Title of Invention

"A FORMULATION COMPRISING AT LEAST ONE QUATERNIZED AMINOALKYLSILOXANE"

Abstract A formulation comprising at least one quaternized aminoalkylsiloxane and b) a hydrophilic, nonionogenic, interface-active compound, wherein the hydrophilic, nonionogenic, interface-active compound (a) is selected from compounds modified with ethylene/propylene oxide (EO/PO) from the group of the fatty alcohols, fatty acids, alcohols, acids, alkylaryl derivatives, fatty amines, glycerides and sorbitan esters, in each of which the number of EO/PO units is between 15 and 150, the ratio of PO units to EO units being equal to or lower than 0.25, and in which the number of ethylene oxide units (EO fraction) is greater than or equal to the number of carbon atoms in the non-EO fraction, or are alkylpolyglycosides, ethylene oxide/propylene oxide copolymers and polyethersiloxanes, and further characterized in that the quaternized aminoalkylsiloxanes are linear or cyclic polysiloxane polymers having repeating structural units of the formulae (10) and (11) where X, Y, R1', R12, R13, R14 , R16, M, B, v, w, n and A- are herein described
Full Text The present invention relates to a formulation comprising at least one quaternized aminoalkylsiloxane.
The invention relates to novel formulations based on quaternized aminoalkylsilicones or -siloxanes, to processes for preparing these formulations and to their use as textile assistants for finishing textile materials.
Silicone softeners are used widely for the finishing of textile materials. For the practical use of the silicone softener emulsions, requirements such as storage stability, thermal stability, resistance toward whiteners and other anionic textile assistants, resistance to pH changes and salt addition and against the action of mechanical energy are of central significance. Particularly the stability against the action of mechanical energy, the shear stability or jet stability, often presents silicone softener emulsions with great difficulties under industrial conditions (cf. R. Zyschka, Melhand Textilberichte 6/2001, 497).
Microemulsions offer the fundamental advantage of thermodynamic stability. In a multitude of publications, the equilibrium phase behavior is treated as a function of the. structure of the oil to be emulsified and/or of the surfactant(s). Likewise systematically studied has been the addition of inorganic salts (cf. M. Kahlweit et al., Langmurr 11[1995], 3382; M. Kahlweit et al., Langmuir 11[1995]). The equilibrium , phase behavior of microemulsions of low molecular weight silicones has likewise been investigated (EP-A. 774482; H. von Berlepsch et al, Progr. Colloid Polymer Science 111[1998], 107).
With regard to' the softening components, combinations of hydrocarbon-based quats with silicone quats (GB-A 1549180) or else silicone polyethers with silicone quats (US-A 4921895) have been proposed.
To improve the hydrophilicity, the widely utilized ammoalkylsiloxanes are increasingly being replaced by polyether-modified ammoalkylsiloxane oils (cf EP-A 578144)
An additional introduction of alkoxysilyl structures into polyether- and ammo-substituted silicones has likewise been proposed (US-A 20020028900)
Finally, true permanently hydrophilic textile softeners based on silicone quats have been disclosed in WO 02/10256, WO 02/10257 and WO 02/10259.
Fine microemulsions of ammoalkylsiloxanes are said to be obtainable m a two-stage process by preparing a concentrate of ammoalkylsiloxane, silicone-insoluble surfactant and a little water with subsequent rapid stirring into water (US-A 4620878)
According to DE-A 3723697, aminosiloxane emulsions are said to become mechanically stable as a result of the use of water-soluble nomonogenic emulsifiers For extreme shear stresses, as are achieved on modem jet plants, it has been found that the inventions disclosed m DE-A 3723697 are insufficient to prevent deposits m the jet plant and on the textiles to be treated.
According to WO 02/10501, ammo functional organosihcon compounds are said to become mechanically stable even m jet dyeing machines without using water-soluble nomonogenic emulsifiers It has been found that the inventions disclosed in WO 02/10501 are likewise not yet sufficient to reliably prevent deposits on differently pretreated textiles.
Mechanical stability of aminosiloxane microemulsions is also said to be achievable by using betaines, optionally m combination with nomonogemc surfactants of the HLB range from 5 to 16 (cf. US-A 5573694, US-A 5520827)
It is known in dyeing technology that complex mixtures which comprise sulfonated alkylnaphthyl derivatives and halogenated hydrocarbons can be utilized as jet-stable dyeing accelerator formulations (US-A 4080166)
Such sulfonated naphthyl derivatives in combination with fatty alcohol ethoxylates have also been proposed for the stabilization of mkjetable formulations (US-A 6302948). The combination of fatty alcohol ethoxylates with pigments of a certain size is likewise said to lead to mkjetable systems (US-A 6099627)
Finally, it is also known that salts of strong acids, e g. Al2(SO4)3 x 18 H2O ensure protonation of catiomc dyes m thermal transfer printing pastes but simultaneously impair their stability (cf US-A 5925701).
It is common to all of the proposals cited that they do not contain any hints to measures by which emulsions or microemulsions of sihcone-based textile softeners, preferably ammosiloxanes and quatemized ammoalkylsiloxanes (sihcone quats) can be stabilized reliably against the action of high mechanical energy input of the modern jet systems m combination with greatly varying liquor ratios and the influence of varying pretreatment preparations on the fibers Moreover, the prior art does not disclose any measures by which the simultaneously occurring high foaming tendency (causes stain formation) of textile softener formulations under high mechanical energy input can be restricted
It is thus an object of the present invention to describe measures by which emulsions or microemulsions of silicon-based textile softeners, preferably quatemized ammoalkylsiloxanes (silicone quats), can be reliably stabilized under the action of high energy input (extremely high shear forces m modern jet systems) in combination with greatly varying liquor ratios, and the influence of varying pretreatment preparations and the foaming tendency can be simultaneously restricted
It has been found that, surprisingly, this object is achieved by the combination of quatemized ammoalkylsiloxanes with highly hydrophihc nomonogemc interface-active compounds (surfactants) and/or highly hydrophihc dispersants and/or salts of polyvalent cations and optionally further customary formulation agents.
The present mvention therefore relates to formulations comprising at least one quatemized armnoalkylsiloxane and at least one compound from the group of
a) the hydrophihc, nonionogenic, interface-active compounds,
b) the hydrophihc dispersants and
c) the salts of di- or tnvalent metals with inorganic acids
Preferred hydrophihc, nomonogemc, interface-active compounds (a) m the context of the invention are substances which lower the surface tension of water to below 45 mN/m. They are in particular compounds modified with ethylene/propylene oxide (EO/PO), optionally unsaturated and/or branched, from the group of the fatty alcohols, fatty acids, alcohols, acids, alkylaryl derivatives, fatty amines, glycendes and sorbitan esters, in each of which the number of EO/PO units is between 15 and 150, the ratio of PO units to EO units being equal to 0 25 or lower than 0 25, and m each of which the number of ethylene oxide umts (EO fraction) is greater than or equal to the number of carbon atoms m the non-EO fraction, or are alkyl-polyglycosides, ethylene oxide/propylene oxide copolymers and polyethersiloxanes.
Hydrophihc dispersants (b) in the context of the invention are substances which, when added to water, lower the surface tension to a value between 72 to 45 mN/m
The preferred compounds (b) are water-soluble polysaccharides such as carboxy-methylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose or compounds of the formula
(Formula Removed)
where
x is from 1.5 to 20, preferably from 1 5 to 10.
The salts (c) are metal salts having a valency of two or higher, preferably calcium, magnesium and aluminum salts, optionally in the form of their hydrates, with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid. The counterions are to be selected m such a way that sufficient water and formulation solubility is ensured at a given stability of the salt. Examples of such salts are Ca(Cl)2, Mg(Cl)2 and A12(SO4)3, optionally in the form of their hydrates.
Specifically, the compounds (a) are those of the formulae
(Formula Removed)
(Formula Removed)
or a polyethersiloxane (9)
(Formula Removed)

