CA2171168C - Aqueous dispersions of organopolysiloxanes - Google Patents
Aqueous dispersions of organopolysiloxanesInfo
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- CA2171168C CA2171168C CA002171168A CA2171168A CA2171168C CA 2171168 C CA2171168 C CA 2171168C CA 002171168 A CA002171168 A CA 002171168A CA 2171168 A CA2171168 A CA 2171168A CA 2171168 C CA2171168 C CA 2171168C
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- organopolysiloxane
- radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to aqueous dispersions of organopolysiloxanes which can be prepared using the starting substances (A) organopolysiloxane containing groups which are capable of condensation, (B) condensation catalyst, (C) organopolysiloxane resin having a molecular weight Mw of not more than 20,000, (D) compounds containing basic nitrogen and (E) polyvinyl alcohol, with the proviso that the solids content of the dispersions is 0.01 to less than 30% by weight.
Description
__ 2171 168 Wa 9450-S
Paper No. 1 AQUEOUS DISPERSIONS OF ORGANOPOLYSILOXANES
Field of the Invention The present invention relates to aqueous dispersicns of organopolysiloxanes which are converted into elastomers after removal of water, processes for their preparation and their use.
Environmental protection measures are increasingly forcing the avoidance of organic solve:as in chemical formulations. More and more aqueous systems are accordingly being used.
Background of the Inventio:~
Aqueous dispersions of organopolysiloxanes are known, US 4,221,688 (R. D. Johnson, Dow Corning Corporation; issued September 9, 1980', describes tie preparation of aqueous silicone dispersions based on hydroxylated diorganopolysiloxane, col'_oidal silicon dioxide and an organic amine or sodium hycroxide.
US 4,244,849 (J.C. Saam, Dow Corning Corporatic_~.;
issued January 13, 1981) discloses aqueous silicone dispersions which have been obtained by addition of alkali metal silicate tc an anionically stabilized aqueous emulsion of polydiorganosiloxane containing hydroxyl end groups. US 4,816,506 (N. Gamon, blacker-Chemie GmbH; issued Mare 28, 1989) a_~d US 5,045,231 (R. Braun, blacker-Chemie GmbH; issued September 3, 1991) and the corresponding DE 39 32 025 A (published April 4, 1991) describe aquecus dispersions which comprise siliconate .n addition to polydiorganosiloxanes containing hydroxy= groups in the terminal units and (organo)metallic compo~,~nds. EP 366 133 A describes a process for the preparation of aqueous emulsions of solid organopolysiloxanes without using organic solvents by dissolving the solid siloxane in a liquid siloxane and emulsifying this solution. EP 572 006 . ~ 2171168 describes aqueous dispersions which differ from the dispersions according to the invention, in that they have a higher solids content and, for fabric coated with these dispersions, no dimensional stability, elasticity, crease-proof treatment or consolidation of glass fiber fabrics is possible.
Summary of the Invention The object of the present invention is to provide aqueous dispersions of organopolysiloxanes which are stable, transparent and ready-to-use without a long storage period, and which allow elastomers to be prepared in a relatively simple manner and within a short time.
Another object of the present invention is to provide elastic fabric having a soft handle, dimensionally stable fabric, crease-proof fabric and glass fiber fabric having improved properties without expensive processes.
The present invention relates to aqueous dispersions of organopolysiloxanes which are prepared using the starting substances (A) an organopolysiloxane containing groups which are capable of condensation, (B) a condensation catalyst, (C) an organopolysiloxane resin having a molecular weight Mw of not more than 20,000, (D) compounds containing basic nitrogen and (E) polyvinyl alcohol, with the proviso that the solids content of the dispersions is 0.01 to less than 30~
by weight.
The organopolysiloxanes (A) employed according to the invention which contain groups which are capable of condensation are preferably those of the formula RO- [ S iR' 20 ] :,-R ( I ) in which R is identical or different and is a hydrogen atom or alkyl radical having 1 to 6 carbon atom(s), R1 is an identical or different hydrocarbon radical . 2171168 having 1 to 18 carbon atom(s), which is optionally substituted by halogen atoms, amino groups, ether groups, ester groups, epoxide groups, mercapto groups, cyano groups or (poly)glycol radicals, the latter being built up from oxyethylene and/or oxypropylene units, and n is an integer of at least 30.
Examples of hydrocarbon radicals R1 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl or tert-pentyl radical;
hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals, such as the vinyl and the allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the a- and the ~3-phenylethyl radical.
Examples of substituted hydrocarbon radicals R1 are halogenated radicals, such as the 3-chloropropyl radical, the 3,3,3-trifluoropropyl radical, chlorophenyl radicals, hexafluoropropyl radicals, such as the 1-trifluoromethyl-2,2,2-trifluoroethyl radical; the 2-(perfluorohexyl)ethyl radical, the 1,1,2,2-tetrafluoro-ethyloxypropyl radical, the 1-trifluoromethyl-2,2,2-trifluoroethyloxypropyl radical, the perfluoroisopropyl-oxyethyl radical and the perfluoroisopropyloxypropyl radical; radicals substituted by amino groups, such as __ ?_111168 the N-(2-aminoethyl)-3-aminopropyl radical, the 3-amino-propyl radical and the 3-(cyclohexylamino)propyl radical;
ether-functional radicals, such as the 3-methoxypropyl radical and the 3-ethoxypropyl radical; cyano-functional radicals, such as the 2-cyanoethyl radical; ester-func-tional radicals, such as the methacryloxypropyl radical;
epoxy-functional radicals, such as the glycidoxypropyl radical, and sulfur-functional radicals, such as the 3-mercaptopropyl radical.
Preferred radicals R' are hydrocarbon radicals having 1 to 10 carbon atom(s), at least 80~, preferably at least 90$, of the radicals R1 being methyl radicals.
Preferred radicals R are hydrogen atoms and alkyl groups having 1 to 4 carbon atom(s), hydrogen atoms and methyl and ethyl radicals being more preferred.
The average value for the number n in formula (I) is chosen such that the organopolysiloxane of formula (I) has a viscosity of more than 30 mPa.s, preferably of more than 10,000 mPa.s, in each case measured at a temperature of 25°C.
Although not stated in formula (I), up to 10 mole of the diorganosiloxane units can be replaced by other siloxane units, although these are usually only present as impurities which are more or less difficult to avoid, such as Rl3SiOli2, R1Si03,2 and Si04,2 units, in which R1 has the meaning given above.
The polydiorganosiloxanes according to formula (I) can be prepared by processes known in the technical field, for example by polymerization or condensation of low molecular weight cyclic or linear organopolysiloxanes blocked at the ends by hydroxyl and/or alkoxy.
Reference may be made, to W. Noll, "Chemistry and Technology of Silicones", 1968, Academic Press Inc., page 218.
The organopolysiloxane (A) employed according to the invention which contains groups which are capable of condensation can be a single type or a mixture of at least two types of such organopolysiloxanes containing groups which are capable of condensation.
Condensation catalysts (B) employed according to the invention are (organo)metallic compounds, such as the salts of carboxylic acids, the alcoholates and the halides of the metals Pb, Zn, Zr, Ti, Sb, Fe, Cd, Sn, Ba, Ca and Mn. (Organo)tin compounds of carboxylic acids having 1 to 18 carbon atoms) and (organo)tin halides, in particular organotin octoates, naphthenates, hexoates, laurates, acetates, bromides and chlorides, are preferred.
Examples of (organo)tin compounds are tin(II) octoate, dibutyltin dilaurate, octyltin triacetate, dioctyltin dioctoate, dioctyltin diacetate, didecyltin diacetate, dibutyltin diacetate, dibutyltin dibromide, dioctyltin dilaurate and trioctyltin acetate. Diorganotin dicarboxylates, in particular dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate and dioctyltin diacetate. are preferred.
The condensation catalyst (B) employed according to the invention can be a single type or a mixture of at least two types of such condensation catalysts.
For preparation of the aqueous organopolysiloxane dispersions according to the invention, the condensation catalyst (B) is employed in amounts of 0.01 to 7 parts by weight, preferably 0.05 to 2.0 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
The organopolysiloxane resin (C) employed according to the invention is one of units of the formula RZaSi.04_a (II) in which R' is the same as R' and a is a number having an average value between'0.5 and 1.95, in particular between 0.8 and 1.8.
The organopolysiloxane resin in formula (II) can contain up to 10$ by weight of Si-bonded hydroxyl groups and/or chlorine atoms and/or alkoxy groups.
Preferred radicals R' in formula (II) are methyl, ethyl, vinyl and phenyl radicals, in particular methyl radicals.
The organopolysiloxane resin (C) employed according to the invention has a molecular weight Mw of not more than 20,000, preferably not more than 10,000, most preferably not more than 4,000.
Examples of the organopolysiloxane resins (C) employed according to the invention are those of units of the formula [CH3Si03,z] and [ (CH3) zSiO] (TD resin C) and those of units of the formula [ (CH3) 3Si01,z] and [SiO4,z]
(MQ resin C).
