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    • 专利摘要:
    low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for their production and use. the present invention discloses low viscosity polyorganosiloxanes comprising a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group, c) at least one terminal ester group, manufacturing methods thereof and their use for the modification of substrate surfaces.
    公开号:BR112014024180B1
    申请号:R112014024180-5
    申请日:2013-03-28
    公开日:2021-07-27
    发明作者:Roland Wagner；Karl-Heinz Stachulla；Karl-Heinz Sockel；Sigfredo Gonzales
    申请人:Momentive Performance Materials Gmbh；
    IPC主号:
    专利说明:

    REFERENCE TO RELATED ORDERS
    [001] This application claims priority to US Provisional Patent application serial number 61/617,173 filed March 29, 2012. FIELD OF THE INVENTION
    [002] The present invention provides a polyorganosiloxane having a low viscosity and comprising quaternary ammonium groups and terminal ester groups, methods for producing and using the same. BACKGROUND OF THE INVENTION
    [003] Silicone quats (silicones containing quaternary ammonium groups that optionally contain polyorganosiloxane substituents) are known to be highly substantive. DE 3719086 describes the reaction of α,w-diepoxides with tertiary amines in the presence of acids yielding α,diquaternary w-siloxanes. They can be used for hair care purposes. DE 3719086 describes tetraalkyl derivatives as well as aromatic imidazolinium derivatives.
    [004] The reaction of a,w-diepoxides with di-tertiary amines in the presence of acids yields polyquaternary polyorganosiloxanes from polylaces (EP-A-282720). The advantage of these materials is a better resistance to washing the hair.
    [005] The reaction of α,w -diepoxides with dimethylamine in the presence of acids yielding polyquaternary polyorganosiloxanes from polylaces having a quat group between the siloxane blocks is disclosed in US 6,730,766.
    [006] Polyquaternary imidazolinium derivatives are described in US 6,240,929. These cationic compounds have improved compatibility with anionic surfactants in cosmetic formulations.
    [007] The incorporation of alkylene oxide fractions in silicone quats is to further increase the hydrophilicity.
    Silicone quats containing quat groups as well as polyethylene oxide fractions in side chains are described in US 5,098,979, US 5,153,294 and US 5,166,297. The substantivity of materials is relatively low.
    Silicone-based block copolymers containing quat functions, which also include polyether fractions, are described in WO 02/10257, WO 02/10259 and US 2002/0103094 A. The alkylene oxide structures are incorporated in the block copolymer as α,w-bifunctional fractions.
    [010] The document US 6,242,554 describes α,w-bifunctional siloxane derivatives containing a polyether and a quat function separated from each other. The substance of these monoquats is insufficient.
    [011] The document US 4,921,895 describes mixtures of polyether siloxanes and quaternary ammonium groups containing siloxane block copolymers for textile finishing purposes. Here, the use of polyether siloxane improves finished products and hydrophilicity.
    [012] US 2007/0286837, US 2007/0041929, US 2008/0292575 and CN 101198311 describe combinations between silicone quats with a siloxane chain length of greater than 200 D-units, and a second silicone for hair conditioning purposes. A possible choice of the second silicone is the choice of polyethers derived from silicone of ethylene oxide or propylene oxide or mixtures thereof. Specific structures are not given.
    [013] None of the prior art descriptions above describe a very simple methodology for the preparation of low viscosity polyorganosiloxanes comprising the quaternary ammonium groups. Low-viscosity materials can incorporate hydrophilicity by improving substituents, such as superfluous or redundant polyethers, thus reducing system complexity. SUMMARY OF THE INVENTION
    [014] The present invention provides a low viscosity silicone (oligomerimeric or polymeric siloxane which is a homopolymer, copolymer or terpolymer) functionalized with quaternary ammonium groups and comprising one or more terminal ester groups as follows: a compound of polyorganosiloxane comprising: a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group, c) at least one terminal ester group wherein the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c ) is less than 100:15, and additionally optionally further comprising: d) at least one polyalkylene oxide group.
    [015] The present invention further provides a method of preparing the compounds of the present invention comprising the reaction of: (i) at least one ditertiary diamine, (ii) at least one aminoalkylating compound comprising at least one diepoxide, and (iii) at least one monofunctional organic acid, wherein at least one compound from compounds (i) and (ii) comprises polyorganosiloxane structural units. DETAILED DESCRIPTION OF THE INVENTION
    [016] The present invention provides low viscosity polyorganosiloxanes comprising the quaternary ammonium groups, their manufacture and use of materials.
    [017] Surprisingly, polyorganosiloxanes comprising quaternary ammonium groups having a low viscosity are achieved by preparing polyorganosiloxane compounds comprising quaternary ammonium groups and terminal ester groups. That is, according to the present invention polyorganosiloxane compounds are provided comprising: a) polyorganosiloxane groups, b) quaternary ammonium groups c) terminal ester groups wherein the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:15, preferably less than 100:20. In a preferred embodiment, the polyorganosiloxane compounds according to the invention further comprise: d) polyalkylene oxide groups.
    [018] The polyorganosiloxane compounds according to the invention are preferably linear copolymer compounds comprising the above-mentioned functional groups a), b) and optionally d) in at least two repeating units, with at least less part of the terminal groups being terminal ester groups that result from the use of monofunctional organic acids as chain terminators (formally product of the type [(AB)x - A] (where x > 1 and A does not denote group A defined in the claims)). However, depending on the stoichiometry of the reagents, the polyorganosiloxane compounds according to the invention may also comprise compounds that result from the reaction of a difunctional monomer, with only one compound at each end thereof ([(AB) type product x - A] (where x = 1 and A does not denote the group A defined in the claims)). In a preferred embodiment, the polyalkylene oxide groups have the general formula:
    wherein A and A' are each independently of the other selected from a single bond or a bivalent organic group having up to 10 carbon atoms and one or more heteroatoms, and E is a polyalkylene oxide group of general formulas:

    [019] In a preferred embodiment of the polyorganosiloxane compounds according to the invention, the at least one polyorganosiloxane group has the general formula: where R1 = C1-C22-alkyl, C1-C22-aryl or fluoroalkyl, n = 0 to 1000, and these may be identical or different, if several S groups are present in the polyorganosiloxane compound, preferably, for example, n is, for example, in the range of 0-200 or >200 to 1000;
    with
    K = is a straight-chain bivalent or trivalent, cyclic and/or branched C2-C40 hydrocarbon residue which is optionally interrupted by -O-, -NH-, trivalent N, -NR1-, -C(O)- , -C(S)-, and optionally substituted with -OH, where R 1 is defined as above, where residues K may be identical or different from each other. In such -KSK- groups the K residue is attached to the silicon atom of the S residue via an -Si-C bond.
    [020] In a preferred embodiment, the polyorganosiloxane compounds according to the invention comprise at least one repeating unit comprising at least one quaternary ammonium group selected from the general formulas:
    a saturated or unsaturated mono or diquaternary heterocycle of formulas
    an aromatic ammonium heterocycle with the formula