where
E is an R1 radical, hydrogen, straight-chain or branched, saturated or mono- or
polyunsaturated C1-C18-alkyl which is optionally mono- or nolysubstituted by
-OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C10-cyclo-alkyl which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl
R1 is straight-chain or branched, saturated or unsaturated C8-C40-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, CV C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-C1-C4-alkylammo, or is C5-C10-cycloalkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1 C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-C1-C4-alkylammo,
R" is straight-chain or branched, saturated or mono- to polyunsaturated C8-C40-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, (Formula Removed)
R is straight-chain or branched C1-C26-alkyl or C6-C10-aryl,
(Formula Removed)
where
Z is a straight-chain or branched alkyl or cycloalkyl radical which
is in each case interrupted by -0- and/or -CO- and may optionally be substituted by at least one OH group,
or
(Formula Removed)

q is from 15 to 150,
ql and q2 are each independently from 0 to 150,
where the sum of ql + q2 — q,
q3, q4, q5 and q6 are each independently from 0 to 150
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 50,
rl and r2 are each independently from 0 to 50
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 50
where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r :q m is from 1 to 50,
m7 and m8 are each independently from 1 to 50 where 2 4, s is from 5 to 150, t is from 5 to 150 where 0 05 or a polyethersiloxane (9')
where
the brackets "{"and"}" shown m formulae (l')-(8') mean that the ethylene oxide or propylene oxide units within these brackets may either be arranged blockwise as shown or else be in any random distribution,
E is an R radical, hydrogen, straight-chain or branched, saturated or mono- or
polyunsaturated C1-C18-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C10-cyclo-alkyl which is optionally mono- or polysubstituted by C1-C4-alkyL -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R! is straight-chain or branched, saturated or unsaturated C8-C40-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylammo, or is C5-C10-cycloalkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-C1-C4-alkylamrno, or is C6-C10-aryl which is optionally substituted, especially by C3-Ci5-alkyl,
R2 is straight-chain or branched, saturated or mono- to polyunsaturated C8-C40-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R3 is straight-cham or branched C1-C26-alkyl or C6-C10-aryl,
R4 is R3 or is a radical of the formulae
(Formula Removed)
where
Z is a straight-chain or branched alkyl or cycloalkyl radical which
is m each case interrupted by -0- and /or -CO- and may optionally be substituted by at least one OH group
or
(Formula Removed)