The organopolysiloxane resin (C) employed according to the invention is preferably one of the formula [CH3Si03,z] o.s-o.s [ (CHs) zSiO] o,z-o,4 having an average molecular weight Mw of between 2500 and 3500, or of the formula [ (CH3) 3Si01izl o.n-o.s fSi~aiz] o.a-o.s having an average molecular weight Mw of between 200 and 10,000 (MQ resin C) , in particular [CH3Si03,z] o.s-o.e [ (CHs) zSiO] o.z-o.a having an average molecular weight Mw of between 500 and 6000.
The organopolysiloxane resin (C) employed according to the invention is partly, soluble in the organopolysiloxane (A) when used in a range of up to 50$
by weight, based on the weight of organopolysiloxane (A).
If the content of [CH3Si03,z] units in the (TD resin C) is less than about 40 mole, the (TD resin C) is of more or less unlimited solubility in the organopolysiloxane (A) . As the content of [CH3Si03iz]
units increases, the solubility decreases, (TD resins C) having a content of [CH3Si03iz] units of about 80 moles is A s _._~ 21 71 1 8 B
soluble in a sufficient amount in the organopolysiloxane (A) .
If the content of [ (CH3);SiOl,~] units in the (MQ resin C) is above about 50 mole, the (MQ resin C) is of more or less unlimited solubility in organopoly-siloxane (A).
The organopolysiloxane resin (C) employed according to the invention can be prepared by processes known by condensation of low molecular weight organopolysiloxane resins in dispersion, it is possible for the low molecular weight organopolysiloxane resins to be prepared by solvolysis and condensation from a solution of the corresponding silanes having Si-bonded chlorine atoms in a water-immiscible solvent by means of an alcohol/water mixture. Reference may be made, to W. Noll, "Chemistry and Technology of Silicones"; Academic Press, Orlando, 1968, pages 190 to 208.
The organopolysiloxane resin (C) employed according to the invention can be a single type or a mixture of at least two types of such organopolysiloxane resins.
To prepare the aqueous organopolysiloxane disper-sions according to the invention, the organopolysiloxane resin (C) preferably is employed in amounts of 0.1 to 100 parts by weight, more preferably 0.5 to 35 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
The compounds (D) employed according to the invention which contain basic nitrogen preferably are those~chosen from the group consisting of compounds of the formula NR33 ( I I I ) in which R3 is an identical or different hydrogen atom or a hydrocarbon radical having 1 to 18 carbon atom(s), which is optionally substituted by hydroxyl groups, halogen atoms, amino groups, ether groups, ester groups, epoxide groups, mercapto ~~~r ~~
groups, cyano groups or (poly)glycol radicals, the latter being built up from oxyethylene and/or oxypropylene units, with the proviso that not more than two R3 in formula (III) are hydrogen atoms, aliphatic cyclic amines, such as, piperidine and morpholine, and organosilicon compounds having at least one organic radical containing basic nitrogen, of units of the formul R4bY~S i ( ORS ) dCa-5-~-a ( IV ) .
in which R4 is identical or different and is a monovalent organic radical free from basic nitrogen, R5 is identical or different and is a hydrogen atom, alkyl radical, alkali metal cation or ammonium or phosphonium group, Y is identical or different and is a monovalent SiC-bonded radicalswith basic nitrogen, b is 0, 1, 2 or 3, c is 0, 1, 2, 3 or 4 and d is 0, 1, 2 or 3, with the proviso that the sum of b, c and d is less than or equal to 4 and at least one radical Y is present per molecule.
The radicals RS are preferably hydrocarbon radicals having 1 to 18 carbon atom(s), the methyl, ethyl and propyl radical being preferred, especially the methyl radical.
Examples of radical R' are the examples of hydrocarbon radicals stated for R1.
The radicals R5 are preferably hydrogen atoms, methyl or ethyl radicals or alkali metal cations, the hydrogen atom, methyl and ethyl radical and sodium and potassium cation being preferred.
Examples of radical R5 are the hydrocarbon radicals stated for radicals, the cations of the alkali metals, such as those of lithium, sodium, potassium, rubidium and cesium, and radicals of the formula + ~64 ( V ) or + PR6a (VI ) in which R6 is an identical or different hydrocarbon radical having 1 to 6 carbon atom(s).
The radicals Y are preferably those of the formula R'zNRB- (VI I ) in which R' is identical or different and is a hydrogen or alkyl, cycloalkyl or aminoalkyl radical and R8 is a divalent hydrocarbon radical.
The examples of alkyl and cycloalkyl radicals R1 also apply in their full scope to alkyl and cycloalkyl radicals R'.
Preferably, at least one hydrogen atom is bonded to each nitrogen atom in the radicals of the formula (VII).
Radicals RB are divalent hydrocarbon radicals having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, in particular the n-propylene radical.
Examples of the radical RB are the methylene, ethylene, propylene, butylene, cyclohexylene, octadecyl ene, phenylene and butenylene radical.
Examples of radicals Y are HZN(CHz)3-, HzN ( CHz ) zNH ( CHz ) z-. HzN ( CHz ) zNH ( CHz ) s-, HZN ( CHz ) z-, H3CNH ( CHz ) 3-, CzHSNH ( CHz ) 3-, H3CNH ( CHz ) z-. CzH~ ( CHz ) z-.
HZN ( CHz ) a-, HZN ( CHz ) s-, H ( NHCH2CHz ) 3-, C4H9NH ( CHz ) zNH ( CHz ) z-, cyclo-C6H11NH ( CHz ) 3-, cyclo-C6H11NH ( CHz ) z-, ( CH3 ) zN ( CHz ) 3-, ( CHs ) zN ( CHz ) z-, ( CzHs ) zN ( CHz ) s- and ( CzHs ) zN ( CHz ) z- .
Y is preferably HZN (CHz) 3-, HZN (CHz) zNH (CHz) ~-, H3CNH ( CHz ) 3-, CZHSNH ( CHz ) 3- or cyclo-C6H11NH ( CHz ) 3-, where HZN (CHz) zNH (CHz) 3- and cyclo-C6H11NH (CHz) 3- are preferred.
If the organosilicon compounds of units of formula (IV) are silanes, b is 0, 1 or 2, preferably 0 or 1, c is 217116$
1 or 2, preferably 1, and d is 1, 2 or 3, preferably 2 or 3, with the proviso that the sum of b, c and d is 4.
Examples of the silanes of formula (IV) according to the invent ion are HZN ( CHZ ) 3-S i ( OCH3 ) 3, HZN ( CHZ ) 3-S i ( OCZHS ) 3, HZN ( CHZ ) 3-S i ( OCH3 ) ~CH3, HzN ( CHZ ) 3-S i ( OCZHS ) ZCH3, HZN ( CHZ ) s Si (OH) 3-x (OM) x, HzN (CHZ) 3-Si (OH) 2-y (OM),,CH3, HZN ( CHZ ) ZNH ( CHZ ) 3-S i ( OCH3 ) ~, HZN ( CHZ ) ZNH ( CHZ ) s-S i ( OCZHS ) s.
HZN ( CHz ) ZNH ( CHZ ) s-S i ( OCH3 ) ZCHs. HZN ( CHz ) zNH ( CHZ ) s-S i ( OOHS ) ZCH3.
HZN ( CHZ ) zNH ( CHZ ) 3-S i ( OH ) 3-x ( OM ) X, HZN ( CHZ ) ZNH ( CHZ ) 3-S
i ( OH ) 2 -y (OM) yCH3, cyclo-C6H11NH (CHZ) 3-Si (OCH3) 3, cyclo-C6H11NH (CHZ) 3-S1 (OCZHS) 3, cyclo-C6H11NH (CHz) 3-S1 (OCH3) ZCH3, cyclo-C6H11NH ( CHZ ) 3-S i ( OOHS ) 2CH3, cyclo-C6H11NH ( CHz ) ~-S i ( OH ) 3-x ( OM ) X
and cyclo-C6H11NH (CH2) 3-Si (OH) 2-y (OM),.CH3, where HZN ( CHz ) 2NH ( CHZ ) s-S i ( OCH3 ) s. HZN ( CH2 ) ZNH ( CHZ ) s-S i ( OCzHS ) 3.
HZN ( CHZ ) ZNH ( CHZ ) 3-S i ( OCH3 ) 2CH3, HZN ( CHZ ) Z-NH ( CHZ ) s-S i ( OCZHS ) ZCH3, HZN ( CHz ) ZNH ( CHz ) =-S i ( OH ) 3-x ( ONa ) X, HZN ( CHz ) ZNH ( CHz ) 3-S i ( OH ) 2-y ( ONa ) YCH3, cyclo-C6H11NH ( CHZ ) s-S1 (OCH3) 3, Cyclo-CoHIINH (CHz) 3-S1 (OC2H5) 3, cyclo-C6H11NH (CHZ) s-Si (OCH3) ZCH3, cyclo-C6H11NH (CHz) 3-Si (OCzHS) ZCH3, cyclo-C6H11NH (CHZ) 3-Si (OH) 3-x (ONa) x and cyclo-C6H11NH (CHZ) s-Si (OH) 2-y (ONa) YCH~ are preferred and HZN (CHZ) ZNH (CHZ) s-S i ( OCH3 ) 3, HEN ( CHZ ) 2-NH ( CHZ ) 3-S i ( OCH3 ) ZCH3, cyc l o-C6H11NH ( CHZ ) s-S i ( OCH3 ) 3, cyclo-C6H11NH ( CHZ ) s-S i ( OCH3 ) zCHs.
