at least 10 carbon
atoms, cationic polymers, silicones insoluble or soluble in the medium of the
formulation, mineral oils, plant oils and animal oils and mixtures thereof, as
described, for example, in WO 99/009939.
The invention further relates to the use of the polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compounds according to the invention for
the production of coatings or agents for surface modification of hard surfaces, such as,
for example, glass, ceramics, tiles, concrete and steel parts, such as automobile bodies
and ship's hulls.
Moreover, the invention preferably relates to the use of the polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds according to
the invention for the production of primers for bonding silicone elastomers to other
substrates, such as steel, aluminum, glass, plastics, such as epoxy resins, polyamides,
polyphenylene sulfides, polyesters, such as polyterephthalates.
In a further preferred embodiment of the invention, this relates to the use of the
polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention for the production of modification agents for
thermoplastic synthetic materials, such as polyolefines, polyamides, polyurethanes,
poly(meth)acrylates, polycarbonates.
In a further preferred embodiment of the invention, this relates to the use of the
polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention for the production of low-temperature impact-
resistance modifiers.
The term "for the production of as it is used above also includes the case that the
polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound is used only for the specified application. This means that the
polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds themselves can be used directly as low-temperature impact-resistance
modifiers. However, they can also be suitably provided in advance, for example by
mixing, compounding, master batch production.
Moreover, the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds can preferably be used as a constituent in adhesives
and sealants, as the basic material for thermoplastic elastomers, such as cable
sheathings (cable coatings), tubes, gaskets, keyboard mats, for membranes, such as
selectively gas-permeable membranes. Another use of the copolymers according to
the invention are coatings, such as anti-fouling, anti-stick coatings, tissue-compatible
coatings, flame-retardant coatings and bio-compatible materials.
They can serve as coating agents for cosmetics, body care products, paint additives,
auxiliary substances in detergents, de-foaming formulations and textile processing, for
modifying resins or modifying bitumen.
Other uses include packaging material for electronic components, insulation or
shielding materials, sealing material in cavities with formation of condensation water,
such as air planes, ships, automobiles, additives for cleaning agents, detergents or care
products, as an additive for body care products, as coating material for wood, paper
and cardboard, as mold-release agent, as a bio-compatible material in medical
applications such as contact lenses, as coating material for textile fibers or textile
fabrics, as coating material for natural fabrics such as, for example, leather or furs, as
material for membranes and as a material for photoactive systems, e.g. for
lithographic processes, optical data recording or optical data transmission.
In a further preferred embodiment of the invention, this relates to the use of the
polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention for the production of viscosity regulators, anti-
static agents, mixture components for silicone rubbers that can be cross-linked
peroxidically or by hydrosilylation (platinum catalysis) to form elastomers, and there
lead to the modification of surface properties, for the modification of the diffusion of
gases, liquids, etc, or modify the swelling behavior of the silicone elastomers, of
softeners for textile fibers for the treatment of textile fibers prior to, during and after
washing, of agents for modifying natural and synthetic fibers, such as hair, cotton
fibers and synthetic fibers, such as polyester fibers and polyamide fibers, as well as
union fabric, of textile finishing agents, as well as of detergent-containing
formulations, such as laundry detergents and cleaning products.
The present invention further relates to novel laundry detergent formulations,
cosmetic formulations, fiber treatment formulations containing the polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds according to
the invention.
Thus, the polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention can be present, for example, in solid or liquid
laundry detergent formulations in contents of approximately 0.1 to 10 % by wt,
relative to the total amount of the formulation, in cosmetic formulations and
formulations for fiber treatment, such as textile care products, in contents of
approximately 0.1 to 50 % by wt. relative to the total amount of the formulation.
Preferably, the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention can be used in the
treatment and finishing of hard surfaces, such as glass, ceramics, tiles, plastic
surfaces, metal surfaces, lacquer surfaces, especially ship's hulls and automobile
bodies, in particular also in drying agent formulations for automatic car washing, as
an adhesive or primer, preferably for the bonding of silicone elastomers to other
substances, such as steel, aluminum, glass, epoxy resins, polyamide, as modifiers, e.g.
low-temperature impact-resistance modifiers and polarity modifiers, for hydrocarbon-
based polymers and silicone-based elastomer systems based on peroxidic and Pt-
catalyzed cross-linking.
Moreover, they can be used for the treatment of natural and synthetic fibers, such as
cotton, wool, polyester- and polyamide-based synthetic fibers, especially in the form
of textiles, in specific agents for fiber treatment, in particular in laundry detergent
formulations containing anionic, non-ionic and cationic surfactants, wherein the
compounds according to the invention can be directly incorporated into the laundry
detergent, can be added in a dosed manner separately to the running washing process
or subsequent to the washing process, and wherein the treated substrates are given
softness, improved elasticity and a decreased tendency to crease while receiving
acceptable hydrophilicity.
They can also serve as a constituent of separate softening systems, especially on the
basis of cationic surfactants, after washing fibers and textiles, as an ironing aid and
agent for preventing or reversing textile creasing.
They can further be used for finishing fibers, especially for the first finishing and
treatment of, for example, cotton, wool, polyester- and polyamide-based synthetic
fibers, especially in the form of textiles, paper and wood.
Moreover, as was already mentioned, they can be used advantageously in cosmetic
systems for the treatment of hair and skin.
Particularly preferred application areas of the polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compounds according to the invention are
also, preferably aqueous, solutions, mixtures, emulsions and micro-emulsions, in
particular as basis for cosmetic formulations.
The polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention can be used as a pure substance, solution,
mixture, emulsion or micro-emulsion, in the form of liquids, creams or pastes as
feedstock for the production of suitable cosmetic formulations according to the
invention having different viscosities.
The method for producing formulations of the polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compounds according to the invention, such
as, for example, for treating substrates, such as hard and soft subtrates, can, for
example, include the following steps:
a) Producing a pre-mixture in the form of solutions, mixtures or emulsions with
the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention, and
b) Producing another mixture using the pre-mixture a) as well as adding of,
optionally, further surfactants, auxiliary substances and other additives, or
c) Combining the steps a) and b) by mixing the constituents with stirrers,
dissolvers, kneaders, pumps, mixing screws, mixing nozzles, low- and high-
pressure emulsifying devices.
The processes are realized using the machines and apparatuses known in the art
(Ullmann's Enzyklopadie), such as, for example, any form of stirrers in suitable
containers, apparatuses or mixing devices, as described above.
Direct mixing of all constituents is possible. However, the preparation of a pre-
mixture is preferred since it leads to a faster and better distribution and is, in part,
indispensable because the various substance groups can otherwise not be mixed with
each other or emulsified or dispersed, or only with considerable effort. Suitable pre-
or intermediate mixtures can preferably be mixtures in the form of solutions, pastes,
creams or other forms of emulsions or dispersions. Particularly preferred is the
production and use of micro-emulsions with 10 to 200 nm mean particle diameter in
cosmetic formulations.
The formulations containing the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention can, for
example, be produced as different form of administration, such as for hair treatment.
Preferably, the compositions containing the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention are used as
cosmetic formulations for the treatment of keratin-containing substrates, such as, for
example, human and animal hair or skin, as alcoholic or polyalcoholic solution or as
emulsion. Depending on the raw materials, auxiliary substances and the mixing
method used during the production, clear, opaque and white formulations are
obtained.
For preparing solutions and mixtures containing the polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds according to
the invention, alcoholic and polyalcoholic solvents as well as their mixtures with