where the brackets "{"and"}" shown m the aforementioned formulae again mean that the ethylene oxide or propylene oxide units withm these brackets may either be arranged blockwise as shown or else may be in any random distribution,
q is from 15 to 150,
ql and q2 are each independently from 0 to 150
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 0 to 150
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 50,
rl and r2 are each mdependently from 0 to 50
where the sum of rl + r2 = r,
where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r . q m is from 1 to 50,
m7 and m8 are each independently from 1 to 50
where 2 the ratio of q : m > 4,
s is from 5 to 150, preferably 15-150,
t is from 5 to 150, preferably from 5 to 150 and in particular from 5 to 20,
where t s 0 0 at least one R4 = R3, and
for formula (9')
0 01 In particular, the compounds (a) are those of the formulae (1) to (9) where
E is hydrogen, straight-cham or branched, saturated or mono- or
polyunsaturated C1-C4-alkyl which is optionally mono- to disubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C6 -cycloalkyl which is m each case optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R1 is straight-cham or branched, saturated or unsaturated C10-C36-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-d-C4-alkylammo, or is C5-C6-cycloalkyl whose alkyl chain is optionally interrupted smgly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-C1-C4-alkylammo,
R" is straight-cham or branched, saturated or mono- to polyunsaturated C10-C36-alkyl which is optionally mono- or polysubstituted by -OH, CrC4-alkoxy, d-C4-alkoxycarbonyl or carbonyl,
R is straight-cham or branched C1-C18-alkyl or C6-C10-aryl,
R4 is an R3 radical or is a radical of the formulae
or
(Formula Removed)
q is from 20 to 100,
ql and q2 are each independently from 20 to 100
where the sum of ql - q2 = q,
q3, q4, q5 and q6 are each independently from 20 to 100
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 20,
rl and r2 are each independently from 0 to 20
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 20
where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r : q m is from 1 to 7,
m7 and m8 are each independently from 1 to 7
where 2 the ratio of q m>4,
s is from 5 to 100,
t is from 5 to 100
where 0 05
0 In particular, the compounds (a) are those of the formulae (1') to (9') where
E is hydrogen, straight-chain or branched, saturated or mono- or
polyunsaturated C1-C4-alkyl which is optionally mono- to disubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C6 -cycloalkyl which is in each case optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R1 is straight-chain or branched, saturated or unsaturated C10-C^-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-C1-C4-alkylammo, or is C5-C6-cycloalkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, ammo, mono- or di-C1-C4-alkylamino, or is C6-C10-aryl which is optionally substituted, especially by C3-C15-alkyl,
R is straight-chain or branched, saturated or mono- to polyunsaturated C10-C36-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
RJ is straight-chain or branched C1-C18-alkyl or C6-C10-aryl, R4 is an R3 radical or is a radical of the formulae
or(Formula Removed)

(Formula Removed)

q is from 20 to 100,
ql and q2 are each independently from 20 to 100
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 20 to 100
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 20,
rl and r2 are each independently from 0 to 20
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 20 where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r q m is from 1 to 7,
m.7 and m8 are each independently from 1 to 7
where 2 the ratio of q m > 4,
s is from 5 to 100, preferably from 15 to 100
t is from 5 to 100, preferably from 5 to 20
where t:s 0 0 at least one R4 = R3,
and
for the formula (9')-
0.01 The compounds (a) are more preferably those of the formulae (1) to (9) where
E is H-, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2- or
CH3C(0)-
R1 is a radical of the formulae
(Formula Removed)
where
nl = from 9 to 23, n2 = from 3 to 23, n3 = from 0 to 18, n4 = from 7 to 23, n5 = from 3 to 15, R" is a radical of the formulae

(Formula Removed)

where
n6 = 8 to to 28, R3 is C1-C18-alkyl or C6-C10-aryl, R4 is an R3 radical or is a radical of the formulae
(Formula Removed)
or
(Formula Removed)

q is from 25 to 60,
ql and q2 are each independently from 25 to 60
q3, q4, q5 and q6 are each independently from 25 to 60
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 10,
rl and r2 are each independently from 0 to 10 where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 10, where the sum of r3 + r4 + r5 + r6 = r, and the ratio of r q (Formula Removed)
R1 is a radical of the formulae
(Formula Removed)
where
nl = from 9 to 23,
n2 = from 3 to 23, preferably from 6 to 23
n3 = from 0 to 18, where, preferably, n2+ n3 n4 = from 7 to 23,
n.5 = from 3 to to 15,
R" is a radical of the formulae
(Formula Removed)
where
n6 = 8 to to 28, R3 is C1-C18-alkyl or C6-C10-aryl, R4 is an R3 radical or is a radical of the formulae
(Formula Removed)

or
(Formula Removed)