HZN ( CHZ ) ZNH ( CHZ ) 3-S i ( OH ) 3-x ( ONa ) X and HzN ( CHZ ) ZNH ( CHZ ) s-Si(OH)2-y(ONa)yCH; are preferred, where x is 0, 1, 2 or 3, y is 0, 1 or 2 and M is the cation of sodium or potassium.
Silanes of formula (IV) are commercially available products and can be prepared by processes customary in silicon chemistry. Reference may be made to W. Noll "Chemie and Technologie der Silicone" [Chemistry and Technology of Silicones], 1968, Verlag Chemie, page 149.
If the organosilicon compounds of units of formula (IV) are organopolysiloxanes, the average value of b is between 0.5 and 2.5, preferably between 1.4 and 2.0, the average value of c is between 0.01 and 1.0, preferably between 0.01 and 0.6, and the average value of d is between 0 and 2.0, preferably between 0 and 0.2, with the proviso that the sum of b, c and d is less than or equal to 3.
The organopolysiloxanes of units of formula (IV) employed according to the invention have a viscosity at 25°C of preferably 5 to 105 mPa.s, preferably 10 to 104 mPa.s.
Examples of the organopolysiloxanes of units of formula (IV) employed according to the invention are H2N{CH2)2NH(IH2)3 (CH )gSiO [(CHg)2Si0]k [CHgSiOJm Si(CHg)3 (IVa) and cyclo-C6H11NH(CHZ)3 (CH3)3Si0 [(CH3)2Si0]k [CH3S10)m Si(CHg)~ (IVb), in which the ratio of k to m is between 2:3 and 9:1 and the sum of k and m is between 10 and 1000, and H2N(CH2)2NH(IH2)3 L(CH3)2Si0]o [Si03~2]p ~(CH3)3Si01~21r (IVc) and cyclo-C6H11NH(CH2)3 [{CH3)2Si0)o [Si03~2Jp [(CH3)38i01~2]r (IVd).
in which the sum of o+p+r is between 10 and 1000, the ratio of o . (o+p+r) is between 0 and 0.9, preferably between 0.2 and 0.7, the ratio of p . (o+p+r) is between 0.05 and 0.6, preferably between 0.1 and 0.5, and the ratio of r . (o+p+r) is between 0.05 and 0.75, preferably between 0.2 and 0.6.
The organopolysiloxanes of units of formula (IV) employed according to the invention are organopolysiloxanes of the formulae (IVa>, (IVb), (IVc) and (IVd) having a viscosity of 20 to 100,000 mPa.s and an amine number of 0.01 to 4.5, those organopolysiloxanes having a viscosity of 100 to 10,000 mPa.s and an amine number of 0.1 to 1.5 being preferred.
The amine number corresponds numerically to the value which indicates the consumption in ml of 1 N HC1 for neutralization of 1 g of aminosiloxane.
Organopolysiloxanes of units of formula (IV) are commercially available products and can be prepared by the processes customary in silicon chemistry. Reference may be made, to W. Noll, "Chemie and Technologie der Silicone" [Chemistry and Technology of Silicones], 1968, Verlag Chemie, page 194.
Examples of amines of formula (II.) are cyclohexylamine, triethylamine, dodecylamine, diethyl n-propylamine, cyclohexylmethylamine, 2-aminoethanol, 2-amino-n-propanol, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol, N,N-diethylethanolamine, N,N-dimethylethanolamine and aniline, where dodecylamine, 2-aminoethanol and 2-amino-2-methyl-1-propanol are preferred and 2-amino-2-methyl-1-propanol is more preferred.
Compounds which are employed as component (D) are organosilicon compounds having at least one organic radical containing basic nitrogen, of units of formula (IV), in particular potassium N-(2-aminoethyl)-3-aminopropylmethylsilanolate and sodium N-(2-aminoethyl)-3-aminopropylmethylsilanolate, and compounds of formulae (IVa) and (IVc).
The compound (D) containing basic nitrogen employed according to the invention can be a single 21 71 1 6g type or a mixture of at least two types of such compounds.
For preparation of the aqueous organopolysiloxane dispersions according to the invention, compound (D) containing basic nitrogen preferably is employed in amounts of 0.1 to 5.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
Polyvinyl alcohols having a molecular weight Mw of between 20,000 and 100,000 and a hydrolysis number of greater than 100 are preferably employed as component (E) .
For preparation of the aqueous organopolysiloxane dispersions according to the invention, component (E) preferably is employed in amounts of 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
The aqueous organopolysiloxane dispersions according to the invention can comprise other components, chosen from the group consisting of plasticizers, foam prevention agents, pigments, soluble dyestuffs, fungicides, odiferous substances and organic solvents which are inert with respect to the dispersions.
Examples of plasticizers are dimethylpolysiloxanes which are blocked at the ends by trimethylsiloxy groups, are liquid at room temperature and have a viscosity of at least 10 mPa.s.
Examples of organic solvents which are inert with respect to the dispersions are hydrocarbons, such as petroleum ether of various boiling ranges, n-pentane, n-hexane, a hexane isomer mixture, toluene and xylene.
A
a I
Of each of the groups of substances mentioned above as other components for the aqueous dispersions according to the invention, in each case one substance of this group or a mixture of at least two different substances of this group can be used as a component.
Solids contents of up to 30'~ by weight are achieved in the aqueous organopolysiloxane dispersions according to the invention. The solids content is to be understood as meaning the proportion by weight of all the constituents of the dispersion, excluding water and, if used, the organic solvent, of the total weight of the dispersion. The aqueous organopolysiloxane dispersions according to the invention preferably have solids contents of 0.01$ to less than 30$ by weight, preferably 0.1$ to 20$ by weight, and amounts in the range from 0.5~ to 15$ by weight are especially preferred. Water is employed in amounts of 30~ to 99.99 by weight, preferably 80$ to 99.90 by weight, and more preferably 85~ to 99.50 by weight.
Desalinated or distilled water is usually used. Water from water mains can also be used if it contains no troublesome impurities, salts or chemicals, mains water can also be used.
Aqueous dyestuff dispersions can be used in an amount range from 0.01 to 3$ by weight.
The aqueous organopolysiloxane dispersions according to the invention can be prepared in the same manner in which aqueous organopolysiloxane dispersions have been prepared.
The preferred procedure for the preparation of the aqueous dispersions according to the invention comprises dissolving the organopolysiloxane resin (C) in the organopolysiloxane (A) containing groups which are capable of condensation and emulsifying the solution with polyvinyl alcohol (E) and water and, other components.
21 71 1 fib The other components, if they are water-soluble.
are either dissolved directly in the water used for the emulsification, or are added to the aqueous dispersion.
The water-insoluble components are either employed as a dispersion or are emulsified together with the solution of component (C) and component (A).
The emulsification or dispersion can be carried out in customary mixing apparatus suitable for the preparation of emulsions or dispersions, such as high-speed stator-rotor stirrer apparatus according to Prof.
P. Willems, known under the registered trademark "Ultra-Turrax~". Reference may also be made to Ullmanns Encyklopadie der Technischen Chemie [Ullmanns Encyclopedia of Industrial Chemistry], Urban &
Schwarzenberg, Munich, Berlin, 3rd edition, Volume 1, page 720.
The aqueous dispersions according to the invention may have a viscosity of 1.5 to 15,000 mPa.s, preferably 1.5 to 5000, and more preferably 1.5 to 1000 mPa.s.
The aqueous organopolysiloxane dispersions according to the invention can be employed for all purposes for which aqueous organopolysiloxane dispersions have been used. For example, they can be used as sealing compositions, paints and coating systems and as electrically insulating or conducting, hydrophobic, non-stick coating systems, or as a base or additive to such systems. The dispersions according to the invention can preferably be used for impregnation of woven fabrics, knitted fabrics, braided fabrics, fiberwoven fabrics or nonwovens, using apparatus customary in the textile industry.
The aqueous organopolysiloxane dispersions according to the invention cure completely at room temperature within a short time after evaporation of n,.:a~,...._ 2~7~~~8 the solvent content, water and, optionally organic solvent, to give elastomers.
The aqueous dispersions according to the inven tion, in particular those which have been prepared using polyvinyl alcohols, have the advantage that they cure completely in thin layers to give transparent elastomers.
The aqueous dispersions according to the invention have the further advantage that they can be slop-padded or applied by the dipping process onto textile materials, such as woven fabric, knitted fabric, braided fabric, fiberwoven fabric or a nonwoven, and can be pressed off in the padder.
Furthermore, it is possible to treat many sub strates, such as paper, textiles, mineral building materials, plastics, wood and many other substrate materials, with the dispersion according to the invention. Treatment can be carried out by dipping or impregnating.