    [021] Wherein R is selected from monovalent organic groups with up to 22 carbon atoms and optionally one or more heteroatoms, and where the free valences on the nitrogen atoms are linked to carbon atoms, and T is selected from a bivalent organic group having up to 20 carbon atoms and one or more heteroatoms. In the present invention, the term qua ternary ammonium group refers to a positively charged nitrogen atom that binds to 4 carbon atoms (formerly known as NR4+ groups).
    [022] In a preferred embodiment, the A and A' groups are selected from groups that result from the reaction of difunctional alkylene polyalkylene oxide compounds with di-tertiary amines (leading to quaternary ammonium groups), or with secondary or di-primary amines (leading to amine or ammonium groups). Such linking groups A and A' can include, for example: a single link,


    [023] In a preferred embodiment of the invention, the terminal ester groups are selected from the group of:

    [024]Where Z is selected from monovalent organic residues with up to 40 carbon atoms, which optionally comprise one or more heteroatoms. As will be explained in detail below these terminal ester groups result from the use of monofunctional organic acids, such as carboxylic acids (-OC(O)-Z), sulfonic acids (-OS(O)2-Z), middle ester sulfuric acid (-OS(O)2O-Z), phosphoric acid monoester (-OP(O)(OZ)OH, phosphoric acid diester (-OP(O)(OZ)2), in reaction with diepoxides .
    [025] In a preferred embodiment, the polyorganosiloxane compounds according to the invention have the general formulas (Ia) and (lb):
    where: m is >0, preferably from 0.01 to 100, more preferably from 0.1 to 100, even more preferably from 1 to 100, especially from 1 to 50, more specifically from 1 to 20, even more specifically from 1 to 10, k is 0 or an average value from > 0 to 50, preferably 1 to 20, more preferably from 1 to 10, M represents a terminal group, comprising ester groups of terminal selected from
    where Z is as defined above, -AE-A'- is as defined above, R2 is selected from hydrogen or R, Y is a group of the formula:
    each as defined above, and T is as defined above.
    [026] Due to the possible presence of amine groups ( (NR. AEA NR ) ) in the polyorganosiloxane compounds according to the invention, they may have protonated ammonium groups, resulting from the protonation of such amine groups with organic acids or inorganics. Such compounds are often referred to as acid addition salts of the polyorganosiloxane compounds according to the invention.
    [027] In a preferred embodiment, the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:20, even more preferably, it is less than 100:30 and is the more preferably less than 100:50. The ratio can be determined by 13C-NMR.
    [028] The polyorganosiloxane compounds according to the invention are preferably manufactured by a process, which comprises the reaction of (i) at least one ditertiary diamine, (ii) at least one aminoalkylation compound comprising at least one diepoxide, and (iii) at least one monofunctional organic acid, wherein at least one compound among compounds (i) and (ii) comprises polyorganosiloxane structural units. In another embodiment of the present process, in addition to components (i) to (iii), component (iv), i.e. di-primary amine or di-secondary amines is reacted in such processes.
    [029] In a preferred embodiment of the process according to the invention, the at least one compound among compounds (i) and (ii) further comprises polyalkylene oxide structural units as described above.
    [030] The present invention further relates to polyorganosiloxane compounds which are obtained by the process according to the invention as described above.
    [031] Another embodiment of the present invention relates to polyorganosiloxane compositions, comprising: A) at least one polyorganosiloxane compound, which comprises a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group, c) at least one terminal ester group, and d) optionally at least one polyalkylene oxide group (as defined above), B) at least one polyorganosiloxane compound comprising at least one different terminal ester group of compound A).
    [032] In the definition of component A), one can refer to the description of the polyorganosiloxane compounds of the invention. Polyorganosiloxane compound B) differs from polyorganosiloxane compound A) preferably in that it does not contain quaternary ammonium groups. Preferred polyorganosiloxane compounds B) result from the reaction of monofunctional organic acids, in particular carboxylic acids, and polyorganosiloxane containing bisepoxides.
    [033] In the polyorganosiloxane compositions according to the invention, the weight ratio of compound A) to compound B) is preferably less than 90:10. Or in other words, the content of component B) is at least 10 percent by weight. In another preferred embodiment of the polyorganosiloxane compositions according to the invention, in compound A) the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:10, even more preferably, it is less than 100:15 and is more preferably less than 100:20.
    [034] Both polyorganosiloxane compounds or polyorganosiloxane compositions according to the invention preferably have a viscosity at 20 °C and a shear rate of 0.1 s-1 (plate-plate system, plate 40mm in diameter, 0.5mm gap width) of less than 100,000 mPa.s (100 Pa.s).
    [035] The present invention further relates to aqueous emulsions comprising at least one polyorganosiloxane compound and/or at least one polyorganosiloxane composition as defined above or below. Such aqueous emulsions preferably comprise at least 30 percent by weight, preferably at least 50 percent by weight, even more preferably at least 80 percent by weight water based on the total weight of the emulsion.
    [036] The present invention further relates to a method of surface treatment, comprising the step of applying polyorganosiloxane compounds, polyorganosiloxane compositions or aqueous emulsions, as defined in any of the following claims, to the surface of a substrate. Any method of application is conceivable, for example simple wetting, contacting, washing, dipping, spraying, brushing, spreading and operations conventionally known in the art may be referred to.
    [037] In this method, preferably, one of the following compositions or formulations, respectively, is applied: cosmetic formulations for skin and hair treatment, selected from conditioners with rinse (Rinse-off) and without rinse (Leave-on ), shampoos, modeling gels, sprays, and pump sprays; formulations for polishing and arming hard surfaces; formulations for drying automobiles and other hard surfaces; formulations for initial armament of textile products and textile fibers; softener formulations, also comprising non-ionogenic or anionic/non-ionogenic or cationic surfactants or betaine for application during or after washing the textiles; laundry formulations for textile washes based on nonionic or anionic/nonionic or cationic surfactants or betaine or formulations to prevent or reverse the wrinkling of textiles. Other preferred embodiments of the invention:
    [038] In polyalkylene oxide the E group of general formulas:

    [039]the indexes are preferably:
    [040]q = 0 to 200, preferably 0 to 100, more preferably 0 to 50, even more preferably 0 to 20, r = 0 to 200, preferably 0 to 100, with more preferably from 0 to 50, even more preferably from 0 to 20, s = 0 to 200, preferably from 0 to 100, more preferably from 0 to 50, even more preferably from 0 to 20, eq + r + s = 1 to 600, preferably from 1 to 100, more preferably from 1 to 50, even more preferably from 1 to 40.
    [041] In the structural unit of polyorganosiloxane with the general formula S:

    [042]where R1 = C1-C22-alkyl, C1-C22-fluoroalkyl or aryl,
    [043]n = 0 to 1000, preferably from 0 to 500, more preferably from 0 to 300, preferably from 0 to 200, especially from 0 to 100 or in some cases > 200 to 1000.
    [044]K (in the -KSK- group) is preferably a bivalent or trivalent, cyclic or branched straight chain C2-C20 hydrocarbon residue which is optionally interrupted by -O-, -NH-, trivalent N, - NR1-, -C(O)-, -C(S)-, and optionally substituted with -OH.
    [045] In the polyorganosiloxanes of the invention, the positive charges resulting from the ammonium group(s), are neutralized with inorganic anions such as chloride, bromide, hydrogen sulfate, sulfate, or organic anions, such as carbo- xylates derived from C1-C30 carboxylic acids, eg acetate, propionate, octanoate, especially from C10-C18 carboxylic acids d, eg decanoate, dodecanoate, tetradecanoate, hexadecanoate, octadecanoate and oleate, alkylpoly- ethercarboxylate, alkyl sulfonate, aryl sulfonate, alkyl aryl sulfonate, alkyl sulfate, alkyl polyether sulfate, phosphates derived from phosphoric acid mono alkyl/aryl ester and phosphoric acid dialkyl/aryl ester. The properties of polyorganosiloxane compounds can be modified, inter alia, based on the selection of acids used.
    [046] Groups of quaternary ammonium, as contained in the polyorganosiloxanes of the present invention are usually generated by reaction of di-tertiary amines, with an alkylating agent, in particular selected from di-epoxides (sometimes also referred to as bis- epoxides) in the presence of monocarboxylic acids and bifunctional alkyl dihalogen compounds.
    [047] R1 is more preferably C1-C18 alkyl, C1-C18 fluoroalkyl and aryl. Furthermore, R1 is preferably C1-C18 alkyl, C1-C6 fluoroalkyl and aryl. Furthermore, R1 is preferably C1-C6 alkyl, C1-C6 fluoroalkyl, more preferably C1-C4 fluoroalkyl, and phenyl. Even more preferably, R1 is methyl, ethyl, trifluoropropyl and phenyl.
    [048] Within the scope of the present invention, the term "C1-C22 alkyl" means that aliphatic hydrocarbon groups have from 1 to 22 carbon atoms which can be straight-chain or branched. Methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl, isopropyl, neopentyl and 1,2,3-trimethyl hexyl serve as examples.
    [049] Within the scope of the present invention, the concept of "C1-C22 fluoroalkyl" means aliphatic hydrocarbon compounds with 1 to 22 carbon atoms which can be straight-chain or branched and are substituted with at least one fluorine atom. Monofluoromethyl, monofluoroethyl, 1,1,1-trifluoroethyl, perfluoroethyl, 1,1,1-trifluoropropyl, 1,2,2-trifluorobutyl are given as examples.
    [050] Within the scope of the present invention, "aryl" means phenyl unsubstituted or substituted one or more times with OH, F, Cl, CF3, C1-C6 alkyl, C1-C6 alkoxy, C3-C7 cycloalkyl, C2 -C6 alkenyl or phenyl. The expression can also mean naphthyl if necessary.
    [051] In a preferred embodiment, the polyorganosiloxane compounds are of general formula (Ia) and (lb):
    where each of the groups is as defined above. In such a formula the repeating units are usually in a statistical array (ie not in a block array).
    [052] In another preferred embodiment, the polyorganosiloxane compounds can also be of one of the general formulas (IIa) or (lib):
    where each of the groups is as defined above. Also in such a formula the repeating units are usually in a statistical arrangement (ie not in a block arrangement). Z in M groups:
    is preferably a straight, cyclic or branched, saturated or unsaturated C1-C20 hydrocarbon radical, preferably C2 to C18, even more preferably a hydrocarbon radical, which may be interrupted by one or more - O-, or -C(O)- and replaced with -OH.
    [053] Preferred M groups are -OC(O)-Z resulting from normal carboxylic acids, in particular with more than 10 carbon atoms, such as dododecanoic acid.
    [054] In a preferred embodiment of the invention, the molar ratio of the polyorganosiloxane containing the repeating group -KSK- and the polyalkylene repeating group -AE-A'- or -A'-EA- is between 100 :1 and 1:100, preferably between 20:1 and 1:20, even more preferably between 10:1 and 1:10.
    [055]In the R group: 1 K') the R groups preferably represent a monovalent, cyclic or branched straight chain C1-C20 hydrocarbon radical, which can be interrupted by one or more -O-, -C (O)- and may be substituted by -OH, T preferably represents a bivalent, cyclic, or branched straight chain bivalent C1-C20 hydrocarbon radical, which may be interrupted by -O-, -C(O) - and can be substituted by hydroxyl.
    [056] The viscosities of pure polymers according to this embodiment of the invention are preferably 500-100,000 mPa.s, preferably 500-70,000 mPa.s, more preferably 500-50,000 mPa, still with more preferably 500-20000 mPa.s, specifically 500-10000 mPa.s, more specifically 500-5000 mPa.s, determined at 20°C and a shear rate of 0.1 s-1. The molecular weight is between 10,000 and 100,000 g/mol measured as mean weight Mw by GPC (gel permeation chromatography) and polystyrene as standard.
    [057] This molar ratio of polyorganosiloxane containing the repeating group -K-SK- and the polyalkylene repeating group -AE-A'- or -A'-EA- can be controlled as shown below, by selecting the ratio molar of the parent compounds, in particular, the ratio of the halogenated α,w alkyl carboxylic acid polyalkylene oxide ester compounds preferably used in the present invention, and the bis-polyorganosiloxane epoxide compounds. The properties of the products depend essentially on the ratio of the source materials used, and on the length of the polyalkylene oxide or polyorganosiloxane blocks contained therein.
    [058] In a preferred embodiment of the invention, K is a bivalent hydrocarbon radical having at least 4 carbon atoms, which contains a hydroxyl group and can be interrupted by an oxygen atom. Such groups include, for example:

    [059] In groups
    preferably, the group -AE-A'- is represented by a group of formula
    wherein A is a single bond or a straight or branched chain, or C1-C6 alkanediyl group with q + r + s = 1 to 300, more preferably from 1 to 100, even more preferably from 1 at 50,
    [060] In the group
    The ethylene oxide and propylene oxide and butylene oxide units can be positioned in any way, for example as statistical copolymer units or as a block copolymer unit.
    [061] The polyorganosiloxane compounds of the invention are preferably produced in a first embodiment by means of a method, in which first the α, w-Si-H functionalized siloxanes of general structure
    are converted, in the presence of a hydrosilylation catalyst and at temperatures of 50°C to 150°C, with 1.0 to 1.5 mol, based on SiH groups, of an alkenyl-epoxide, which has a terminal olefinic bond , wherein the alkenyl epoxide contains at least 4 carbon atoms, and may additionally contain a non-cyclic ether group. Vinyl cyclohexene oxide and allyl glycide ether are preferably used as epoxy-functional precursors for the production of epoxy-functionalized siloxanes. Excess olefinic epoxide is then removed if necessary.
    [062] The bisepoxide is preferably reacted with a mixture of a diamine, for example, the preferred diamine of the formula
    with R and T as defined above, and a halogenated alkyl carboxylic acid ester α, w, preferably of the formula
    wherein AEA' or A'-EA are defined as above and X is a usual parent nucleophilic group, preferably chloride or bromide, with the proviso that X is linked to a terminal -CH2 group, in the presence of an acid organic at preferential temperatures of 40 to 150 °C, where the molar ratio of tertiary amino groups : halo carboxylic ester groups is, for example > 1:1, the molar ratio of tertiary amino groups: ∑ (epoxy groups + halocarboxylic ester groups) is, for example, < 1:1, preferably < 0.98: 1, more preferably < 0.9: 1, even more preferably < 0.7: 1, especially < 0.5: 1, the molar ratio of organic acid : epoxy groups ranges from 3: 1 to 1:1, preferably from 2: 1 to 1:1, more preferably between 1 .5: 1 to 1:1, even more preferably from 1.2: 1 to 1:1, especially from 1:1.
    [063] This means that, for example, either by reducing the molar amount of tertiary amine and/or by increasing the molar amount of organic acids, the low viscosity polyorganosiloxane compounds of the present invention can be synthesized.
    [064] In a variation of the preferred embodiment, species containing the various amino acid groups can be added to the batch along with the halocarboxylic ester derivatives, if necessary, with the simultaneous addition of equimolar amounts of acid. It is also within the scope of the invention, however, to first cause epoxy derivatives, halo carboxylic ester derivatives and di-tertiary amines to react in the presence of an amount of acid that is equivalent to the epoxy groups and then, if necessary, adding the alkylene oxide derivatives that contain primary or secondary amino groups, if necessary, with the addition of equivalence point acids with the amino groups.
    [065] It is likewise possible to make the halocarboxylic ester derivatives and the di-tertiary amines to react, forming hydrophilic blocks, and then add the epoxide derivatives, if necessary, adding the oxide derivatives. alkylene containing primary or secondary amino groups, in the presence of an amount of acid that is equivalent to the epoxy groups in the reaction mixture.
    [066] It is preferred to use the bis halocarboxylic acid esters of polyalkyleneoxides, such as esters of alpha polyethylene oxides, omega-bis-chloroacetic oxides, alpha-terminated polyalkylene oxides, omega diamino (Jefamine®) and polyalkylene oxides terminated with alpha, omega diepoxy such as DER® eg 632 or 636 as precursors to the polyalkylene oxide moiety in siloxane copolymers.
    [067]During the time that the individual components are added, the sequential distribution in the polymers to be formed can be influenced.
    [068] It is further within the scope of the present invention to cause various siloxane components and/or alkylene oxide derivatives of different chain lengths to react while maintaining the desired overall stoichiometry. From this follows, for example, the possibility of creating a desired siloxane chain length using a single siloxane component, or by the intentional mixing of several siloxane components. Similarly, it is possible to prepare an advantageous average block length of alkylene oxide in the form of a monomodal, bimodal or polymodal dispersion. Furthermore, a desired portion of alkylene oxides can be variably distributed between the halocarboxylic ester components and the amino acid components.
    [069] The source materials for the production of α, w carboxylic carboxylic esters preferably have the formula
    wherein X is preferably chlorine, bromine, are conveniently low molecular weight, oligomeric and polymeric alkylene oxides of the general composition wherein q, rs have the meanings indicated above. Preferred representatives are diethylene glycol, triethylene glycol, tetraethylene glycol, oligoethylene glycols having molar weights from 300 to 1000 g/mol, especially from approximately 400, approximately 600, and approximately 800, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycols with molar weights of 300 to 3000 g/mol, especially approximately 300, approximately 600 and approximately 2000 and poly(ethylene-propylene) glycol copolymers having molar weights of 300 to 3000 g/mol. Esterification is carried out using known methods. For descriptions of said methods see WO 02/10257, example 11a.
    [070] Preferred alkylene oxide derivatives used in accordance with the invention are commercially available under the name Jeffamine® (Huntsman Corp).
    [071] The alkylation and quaternization reactions are preferably carried out in polar organic solvents.
    [072] Suitable solvents are, for example, organic solvents and water, including, in particular, mixtures of organic solvents and water, preferably polar organic solvents and water. Polar organic solvents generally include those comprising at least one heteroatom, such as, in particular, oxygen, for example alcohols, especially methanol, ethanol, i-propanol and n-butanol; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, methyl-, ethyl- and -butyl ethers, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, methyl-, ethyl- and -butyl ethers and 1,3 propylene glycol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate, butyl acetate, methoxy propyl acetate and 2-ethylhexyl acetate; ethers such as tetrahydrofuran; and nitro compounds such as nitromethane.