q is from 25 to 60,
ql and q2 are each independently from 25 to 60
q3, q4, q5 and q6 are each independently from 25 to 60
where the sum of q3 + q4 + q5 + q6 - q,
r is from 0 to 10.
rl and r2 are each independently from 0 to 10
where the sum of rl + r2 = r,
r3, r4, r5 and x6 are each independently from 0 to 10
where the sum of r3 + r4 + r5 + r6 - r, and
the ratio of r q for the formula (9')
0.01 Very particular preference is given to inventive formulations which comprise, as compound (a), the ester of stearic acid and 40 mol of EO
The inventive formulations comprise at least one aminoalkylsiloxane compound quatermzed on the nitrogen (silicone quat) Such compounds and their preparation are known, for example, from WO 02/10 256, WO 02/10 257, WO 02/10 259, EP 282 720, EP 17 121, DE-A 100 36 533, DE-A 100 36 539, DE-A 100 36 532, DE-A 100 36 522 and DE -A 102 12 470
The quatermzed aminoalkylsiloxane compounds present m the inventive formulations preferably correspond to linear or cyclic polysiloxane polymers of WO 02-10259 having repeating essential structural units of the formulae (10) and (11)
(Formula Removed)
where
X is a divalent hydrocarbon radical having at least 4 carbon atoms which may have a hydroxyl group, preferably has a hydroxyl group, and which may be interrupted by one oxygen atom, and the X groups in the repeating units may be the same or different,
Y is a divalent hydrocarbon radical having at least 2 carbon atoms which has a hydroxyl group and which may be interrupted by one or more oxygen or nitrogen atoms,
R11, R12, R13 and R14 are the same or different and are each alkyl radicals having from 1 to 4 carbon atoms or benzyl radicals, or the Rn and R13 or R12 and R14 radicals may in each case be constituents of a bridging alkylene radical,
R16 is H or an alkyl radical having from 1 to 20 carbon atoms which may be oxygen-substituted,
M is the structure -B-0-(EOx)v(POx)w-B-, where
EOx is an ethylene oxide unit and POx is a propylene oxide umt,
v is from 0 to 200,
w is from 0 to 200,
v+w > 1,
n is from 2 to 1000 where the n m the repeating units may be the same or different,
A- is an inorganic or organic anion.
The inventive formulations in some cases also comprise any mixtures of the above-designated quatemized armnoalkylsiloxane compounds with the corresponding nonquaternized compounds In these nonquatermzed compounds, m each case one of the Rn or R12 radicals or R13 or R14 radicals m the mam chain on the nitrogen atoms in the formula (10) is thus absent
The quatemized armnoalkylsiloxane compounds which are preferred in accordance with the invention form part of the subject-matter of WO 02/10 259 and are described there generally and specifically The contents of WO 02/10 259 are incorporated fully by the present application.
In a preferred embodiment of the invention, the amounts of hydrophihc, nonionogenic, interface-active compounds (a) and/or hydrophihc dispersants (b) and/or salts (c) to the amounts of quatemized armnoalkylsiloxane compounds are m a weight ratio n of Ω = 0 05 to 10, preferably Ω = 0 05 to 5, especially Ω = 0 05 to 3, very especially Ω = 0 05 to 1 Ω. illustrates only the ratio of total amount of component (a) to (c) to amount of silicone quat. When the amounts of additive (a) and/or (b) and/or (c) are too small, the effective stabilization m the fiber finishing is