water, oil-containing and common silicones (inter alia polydimethylsiloxane) as well
as binary and ternary mixtures of solvents and/or oil-containing substances and/or
silicones are preferably suitable. In this case, particularly preferred solvents are
ethanol, isopropanol, ethylene glycol and ethylene glycol ether, polyethylene glycols
and their ethers, propylene glycol and propylene glycol ethers, polypropylene glycol
and their ethers and glycerin and mixtures thereof. Particularly preferred oil-
containing substances include mineral oil products as well as oils of plant, animal and
synthetic origin and mixtures thereof. Particularly preferred silicones different from
the polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention, such as cyclic and linear
polydimethylsiloxanes and mixtures thereof, such as, for example, (according to
INCI) cyclomethicones, cyclotetrasiloxanes, cyclopentasiloxanes, cyclohexasiloxanes,
dimethicones with a viscosity range of 0.65 to 60,000,000 mPa.s at 25°C and
dimethiconol with a viscosity range of 10 to 60,000,000 mPa.s at 25°C.
Preferred solutions and mixtures containing the polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compounds according to the invention have
the following composition in % by wt., relative to the total weight of the composition:
Solutions or mixtures:
0.1 - 99.9 % polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the
invention
0.1 - 99.9 % solvents and/or oil and/or silicones, and/or water
Compositions of the emulsions of the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention:
For preparing the emulsions, water and non-ionic, cationic and amphoteric surfactants
and surfactant mixtures are generally used. Furthermore, emulsions may contain
auxiliary substances, such as, for example, inorganic and organic acids, bases and
buffers, salts, thickening agents, stabilizers for emulsions, such as, for example,
"xanthan gum", preserving agents, foam stabilizers, de-foaming agents and solvents,
such as, for example, alcohols (ethanol, isopropanol, ethylene glycol, polyethylene
glycol, propylene glycol, polypropylene glycol, glycol ether and glycerin and
mixtures thereof).
The polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention used in the emulsions may themselves also
serves as emulsifiers in the preparation of emulsions.
A preferred emulsion that can preferably be used for the production of cosmetic
formulations, consists, for example, of the following constituents in % by wt., relative
to the total amount of the composition:
10-50% polycarbonate-polyorganosiloxane-
and/or polyurethane-polyorganosiloxane compounds
according to the invention,
1-35 % surfactants,
0-10 % auxiliary substances,
0-20 % solvents,
to 100% supplemented with water.
Micro-emulsions for cosmetic formulations, the finishing of textiles and other fiber-
like substrates, or the coating of hard surfaces:
The preparation of micro-emulsions with a high active content of polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds according to
the invention is particular preferred, since they, in addition to the possibility of
preparing clear cosmetic formulations, offer the additional advantage of being simple,
with regard to the process, to work into ("cold process") aqueous formulations. There
is the possibility of using the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention in the preparation of
micro-emulsions in the form of the above described solutions and mixtures. A
preferred active content of the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention in the
emulsion is between 5 and 60% by wt., particularly preferably 10-50% by wt., relative
to the total amount of the composition.
An especially preferred micro-emulsion consists of the following constituents, which,
however, do not limit the invention, in % by wt. relative to the total amount of the
micro-emulsion.
20 - 80 % Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the
invention
0 - 35 % Surfactants
0 - 10 % Auxiliary substances
0-20 % Solvents
to 100 % supplemented with water.
Another subject matter of the invention is the use of the solutions, mixtures or
emulsions prepared with the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention in a cosmetic formulation.
These cosmetic formulations are prepared using the previously prepared solutions or
emulsions, however, they can also be prepared directly from the individual
constituents.
Cosmetic formulations:
Cosmetic formulations include, for example:
So-called "rinse-off' products, such as, for example, "2-in-1" shampoos, "body wash"
and hair conditioner for treating hair during and after washing or after dyeing or the
treatment of hair prior to bleaching, curling or uncurling, as well as so-called "leave-
in" products, such as hair tonics, care creams, styling creams, hair gels, hair styling
products, hair setting products, hair sprays, pump sprays, blow-waving compositions
and blow-drying setting compositions. The formulations moreover also include hair
dyes, which can be differentiated into 3 types according to the resistance of the color
result achieved to washing - permanent, semipermanent and temporary hair dyes. The
term hair in this case includes all keratin-containing fibres, but in particular human
hair. The hair dyes contain, for example, conventional silicones, surfactants, auxiliary
substances and dyes, in addition to the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention. Each of
these ingredients can be used either by itself or in combination with further
ingredients, and represents additional functions in the formulations which serve to
increase the volume, the ease of combing and the gloss and to reduce washing out of
the color from and out of dyed keratin-containing substrates, such as, for example
human and animal hair, and contain at least one polyurethane and polyester-
polysiloxane compound according to the invention.
The abbreviations mentioned in connection with the cosmetic formulations are
explained in the INCI (The Cosmetic, Toiletry and Fragrance Association,
Washington D.C.).
The silicones included here in addition to the polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compounds according to the invention
include, for example:
Cyclic, linear and branched polydimethylsiloxanes having a viscosity of 0.65-
200,000,000 mPas at 25°C and mixtures thereof, such as e.g.
octaorganocyclotetrasiloxanes, octamethylcyclotetrasiloxanes, decaorganocyclo-
pentasiloxanes and dodecaorganocyclohexasiloxanes, wherein the organic residue
preferably denotes methyl, such as SF 1173, SF 1202, SF 1217, SF 1204 and SF 1258
from GE Bayer Silicones, dimethicones, such as the Baysilone M oils (M3 to M
2,000,000), SE 30, SF 1214, SF 1236, SF 1276 and CF 1251 from Momentive
Performance Materials, and dimethiconols, such as Baysilone abhesive ZWTR/OH,
i.e. SiOH-terminated polydimethylsiloxanes 2-20kPa.s from Momentive Performance
Materials and DC 1501 and DC 1503 from Dow Corning.
The use of the polydimethylsiloxanes described above in the form of non-ionic,
anionic and cationic emulsions, such as e.g. SM 2169, SM 2785, SM 555, SM 2167
and SM 2112 from Momentive Performance Materials, in combination with
emulsions of the polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention and/or the use of mixtures
and solutions of the polydimethylsiloxanes described above with the polycarbonate-
polyorganosiloxane and/or polyurethane-polyorganosiloxane compounds compounds
according to the invention is particularly preferred in this case, since particular
properties of hair care products can be derived from these combinations, such as has
already been described extensively in the literature for amino-functional silicones
known to date (WO 99/44565, WO 99/44567, WO 99/49836, WO 99/53889, WO
97/12594, US 6,028,031, EP 0811371, WO 98/18443, WO 98/43599 and US 2002-
0182161).
Solid silicones, so-called MQ resins, such as e.g. SR 1000 from Momentive
Performance Materials, and solutions thereof in solvents, such as the above-
mentioned silicones and aliphatic solvents, such as e.g. isododecane, are also suitable.
Organofunctional silicones, such as alkyl-, aryl-, arylalkyl-, phenyl-, fluoroalkyl- and
polyether-modified silicones, such as the types SF 1632, SF 1642, SF 1555, Baysilone
CF 1301, Baysilone PK 20, FF 157, SF 1188A, SF 1288 and SF 1388 from
Momentive Performance Materials, are also suitable.
Surfactants:
Surfactants as ingredients of cosmetic formulations are described in A. Domsch: Die
kosmetischen Praparate, Verlag fur Chem. Industrie, 4th edition, 1992, in
Kosmetikjahrbuch 1995, Verlag fur chemische Industrie, 1995, and H. Stache,
Tensidtaschenbuch, 2nd edition, Carl Hanser Verlag, 1981.
Anionic Surfactants:
By way of example but without being limited thereto, the following anionic
surfactants are suitable as a constituent of the formulations:
Alkyl sulfates, alkyl ether sulfates, alkaryl sulfates, olefinsulfonates, alkylamide ether
sulfates, acyl isethionates, acyl glutamates, alkyl ether carboxylates, methyl taurides
and taurides, sarcosides, sulfosuccinates, protein-fatty acid condensates, alkyl
phosphates and alkyl ether phosphates. The free acids and alkali metal salts and
magnesium, ammonium and mono-, di- and triethanolamine salts thereof can be used
in this case.
The alkyl and acyl groups typically contain 8-18 C atoms and can be unsaturated. The
alkyl ether sulfates, alkylamide ether sulfates, alkyl ether carboxylates and alkyl ether
phosphates can contain 1-10 ethylene oxide or propylene oxide units or a combination
of ethylene oxide and propylene oxide units.
Amphoteric Surfactants:
By way of example but without being limited thereto, the following amphoteric
surfactants are suitable as a constituent of the formulations:
Alkylbetaines, alkylamidobetaines, sulfobetaines, acetates and diacetates,
imidazolines, propionates and alkylamine oxides.