The aqueous dispersions according to the invention are prepared as described above, by preparing a dispersion having a solids content of 30$ to 90$ by weight, preferably 40~ to 85~ by weight. This dispersion is initially introduced into a stirring or mixing apparatus, such as a Z kneader, dissolver or stirrer. While mixing intensively, the desired amount of water is added, initially in small portions and later, when the viscosity drops, in larger portions, the volume ratio of the small to the large portion being 1:2 to 1:20, preferably 1:2 to 1:10, more preferably 1:2 to 1:5. The number of small portions is 2 to 20, preferably 2 to 10, more preferably 2 to 5.
The number of large portions is 2 to 20, preferably~2 to 10, more preferably 2 to 5. After each addition of water, the mixture is stirred, mixed or kneaded until a homogeneous mass is obtained. The time required for the 2~ ~'T. X68 total mixing operation depends on the mixing tool used, and varies in the range from 1 to 60 minutes. The mixing operation is carried out at room temperature, under normal pressure. The mixing operation can also be carried out at temperatures in the range from 5°C to 60°C. A reduced or evaluated pressure is possible in principle.
The dispersion according to the invention prepared in this way is applied to textile materials by processes customary in the textile finishing industry, such as slop padding, dipping with or without a subse-quent padder, knife coating or coating by roller application, screen printing or screen roll printing or spraying.
Drying and vulcanization are carried out in customary heating tunnels which can be temperature-controlled by hot air or infrared radiation or other energy sources. The preferred temperature range is 50° - 200°C. Since some types of textile are not resistant to heat, the upper temperature limit is usually determined by the heat resistance of the textile. The residence time in the drying oven depends on the temperature in the heating tunnel and is preferably 0.5 to 30 minutes.
The textiles, woven fabric, knitted fabric, braided fabric, fiberwoven fabric or nonwoven treated according to the invention have the following advantages:
Elastic textiles are usually obtained by using mixed yarns of cotton and synthetic fibers, such as nylon, polyester, polyurethane and the like. These mixed yarns are usually woven or knitted. This type of textile is difficult to process and thus relatively expensive.
If a pure cotton material which is knitted or woven is treated with the dispersion according to the 2~ lT ~~8 invention, a textile material having elastic properties is obtained after the treatment. In addition, a pleasant soft handle is achieved. Such textiles are preferably suitable for sports clothing. However, the fields of use of such textiles are virtually unlimited.
Sleeve cuffs and structuring ribs of underwear and clothing of wool and acrylic fibers and/or cotton show a poor dimensional stability. If treatment with the dispersion according to the invention is carried out, a good dimensional stability (recovery effect) is achieved. Greater or lesser elastic properties can be achieved, depending on the amount applied.
In the field of high-quality clothing, Greaseproof textiles expected by the consumer limited the possible use of yarns almost exclusively to synthetic fibers.
However, if fabrics of wool, cotton or mixtures thereof or blended fabrics of wool or cotton with synthetic fibers are treated with the dispersion according to the invention, predominantly Greaseproof textiles are formed.
Fabric of glass fibers frays severely at the cutting points, and fraying at the cut edges is prevented by the treatment. Glass dust formed by the fine glass fibers breaking is fixed by treatment with the dispersion according to the invention. Furthermore, a glass fabric treated in this way shows elastic properties.
In the examples described below, all the parts and percentages data relate to the weight, unless stated otherwise. All the viscosity data are based on a temperature of 25°C. Unless stated otherwise, the following examples were carried ou~ under a pressure of the surrounding atmosphere, at about 1000 hPa, and at room temperature, at about 22°C, or at a temperature which is established when the reactants are brought ' 21 71 1 68 - together at room temperature without additional heating or cooling.
Example 1 I) Preparation of an aqueous dispersion of condensation catalyst (B) 125 g of dibutyltin dilaurate are emulsified together with 10 g of tributylphenol polyglycol ether (commercially obtainable under the name "Sapogenat'1''"' T130" from Hoechst AG) and 365 g of water.
Example 2 200 g of a,w-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s and 5.00 g of [CH3Si03iz] o.s [ lCH3) zSiO] o,~ having an average molecular weight Mw of 3000 are mixed. The mixture is then converted into an emulsion with 25.0 g of water and 50 g of a loo strength solution of a polyvinyl alcohol having a molecular weight Mw of 36,000 and a hydrolysis number of 20 (commercially obtainable under the name "Polyviol'I''°' G 10/20" from blacker-Chemie GmbH) in water with the aid of an Ultra-TurraxTM mixer. After addition of 2.8 g of 3-(2-aminoethylamino)propyl-functional poly dimethylsiloxane having a viscosity of 1000 mPa.s and an amine number of 0.3 (comercially obtainable under the name "Finish WR'1'M 1300" from blacker-Chemie GmbH, Munich) and 1.4 g of the aqueous dispersion of condensation catalyst (B) described in Example 1 under I, a white, stable aqueous dispersion which can be stored for at least 6 months is obtained.
Example 3 100 g of the product obtained according to Example 2 is initially introduced into a Z kneader and, while kneading constantly, 100 g of water are added, initially in portions of 5 times 5 g and later in portions of 5 times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is obtained.
An aqueous organopolysiloxane dispersion which comprises a solids content of 43~ by weight and has a viscosity of 4,600 mPa.s is obtained.
150 g of the dispersion thus obtained are poured into 3 liter of water, while stirring slowly. A
homogeneous aqueous dispersion having a solids content of 2~ by weight is obtained.
A knitted cotton fabric having a weight of 90 g/ m2 is dipped into the dispersion thus obtained and pressed off in a padder at a pressure of 3 kp/cm2. It is dried in a hot air oven at 150°C
for 3 minutes.
The weight per unit area of the textile is now 94 g/m2. The knitted cotton fabric shows elastic properties. If a non-treated piece of fabric of 20 x 20 cm is stretched with a tensile force of 5 kp, the measurements are 16 x 25 cm after a resting time of 2 minutes.
The coated piece of fabric is again 20 x 20 cm after the stretching and resting operation.
Example 4 100 g of the product obtained according to Example 2 are stirred with a dissolver disk and, while stirring constantly, 100 g of water are added, initially in portions of 5 times 5 g and later in portions of 5 times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is achieved.
2~ ~T~ r~s, liter of water are then rapidly added with further stirring. A homogeneous dispersion having a solids content of 0.8~ by weight is obtained.
Knitted sleeve cuffs of wool/acrylic fiber mixed 5 yarn are dipped into the dispersion thus obtained and, after draining off briefly, are dried in a hot air oven at 100°C for 10 minutes. The sleeve cuffs thus treated show a clearly improved dimensional stability compared with untreated 10 goods. This effect is intensified further after a storage time of 3 days in air.
Example 5 100 g of the product obtained according to Example 2 are stirred with a blade stirrer at high speed and, while stirring constantly, 100 g of water are added, initially in portions of 5 times 5 g and later in portions of S times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is achieved.
16 liter of water are then rapidly added with further stirring. A homogeneous dispersion having a solids content of 0.5= by weight is obtained.
This dispersion is applied to a cotton/polyester 80/20 blended fabric using a slop-padding roller and is dried in a hot air oven at 120°C for 5 minutes.
The fabric thus treated is stored in air for 3 days. After severe creasing, no folds or crease points are detectable.
The non-treated fabric shows clear crease points and folds after the same crease treatment.
Example 6 100 g of the product obtained according to Example 2 are initially introduced into a Z kneader and, while kneading constantly, 100 g of water are added, initially in portions of 5 times g and later in portions of 5 times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is achieved. An aqueous organopolysiloxane dispersion which 5 comprises a solids content of 43~ by weight and has a viscosity of 4,600 mPa.s is obtained.
150 g of this dispersion thus obtained are poured into 1 liter of water while stirring slowly.
A homogeneous aqueous dispersion having a solids content of 5.5$ by weight is obtained.
This dispersion is applied to a glass fiber fabric having a weight of 120 g/m' using a coating knife.
After drying in a hot air oven at 180°C for 2 minutes, a fabric weight of 136 g/mz is determined.
The glass fabric coated in this way does not fray at the cut edges and shows elastic properties.
Even after vigorous movements, no glass dust is released.
Example 7 The product obtained according to Example 2 is spread onto glass fabric having a fabric weight of 240 g/ m2 using a spatula. The fabric is dried in a hot air oven at 150°C for 3 minutes. A coating with many bubbles is obtained. The coating weight is 220 g/mz. A thin coating cannot be achieved.
Coating processes such as dipping or spraying are not possible.
Example 8 100 g of the product obtained according to Example 2 and 100 g of water (in one portion) were stirred for 1 hour using a blade stirrer. No homogeneous dispersion was obtained. The mixture contains many particles of very high viscosity. If the mixture is diluted with a further 10 liter of water as in Example 4, a milky inhomogeneous liquor is obtained. No changes or effects can be observed on fabrics which have been dipped padded and dried at 100°C for 10 minutes.
Paper No. 1 AQUEOUS DISPERSIONS OF ORGANOPOLYSILOXANES
Field of the Invention The present invention relates to aqueous dispersicns of organopolysiloxanes which are converted into elastomers after removal of water, processes for their preparation and their use.