always be maintained under strong mechanical shear, high temperatures, long finishing cycles Very large additive amounts are uneconomic and can change the hand of the textile m an undesired manner
The additives a) to c) described may be added in two ways It is possible firstly to introduce the inventive additives directly into the formulations. Secondly, it may be favorable under practice conditions to first dilute the formulations to use concentration and to subsequently add the inventive additives to the liquor prepared
In addition to components (a) and/or (b) and/or (c), the inventive formulations may also comprise further interface-active components (f) which enable emulsification or microemulsification
These components (f) are customary formulation agents, known to those skilled m the art, for preparing the silicone (micro)emulsions which, however, alone are not stable against high energy input Such preferred components fl) to f6) include- (fl) oxalkylation products which are obtainable by alkoxylating, with ethylene oxide or propylene oxide, condensation products of phenolic OH-contammg aromatics with formaldehyde and NH functional groups. f2) nonionic or lomcally modified compounds from the group of the alkoxylates, alkylolamides, esters, amine oxides and alkylpolyglycosides, especially reaction products of alkylene oxides with alkylatable compounds, for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, carboxamides and resin acids They are, for example, ethylene oxide ethers from the class of the reaction products of ethylene oxide with saturated and/or unsaturated fatty alcohols having from 6 to 25 carbon atoms (commercially available, for example, m the form of Renex® product series) or alkylphenols having from 4 to 12 carbon atoms m the alkyl radical or saturated and/or unsaturated fatty amines having from 14 to 20 carbon atoms or saturated and/or unsaturated fatty acids having from 14 to 22 carbon atoms, or estenfication and/or arylation products which are prepared from natural or modified, optionally hydrogenated castor oil fatty substances and are optionally joined to give repeating units by estenfication with
dicarboxylic acids f3) ionic or noniomc compounds from the group of the reaction products of alkylene oxide with sorbitan esters [Tween, ICI], oxalkylated acety-lenediols and glycols, oxalkylated phenols, especially phenol/styrene polyglycol ethers f4) ionic or noniomc polymeric surface-active agents from the group of the homo- and copolymers, graft polymers and graft copolymers and random and linear block copolymers. f5) anionic surface-active agents, for example alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccmamides, paraffin sulfonates, olefin sulfonates, sarcosmates, isothionates and taurates f6) amphoteric surface-active agents such as betames and ampholytes especially glycmates, propionates and imidazolines
Particularly preferred formulation constituents (f) are alkoxylated fatty alcohols, branched fatty alcohols and fatty acids having from 4 to 14 alkoxy units, very particularly preferred formulation constituents (f) are alkoxylated fatty alcohols, branched fatty alcohols havmg from 6 to 12 alkoxyl units, especially formulations which contain the ether of tndecyl alcohol with 12 mol of EO, the ether of tndecyl alcohol with 6 mol of EO.
The formulation constituents are generally added m customary amounts to the inventive formulation. Preference is given to adding the components (f) m amounts of from 1 to 200% by weight, preferably from 10 to 80% by weight, more preferably 10-50% by weight, based on the quatemized ammoalkylsiloxane
In addition to component(s) (a) to (c), the formulations, m each case alone or m combination, and the additives (f) may also compnse further assistants in the amounts customary for these assistants
Typical assistants m the context of the invention include leveling agents, wetting agents, lustenng agents, fiber protection agents, antislip agents and further prior art assistants A good overview of the inventive assistants can be found in Chwala/ Anger, Handbuch der Textilhilfsmittel. Verlag Chemie, Wemhem 1977
Furthermore, buffer systems may be used to obtain an optimal pH value during the finishing
To prepare the inventive formulations, the quatemized ammoalkylsiloxane compounds may be mixed with components (a), (b) and/or (c), optionally with addition of further, abovementioned constituents, preferably within a temperature range of from 20 to 90°C, more preferably of from 25 to 70°C, most preferably from 30 to 60°C
The quatemized aminoalkylsiloxanes are preferably added to the compound(s) (a), (b) and/or (c), particular preference is given to initially charging the quatemized ammoalkylsiloxane (silicone quat) and completing the emulsion formulation by adding the compound(s) (a), (b) and/or (c) and optionally further additives
The inventive formulations are outstandingly suitable as textile softeners in the finishing of textile structures, especially those made of cotton, keratin fibers, preferably wool, silk or synthetic fibers or, for example, used very efficiently for the finishing of textile structures made of mixtures of cotton with polyester, polyamide, polyacrylonitnle, wool or silk. Excellent results are equally achieved m the finishing of textile structures made of synthetic fibers, especially made of polyester, polyamide, polypropylene or mixtures thereof
Textile structures are preferably wovens, knits, including formed-loop knits, and nonwovens
It has been found that the inventive formulations are particularly advantageous for the finishing of cotton or cotton-contammg textiles which have been pretreated with anionic hghteners by the jet process
When the inventive formulations are used, it is possible not only to achieve outstanding softener results but also an improvement in other properties of the textile such as the solubility or an increase m the gloss
The finishing is generally effected by the continuous process (pad mangle or backwasher process) or by the exhaustion process (jet process). When the inventive formulations are employed by one of these finishing processes, it has been found to be advantageous to maintain the following technological parameters
• Continuous (for example pad mangle, backwasher)
1 At 11% silicone concentration 5-50 g/1, preferably 10-40 gi\ and especially
10-25 g/1 of SΩ (= silicone quat) formulation + a) to c)
2 Finishing temperature Room temperature
3. Drying temperature- 75-105°C in a forced-air drying cabinet
or 10-60 sec on a tenter frame at 150°C, particularly 30-45 sec
4. Time m the forced-air drying cabinet 10-20 minutes
• Exhaustion process (for example jet, winchbeck)
1 At 11 % silicone concentration 10-5 0%, preferably 1.5-3 5% and
especially 15-2 5%
2. Finishing temperature: 30-60°C, preferably 35-50°C and
especially 35-45°C
3 Heating rate 2-4°C/mmute
4 Finishing time- 15-25 minutes
5 Liquor ratio from 1 5 to 1 50, particularly from 1:10
tol 30
6 Drying temperature 75-105°C in a forced-air drying cabinet
or 10-60 sec on a tenter frame at 150°C, particularly 30-45 sec
7 Time m the forced-air drying cabinet 10-20 minutes
Examples
In the formulations which follow, a silicone quat (SΩ) synthesized according to WO 02/10259, Example 1, was used which had the following structural elements and is prepared as follows
la) A 1 liter three-neck flask was initially charged at room temperature with 24 g of water and 4.18 g (0 048 mol of tertiary ammo groups) of N,N,N',N'-tetramethyl-1.6-hexanediamme and 3 8 g (0 012 mol of primary ammo groups) of an alkylene oxide derivative, obtainable under the trade name Jeffamin® ED 600, of the structure
H2NCH(CH3)CH2[OCH2CH(CH3)]a(OCH2CH2)9[OCH2CH(CH3)]bNH2 where a+b = 36
Within 5 minutes, 12 0 g (0.03 mol) of dodecanoic acid in the form of a 50% solution m 2-propanol and 1.8 g (0.03 mol) of acetic acid were added. After the mixture had been heated to 50°C, 194.1 g (0 06 mol of epoxy groups) of an epoxy siloxane of the average composition
(Formula Removed)
and 30 ml of 2-propanol were added dropwise within 30 minutes The yellow, opaque mixture was heated to reflux temperature for 6 hours After removal of all constituents volatile up to 100°C and at a reduced pressure of 2 mmHg, 204 g of a slightly yellow, opaque material were obtained which contains the following structural elements
(Formula Removed)
Startmg from this silicone material, three microemulsion concentrates of the following composition were prepared
(Table Removed)
These three microemulsion concentrates (about 40% based on SΩ) are diluted
uniformly with water to 11% silicone quat content m each case Of these 11%
transparent microemulsions, in each case 6 g (absolute amount of silicone quat
0 66 g) are withdrawn, mixed intensively with 6000 ml of water and optionally
additives and utilized for jet finishing under the following boundary conditions-
Jet type Mathis Labor-Jumbo-Jet
Jet pump Level 6 (highest possible shear)
Amount of water m the jet- 6000 ml
Finishing. 15 minutes at 40°C
Drying 80°C
Textile 300 g bleached and with optical bnghtener (e g Blankophor® BA treated
cotton pullover)
The following table summanzes the results of the finishing experiments
(Table Removed)
* Deposits on glass and steel parts of the jet
** Having a sihcone-hke softness with volume increase
*** Drop absorption time Renex® 36, trade name of ICI surfactants; tndecyl alcohol-(EO)i2-OH
Renex® 30, trade name of ICI surfactants; tndecyl alcohol-(EO)6-OH
Crodet® S40, trade name of Croda GmbH, stearic acid-(EO)40-OH
Experiment 1 describes the unacceptable result of a nonmventive prior art experiment. Doubling of the amount of both Renex surfactants does not lead to prevention of deposits (Experiment 2, noninventive)
Expenments 3 and 4 demonstrate that an inventive addition of salts of polyvalent cations can reliably prevent deposits Aluminum salts are more effective than magnesium compounds
Expenment 5 shows that an inventive incorporation of hydrophihc interface-active compounds directly into the formulation reliably prevents deposits It is also true of a likewise inventive partial subsequent addition (Expenment 6) or inventive full addition (Expenment 7) of this hydrophihc interface-active compound