    [073] It is preferable to carry out the reaction with a weight ratio of ∑ of the polymeric components: ∑ (organic solvents + water) in a weight range from 100:0 to 20:80, preferably from 99,999:0.001 to 20 :80, more preferably, from 95:5 to 20:80, even more preferably, from 95:5 and 50:50, even more preferably, from 95:5 to 60:40.
    [074] The amount of water in the reaction composition varies in one way from 0.5% by weight - 0.1% by weight, in another, preferably 0.01 - 0.1; in another embodiment, the amount is in the range of 2-10% by weight and preferably between 0.5 - 2% by weight. In a preferred embodiment of the invention, the desired amount of water is added separately. It is also possible to add the desired amount of water, i.e. in the form of azeotrope solvents or by the amount that is present in commercial grades.
    [075] The above-described polyorganosiloxane compounds comprising quaternary ammonium functions and ester functions may contain individual molecules that contain quaternary ammonium functions and no ester functions, molecules that contain quaternary ammonium functions and ester functions, as well as molecules that contain ester functions and no quaternary ammonium functions.
    [076] The above-described polyorganosiloxane compounds that comprise quaternary ammonium functions and ester functions are to be understood as mixtures of molecules that comprise a certain average amount and ratio of both parts.
    [077] Another less preferred embodiment of the invention concerns with polyorganosiloxane positions, comprising: A) at least one polyorganosiloxane compound, comprising a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group , c) at least one terminal ester group, and B) at least one polyorganosiloxane compound comprising at least one terminal ester group, different from compound A).
    [078] Such polyorganosiloxane compositions comprising quaternary ammonium functions and polyorganosiloxane compounds comprising ester functions are physically mixed in order to adjust the desired ratio of quat (N+):ester and the desired viscosity according to the invention. Both compounds are mixed in a ratio that fulfills the above-described viscosity requirement according to the invention. The blends have a viscosity at 20°C and a shear rate of 0.1 s-1 of < 100,000 mPa.s, preferably < 50,000 mPa.s, even more preferably < 20,000 mPa.s, more specifically < 10000 mPa.s, more specifically, < 5000 mPa.s. Polyorganosiloxane compounds A) comprising quaternary ammonium functions are, for example, known from WO 02/10257. The synthesis of polyorganosiloxane compounds comprising ester functions is known from WO 2011/064255. They can, for example, be synthesized from the corresponding epoxy siloxanes by esterification with acids in the presence of a tertiary amine catalyst. Preferred polyorganosiloxane compounds B) comprising ester functions are modified α,w-ester derivatives of the structure M-(K-Sn-K)-M having a siloxane chain length in the range of n = 0 to 1000 preferably from 0 to 500, more preferably from 0 to 300, even more preferably from 0 to 200, especially from 0 to 100. Alternatively, derivatives such as comb comprising ester function as side groups on a difunctional siloxane unit (OSi-MeR* with R* = carbon-linked ester group)), and optionally terminal ester fractions (O1/2SiMe2R*, with R* = carbon-linked ester group) with the same range of n-chain length are also preferred. The number of desyloxy units containing ester groups is preferably from 1 to 500, preferably from 1 to 250, more preferably from 1 to 150, even more preferably from 1 to 100, especially from 1 to 50, even more specific, from 1 to 25.
    [079] The preferred monofunctional organic acids that produce the acid esters are those that form the counterions referred to above. Preferred examples are C1-C30 carboxylic acids, eg C2, C3, C8, C10-C18 carboxylic acids, eg C12, C14, C16 acids, saturated, unsaturated and hydroxy-functionalized C18 acids, alkyl polyethercarboxylic acids , alkyl sulfonic acids, aryl sulfonic acids, alkyl aryl sulfonic acids, alkyl sulfuric acids, alkyl polyether sulfuric acids, mono-alkyl/aryl phosphoric acid esters and di-alkyl/aryl phosphoric acid esters.
    [080] The invention further relates to the use of the polyorganosiloxane compounds described above in cosmetic formulations for the treatment of skin and hair, in polishing agents for the treatment and coating of hard surfaces, in formulations for drying cars and others hard surfaces, for example, following automatic washing, for textile and textile fiber finishing, as separate softeners for use after textiles are washed with non-ionogenic or anionic/non-ionogenic detergent formulations, as softeners in formulations for washing fabrics that are based on nonionic or anionic/nonionic surfactants, and as a means of preventing or removing wrinkles in textiles.
    [081] The invention further relates to the use of the polyorganosiloxane compounds described above as hydrophilic wash-resistant softeners, for use in finishing original textiles. The invention further relates to compositions which contain at least one of the polyorganosiloxane compounds, together with at least one additional component which is generally used in such a composition.
    [082] In the following, a series of typical examples of these types of compositions is provided, in which the polyorganosiloxane compounds of the invention can be used to advantage:
    Typical adjuvants for these types of compositions are, for example, the materials described in A. Domsch: Die kosmetischen Praeparate [Cosmetic Preparations] Vol. I and II, 4th Edition, Verl. fuer chem. Industrie [Publishers for the Chemical Industry], U. Ziolkowsky KG, Augsburg, and the International Cosmetic Ingredient Dic tionary and Handbook 7th Ed. 1997 by JA Wenninger, GN McEwen Vol. 1-4 by The Cosmetic, Toiletry and Fragrance Association Washington DC Anionic Shampoo
    [084]This formulation example is intended as a base formulation. Anionic shampoos commonly contain, but are not limited to, the following components: • Alkyl sulfates, alkyl ether sulfates, sodium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, ammonium sulfate, TEA-lauryl ether sulfate, alkylbenzene sulfonates, α-olefin sulfonates, paraffin sulfonates, sulfo succinates, N-acyl taurides, sulfate-glycerides, sulfated alkanolamides, carboxylate salts, N-acyl-amino acid salts, silicones, etc.