Environmental protection measures are increasingly forcing the avoidance of organic solve:as in chemical formulations. More and more aqueous systems are accordingly being used.
Background of the Inventio:~
Aqueous dispersions of organopolysiloxanes are known, US 4,221,688 (R. D. Johnson, Dow Corning Corporation; issued September 9, 1980', describes tie preparation of aqueous silicone dispersions based on hydroxylated diorganopolysiloxane, col'_oidal silicon dioxide and an organic amine or sodium hycroxide.
US 4,244,849 (J.C. Saam, Dow Corning Corporatic_~.;
issued January 13, 1981) discloses aqueous silicone dispersions which have been obtained by addition of alkali metal silicate tc an anionically stabilized aqueous emulsion of polydiorganosiloxane containing hydroxyl end groups. US 4,816,506 (N. Gamon, blacker-Chemie GmbH; issued Mare 28, 1989) a_~d US 5,045,231 (R. Braun, blacker-Chemie GmbH; issued September 3, 1991) and the corresponding DE 39 32 025 A (published April 4, 1991) describe aquecus dispersions which comprise siliconate .n addition to polydiorganosiloxanes containing hydroxy= groups in the terminal units and (organo)metallic compo~,~nds. EP 366 133 A describes a process for the preparation of aqueous emulsions of solid organopolysiloxanes without using organic solvents by dissolving the solid siloxane in a liquid siloxane and emulsifying this solution. EP 572 006 . ~ 2171168 describes aqueous dispersions which differ from the dispersions according to the invention, in that they have a higher solids content and, for fabric coated with these dispersions, no dimensional stability, elasticity, crease-proof treatment or consolidation of glass fiber fabrics is possible.
Summary of the Invention The object of the present invention is to provide aqueous dispersions of organopolysiloxanes which are stable, transparent and ready-to-use without a long storage period, and which allow elastomers to be prepared in a relatively simple manner and within a short time.
Another object of the present invention is to provide elastic fabric having a soft handle, dimensionally stable fabric, crease-proof fabric and glass fiber fabric having improved properties without expensive processes.
The present invention relates to aqueous dispersions of organopolysiloxanes which are prepared using the starting substances (A) an organopolysiloxane containing groups which are capable of condensation, (B) a condensation catalyst, (C) an organopolysiloxane resin having a molecular weight Mw of not more than 20,000, (D) compounds containing basic nitrogen and (E) polyvinyl alcohol, with the proviso that the solids content of the dispersions is 0.01 to less than 30~
by weight.
The organopolysiloxanes (A) employed according to the invention which contain groups which are capable of condensation are preferably those of the formula RO- [ S iR' 20 ] :,-R ( I ) in which R is identical or different and is a hydrogen atom or alkyl radical having 1 to 6 carbon atom(s), R1 is an identical or different hydrocarbon radical . 2171168 having 1 to 18 carbon atom(s), which is optionally substituted by halogen atoms, amino groups, ether groups, ester groups, epoxide groups, mercapto groups, cyano groups or (poly)glycol radicals, the latter being built up from oxyethylene and/or oxypropylene units, and n is an integer of at least 30.
Examples of hydrocarbon radicals R1 are alkyl radicals, such as the methyl, ethyl, n-propyl, iso propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl or tert-pentyl radical;
hexyl radicals, such as the n-hexyl radical; heptyl radicals, such as the n-heptyl radical; octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; nonyl radicals, such as the n-nonyl radical; decyl radicals, such as the n-decyl radical; dodecyl radicals, such as the n-dodecyl radical; octadecyl radicals, such as the n-octadecyl radical; alkenyl radicals, such as the vinyl and the allyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl and cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical and the a- and the ~3-phenylethyl radical.
Examples of substituted hydrocarbon radicals R1 are halogenated radicals, such as the 3-chloropropyl radical, the 3,3,3-trifluoropropyl radical, chlorophenyl radicals, hexafluoropropyl radicals, such as the 1-trifluoromethyl-2,2,2-trifluoroethyl radical; the 2-(perfluorohexyl)ethyl radical, the 1,1,2,2-tetrafluoro-ethyloxypropyl radical, the 1-trifluoromethyl-2,2,2-trifluoroethyloxypropyl radical, the perfluoroisopropyl-oxyethyl radical and the perfluoroisopropyloxypropyl radical; radicals substituted by amino groups, such as __ ?_111168 the N-(2-aminoethyl)-3-aminopropyl radical, the 3-amino-propyl radical and the 3-(cyclohexylamino)propyl radical;
ether-functional radicals, such as the 3-methoxypropyl radical and the 3-ethoxypropyl radical; cyano-functional radicals, such as the 2-cyanoethyl radical; ester-func-tional radicals, such as the methacryloxypropyl radical;
epoxy-functional radicals, such as the glycidoxypropyl radical, and sulfur-functional radicals, such as the 3-mercaptopropyl radical.
Preferred radicals R' are hydrocarbon radicals having 1 to 10 carbon atom(s), at least 80~, preferably at least 90$, of the radicals R1 being methyl radicals.
Preferred radicals R are hydrogen atoms and alkyl groups having 1 to 4 carbon atom(s), hydrogen atoms and methyl and ethyl radicals being more preferred.
The average value for the number n in formula (I) is chosen such that the organopolysiloxane of formula (I) has a viscosity of more than 30 mPa.s, preferably of more than 10,000 mPa.s, in each case measured at a temperature of 25°C.
Although not stated in formula (I), up to 10 mole of the diorganosiloxane units can be replaced by other siloxane units, although these are usually only present as impurities which are more or less difficult to avoid, such as Rl3SiOli2, R1Si03,2 and Si04,2 units, in which R1 has the meaning given above.
The polydiorganosiloxanes according to formula (I) can be prepared by processes known in the technical field, for example by polymerization or condensation of low molecular weight cyclic or linear organopolysiloxanes blocked at the ends by hydroxyl and/or alkoxy.
Reference may be made, to W. Noll, "Chemistry and Technology of Silicones", 1968, Academic Press Inc., page 218.
The organopolysiloxane (A) employed according to the invention which contains groups which are capable of condensation can be a single type or a mixture of at least two types of such organopolysiloxanes containing groups which are capable of condensation.
Condensation catalysts (B) employed according to the invention are (organo)metallic compounds, such as the salts of carboxylic acids, the alcoholates and the halides of the metals Pb, Zn, Zr, Ti, Sb, Fe, Cd, Sn, Ba, Ca and Mn. (Organo)tin compounds of carboxylic acids having 1 to 18 carbon atoms) and (organo)tin halides, in particular organotin octoates, naphthenates, hexoates, laurates, acetates, bromides and chlorides, are preferred.
Examples of (organo)tin compounds are tin(II) octoate, dibutyltin dilaurate, octyltin triacetate, dioctyltin dioctoate, dioctyltin diacetate, didecyltin diacetate, dibutyltin diacetate, dibutyltin dibromide, dioctyltin dilaurate and trioctyltin acetate. Diorganotin dicarboxylates, in particular dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate and dioctyltin diacetate. are preferred.
The condensation catalyst (B) employed according to the invention can be a single type or a mixture of at least two types of such condensation catalysts.
For preparation of the aqueous organopolysiloxane dispersions according to the invention, the condensation catalyst (B) is employed in amounts of 0.01 to 7 parts by weight, preferably 0.05 to 2.0 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
The organopolysiloxane resin (C) employed according to the invention is one of units of the formula RZaSi.04_a (II) in which R' is the same as R' and a is a number having an average value between'0.5 and 1.95, in particular between 0.8 and 1.8.
The organopolysiloxane resin in formula (II) can contain up to 10$ by weight of Si-bonded hydroxyl groups and/or chlorine atoms and/or alkoxy groups.
Preferred radicals R' in formula (II) are methyl, ethyl, vinyl and phenyl radicals, in particular methyl radicals.
The organopolysiloxane resin (C) employed according to the invention has a molecular weight Mw of not more than 20,000, preferably not more than 10,000, most preferably not more than 4,000.
Examples of the organopolysiloxane resins (C) employed according to the invention are those of units of the formula [CH3Si03,z] and [ (CH3) zSiO] (TD resin C) and those of units of the formula [ (CH3) 3Si01,z] and [SiO4,z]
(MQ resin C).
The organopolysiloxane resin (C) employed according to the invention is preferably one of the formula [CH3Si03,z] o.s-o.s [ (CHs) zSiO] o,z-o,4 having an average molecular weight Mw of between 2500 and 3500, or of the formula [ (CH3) 3Si01izl o.n-o.s fSi~aiz] o.a-o.s having an average molecular weight Mw of between 200 and 10,000 (MQ resin C) , in particular [CH3Si03,z] o.s-o.e [ (CHs) zSiO] o.z-o.a having an average molecular weight Mw of between 500 and 6000.
The organopolysiloxane resin (C) employed according to the invention is partly, soluble in the organopolysiloxane (A) when used in a range of up to 50$
by weight, based on the weight of organopolysiloxane (A).