We claim
1. A formulation comprising at least one quaternized aminoalkylsiloxane and a) a hydrophilic, nonionogenic, interface-active compounds, wherein the hydrophilic, nonionogenic, interface-active compounds (a) are modified with ethylene/propylene oxide (EO/PO) from the group of the fatty alcohols, fatty acids, alcohols, acids, alkylaryl derivatives, fatty amines, glycerides and sorbitan esters, in each of which the number of EO/PO units is between 15 and 150, the ratio of PO units to EO units being equal to or lower than 0.25, and in which the number of ethylene oxide units (EO fraction) is greater than or equal to the number of carbon atoms in the non-EO fraction, or are alkyl-polyglycosides, ethylene oxide/propylene oxide copolymers and polyethersiloxanes, and further characterized in that the quaternized aminoalkylsiloxanes are linear or cyclic polysiloxane polymers having repeating structural units of the formulae (10) and (11)
(Formula Removed)
where
X is a divalent hydrocarbon radical having at least 4 carbon atoms which optionally has a hydroxyl group and which is optionally interrupted by one oxygen atom, and the X groups in the repeating units are the same or different,
Y is a divalent hydrocarbon radical having at least 2 carbon atoms which optionally has a hydroxyl group and which optionally is interrupted by one or more oxygen or nitrogen atoms,
R11, R12, R13 and R14 are the same or different and are each alkyl radicals having from 1 to 4 carbon atoms or benzyl radicals, or the R1 and R3 or R2 and R4 radicals may in each case be constituents of a bridging alkylene radical,
R16 is H or an alkyl radical having from 1 to 20 carbon atoms which is optionally oxygen-substituted,
M is the structure -B-O-(EOx)v(POx)w-B-, where
EOx is an ethylene oxide unit and POx is a propylene oxide unit,
B is straight-chain or branched C2-C6-alkylene,
v is from 0 to 200,
w is from 0 to 200,
v+w ≥ 1,
n is from 2 to 1000 where the n in the repeating units is the same or different,
A- is an inorganic or organic anion.
2. The formulation as claimed in claim 1, wherein it optionally comprises a hydrophilic dispersant (b).
12. The formulation as claimed in any of claims 1 to 2, wherein it optionally comprises c) the salts of di- or trivalent metals with inorganic acids.
13. The formulation as claimed in claim 1, wherein compound (a) is a compound of the formulae (1) to (9)
(Formula Removed)
where
E is an R1 radical, hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C1-C18-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C10-cycloalkyl which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl
R1 is straight-chain or branched, saturated or unsaturated C8-C40-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino, or is C5-C10-cycloalkyl whose alkyl chain is optionally singly or multiply by oxygen mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino,
R2 is straight-chain or branched, saturated or mono- to polyunsaturated C8-C40-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R3 is straight-chain or branched C1-C26-alkyl or C6-C10-aryl, R4 is R3 or a radical of the formulae
(Formula Removed)
where
Z is a straight-chain or branched alkyl or cycloalkyl radical which is in each
case optionally interrupted by -O- and/or -CO- and is optionally be
substituted by at least one OH group,
(Formula Removed)
q is from 15 to 150,
ql and q2 are each independently from 0 to 150
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 0 to 150 where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 50,
rl and r2 are each independently from 0 to 50
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 50
where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r : q ≤ 0.25,
m is from 1 to 50,
m7 and m8 are each independently from 1 to 50
where 2 ≤ m7+m8 and the sum of m7 + m8 = m +1, and
the ratio of q : m ≥ 4,
s is from 5 to 150,
t is from 5 to 150 where 0.05 ≤ s : t ≤ 20,
0≤zl≤2000,
0≤z2≤2000,
at least one R4 # R3, and
0.01 ≤ Σ alkyl radicals R3 : Σ q+r ≤ 1.
5. The formulation as claimed in one of claims 1 to 4, wherein compound (a) is a compound of the formulae (1) to (9) as claimed in claim 4, where
E is hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C1-C4-alkyl which is optionally mono- to disubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C6 -cycloalkyl which is in each case optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R1 is straight-chain or branched, saturated or unsaturated C10-C36-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino, or is C5-C6-cycloalkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino,
R2 is straight-chain or branched, saturated or mono- to polyunsaturated C10-C36-alkyl which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R3 is straight-chain or branched C1-C18-alkyl or C6-C10-aryl,
R4 is an R3 radical or is a radical of the formulae
-CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E, or
-CH2CH2CH2-O-[CH2CH2O]q-[CH2CH(CH3)O]r-E,
ql and q2 are each independently from 20 to 100
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 20 to 100
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 20,
rl and r2 are each independently from 0 to 20
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 20
where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r: q ≤ 0.25,
m is from 1 to 7,
m7 and m8 are each independently from 1 to 7
where 2 ≤ m7+m8 and the sum of m7 + m8 = m, and
the ratio of q : m ≥ 4,
s is from 5 to 100,