The alkyl and acyl groups in this case contain 8-19 C atoms.
Non-ionic Surfactants:
By way of example but without being limited thereto, the following non-ionic
surfactants are suitable as a constituent of the formulations:
Alkyl ethoxylates, aryl ethoxylates, ethoxylated esters, polyglycolamides,
polysorbates, glycerol-fatty acid ethoxylates, alkylphenol polyglycol ethers and sugar
surfactants, such as e.g. alkyl glycosides.
Cationic Surfactants:
In the case of cationic surfactants, a distinction is made between pure cationic
surfactants and cationic polymers.
Pure cationic Surfactants:
By way of example but without being limited thereto, the following non-ionic
surfactants are suitable as a constituent of the formulations:
Monoalkylquats, dialkylquats, trialkylquats, tetraalkylquats, benzylammonium salts,
pyridine salts, alkanolammonium salts, imidazoline salts, oxazoline salts, thiazoline
salts, salts of amine oxides and sulfone salts, wherein the term "quat" implies the
presence at least of one quaternary ammonium group.
Cationic Polymers:
For "2-in-1" shampoos in particular, cationically modified polymers are also used in
addition to the pure cationic surfactants. A comprehensive description of these
polymers is given in US 5,977,038 and WO 01-41720 Al. Cationic polyacrylamides,
cationic protein derivatives, hydroxyalkylcellulose ethers and cationic guar
derivatives are preferred in this case. Cationic guar derivatives with the CTFA name
guar hydroxypropyltrimonium chloride are particularly preferred. These types are
available under the trade names Cosmedia Guar C 261 (Henkel), Diagum P 5070
(Diamalt) and Jaguar C types and Jaguar EXCEL from Rhodia.
Auxiliary Substances:
Auxiliary substances as ingredients in particular of cosmetic formulations are
described in: A. Domsch, Die kosmetischen Praparate, Verlag fur Chem. Industrie,
4th edition, 1992; and in: Kosmetikjahrbuch 1995, Verlag fur Chemische Industrie,
1995.
By way of example but without being limited thereto, the following auxiliary
substances are suitable as a constituent of the formulations:
Inorganic and organic acids, bases and buffers, salts, alcohols, such as e.g. ethanol,
isopropanol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene
glycol, glycol ethers and glycerol, thickeners, stabilizers for emulsions, such as e.g.
xanthan gum, re-oiling agents, preservatives, foam stabilizers, defoamers, pearlescent
and opacifying agents, such as e.g. glycol distearates and titanium dioxide, collagen
hydrolysate, keratin hydrolysate, silk hydrolysate, antidandruff active compounds,
such as e.g. zinc pyrithione, salicylic acid, selenium disulfide, sulfur and tar
preparations, polymeric emulsifiers, vitamins, dyestuffs, UV filters, bentonites,
perfume oils, fragrances, styling polymers, moisturizers, plant extracts and further
natural or nature-identical raw materials.
It is known that by the addition of oil- and water-soluble UV filters (sunscreen
compositions) or combinations of UV filters in cosmetic formulations for care and
treatment of keratin-containing substrates, such as human and animal hair, the
degradation of dyestuffs and therefore the bleaching out and fading of colored keratin-
containing substrates by UV radiation can be reduced decisively or even prevented
completely.
Ingredients for Hair Dyes:
Dyestuffs and other ingredients of hair dyes are described in: A. Domsch, Die
kosmetischen Praparate, Verlag fur chem. Industrie, 4th edition, 1992. Dyestuffs are
described in: Ordinance on cosmetic agents (Cosmetics Ordinance),
Bundesgesetzblatt 1997, part I p. 2412, .sctn.3 and annex 3 and in European
Community (EC) Directive, 76/68/EEC, annex IV.
In the following, hair dyes are differentiated into permanent, semipermanent and
temporary hair dyes.
Permanent Hair Dyes:
Permanent colorings which are not washed out even by washing the hair several times
(more than 10) are formed by chemical reaction between dyestuff precursors under
oxidative conditions by hydrogen peroxide. The mixture of the corresponding
components determines the color result which can be achieved in this case.
In the case of the precursors, a distinction is made between oxidation bases
(developers) and coupling components (modifiers).
Oxidation Bases:
By way of example but without being limited thereto, the following oxidation bases
are suitable as a constituent of the formulations:
m- and p-phenylenediamines (diaminobenzenes), N-substituted derivatives and salts
thereof, N-substituted derivatives of o-phenylenediamine, o-, m- and p-
toluoylenediamines (methyl-diaminobenzenes), N-substituted derivatives and salts
thereof, p-amino-diphenylamine and its hydrochloride and sulfate, o-, m- and p-
aminophenol and its hydrochloride, 2,4-diaminoisosulfate (4-methoxy-m-
phenylenediamine sulfate), o-chloro-p-phenylenediamine sulfate, picramic acid (2,4-
dinitro-6-aminophenol) and 2,4-dinitro-1-naphtholsulfonic acid and the sodium salt
thereof.
Coupling Components:
By way of example but without being limited thereto, the following coupling
components are suitable as a constituent of the formulations:
Hydroquinone (1,4-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene),
pyrocatechol (1,2-dihydroxybenzene), a-naphthol (1-hydroxynaphthalene), pyrogallol
(1,2,3-trihydroxybenzene) and 2,6-diaminopyridine.
Oxidation bases and coupling components are conventionally incorporated with
surfactants into oil-in-water emulsions, but simple solutions or shampoos are also
known as formulations. The formulations moreover contain antioxidants, such as e.g.
sodium sulfite, sodium dithionite, ascorbic acid or thioglycolic acid, to stabilize the
precursors and are adjusted to a pH-value of between 8 and 12 (preferably 9-11) with
alkaline substances, such as e.g. ammonia. Surfactants as wetting agents, complexing
agents for heavy metals, fragrances for masking the ammonia smell, conditioners for
improving the feel of the hair and for protecting the hair and solvents, such as ethanol,
ethylene glycol, glycerol or benzyl alcohol, are moreover added.
Permanent hair dyes are typically on offer as 2-component systems comprising the
color solution, cream or shampoo described above and the developer solution. The
developer solution in this case contains between 6-12% of hydrogen peroxide, and
constituents of the formulation containing the color components can optionally also
be added. The peroxide solution, however, must be thoroughly stabilized in this case.
Semipermanent Hair Dyes:
Semipermanent colorings have been developed to maintain the coloring for 6-10
washes with shampoo. So-called direct dyestuffs which essentially belong to the
group of nitro, azo and anthraquinone dyestuffs are used in this case. These dyestuffs
are small enough to penetrate into the hair. Formulations which are typically
employed are solutions, creams, shampoos or also aerosol foams. The composition is
comparable to the formulations containing the color component which are as
permanent hair colorings.
Temporary Hair Dyes:
In contrast to the semipermanent hair dyes, temporary colorings, also called tints,
contain larger dyestuff molecules which are not capable of penetrating into the hair.
They have been developed to maintain the coloring for 1-6 washes. Azo and basic
dyestuffs and azine and thiazine derivatives are typically employed in this case. The
statements regarding the semipermanent and permanent hair dyes apply to the
composition of the formulations. Dyestuffs and other ingredients of hair dyes are
described in: A. Domsch, Die kosmetischen Praparate, Verlag fur chem. Industrie, 4th
edition, 1992. Dyestuffs are described in: Ordinance on cosmetic agents (Cosmetics
Ordinance), Bundesgesetzblatt 1997, part I p. 2412, .sctn.3 and annex 3 and in
European Community (EC) Directive, 76/68/EEC, annex IV.
The following recipes, which do not, however, limit the invention, in which each
functional active compound can occur as an individual compound or as a mixture of
several compounds of this category have been found to be particularly advantageous
for the use of the mixtures containing the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds compounds according to the invention
in cosmetic formulations.
A typical shampoo formulation according to the invention, which does not, however,
limit the invention, for care and conditioning of hair comprises the following
constituents in % by wt, in each case relative to the total formulation:
0.01 - 10 % Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention
2-15 % Anionic surfactant
0-10 % Amphoteric surfactant
0 - 15 % Non-ionic surfactant
0-10 % Cationic surfactant
0-10 % Silicone- conditioners (co-adjuvants)
0-10 % Auxiliary substances
to 100% supplemented by water.
A specific shampoo formulation, which does not, however, limit the invention,
comprises the following constituents in % by wt.:
0.1-12% Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention
1 - 35 % sodium or ammonium lauryl or
laureth sulfate (20 - 30%)
1-6 % Cocoamidopropylbetaine (25 - 35%)
0-3 % Guar Hydroxypropyltrimonium Chloride
0-5 % Polyquaternium-10
0- 12 % Silicone- conditioners (co-adjuvants)
0.01 - 1 % Disodium EDTA
0.01 - 1% Phenoxyethynol (and) methylparaben (and)
butylparaben (and) ethylparaben (and) propylparaben
0-1 % Perfume (fragrance)
0-1 % Dyestuffs
0-1 % Citric acid
0-2 % Sodium chloride
to 100% supplemented with water.
A typical hair conditioner according to the invention, which does not, however, limit
the invention, for care and conditioning of hair comprises the following constituents
in % by wt.:
0.1 -15 % Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention
0-10 % Amphoteric surfactant
0.1 - 15 % Non-ionic surfactant
0-10 % Cationic surfactant
0-15 % Silicone- conditioners (co-adjuvants)
0-20 % Auxiliary substances
to 100 % supplemented with water.
A specific composition of a hair conditioner, which does not, however, limit the
invention, comprises the following constituents in % by wt.:
0.5-15% polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention (as a
43.5% emulsion in water with non-ionic emulsifiers)
0- 15 % Silicone- conditioners (co-adjuvants)
0-10 % Cetrimonium chloride (25 - 35%)
0-3 % Guar Hydroxypropyltrimonium Chloride
1-10 % Cetearyl alcohol
0-10 % Glycerin
0.01 - 1% Phenoxyethynol (and) methylparaben (and)
butylparaben (and) ethylparaben (and) propylparaben
0-1 % Perfume (fragrance)
0-1 % Dyestuffs
0-1 % Citric acid
to 100% supplemented with water.
A typical hair care treatment according to the invention, which does not, however,
limit the invention, for care and conditioning of hair comprises the following
constituents in % by wt.:
0.4 - 20 % Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention
0-15 % Non-ionic surfactant
0-10 % Cationic surfactant
0-20 % Silicone- conditioners (co-adjuvants)
0-20 % Auxiliary substances
to 100 % supplemented with water.
A specific hair care treatment, which does not, however, limit the invention,
comprises the following constituents in % by wt.:
1-20 % polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention (as a
43.5% emulsion in water with non-ionic emulsifiers)
0.5 - 10 % Stearyl alcohol (and) Steareth-7 (and) Steareth-10
0-20 % Silicone- conditioners (co-adjuvants)
0-10 % Cetrimonium chloride (25 - 35%)
0-3 % Guar Hydroxypropyltrimonium Chloride
0-5 % Dimethicones
0-5 % Paraffin oil
1-10 % Stearyl alcohol
0-10 % Glycerin
0.01- 1% Phenoxyethynol (and) methylparaben (and) butylparaben (and)
ethylparaben (and) propylparaben
0-1 % Perfume (fragrance)
0-1 % Dyestuffs
0-1 % Citric acid
0-2 % Sodium chloride
to 100 % supplemented with water.
A quite specific hair care treatment, which does not, however, limit the invention,
comprises the following constituents in % by wt.:
2-5 % polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention (as a
43.5% emulsion in water with non-ionic emulsifiers)
0-5 % Silicone- conditioners (co-adjuvants)
0-2 % Cetrimonium chloride (25 - 35 %)
0.5 - 5 % Glycerin
0.25 - 2.5 % Propylene glycol
0.05-0.2% Perfume
0.1-0.5 % Polysorbate 20
to 100 % supplemented with water.
A typical dyestuffs-containing formulation according to the invention, which does
not, however, limit the invention, for temporary, semipermanent or permanent hair
coloring, care and conditioning of hair comprises the following constituents in % by
wt.:
0.1 - 10 % Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the
invention
1 - 10 % Hair dyestuff precursors or dyestuffs, depending on
desired hair color
0 - 15 % Anionic surfactant
0 - 10 % Amphoteric surfactant
0 - 10 % Non-ionic surfactant
0 - 10 % Cationic surfactant
0 - 1 % Sodium sulfite
0 - 5 % Buffer
0-10% Silicone- conditioners (co-adjuvants)
0 - 10 % Auxiliary substances
to 100% Water.
A specific color cream according to the invention, which does not, however, limit the
invention, for permanent hair coloring comprises the following constituents in % by
wt.:
0.1 -10% polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention (as a
20% emulsion in water with non-ionic emulsifiers)
1 - 5 % Hair dyestuff precursors or dyestuffs, depending on
desired hair color
2 - 15 % Anionic surfactant
0 - 10 % Amphoteric surfactant
0 - 10 % Non-ionic surfactant
0 - 10 % Cationic surfactant
0.1-1% Sodium sulfite
0.1-5% Buffer for pH = 8-12
0-10 % Silicone-conditioners (co-adjuvants)
0 - 10 % Auxiliary substances
to 100 % Water.
A specific color solution according to the invention, which does not, however, limit
the invention, for permanent hair coloring comprises the following constituents in %
by wt.:
0.1 -10% polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention (as a
20% emulsion in water with non-ionic emulsifiers)
1 - 5 % Hair dyestuff precursors or dyestuffs, depending on desired hair
color
0.1-1% Sodium sulfite
5 - 15 % Propylene glycol
5-15 % Ammonia (28'%)
10 - 30 % Oleic acid
5-15% Isopropanol
10 - 30 % Alkanolamide
0-10 % Silicone-conditioners (co-adjuvants)
to 100% Water.
A typical developer formulation according to the invention, which does not, however,
limit the invention, for permanent hair coloring comprises the following constituents
in%by wt.:
0.1-10% Polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention
10-30% Hydrogen peroxide (30 %)
0 - 15 % Anionic surfactant
0 - 10 % Amphoteric surfactant
0 - 10 % Non-ionic surfactant
0 - 10 % Cationic surfactant
0 - 5 % Buffer or acid for pH = 2 - 6
0 - 10 % Silicone-conditioners (co-adjuvants)
0 - 10 % Auxiliary substances
to 100 % Water.
A specific developer cream according to the invention, which does not, however, limit
the invention, for permanent hair coloring comprises the following constituents in %
by wt.:
0.1-5% polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compounds according to the invention (as a
20% emulsion in water with non-ionic emulsifiers)
10 - 30 % Hydrogen peroxide (30 %)
0- 5 % Silicone-conditioners (co-adjuvants)
1-10% Cetearyl alcohol
0.5 - 5 % Trideceth-2 carboxamide MEA
0.5 - 5 % Ceteareth-30
0,5 - 5 % Glycerin
0,05-2% Pentasodium pentetate (pentasodium
diethylenetriaminepentaacetate
0,05 - 2 % sodium stannate
0.05 - 2 % Tetrasodiumpyro phosphate
to 100% Water.
It has been found in this case that the solutions or mixtures according to the invention
are preferably suitable for the preparation of cosmetic formulations, such as for the
treatment, conditioning, cleansing and/or care of colored substrates or substrates
which are to be colored.
That is to say, the formulations containing at least one polycarbonate-
polyorganosiloxane and/
or polyurethane-polyorganosiloxane compound invention can be employed in
particular for cleansing, care and conditioning of fibrous or flat substrates, and if these
are colored and the color impression thereof is to be largely retained.
The formulations containing at least one polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compound according to the invention can
furthermore serve for the cleansing, care and the treatment and the conditioning of
keratin-containing substrates, since they are suitable as cleansing compositions for
wool, for washing and/or increasing the volume and/or the ease of combing and/or the
gloss and/or for reducing the washing out of the color from and out of colored keratin-
containing substrates or from keratin-containing substrates which are simultaneously
to be colored, such as e.g. human and animal hair.
The formulations containing at least one polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compound according to the invention can
furthermore be used in particular for the cleansing, care and the treatment, cleansing
and care of keratin-containing fibres or hair before, during and/or after the coloring
operation, since the hair dyes formulated therewith lead simultaneously to an
improvement in the softness and/or to a reduction in the wet and dry combing forces
and/or to an increase in the gloss and/or to an increase in the hair volume and/or to a
reduction in the washing out of dyestuffs from and out of tinted and dyed hair.
Softener Formulations
With respect to the administration form, on the one hand it is possible to incorporate
the polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compounds according to the invention into non-transparent softener dispersions or
softener emulsions or transparent micro-emulsions or solutions.
Typical further components for such non-transparent or transparent formulations are:
- quaternary ammonium compounds, preferably quaternary ammonium
compounds containing alkanoic acid ester units, as softeners,
organic solvents, preferably mono- and polyhydric alcohols, such as
ethanol, 2-propanol, ethylene glycol, 1,2-propylene glycol, hexylene glycol,
dipropylene glycol, esters and ethers of glycols and oligoglycols, such as
dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether,
diethylene glycol diacetate, to improve the solubility and transparency of the
formulation,
Diols and higher alcohols of longer-chain hydrocarbons, for example 2,2,4-
trimethyl-l,3-pentanediol, to increase the solubilizability of the softener
components,
- nonionogenic surfactants, preferably alkoxylates of branched or unbranched
C8 to C40 alcohols and fatty acid esters of alkylene oxides for stabilizing
emulsions or preparation of micro-emulsions
- Perfumes
Viscosity regulators
Dyestuffs
Perservatives
The additional functional components listed and preferred representatives are known,
for example, from US 6,376,455.
On the other hand, it is possible to apply the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds according to the invention to solid
carriers in the context of laundry freshener systems, and then to bring these into
contact, in the laundry dryer, with textiles which are to be freshened and/or softened.
Laundry freshener systems with carriers and functional components thereof are
known, for example, from US 4,824,582, US 4,808,086, US 4,756,850, US 4,749,596
and US 3,686,025.
Typical components for such laundry freshener systems with carriers are:
fatty amines or complexes thereof with anionic surfactants as conditioning
agent
- quaternary ammonium compounds, preferably quaternary ammonium compounds
containing alkanoic acid ester units, as softeners,
nonionogenic softeners, for example based on sorbitan esters or fatty alcohol
alkoxylates
"soil release agents", for example based on cellulose ethers, guar gum or
terephthalic acid block copolymers.
The carrier material is a sponge-like or porous sheet-like material which has a
sufficient capacity for uptake of the laundry freshener formulation. "Woven" and
nonwoven" materials are employed. They are materials based on natural or synthetic
polymers, such as wool, cotton, sisal, linen, cellulose esters, polyvinyl compounds,
polyolefins, polyamides, polyurethanes and polyesters.
The invention furthermore relates to a reactive composition comprising at least one
compound of the formula (6)