If the content of [CH3Si03,z] units in the (TD resin C) is less than about 40 mole, the (TD resin C) is of more or less unlimited solubility in the organopolysiloxane (A) . As the content of [CH3Si03iz]
units increases, the solubility decreases, (TD resins C) having a content of [CH3Si03iz] units of about 80 moles is A s _._~ 21 71 1 8 B
soluble in a sufficient amount in the organopolysiloxane (A) .
If the content of [ (CH3);SiOl,~] units in the (MQ resin C) is above about 50 mole, the (MQ resin C) is of more or less unlimited solubility in organopoly-siloxane (A).
The organopolysiloxane resin (C) employed according to the invention can be prepared by processes known by condensation of low molecular weight organopolysiloxane resins in dispersion, it is possible for the low molecular weight organopolysiloxane resins to be prepared by solvolysis and condensation from a solution of the corresponding silanes having Si-bonded chlorine atoms in a water-immiscible solvent by means of an alcohol/water mixture. Reference may be made, to W. Noll, "Chemistry and Technology of Silicones"; Academic Press, Orlando, 1968, pages 190 to 208.
The organopolysiloxane resin (C) employed according to the invention can be a single type or a mixture of at least two types of such organopolysiloxane resins.
To prepare the aqueous organopolysiloxane disper-sions according to the invention, the organopolysiloxane resin (C) preferably is employed in amounts of 0.1 to 100 parts by weight, more preferably 0.5 to 35 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
The compounds (D) employed according to the invention which contain basic nitrogen preferably are those~chosen from the group consisting of compounds of the formula NR33 ( I I I ) in which R3 is an identical or different hydrogen atom or a hydrocarbon radical having 1 to 18 carbon atom(s), which is optionally substituted by hydroxyl groups, halogen atoms, amino groups, ether groups, ester groups, epoxide groups, mercapto ~~~r ~~
groups, cyano groups or (poly)glycol radicals, the latter being built up from oxyethylene and/or oxypropylene units, with the proviso that not more than two R3 in formula (III) are hydrogen atoms, aliphatic cyclic amines, such as, piperidine and morpholine, and organosilicon compounds having at least one organic radical containing basic nitrogen, of units of the formul R4bY~S i ( ORS ) dCa-5-~-a ( IV ) .
in which R4 is identical or different and is a monovalent organic radical free from basic nitrogen, R5 is identical or different and is a hydrogen atom, alkyl radical, alkali metal cation or ammonium or phosphonium group, Y is identical or different and is a monovalent SiC-bonded radicalswith basic nitrogen, b is 0, 1, 2 or 3, c is 0, 1, 2, 3 or 4 and d is 0, 1, 2 or 3, with the proviso that the sum of b, c and d is less than or equal to 4 and at least one radical Y is present per molecule.
The radicals RS are preferably hydrocarbon radicals having 1 to 18 carbon atom(s), the methyl, ethyl and propyl radical being preferred, especially the methyl radical.
Examples of radical R' are the examples of hydrocarbon radicals stated for R1.
The radicals R5 are preferably hydrogen atoms, methyl or ethyl radicals or alkali metal cations, the hydrogen atom, methyl and ethyl radical and sodium and potassium cation being preferred.
Examples of radical R5 are the hydrocarbon radicals stated for radicals, the cations of the alkali metals, such as those of lithium, sodium, potassium, rubidium and cesium, and radicals of the formula + ~64 ( V ) or + PR6a (VI ) in which R6 is an identical or different hydrocarbon radical having 1 to 6 carbon atom(s).
The radicals Y are preferably those of the formula R'zNRB- (VI I ) in which R' is identical or different and is a hydrogen or alkyl, cycloalkyl or aminoalkyl radical and R8 is a divalent hydrocarbon radical.
The examples of alkyl and cycloalkyl radicals R1 also apply in their full scope to alkyl and cycloalkyl radicals R'.
Preferably, at least one hydrogen atom is bonded to each nitrogen atom in the radicals of the formula (VII).
Radicals RB are divalent hydrocarbon radicals having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, in particular the n-propylene radical.
Examples of the radical RB are the methylene, ethylene, propylene, butylene, cyclohexylene, octadecyl ene, phenylene and butenylene radical.
Examples of radicals Y are HZN(CHz)3-, HzN ( CHz ) zNH ( CHz ) z-. HzN ( CHz ) zNH ( CHz ) s-, HZN ( CHz ) z-, H3CNH ( CHz ) 3-, CzHSNH ( CHz ) 3-, H3CNH ( CHz ) z-. CzH~ ( CHz ) z-.
HZN ( CHz ) a-, HZN ( CHz ) s-, H ( NHCH2CHz ) 3-, C4H9NH ( CHz ) zNH ( CHz ) z-, cyclo-C6H11NH ( CHz ) 3-, cyclo-C6H11NH ( CHz ) z-, ( CH3 ) zN ( CHz ) 3-, ( CHs ) zN ( CHz ) z-, ( CzHs ) zN ( CHz ) s- and ( CzHs ) zN ( CHz ) z- .
Y is preferably HZN (CHz) 3-, HZN (CHz) zNH (CHz) ~-, H3CNH ( CHz ) 3-, CZHSNH ( CHz ) 3- or cyclo-C6H11NH ( CHz ) 3-, where HZN (CHz) zNH (CHz) 3- and cyclo-C6H11NH (CHz) 3- are preferred.
If the organosilicon compounds of units of formula (IV) are silanes, b is 0, 1 or 2, preferably 0 or 1, c is 217116$
1 or 2, preferably 1, and d is 1, 2 or 3, preferably 2 or 3, with the proviso that the sum of b, c and d is 4.
Examples of the silanes of formula (IV) according to the invent ion are HZN ( CHZ ) 3-S i ( OCH3 ) 3, HZN ( CHZ ) 3-S i ( OCZHS ) 3, HZN ( CHZ ) 3-S i ( OCH3 ) ~CH3, HzN ( CHZ ) 3-S i ( OCZHS ) ZCH3, HZN ( CHZ ) s Si (OH) 3-x (OM) x, HzN (CHZ) 3-Si (OH) 2-y (OM),,CH3, HZN ( CHZ ) ZNH ( CHZ ) 3-S i ( OCH3 ) ~, HZN ( CHZ ) ZNH ( CHZ ) s-S i ( OCZHS ) s.
HZN ( CHz ) ZNH ( CHZ ) s-S i ( OCH3 ) ZCHs. HZN ( CHz ) zNH ( CHZ ) s-S i ( OOHS ) ZCH3.
HZN ( CHZ ) zNH ( CHZ ) 3-S i ( OH ) 3-x ( OM ) X, HZN ( CHZ ) ZNH ( CHZ ) 3-S
i ( OH ) 2 -y (OM) yCH3, cyclo-C6H11NH (CHZ) 3-Si (OCH3) 3, cyclo-C6H11NH (CHZ) 3-S1 (OCZHS) 3, cyclo-C6H11NH (CHz) 3-S1 (OCH3) ZCH3, cyclo-C6H11NH ( CHZ ) 3-S i ( OOHS ) 2CH3, cyclo-C6H11NH ( CHz ) ~-S i ( OH ) 3-x ( OM ) X
and cyclo-C6H11NH (CH2) 3-Si (OH) 2-y (OM),.CH3, where HZN ( CHz ) 2NH ( CHZ ) s-S i ( OCH3 ) s. HZN ( CH2 ) ZNH ( CHZ ) s-S i ( OCzHS ) 3.
HZN ( CHZ ) ZNH ( CHZ ) 3-S i ( OCH3 ) 2CH3, HZN ( CHZ ) Z-NH ( CHZ ) s-S i ( OCZHS ) ZCH3, HZN ( CHz ) ZNH ( CHz ) =-S i ( OH ) 3-x ( ONa ) X, HZN ( CHz ) ZNH ( CHz ) 3-S i ( OH ) 2-y ( ONa ) YCH3, cyclo-C6H11NH ( CHZ ) s-S1 (OCH3) 3, Cyclo-CoHIINH (CHz) 3-S1 (OC2H5) 3, cyclo-C6H11NH (CHZ) s-Si (OCH3) ZCH3, cyclo-C6H11NH (CHz) 3-Si (OCzHS) ZCH3, cyclo-C6H11NH (CHZ) 3-Si (OH) 3-x (ONa) x and cyclo-C6H11NH (CHZ) s-Si (OH) 2-y (ONa) YCH~ are preferred and HZN (CHZ) ZNH (CHZ) s-S i ( OCH3 ) 3, HEN ( CHZ ) 2-NH ( CHZ ) 3-S i ( OCH3 ) ZCH3, cyc l o-C6H11NH ( CHZ ) s-S i ( OCH3 ) 3, cyclo-C6H11NH ( CHZ ) s-S i ( OCH3 ) zCHs.
HZN ( CHZ ) ZNH ( CHZ ) 3-S i ( OH ) 3-x ( ONa ) X and HzN ( CHZ ) ZNH ( CHZ ) s-Si(OH)2-y(ONa)yCH; are preferred, where x is 0, 1, 2 or 3, y is 0, 1 or 2 and M is the cation of sodium or potassium.