t is from 5 to 100
where 0.05 ≤ s : t ≤ 20,
0≤zl≤2000,
0 ≤ z2 ≤ 2000,
at least one R4 # R3, and
0.01 ≤ Σ alkyl radicals R3 :Σq+r≤ 0.5.
6. The formulation as claimed in claim 1, wherein compound (a) is a compound of the formulae (1') to (9')
or a polyethersiloxane (9')
(Formula Removed)
where
the brackets "{"and"}" shown in formulae (l')-(8') ethylene oxide or propylene oxide units is either be arranged blockwise as shown or else be in any random distribution, E is an R1 radical, hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C1-C18-alkyl which is optionally mono- or poly substituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C10-cycloalkyl which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R1 is straight-chain or branched, saturated or unsaturated C8-C40-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino, or is C5-C10-cycloalkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino, or is C6-C10-aryl which is optionally substituted, especially by C3-C15-alkyl,
R2 is straight-chain or branched, saturated or mono- to polyunsaturated C8-C40-alkyl
which is optionally mono- or polysubstituted by
-OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R3 is straight-chain or branched C1-C26-alkyl or C6-C10-aryl, R4 is R3 or is a radical of the formulae
(Formula Removed)
-E
where
Z is a straight-chain or branched alkyl or cycloalkyl radical which is in each
case optionally interrupted by -O- and /or -CO- and may optionally be
substituted by at least one OH group
or
(Formula Removed)
q is from 15 to 150,
ql and q2 are each independently from 0 to 150
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 0 to 150
where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 50,
rl and r2 are each independently from 0 to 50
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 50
where the sum of r3 + r4 + r5 + r6 = r, and the ratio of r : q ≤ 0.25,
m is from 1 to 50,
m7 and m8 are each independently from 1 to 50
where 2 ≤ m7+m8, and

the ratio of q : m≥4,
s is from 5 to 150, preferably 15-150,
t is from 5 to 150, preferably from 5 to 150 and in particular from 5 to 20,
0≤zl≤2000,
0 ≤ z2 ≤ 2000,
at least one R4 # R3, and
for formula (9'):
0.01 ≤ Σ alkyl radicals R3 : Σ q+r ≤ 1.
7. The formulation as claimed in any of claims 1 to 3 or 6, wherein compound (a) is a compound of the formulae (1') to (9') as claimed in claim 6, where
E is hydrogen, straight-chain or branched, saturated or mono- or polyunsaturated C1-C4-alkyl which is optionally mono- to disubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, or is C5-C6 -cycloalkyl which is in each case optionally mono- or polysubstituted by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R1 is straight-chain or branched, saturated or unsaturated C10-C36-alkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally mono- or polysubstituted by -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl, amino, mono- or di-C1-C4-alkylamino, or is C5-C6-cycloalkyl whose alkyl chain is optionally interrupted singly or multiply by oxygen and/or nitrogen atoms and which is optionally singly or multiply by C1-C4-alkyl, -OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl, or is C6-C10-aryl which is optionally substituted, especially by C3-C15-alkyl,

R2 is straight-chain or branched, saturated or mono- to polyunsaturated C10-C36-alkyl
which is optionally mono- or polysubstituted by
-OH, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or carbonyl,
R3 is straight-chain or branched C1-C18-alkyl or C6-C10-aryl,
R4 is an R3 radical or is a radical of the formulae
(Formula Removed)
q is from 20 to 100,
ql and q2 are each independently from 20 to 100
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 20 to 100 where the sum of q3 + q4 + q5 + q6 = q,
r1 and r2 are each independently from 0 to 20
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 20

where the sum of r3 + r4 + r5 + r6 = r, and
the ratio of r : q ≤ 0.25,
m is from 1 to 7,
m7 and m8 are each independently from 1 to 7
where 2 ≤ m7+m8, and
the ratio of q : m≥4,
s is from 5 to 100, preferably from 15 to 100 t is from 5 to 100, preferably from 5 to 20
where t:s ≤ 0.25,
0≤ zl ≤ 2000,
0 ≤ z2 ≤ 2000,
at least one R4# R3,
and
for the formula (9'):
0.01 ≤ Σ alkyl radicals R3 : Σ q ≤ 0.5.
8. The formulation as claimed in one of claims 1 to 5, wherein compound (a) corresponds to the formulae (1) to (9) as claimed in claim 4, where

E is H, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-,
CH3CH2CH2CH2- or CH3C(O)-,
R1 is a radical of the formulae
(Formula Removed)
where
nl = from 9 to 23,
n2 = from 3 to 23,
n3 = from 0 to 18,
n4 = from 7 to 23,
n5 = from 3 to to 15,

R2 is a radical of the formulae
(Formula Removed)
where
n6 = 8 to to 28, R3 is C1-C18-alkyl or C6-C10-aryl, R4 is an R3 radical or is a radical of the formulae
(Formula Removed)
q is from 25 to 60,
ql and q2 are each independently from 25 to 60
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 25 to 60

where the sum of q3 + q4 + q5 + q6 = q,
r is from 0 to 10,
r1 and r2 are each independently from 0 to 10
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 10,
the ratio of r : q ≤ 0.25, and
for the formula (9):
0.01 ≤ Σ alkyl radicals R3: Σ q+r ≤ 0.1.
9. The formulation as claimed in one of claims 1 to 3 and 6 to 7, wherein compound (a) corresponds to the formulae (1) to (9') as claimed in claim 6, where
E is H, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2- or CH3C(O)-
R1 is a radical of the formulae
(Formula Removed)

nl = from 9 to 23,
n2 = from 3 to 23, preferably from 6 to 23
n3 = from 0 to 18, where, preferably, n2+ n3 ≤ 31,
n4 = from 7 to 23,
n5 = from 3 to to 15,
R2 is a radical of the formulae