wherein R, R1, R2 and ST1 are defined as above, and p > 2,
and at least one compound of the formula (7)

wherein ST2 and Y are defined as above, and wherein q > 2,
provided that at least one of the residues ST1 and ST2 comprises a
polyorganosiloxane residue.
Preferably in this case, Y is NR6 wherein R6 is as defined above, particularly
preferably hydrogen.
at least one compound of the formula (8)

wherein ST3, Y and R are defined as above, and
at least one compound of the formula (10)

wherein Q is defined as above, and
provided that at least one of the residues ST1, ST3 and/or ST4 comprises a
polyorganosiloxane residue.
In this case R, R1, R2 preferably are, in each case, hydrogen, Y is preferably NR6,
wherein R6 is as defined above, particularly preferably hydrogen.
The invention further relates to cured compositions, obtainable by curing the
aforementioned reactive compositions. Curing of the reactive compositions is carried
out, in particular, in order to prepare coatings on substrates, such as fibers, hard
surfaces, such as on plastics, metal etc. Curing can take place at temperatures of from
room temperature (20°C) to about 250°C. As is explained above, it is also possible to
use reactive cross-linking agents during or also after the reaction of the cyclic
dicarbonates, such as, e.g., polyisocyanates.
It is also possible to prepare thermoplastic, elastomeric or duroplastic molded articles
or sealants in this manner.
The present invention is illustrated in more detail by the following examples.
EXAMPLES
Example 1
Synthesis of a carbonate-terminated siloxane
Under N2, 400 g of an epoxy-terminated polyether of the structure