    Non-Ionic Shampoo
    [085]This formulation example is intended for a base formulation. Nonionic shampoos commonly contain, but are not limited to, the following components: • Monoalkanolamides, monoethanolamides, monoisopropanolamides, polyhydroxy derivatives, sucrose monolaurate, polyglycerin ether, amine oxides, polyethoxylated derivatives, sorbitol derivatives , silicones, etc.

    Amphoteric Shampoo
    [086]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: • N-alkyl-iminodipropionates, N-alkyl-iminopropionates, amino acids, amino acid derivatives, starch betaine, imidazolinium derivatives, sulfobetainates, be- tains, sultains, silicones, etc.
    cationic shampoo
    [087]This formulation example is for a base formulation only. Formulations in this category usually contain, but are not limited to, the following components: • Bis-quaternary ammonium compounds, bis(acetyl trialkylammonium) diamines, amidoamines, alkyl ammonium esters, silicones, etc.
    Adjustment Agents
    [088]This formulation example is for a base formulation only. Formulations in this category usually contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycol esters, glycols, glycerin , glycerin esters, lanolin, lanolin derivatives, mineral oil, petrolatum, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickeners, silicones, etc.

    Rinse Adjustment Agents (Clear Rinse-Off)
    [089]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, fatty acid ethoxylated esters, fatty alcohols, ethoxylated fatty alcohols, glycol esters, glycols , glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petrolatum, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickening agents, silicones, etc.
    Hair Foam Adjusting Agents
    [090]This formulation example is intended for a base formulation. Formulations in this category contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, fatty acid ethoxylated esters, fatty alcohols, ethoxylated fatty alcohols, glycol esters, glycols, glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petrolatum, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, wetting agents, agents thickeners, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, fluorinated aerosol propellants, dimethyl ether, compressed CFC gases, etc.
    Pump Spray (Setting Agents) for Hair
    [091]This formulation example is for a base formulation only. Formulations in this category usually contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycol esters, glycols, glycerin , glycerin esters, lanolin, lanolin derivatives, mineral oil, petrolatum, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickening agents , silicones, solvents, ethanol, isopropanol, isoparaffin solvents, etc. Components % by weight Polyorganosiloxane compound
    Hair Adjusting Agent Spray
    [092]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: • Fatty acids, fatty acid esters, ethoxylated fatty acids, fatty acid ethoxylated esters, fatty alcohols, ethoxylated fatty alcohols, glycol esters, glycols , glycerin, glycerin, lanolin esters, lanolin derivatives, mineral oil, petroleum jelly derivatives, lecithin, lecithin, wax derived waxes, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, agents thickeners, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, fluoride aerosol propellants, dimethyl ether, compressed CFC gases etc.

    Hair Adjusting Agent Gel
    [093]This formulation example is conceived as a basic formulation. Formulations in this category usually contain, but are not limited to, the following components: thickening agents, cellulose derivatives, acrylic acid derivatives, fixing polymers, conditioning chemicals, glycols, glycol esters, glycerin, glycerin esters, lanolin , lanolin derivatives, mineral oil, petrolatum, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, silicones, solvents, ethanol, isopropanol, solvents of isoparaffin, etc.

    [094]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: cationic hydrocarbon-based conditioning agents, silicone-based cationic conditioning agents, high melting fatty compounds, ester compounds such as low melting oil, thickening agents, cellulose derivatives, fixing polymers, ethylene glycols, propylene glycols, glycol esters, glycerin, glycerin esters, monohydric alcohols, polyhydric alcohols, cationic polymers, co-emulsifiers of betaine and non-ionics, silicones, complexing agents, solvents, flavors, vitamins, solvents, etc.

    [095]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: • Fixative polymers, lacquers, acrylic acid derivatives, cellulose derivatives, vinyl derivatives, conditioning chemicals, glycols, glycol esters , glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petrolatum, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickening agents , silicones, solvents, ethanol, isopropanol, isoparaffin solvents, etc.
    Hair Styling Spray
    [096]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: • Fixative polymers, lacquers, vinyl derivatives, fatty acids, fatty acid esters, ethoxylated fatty acids, ethoxylated fatty acid esters, fatty alcohols, ethoxylated fatty alcohols, glycol esters, glycols, glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, amino acid derivatives, humectants, thickening agents, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, CFC fluorinated aerosol propellants, dimethyl ether, compressed gases, etc.


    [097]This formulation example is intended for a base formulation. Formulations in this category usually contain, but are not limited to, the following components: • Vinyl derivatives, fixative polymers, lacquers, fatty acids, fatty acid esters, ethoxylated fatty acids, fatty acid esters, fatty alcohols, alcohols ethoxylated fatty acids, glycol esters, glycols, glycerin, glycerin esters, lanolin, lanolin derivatives, mineral oil, petroleum jelly, lecithin, lecithin derivatives, waxes, wax derivatives, cationic polymers, proteins, protein derivatives, amino acids, derivatives amino acids, humectants, thickening agents, silicones, solvents, ethanol, isopropanol, isoparaffinic solvents, butane, propane, isobutane, CFC fluorinated aerosol propellants, dimethyl ether, compressed gases, etc.