Silanes of formula (IV) are commercially available products and can be prepared by processes customary in silicon chemistry. Reference may be made to W. Noll "Chemie and Technologie der Silicone" [Chemistry and Technology of Silicones], 1968, Verlag Chemie, page 149.
If the organosilicon compounds of units of formula (IV) are organopolysiloxanes, the average value of b is between 0.5 and 2.5, preferably between 1.4 and 2.0, the average value of c is between 0.01 and 1.0, preferably between 0.01 and 0.6, and the average value of d is between 0 and 2.0, preferably between 0 and 0.2, with the proviso that the sum of b, c and d is less than or equal to 3.
The organopolysiloxanes of units of formula (IV) employed according to the invention have a viscosity at 25°C of preferably 5 to 105 mPa.s, preferably 10 to 104 mPa.s.
Examples of the organopolysiloxanes of units of formula (IV) employed according to the invention are H2N{CH2)2NH(IH2)3 (CH )gSiO [(CHg)2Si0]k [CHgSiOJm Si(CHg)3 (IVa) and cyclo-C6H11NH(CHZ)3 (CH3)3Si0 [(CH3)2Si0]k [CH3S10)m Si(CHg)~ (IVb), in which the ratio of k to m is between 2:3 and 9:1 and the sum of k and m is between 10 and 1000, and H2N(CH2)2NH(IH2)3 L(CH3)2Si0]o [Si03~2]p ~(CH3)3Si01~21r (IVc) and cyclo-C6H11NH(CH2)3 [{CH3)2Si0)o [Si03~2Jp [(CH3)38i01~2]r (IVd).
in which the sum of o+p+r is between 10 and 1000, the ratio of o . (o+p+r) is between 0 and 0.9, preferably between 0.2 and 0.7, the ratio of p . (o+p+r) is between 0.05 and 0.6, preferably between 0.1 and 0.5, and the ratio of r . (o+p+r) is between 0.05 and 0.75, preferably between 0.2 and 0.6.
The organopolysiloxanes of units of formula (IV) employed according to the invention are organopolysiloxanes of the formulae (IVa>, (IVb), (IVc) and (IVd) having a viscosity of 20 to 100,000 mPa.s and an amine number of 0.01 to 4.5, those organopolysiloxanes having a viscosity of 100 to 10,000 mPa.s and an amine number of 0.1 to 1.5 being preferred.
The amine number corresponds numerically to the value which indicates the consumption in ml of 1 N HC1 for neutralization of 1 g of aminosiloxane.
Organopolysiloxanes of units of formula (IV) are commercially available products and can be prepared by the processes customary in silicon chemistry. Reference may be made, to W. Noll, "Chemie and Technologie der Silicone" [Chemistry and Technology of Silicones], 1968, Verlag Chemie, page 194.
Examples of amines of formula (II.) are cyclohexylamine, triethylamine, dodecylamine, diethyl n-propylamine, cyclohexylmethylamine, 2-aminoethanol, 2-amino-n-propanol, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol, N,N-diethylethanolamine, N,N-dimethylethanolamine and aniline, where dodecylamine, 2-aminoethanol and 2-amino-2-methyl-1-propanol are preferred and 2-amino-2-methyl-1-propanol is more preferred.
Compounds which are employed as component (D) are organosilicon compounds having at least one organic radical containing basic nitrogen, of units of formula (IV), in particular potassium N-(2-aminoethyl)-3-aminopropylmethylsilanolate and sodium N-(2-aminoethyl)-3-aminopropylmethylsilanolate, and compounds of formulae (IVa) and (IVc).
The compound (D) containing basic nitrogen employed according to the invention can be a single 21 71 1 6g type or a mixture of at least two types of such compounds.
For preparation of the aqueous organopolysiloxane dispersions according to the invention, compound (D) containing basic nitrogen preferably is employed in amounts of 0.1 to 5.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
Polyvinyl alcohols having a molecular weight Mw of between 20,000 and 100,000 and a hydrolysis number of greater than 100 are preferably employed as component (E) .
For preparation of the aqueous organopolysiloxane dispersions according to the invention, component (E) preferably is employed in amounts of 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, in each case based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
The aqueous organopolysiloxane dispersions according to the invention can comprise other components, chosen from the group consisting of plasticizers, foam prevention agents, pigments, soluble dyestuffs, fungicides, odiferous substances and organic solvents which are inert with respect to the dispersions.
Examples of plasticizers are dimethylpolysiloxanes which are blocked at the ends by trimethylsiloxy groups, are liquid at room temperature and have a viscosity of at least 10 mPa.s.
Examples of organic solvents which are inert with respect to the dispersions are hydrocarbons, such as petroleum ether of various boiling ranges, n-pentane, n-hexane, a hexane isomer mixture, toluene and xylene.
A
a I
Of each of the groups of substances mentioned above as other components for the aqueous dispersions according to the invention, in each case one substance of this group or a mixture of at least two different substances of this group can be used as a component.
Solids contents of up to 30'~ by weight are achieved in the aqueous organopolysiloxane dispersions according to the invention. The solids content is to be understood as meaning the proportion by weight of all the constituents of the dispersion, excluding water and, if used, the organic solvent, of the total weight of the dispersion. The aqueous organopolysiloxane dispersions according to the invention preferably have solids contents of 0.01$ to less than 30$ by weight, preferably 0.1$ to 20$ by weight, and amounts in the range from 0.5~ to 15$ by weight are especially preferred. Water is employed in amounts of 30~ to 99.99 by weight, preferably 80$ to 99.90 by weight, and more preferably 85~ to 99.50 by weight.
Desalinated or distilled water is usually used. Water from water mains can also be used if it contains no troublesome impurities, salts or chemicals, mains water can also be used.
Aqueous dyestuff dispersions can be used in an amount range from 0.01 to 3$ by weight.
The aqueous organopolysiloxane dispersions according to the invention can be prepared in the same manner in which aqueous organopolysiloxane dispersions have been prepared.
The preferred procedure for the preparation of the aqueous dispersions according to the invention comprises dissolving the organopolysiloxane resin (C) in the organopolysiloxane (A) containing groups which are capable of condensation and emulsifying the solution with polyvinyl alcohol (E) and water and, other components.
21 71 1 fib The other components, if they are water-soluble.
are either dissolved directly in the water used for the emulsification, or are added to the aqueous dispersion.
The water-insoluble components are either employed as a dispersion or are emulsified together with the solution of component (C) and component (A).
The emulsification or dispersion can be carried out in customary mixing apparatus suitable for the preparation of emulsions or dispersions, such as high-speed stator-rotor stirrer apparatus according to Prof.
P. Willems, known under the registered trademark "Ultra-Turrax~". Reference may also be made to Ullmanns Encyklopadie der Technischen Chemie [Ullmanns Encyclopedia of Industrial Chemistry], Urban &
Schwarzenberg, Munich, Berlin, 3rd edition, Volume 1, page 720.
The aqueous dispersions according to the invention may have a viscosity of 1.5 to 15,000 mPa.s, preferably 1.5 to 5000, and more preferably 1.5 to 1000 mPa.s.
The aqueous organopolysiloxane dispersions according to the invention can be employed for all purposes for which aqueous organopolysiloxane dispersions have been used. For example, they can be used as sealing compositions, paints and coating systems and as electrically insulating or conducting, hydrophobic, non-stick coating systems, or as a base or additive to such systems. The dispersions according to the invention can preferably be used for impregnation of woven fabrics, knitted fabrics, braided fabrics, fiberwoven fabrics or nonwovens, using apparatus customary in the textile industry.
The aqueous organopolysiloxane dispersions according to the invention cure completely at room temperature within a short time after evaporation of n,.:a~,...._ 2~7~~~8 the solvent content, water and, optionally organic solvent, to give elastomers.
The aqueous dispersions according to the inven tion, in particular those which have been prepared using polyvinyl alcohols, have the advantage that they cure completely in thin layers to give transparent elastomers.
The aqueous dispersions according to the invention have the further advantage that they can be slop-padded or applied by the dipping process onto textile materials, such as woven fabric, knitted fabric, braided fabric, fiberwoven fabric or a nonwoven, and can be pressed off in the padder.
Furthermore, it is possible to treat many sub strates, such as paper, textiles, mineral building materials, plastics, wood and many other substrate materials, with the dispersion according to the invention. Treatment can be carried out by dipping or impregnating.
The aqueous dispersions according to the invention are prepared as described above, by preparing a dispersion having a solids content of 30$ to 90$ by weight, preferably 40~ to 85~ by weight. This dispersion is initially introduced into a stirring or mixing apparatus, such as a Z kneader, dissolver or stirrer. While mixing intensively, the desired amount of water is added, initially in small portions and later, when the viscosity drops, in larger portions, the volume ratio of the small to the large portion being 1:2 to 1:20, preferably 1:2 to 1:10, more preferably 1:2 to 1:5. The number of small portions is 2 to 20, preferably 2 to 10, more preferably 2 to 5.
The number of large portions is 2 to 20, preferably~2 to 10, more preferably 2 to 5. After each addition of water, the mixture is stirred, mixed or kneaded until a homogeneous mass is obtained. The time required for the 2~ ~'T. X68 total mixing operation depends on the mixing tool used, and varies in the range from 1 to 60 minutes. The mixing operation is carried out at room temperature, under normal pressure. The mixing operation can also be carried out at temperatures in the range from 5°C to 60°C. A reduced or evaluated pressure is possible in principle.