are mixed with 4 g tetrabutyl ammonium bromide and heated to 130°C.
CO2 is supplied at an overpressure of 200 mbar for a total of 19 hours.
Volatiles are then removed by heating within 1 hour at 130°C in an oil-pump vacuum.
Yield 326g of a carbonate of the structure

Example 2
Synthesis of a block copolymer starting from a siloxane-based carbonate
Under N2, 50g (12.47 mmol) of a carbonate-terminated siloxane according to
Example 1

and 2.55 g (29.9 mmol) H2NCH2CH2CH2N(CH3)2 are heated to reflux temperature for
10 hours in 66 g 2-propanol. The conversion of the carbonate groups determined by
1H-NMR is 96 %. The batch is heated to reflux temperature for another 3 hours.
Then 13.1 g (12.47 mmol) of a chloroacetic acid ester of the structure

is added dropwise and the mixture is heated to reflux temperature for another 10
hours. A transparent, amber solution is obtained. The polymer contains the following
structural elements

Example 3
Synthesis of a carbonate-terminated hydrocarbon
Under N2, 200 g of a commercially available epoxy-terminated polyether of the
structure

is mixed with 2 g tetrabutyl ammonium bromide and heated to 130°C.
CO2 is supplied at an overpressure of 200 mbar for a total of 20 hours.
Volatiles are then removed by heating within 1 hour at 130°C in an oil-pump vacuum.
It was determined, with 'H-NMR spectroscopy, that the polyether carbonate formed

does not contain any epoxy groups anymore. Yield 203 g.
Example 4
Synthesis of a block copolymer starting from a hydrocarbon-based carbonate
Under N2, 10 g (16 mmol) of the carbonate-terminated polyether according to
Example 3

and 3.3 g (32 mmol) H2NCH2CH2CH2N(CH3)2 are dissolved in 59 g propylene glycol
monomethylether and heated for 9 hours to 115-120°C. Then 45.5 g (16 mmol) of a
chloroacetic acid ester of the structure

is prepared by Pt-catalyzed hydrosilylation of CH=CCH2OC(O)CH2Cl with a
corresponding a,?-SiH terminated siloxane in analogy to WO 02/10256 Example 1,
added dropwise, and the mixture is heated for another 10 hours to 120-125°C. A
transparent, reddish solution is obtained. The polymer contains the following
structural elements