(Formula Removed)
where
n6 = 8 to to 28,
R3 is C1-C18-alkyl or C6-C10-aryl, R4
is an
R3 radical or is a radical of the formulae
(Formula Removed)
q is from 25 to 60,
ql and q2 are each independently from 25 to 60
where the sum of ql + q2 = q,
q3, q4, q5 and q6 are each independently from 25 to 60 where the sum of q3 + q4 + q5 + q6 = q,

r is from 0 to 10,
r1 and r2 are each independently from 0 to 10
where the sum of rl + r2 = r,
r3, r4, r5 and r6 are each independently from 0 to 10,
where the sum of r3 + r4 + r5 + r6 = r, and
for the formula (9'):
0.01 ≤ Σ alkyl radicals R3:1 q ≤ 0.1.
10. The formulation as claimed in claim 2, wherein the compounds (b) are carboxymethyl-
cellulose, hydroxyethylcellulose, methylhydroxypropylcellulose or a compound of the
formula
(Formula Removed)
where
x is from 1.5 to 20, preferably from 1.5 to 10.
11. The formulation as claimed in any one of claims 1 to 10, wherein the compound (a) is the
ester of stearic acid and 40 mol of EO.
14. The formulation as claimed in any of claims 1 to 11, wherein, as a further component, at least one compound (f) from the group of the interface-active compounds and emulsifiers is present.
15. The formulation as claimed in claim 12, wherein, as interface-active substances f) the ether of tridecyl alcohol with 12 mol of EO and the ether of tridecyl alcohol with 6 mol of EO are present.
16. The formulation as claimed in one of claims 1 to 13, wherein the amounts of hydrophilic, nonionogenic, interface-active compounds (a) and hydrophilic dispersants (b) and salts (c) to the amounts of quaternized aminoalkylsiloxane compounds are in a weight ratio Ω of Ω = 0.05 to 10.
15. Formulation as claimed in any of the preceding claim whenever used as a textile softener.

Documents:

3572-DELNP-2004-Abstract-(13-12-2011).pdf

3572-delnp-2004-abstract.pdf

3572-DELNP-2004-Claims-(13-12-2011).pdf

3572-delnp-2004-Claims-(13-12-2012).pdf

3572-delnp-2004-Claims-(31-12-2012).pdf

3572-delnp-2004-claims.pdf

3572-DELNP-2004-Correspondence Others-(13-12-2011).pdf

3572-delnp-2004-Correspondence Others-(13-12-2012).pdf

3572-delnp-2004-Correspondence Others-(31-12-2012).pdf

3572-delnp-2004-Correspondence-Others-(04-10-2011).pdf

3572-delnp-2004-Correspondence-others-(15-01-2013).pdf

3572-delnp-2004-correspondence-others.pdf

3572-DELNP-2004-Description (Complete)-(13-12-2011).pdf

3572-delnp-2004-description (complete).pdf

3572-DELNP-2004-Form-1-(13-12-2011).pdf

3572-delnp-2004-form-1.pdf

3572-delnp-2004-Form-13-(13-12-2012).pdf

3572-delnp-2004-form-18.pdf

3572-DELNP-2004-Form-2-(13-12-2011).pdf

3572-delnp-2004-form-2.pdf

3572-delnp-2004-Form-3-(04-10-2011).pdf

3572-delnp-2004-Form-3-(15-01-2013).pdf

3572-delnp-2004-form-3.pdf

3572-delnp-2004-form-5.pdf

3572-DELNP-2004-GPA-(13-12-2011).pdf

3572-delnp-2004-GPA-(13-12-2012).pdf

3572-delnp-2004-GPA-(31-12-2012).pdf

3572-delnp-2004-pct-210.pdf

3572-delnp-2004-pct-304.pdf

3572-DELNP-2004-Petition-137-(13-12-2011).pdf


Patent Number 255778
Indian Patent Application Number 3572/DELNP/2004
PG Journal Number 13/2013
Publication Date 29-Mar-2013
Grant Date 21-Mar-2013
Date of Filing 16-Nov-2004
Name of Patentee GE BAYER SILICONES GMBH & CO. KG.
Applicant Address FALKENBERG 1, 40699 ERKRATH, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 WINFRIED GUTH AM HAGEN 9, D-51519 ODENTHAL, GERMANY
2 RAINER IDEL MUHLENSTR. 69, D-42929 WERMELSKIRCHEN, GERMANY
3 DETLEV KIERSPE AN DEN IRLEN 9, D-40764 LANGENFELD, GERMANY
4 FRIEDRICH KOCH MORGENGRABEN 10, D-51061 KOLN, GERMANY
5 PETER LANDENBERGER VITITORWALL 4, D-38640 GOSLAR, GERMANY
6 HELMUT-MARTIN MEIER AM OBERSTHOF 3, D-40883 RATINGEN, GERMANY
7 HORST LANGE TIEFBAUWEG 34, D-44879 BOCHUM, GERMANY
8 ROLAND WAGNER KOLBERGERSTR. 40, D-53175 BONN, GERMANY
9 JURGEN KROTT AHRSTR. 28A, D-51371 LEVERKUSEN, GERMANY
10 ANNETTE MOLLER WEIDENBUSCH 63, D-51381 LEVERKUSEN, GERMANY
PCT International Classification Number D06M 15/643
PCT International Application Number PCT/EP2003/004965
PCT International Filing date 2003-05-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102 21 521.9 2002-05-14 Germany