    [098] The use of the polyorganosiloxane derivatives specified in the invention for applications in the hair care field produces favorable results with regard to strengthening, shine, fixation (maintenance), body, volume, moisture regulation, color retention, protection against environmental factors (UV, salt water, etc.), control, antistatic properties, ability to dye, etc. EXAMPLES
    [099] The following examples are intended to describe the present invention in greater detail, without limiting its scope. Example 1 (non-inventive polyorganosiloxane)
    [0100] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 150 g (58.7 mmol of epoxy groups) of a silicone diepoxide of the structure
    0.91 g (CH2Cl7 mmol) CI('H2('(())()('H2CH:()('H3CH2OC(O)CH2Cl), 12.56g (62.8 mmol) lauric acid, 6, 06 g of N,N,N',N'-tetramethyl hexanediamine (70.3 mmol of tert-amine.), 31.8 g of 2-propanol and 10.7 g of distilled water are mixed together at room temperature. The mixture is heated at reflux for 13.5 hours, then the solvents are removed and the material is analyzed by means of NMR (Nuclear Magnetic Resonance) and viscometry (see Tab. 1). Example 2 (inventive polyorganosiloxane)
    [0101] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 150 g (58.7 mmol of epoxy groups) of a silicone diepoxide of the structure
    0.91 g (7 mmol CH2Cl) CICH2C(O)OCH2CH:O(H2CH2()C(O)('H2('1, 12.56 g (62.8 mmol)) lauric acid, 4.54 g of N,N,N',N'-tetramethyl hexanediamine (52.8 mmol of tert-amine.), 31.5 g of 2-propanol and 10.5 g of distilled water are mixed together at room temperature. heated at reflux for 13.5 hours, then the solvents are removed and the material is analyzed by means of NMR and viscometry (see Tab. 1). Example 3 (inventive polyorganosiloxane)
    [0102] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 150 g (58.7 mmol of epoxy groups) of a silicone diepoxide of the structure
    0.91 g (7 mmol CH2Cl) ClCII2C(O)OCII2CII2OCII2CII 10QOiCIbCl, 12.56 g (62.8 mmol) lauric acid, 3.03 g N,N,N',N'-tetramethyl hexanediamine (35 .2 mmol of tert amine groups), 31.2 g of 2-propanol and 10.4 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 13.5 hours. Then, the solvents are removed and the material is analyzed by means of NMR and viscometry (see Tab. 1.). Example 4 (inventive polyorganosiloxane)
    [0103] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 150 g (58.7 mmol of epoxy groups) of a silicone diepoxide of the structure
    0.91g (7 mmol of CH2 Cl) ClClbCfOJOCIbCIbOCCIbCIl jOCiOj ClbCl, 12.56 g (62.8mmol) of lauric acid, 1.51 g of N,N,N',N'-tetramethyl hexanediamine (17.6 mmol of tert groups -amino), 30.9 g of 2-propanol and 10.3 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 13.5 hours. Then the solvents are removed and the material is analyzed by means of NMR and viscometry (see Tab. 1.). Table 1
    *4 g of polyorganosiloxane material was added to 200 g of water and mixed with an Ultra Thurrax. ** (13C-NMR)
    [0104]The data show that Example 1 produces a material that contains some ester functions but has very high viscosity. As a result, a very weak, irregular, lumpy and sticky dispersion in water is formed. Examples 2 to 4 show that reaction protocols according to the invention produce low viscosity materials which can be easily dispersed in small droplets having sufficient stability. Example 5 (inventive polyorganosiloxane composition)
    [0105] The product of Example 1 is mixed with a lauroyl ester modified siloxane of the structure
    which was synthesized from the corresponding epoxy siloxane, lauric acid and triethylamine (catalyst) in propylene glycol monomethyl ether according to document WO 2011/064255.
    [0106] Mixing experiments are summarized in Tab.2. Table 2
    * 4 g of polyorganosiloxane material was added to 200 g of water and mixed with an Ultra Thurrax.
    [0107]The data for Examples 5.2 to 5.5 in table 2 show that physical mixing of the non-inventive material from Example 1 with an ester-modified siloxane results in mixtures that can be dispersed in water. Example 6 (starting material)
    [0108] In a 250 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 22.83g of allylglycidic ether (200 mmol of epoxy groups) and 63.3g (200 mmol of epoxy groups) amino) of a structure amine
    (Jeffamine ED 600, Huntsman) were mixed at room temperature. The mixture is heated to 120°C for 90 minutes. The volatiles are then removed at 120 °C/2000 Pa (20 mbar) for 30 minutes. A slightly brownish liquid from the structure.
    is obtained. Solids content at 160 °C/15 min of 98.0% Example 7 (inventive polyorganosiloxane)
    [0109] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 132.8g (52 mmol of epoxy groups) of a silicone diepoxide of the structure
    10.4 g (52 mmol) of lauric acid, 3.22 g (37.4 mmol of tert-amine.) of [N,N,N',N'-Tetramethyl hexanediamine), 4.48 g (10, 4 mmol of amino groups) of starting material from Example 6, 18.7 g of propylene glycol monomethyl ether and 8.9 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 6 hours. Then, the solvents are removed and the material is analyzed by means of NMR and viscometry (see Tab. 3.). Example 8 (inventive polyorganosiloxane)
    [0110] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 132.8 g (52 mmol of epoxy groups) of a silicone diepoxide of the structure
    10.4 g (52 mmol) of lauric acid, 1.24 g (15.6 mmol of tert-amine.) N,N,N',N'-tetramethyl hexanediamine, 4.48 g (10.4 mmol of sec-amino groups) of starting material from Example 6, 17.6 g of propylene glycol monomethyl ether and 8.8 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 6 hours. Then, the solvents are removed and the material is analyzed by means of NMR and viscometry (see Tab. 3.). Table 3
    * 4 g of polyorganosiloxane material was added to 200 g of water and mixed with an Ultra Thurrax. ** (13C-NMR)
    [0111]The examples show that the polyorganosiloxanes according to the invention produce materials of low viscosity that can be easily dispersed in water to small droplets having a sufficient stability. Example 9 (inventive polyorganosiloxane)
    [0112] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 300 g (23.46 mmol of epoxy groups) of a silicone diepoxide of the structure
    0.36 g (2.8 mmol CH2Cl), 5.02 g (25.1 mmol) lauric acid, 1.21 g N,N,N',N'-(tetramethyl hexanediamine (14.05 mmol) of tert-amino groups), 57.7 g of 2-propanol and 19.24 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 13.5 hours. During the reaction, after 2 hours, 1g triethylamine is added. Then the solvents are removed and the material is analyzed by means of solids and viscometry. % Solids (120 °C/30 min): 97.24 Viscosity MPa.s (20 °C 0, 1 s-1): 10.600 Example 10 (inventive polyorganosiloxane) Example 10 (inventive polyorganosiloxane)
    [0113] In a 500 ml three-neck flask, equipped with a reflux condenser, a thermometer and a mechanical stirrer, 300 g (23.46 mmol of epoxy groups) of a silicone diepoxide of the structure
    0.36 g (2.8 mmol of CH2Cl C1CH2C(O)OCH2CH2OCH2CH2OC(O)CH2Cl1, 5.02 g (25.1 mmol) of lauric acid, 0.605 g of N,N,N',N'-tetramethyl hexanediamine (7.02 mmol of tert-amino groups), 57.5 g of 2-propanol and 18.88 g of distilled water are mixed at room temperature. The mixture is heated to reflux for 13.5 hours. During the reaction After 2 hours, 1 g of triethylamine is added. Then the solvents are removed and the material is analyzed by means of solids and viscometry. Solids % (120 °C/30 min): 96.62 Viscosity mPa .s (20°C 0.1 s-1): 3500
    [0114]Examples 9 to 10 show that low-viscosity polyorganosiloxanes according to the invention can be synthesized from long-chain epoxide precursors.
    权利要求:
    Claims (29)
    [0001]
    1. Linear polyorganosiloxane copolymer of the type [(AB)XA] wherein X>1 does not denote the group A defined in the following claims comprising: a) at least one polyorganosiloxane group in at least two repeating units, b) at least one quaternary ammonium group in at least two repeating units, c) at least one terminal ester group with at least part of the terminal groups being terminal ester groups c) resulting from the use of monofunctional organic acids as chain terminators , and d) optionally, at least one polyalkylene oxide group in at least two repeating units, CHARACTERIZED by the fact that the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100 :15.
    [0002]
    2. Linear polyorganosiloxane copolymer, according to claim 1, CHARACTERIZED by the fact that the polyalkylene oxide group d) has the general formula:
    [0003]