Example 5
Under N2, 150 g (390 mmol NH2; 2.6 mmol NH2/g) of a commercially available
ethoxy-funktionalized amino-siloxane of the structure

and a solution of 0.5 g KOH in 1.5 g methanol are received in 180 g dipropylene
glycol monobutylether. The mixture is heated to 120-130°C. After applying a slight
vacuum (380mm Hg), 24.8 g of low boilers are distilled off. 0.6 g acetic acid are
subsequently added. The batch is then heated to 135°C for 0.5 hours, with a slight
vacuum (380 mm Hg) being applied in order to remove residual volatiles.
289 g of a product are obtained with an amine content of 1.348 mmol NH2/g and the
structure

Example 6
Synthesis of a carbonate-terminated polyurethane-polyorganosiloxane
compound according to the invention
Under N2, 9.25 g (12.47 mmol NH2 groups; 1.348 mmol NH2/g) of the alkoxy-
functionalized amino-siloxane according to Example 5

49.25 g (12.47 mmol corresponding to 24.94 mmol cyclocarbonate groups) of a
carbonate-terminated siloxane of the structure

which was prepared in analogy to example 1, was dissolved in 61 g propylene glycol
monomethylether and heated for 13 hours to 120-122°C. A compound of the formula

is obtained, wherein the indices m and n correspond to those of the starting materials
and R corresponds to alkoxy, as in the starting amine.
Example 7
Synthesis of the block copolymer with alkoxysilyl groups capable of cross-linking
1.27 g (12.47mmol) H2NCH2CH2CH2N(CH3)2 are added to the solution of the
compounds of Example 6. The mixture is kept for another 9 hours at 120-122°C.
Finally, 6.55 g (6.235 mmol) of a chloroacetic ester of the structure

is added and the bnatch is stirred for 9 hours at 120-125°C.
A slightly opaque, yellowish, viscous solution is obtained, wherein the polymer has
the following structural elements

The polymers according to the Examples 2, 4, 6 and 7, in an amount of, for example,
0.5-3%, can be worked into powdery and liquid laundry detergents that are in
particular based on anionic and/or non-ionogenic surfactants, and there exhibit their
softening effect on the fiber materials to be cleansed.
EXAMPLE 8:
Synthesis of a carbonate-terminated siloxane
Under N2, 400 g of an epoxy-terminated polyether of the structure

are mixed with 4 g tetrabutyl ammonium bromide and heated to 130°C.
CO2 is supplied at an overpressure of 200 mbar for a total of 34 hours.
Volatiles are then removed by heating within 1 hour at 130°C in an oil-pump vacuum.
Yield 376g of a carbonate of the structure

Example 9
Synthesis of a carbonate-terminated hydrocarbon
Under N2, 200 g of a commercially available epoxy-terminated polyether of the
structure

is mixed with 2 g tetrabutyl ammonium bromide and heated to 130°C.
CO2 is supplied at an overpressure of 200 mbar for a total of 20 hours.
Volatiles are then removed by heating within 1 hour at 130°C in an oil-pump vacuum.
It was determined, with 1H-NMR spectroscopy, that the polyether carbonate formed

does not contain any epoxy groups anymore. Yield 203 g.
Example 10
Synthesis of a block copolymer, starting from a siloxane-based carbonate and a
hydrocarbon-based carbonate
Under N2, 55.8g (8 mmol) of the carbonate-terminated siloxane according to Example
8

5g (8 mmol) of the carbonate-terminated hydrocarbon according to Example 9

and 2.3 g (16 mmol) H2NCH2CH2CH2N(CH3)CH2CH2CH2NH2 are dissolved in 63 g
propylene glycol monomethylether and heated for 12 hours to 118°C.
Then, 1.96 g (16 mmol) ClCH2C(O)OCH2CH3 and 35 g propylene glycol
monomethylether are added dropwise and the mixture is kept at 118°C for another 8
hours. A slightly opaque viscous solution is obtained.
The polymer formed contains the following structural elements in a molar ration 1 : 1

The polymer according to Example 10, preferably in an amount of 0.5-3%, can be
worked into powdery and liquid laundry detergents that are in particular based on
anionic and/or non-ionogenic surfactants, and there exhibits its softening effect on the
fiber materials to be cleansed.
We claim:
1. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound, containing at least one structural element of the formula (1):

wherein
R is respectively selected from hydrogen, alkyl, or a bond to the residue ST1,
with cyclic structures forming if R represents a bond to the residue ST1,
R1 is respectively selected from hydrogen, alkyl, or a bond to the residue
ST1, with cyclic structures forming if R represents a bond to the residue
ST1,
R2 is respectively selected from hydrogen, alkyl, or a bond to the residue
ST1, with cyclic structures forming if R1 represents a bond to the residue
ST1,
ST1 is a di- or polyvalent, straight-chained, cyclic or branched, saturated,
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue
with up to 1000 carbon atoms, which may contain one or more groups
selected from:
-O-,
-C(O)-, and
a polyorganosiloxane unit with 2 to 1000 silicon atoms,
wherein
ST1 contains no groups of the formula -O-C(O)-O- and no groups of the
formula -O-C(O)-NH-,
wherein, if a plurality of residues ST1 is present, they may be the same or
different,
Y is selected independently from one another from: -O-, -S- and
-NR6-, wherein
R6 is hydrogen or a straight-chained, cyclic or branched, saturated,
unsaturated or aromatic hydrocarbon residue with up to 40 carbon
atoms, which may contain one or more groups selected from -O-, -
C(O)-, -NH- and -NR3-, wherein R3 is defined as above, or
R6 represents a bond to the residue ST2 while forming cyclic
structures,
ST2 is a di- or polyvalent, straight-chained, cyclic or branched, saturated,
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue
with up to 1000 carbon atoms, which may contain one or more groups
selected from:

a polyorganosiloxane unit with 2 to 1000 silicon atoms,
wherein
R3 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 40 carbon atoms, which may
contain one or more groups selected from -O-, -C(O)- and -NH-, and
may optionally be substituted by a silyl group, and
R5 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 100 carbon atoms, which may
contain one or more groups selected from -O-, -C(O)- and -NH-, and
may optionally be substituted by a silyl group, or two residues R
form, with the nitrogen atom to which they are bonded, a 5 to 7-
membered ring, which may optionally contain one or two further
hetero atoms, or R5, together with R6, forms a divalent alkylene
residue which leads to the formation of a cyclic structure including Y
and ST2,
wherein, if a plurality of residues ST2 is present, they may be the same or
different,
provided that at least one of the residues ST1 and/or ST2 comprises a
polyorganosiloxane residue,
or acid addition compounds and/or salts thereof.
2. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to claim 1, wherein at least one of the residues R, R1
and R2 is hydrogen.
3. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to claim 2, wherein the residues R, R1 and R2 are
hydrogen.
4. Linear polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compound according to any one of the claims 1 to 3.
5. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to according to any one of the claims 1 to 4, wherein
ST1 and ST2 are each divalent residues.
6. Branched polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compound according to according to any one of the
claims 1 to 3.
7. Branched polycarbonate-polyorganosiloxane and/or polyurethane-
polyorganosiloxane compound according to claim 6, wherein the branching
of the polymer chain takes place via at least one of the residues ST1 or ST2.
8. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to any one of the claims 1 to 7, containing at least one
polyorganosiloxane residue of the formula (2):

wherein
R4 is a straight-chained, cyclic or branched, saturated, unsaturated or
aromatic hydrocarbon residue with up to 20 carbon atoms, and/or R4 is an
alkoxy residue, the alkyl part of which is a straight-chained, cyclic or
branched, saturated alkyl residue with up to 20 carbon atoms, which may
contain one or more oxygen atoms, and

wherein s is defined as above, and
r=1 to 12.
16. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to according to any one of the claims 1 to 15, wherein
ST2 represents a residue of the formula (5)

wherein
R5 is defined as above,
ST3 is a di- or polyvalent, straight-chained or cyclic or branched, saturated or
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue
with 2 to 100 carbon atoms, which may contain -O-, -C(O)-, -NH- and/or -
NR3-, wherein R is defined as above, and
ST4 is a di- or polyvalent, straight-chained or cyclic or branched, saturated or
unsaturated or aromatic, substituted or unsubstituted hydrocarbon residue
with 2 to 100 carbon atoms, which may contain -O-, -C(O)-, -NH- and/or -
NR - , and/or a polyorganosiloxane unit with 2 to 500, wherein R is defined
as above, and
A- is an organic or inorganic anion.
17. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to according to any one of the claims 1 to 16 of the
following formula (3)

wherein
R, R1, R2, ST1, ST3, ST4, R6 and R5 are defined as above, and
A- is an organic or inorganic anion,
provided that at least one of the residues ST1, ST3 and ST4 contains a
polyorganosiloxane residue.
18. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to any one of the claims 1 to 17, wherein ST1 and/or
ST2 are selected from the group consisting of polyorganosiloxane-containing
residues, polyether-containing residues, polyorganosiloxane- and polyether-
containing residues, monocyclic or polycyclic hydrocarbon residues, acyclic,
optionally oxygen-containing hydrocarbon residues and optionally oxygen-
containing hydrocarbon residues comprising aromatic groups.
19. Polycarbonate-polyorganosiloxane and/or polyurethane-polyorganosiloxane
compound according to according to any one of the claims 1 to 18, wherein
the residues ST1 and/or ST2 contain a polyalkyleneoxy group.
20. Method for preparing the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compound according to according to any
one of the claims 1 to 19, which comprises the reaction of a compound of the
formula (6)

wherein R, R1, R2 and ST1 are defined as above, and p > 2,
with at least one compound of the formula (7)

wherein ST and Y are defined as above, and wherein q > 2.
21. Method according to claim 20, wherein Y = NR6 , wherein R6 is as defined
above, preferably hydrogen.
22. Method for preparing the polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compound according to according to any
one of the claims 1 to 19, which comprises the reaction of a compound of the
formula (6)

wherein R, R1, R2 and ST are defined as above, and p > 2,
with a compound of the formula (8)
HY-ST3-NR52,
wherein ST3, Y and R5 are defined as above,
and a compound of the formula (9)
ST4V(-Q)t,
wherein
Q is a residue capable of alkylating an amino group, ST4V,together with the
molecule part arising from Q after the quaternating reaction, forms the
residue ST4, and t > 2.
23. Method according to claim 22, wherein Y = NR6 , wherein R6 is as defined
above, preferably hydrogen.
24. Method according to claim 22 or 23, wherein Q is selected from epoxy
groups and haloalkyl groups.
25. Laundry detergent formulations, cosmetic formulations or formulations for
fiber treatment, containing at least one polycarbonate-polyorganosiloxane
and/or polyurethane-polyorganosiloxane compound according to any one of
the claims 1 to 19.
26. Reactive composition comprising at least one compound of the formula (6)

wherein R, R1, R2 and ST1 are defined as above, and p > 2,
and at least one compound of the formula (7)
ST2-(Y-H)q,
wherein ST2 and Y are defined as above, and wherein q > 2,
provided that at least one of the residues ST1 and ST2 comprises a
polyorganosiloxane residue.
27. Reactive composition according to claim 26, wherein Y = NR6, wherein R6
is as defined above, preferably hydrogen.
28. Reactive composition comprising at least one compound of the formula (6)

wherein R, R1, R2 and ST1 are defined as above, and p > 2, and
at least one compound of the formula (8)
HY-ST3-NR52,
wherein ST3, Y and R5 are defined as above, and
at least one compound of the formula (10)
Q-STV-Q,
wherein Q is defined as above, and
provided that at least one of the residues ST1, ST3 and/or ST4 comprises a
polyorganosiloxane residue.
23. Reactive composition according to claim 26, wherein R, R1, R2 are each
hydrogen, Y= NR6, wherein R6 is as defined above, preferably hydrogen.
30. Cured composition, obtainable by curing the reactive compositions according
to any one of the claims 15 to 27
31. Cured composition according to claim 28, selected from a coating and an
elastomer.

The present invention relates to novel polycarbonate-polyorganosiloxane and/or
polyurethane-polyorganosiloxane compounds, methods for their production, their use,
functional formulations containing them, precursors for their production, as well as
reactive compositions containing the aforementioned precursors.