    3. Linear polyorganosiloxane copolymer, according to claim 1 or 2, CHARACTERIZED by the fact that the polyorganosiloxane group a) has the general formula:
    [0004]
    4. Linear polyorganosiloxane copolymer according to any one of claims 1 to 3, CHARACTERIZED by the fact that the quaternary ammonium group b) is selected from the general formulas:
    [0005]
    5. Linear polyorganosiloxane copolymer, according to any one of claims 2 to 4, CHARACTERIZED by the fact that A and A' are selected from the following groups:
    [0006]
    6. Linear polyorganosiloxane copolymer according to any one of claims 1 to 5, CHARACTERIZED by the fact that the terminal ester group c) is selected from the group of:
    [0007]
    7. Linear polyorganosiloxane copolymer according to any one of claims 1 to 6, CHARACTERIZED by the fact that it has the formula selected from the general formulas (Ia) and (lb):
    [0008]
    8. Linear polyorganosiloxane copolymer according to any one of claims 1 to 7, CHARACTERIZED by the fact that it has protonated ammonium groups.
    [0009]
    9. Process for the manufacture of linear polyorganosiloxane copolymer, as defined in any one of claims 1 to 8, CHARACTERIZED by the fact that it comprises the reaction of (i) at least one ditertiary diamine, (ii) at least one aminoalkylation compound which comprises at least one diepoxide, and (iii) at least one monofunctional organic acid, wherein at least one compound from compounds (i) and (ii) comprises polyorganosiloxane structural units.
    [0010]
    10. Polyorganosiloxane composition CHARACTERIZED by the fact that it comprises: A) at least one linear polyorganosiloxane copolymer as defined in any one of claims 1 to 8, and B) at least one polyorganosiloxane compound comprising at least one ester group terminal, different from compound A).
    [0011]
    11. Polyorganosiloxane composition according to claim 10, CHARACTERIZED by the fact that the weight ratio of compound A) to compound B) is less than 90:10.
    [0012]
    12. Linear polyorganosiloxane copolymer, according to any one of claims 1 to 8, or polyorganosiloxane compositions, according to claim 10 or 11, CHARACTERIZED by the fact that it has a viscosity at 20° C and a shear rate of 0.1 s-1 below 100,000 mPa.s, measured using a plate-to-plate system, plate diameter 40 mm, gap width 0.5 mm.
    [0013]
    13. Aqueous emulsions CHARACTERIZED by the fact that they comprise at least one linear polyorganosiloxane copolymer, as defined in any one of claims 1 to 8, or a polyorganosiloxane composition as defined in claim 10 or 11.
    [0014]
    14. Surface treatment method CHARACTERIZED in that it comprises the step of applying the linear polyorganosiloxane copolymer, as defined in any one of claims 1 to 8, a polyorganosiloxane composition, as defined in claim 10 or 11, or an aqueous emulsion of these to the surface of a substrate.
    [0015]
    15. Method according to claim 14, CHARACTERIZED by the fact that the polyorganosiloxane compositions or emulsions applied comprise one of the following: cosmetic formulations for skin and hair care, selected from rinse-off conditioners (rinse-off ) and no-rinse (leave-on), shampoos, styling gels, sprays and pump sprays; polishing formulations for the treatment and armament (outfitting) of hard surfaces; formulations for drying automobiles and other hard surfaces; formulations for initial armament of textile products and textile fibers; softener formulations further comprising non-ionogenic or anionic/non-ionogenic or cationic surfactants or betaine for application during or after washing textiles; laundry formulations for textile washes based on nonionic or anionic/nonionic or cationic surfactants or betaine or formulations to prevent or reverse textile wrinkling.
    [0016]
    A polyorganosiloxane composition comprising: (1) a linear polyorganosiloxane copolymer of the [(AB)XA] type wherein X>1 and A does not denote the group A defined in the following claims which comprises: a) at least one group of polyorganosiloxane in at least two repeating units, b) at least one quaternary ammonium group in at least two repeating units, c) at least one terminal ester group with at least part of the terminal groups being terminal ester groups c ) which result from the use of monofunctional organic acids as chain terminators, CHARACTERIZED by the fact that the composition further comprises (8) an additional polyorganosiloxane compound comprising at least one terminal ester group, which are (9) modified derivatives with α, w ester of the M-(KSK)-M structure with
    [0017]
    17. Composition, according to claim 16, CHARACTERIZED by the fact that the polyorganosiloxane group a has the general formula:
    [0018]
    18. Composition, according to claim 16 or 17, CHARACTERIZED by the fact that the quaternary ammonium group b) is selected from the general formulas:
    [0019]
    19. Composition, according to any one of claims 16 to 18, CHARACTERIZED by the fact that the terminal ester groups c) are selected from the group of:
    [0020]
    20. Composition according to any one of claims 16 to 19, CHARACTERIZED by the fact that compound A) further comprises d) at least one polyalkylene oxide group.
    [0021]
    21. Composition, according to claim 20, CHARACTERIZED by the fact that the polyalkylene oxide group has the general formula:
    [0022]
    22. Composition, according to claim 21, CHARACTERIZED by the fact that A and A' are selected from the following groups:
    [0023]
    23. Composition according to any one of claims 16 to 22, CHARACTERIZED by the fact that compound A) has a formula selected from the general formulas (Ia) and (lb):
    [0024]
    24. Composition according to any one of claims 16 to 23, CHARACTERIZED by the fact that compound A) has protonated ammonium groups; and/or wherein in compound A) the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:10 and preferably 100:15.
    [0025]
    25. Composition according to any one of claims 16 to 24, CHARACTERIZED by the fact that the weight ratio of component A) to component B) in the composition is between 90:10 and 25:75, preferably between 90:10 and 50:50, between 90:10 and 75:25 or between 72:25 and 50:50.
    [0026]
    26. Composition according to any one of claims 16 to 25, CHARACTERIZED by the fact that the composition has a viscosity at 20 °C and a shear rate of 0.1 s-1 measured as described in the descriptive report below 50,000 mPa.s.
    [0027]
    27. Process for the manufacture of a composition, as defined in any one of claims 16 to 26, CHARACTERIZED by the fact that it includes a process for the production of compound A), which comprises the reaction of (i) at least one ditertiary diamine , (ii) at least one aminoalkylating compound comprising at least one diepoxide, and (iii) at least one monofunctional organic acid, wherein at least one compound from compounds (i) and (ii) comprises polyorganosiloxane structural units .
    [0028]
    28. Aqueous emulsions CHARACTERIZED by the fact that they comprise at least one composition as defined in any one of claims 16 to 26.
    [0029]
    29. Surface treatment method CHARACTERIZED in that it comprises the step of applying a composition, as defined in any one of claims 16 to 26, or an emulsion, as defined in claim 28, to the surface of a substrate, in which the The composition or emulsion is preferably one of the following: cosmetic formulations for skin and hair care, selected from rinse-off and leave-on conditioners, shampoos, styling gels, sprays and sprays of pump; polishing formulations for the treatment and armament (outfitting) of hard surfaces; formulations for drying automobiles and other hard surfaces; formulations for initial armament of textile products and textile fibers; softener formulations further comprising non-ionogenic or anionic/non-ionogenic or cationic surfactants or betaine for application during or after washing textiles; laundry formulations for textile washes based on non-ionic or anionic/non-ionic or cationic surfactants or betaine or formulations to prevent or reverse textile wrinkling. or cationics or betaine or formulations to prevent or reverse textile wrinkling.
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    JP2015519415A|2015-07-09|
    CN104321386B|2018-04-10|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-27| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261617173P| true| 2012-03-29|2012-03-29|
    US61/617,173|2012-03-29|
    PCT/US2013/034248|WO2013148935A1|2012-03-29|2013-03-28|Low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for the production and the use thereof|
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