The dispersion according to the invention prepared in this way is applied to textile materials by processes customary in the textile finishing industry, such as slop padding, dipping with or without a subse-quent padder, knife coating or coating by roller application, screen printing or screen roll printing or spraying.
Drying and vulcanization are carried out in customary heating tunnels which can be temperature-controlled by hot air or infrared radiation or other energy sources. The preferred temperature range is 50° - 200°C. Since some types of textile are not resistant to heat, the upper temperature limit is usually determined by the heat resistance of the textile. The residence time in the drying oven depends on the temperature in the heating tunnel and is preferably 0.5 to 30 minutes.
The textiles, woven fabric, knitted fabric, braided fabric, fiberwoven fabric or nonwoven treated according to the invention have the following advantages:
Elastic textiles are usually obtained by using mixed yarns of cotton and synthetic fibers, such as nylon, polyester, polyurethane and the like. These mixed yarns are usually woven or knitted. This type of textile is difficult to process and thus relatively expensive.
If a pure cotton material which is knitted or woven is treated with the dispersion according to the 2~ lT ~~8 invention, a textile material having elastic properties is obtained after the treatment. In addition, a pleasant soft handle is achieved. Such textiles are preferably suitable for sports clothing. However, the fields of use of such textiles are virtually unlimited.
Sleeve cuffs and structuring ribs of underwear and clothing of wool and acrylic fibers and/or cotton show a poor dimensional stability. If treatment with the dispersion according to the invention is carried out, a good dimensional stability (recovery effect) is achieved. Greater or lesser elastic properties can be achieved, depending on the amount applied.
In the field of high-quality clothing, Greaseproof textiles expected by the consumer limited the possible use of yarns almost exclusively to synthetic fibers.
However, if fabrics of wool, cotton or mixtures thereof or blended fabrics of wool or cotton with synthetic fibers are treated with the dispersion according to the invention, predominantly Greaseproof textiles are formed.
Fabric of glass fibers frays severely at the cutting points, and fraying at the cut edges is prevented by the treatment. Glass dust formed by the fine glass fibers breaking is fixed by treatment with the dispersion according to the invention. Furthermore, a glass fabric treated in this way shows elastic properties.
In the examples described below, all the parts and percentages data relate to the weight, unless stated otherwise. All the viscosity data are based on a temperature of 25°C. Unless stated otherwise, the following examples were carried ou~ under a pressure of the surrounding atmosphere, at about 1000 hPa, and at room temperature, at about 22°C, or at a temperature which is established when the reactants are brought ' 21 71 1 68 - together at room temperature without additional heating or cooling.
Example 1 I) Preparation of an aqueous dispersion of condensation catalyst (B) 125 g of dibutyltin dilaurate are emulsified together with 10 g of tributylphenol polyglycol ether (commercially obtainable under the name "Sapogenat'1''"' T130" from Hoechst AG) and 365 g of water.
Example 2 200 g of a,w-dihydroxypolydimethylsiloxane having a viscosity of 80,000 mPa.s and 5.00 g of [CH3Si03iz] o.s [ lCH3) zSiO] o,~ having an average molecular weight Mw of 3000 are mixed. The mixture is then converted into an emulsion with 25.0 g of water and 50 g of a loo strength solution of a polyvinyl alcohol having a molecular weight Mw of 36,000 and a hydrolysis number of 20 (commercially obtainable under the name "Polyviol'I''°' G 10/20" from blacker-Chemie GmbH) in water with the aid of an Ultra-TurraxTM mixer. After addition of 2.8 g of 3-(2-aminoethylamino)propyl-functional poly dimethylsiloxane having a viscosity of 1000 mPa.s and an amine number of 0.3 (comercially obtainable under the name "Finish WR'1'M 1300" from blacker-Chemie GmbH, Munich) and 1.4 g of the aqueous dispersion of condensation catalyst (B) described in Example 1 under I, a white, stable aqueous dispersion which can be stored for at least 6 months is obtained.
Example 3 100 g of the product obtained according to Example 2 is initially introduced into a Z kneader and, while kneading constantly, 100 g of water are added, initially in portions of 5 times 5 g and later in portions of 5 times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is obtained.
An aqueous organopolysiloxane dispersion which comprises a solids content of 43~ by weight and has a viscosity of 4,600 mPa.s is obtained.
150 g of the dispersion thus obtained are poured into 3 liter of water, while stirring slowly. A
homogeneous aqueous dispersion having a solids content of 2~ by weight is obtained.
A knitted cotton fabric having a weight of 90 g/ m2 is dipped into the dispersion thus obtained and pressed off in a padder at a pressure of 3 kp/cm2. It is dried in a hot air oven at 150°C
for 3 minutes.
The weight per unit area of the textile is now 94 g/m2. The knitted cotton fabric shows elastic properties. If a non-treated piece of fabric of 20 x 20 cm is stretched with a tensile force of 5 kp, the measurements are 16 x 25 cm after a resting time of 2 minutes.
The coated piece of fabric is again 20 x 20 cm after the stretching and resting operation.
Example 4 100 g of the product obtained according to Example 2 are stirred with a dissolver disk and, while stirring constantly, 100 g of water are added, initially in portions of 5 times 5 g and later in portions of 5 times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is achieved.
2~ ~T~ r~s, liter of water are then rapidly added with further stirring. A homogeneous dispersion having a solids content of 0.8~ by weight is obtained.
Knitted sleeve cuffs of wool/acrylic fiber mixed 5 yarn are dipped into the dispersion thus obtained and, after draining off briefly, are dried in a hot air oven at 100°C for 10 minutes. The sleeve cuffs thus treated show a clearly improved dimensional stability compared with untreated 10 goods. This effect is intensified further after a storage time of 3 days in air.
Example 5 100 g of the product obtained according to Example 2 are stirred with a blade stirrer at high speed and, while stirring constantly, 100 g of water are added, initially in portions of 5 times 5 g and later in portions of S times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is achieved.
16 liter of water are then rapidly added with further stirring. A homogeneous dispersion having a solids content of 0.5= by weight is obtained.
This dispersion is applied to a cotton/polyester 80/20 blended fabric using a slop-padding roller and is dried in a hot air oven at 120°C for 5 minutes.
The fabric thus treated is stored in air for 3 days. After severe creasing, no folds or crease points are detectable.
The non-treated fabric shows clear crease points and folds after the same crease treatment.
Example 6 100 g of the product obtained according to Example 2 are initially introduced into a Z kneader and, while kneading constantly, 100 g of water are added, initially in portions of 5 times g and later in portions of 5 times 10 g and finally 25 g. The next portion of water is added only when a homogeneous mixture is achieved. An aqueous organopolysiloxane dispersion which 5 comprises a solids content of 43~ by weight and has a viscosity of 4,600 mPa.s is obtained.
150 g of this dispersion thus obtained are poured into 1 liter of water while stirring slowly.
A homogeneous aqueous dispersion having a solids content of 5.5$ by weight is obtained.
This dispersion is applied to a glass fiber fabric having a weight of 120 g/m' using a coating knife.
After drying in a hot air oven at 180°C for 2 minutes, a fabric weight of 136 g/mz is determined.
The glass fabric coated in this way does not fray at the cut edges and shows elastic properties.
Even after vigorous movements, no glass dust is released.
Example 7 The product obtained according to Example 2 is spread onto glass fabric having a fabric weight of 240 g/ m2 using a spatula. The fabric is dried in a hot air oven at 150°C for 3 minutes. A coating with many bubbles is obtained. The coating weight is 220 g/mz. A thin coating cannot be achieved.
Coating processes such as dipping or spraying are not possible.
Example 8 100 g of the product obtained according to Example 2 and 100 g of water (in one portion) were stirred for 1 hour using a blade stirrer. No homogeneous dispersion was obtained. The mixture contains many particles of very high viscosity. If the mixture is diluted with a further 10 liter of water as in Example 4, a milky inhomogeneous liquor is obtained. No changes or effects can be observed on fabrics which have been dipped padded and dried at 100°C for 10 minutes.
Claims (12)
1. An aqueous dispersion of an organopolysiloxane which is prepared from (A) an organopolysiloxane containing groups which are capable of condensation, (B) a condensation catalyst, (C) an organopolysiloxane resin having a molecular weight Mw of not more than 20,000, (D) compounds containing basic nitrogen and (E) polyvinyl alcohol, with the proviso that the solids content of the dispersions is 0.01% to less than 30% by weight.
2. An aqueous dispersion as claimed in claim 1, wherein the polyvinyl alcohol (E) is present in amounts of from 0.5 to 10 parts by weight, based on 100 parts by weight of the organopolysiloxane (A).
3. An aqueous dispersion as claimed in claim 1, wherein wherein the polyvinyl alcohol (E) has a molecular weight Mw from 20,000 and 100,000 and a hydrolysis number greater than 100.
4. An aqueous dispersion as claimed in claim 1, wherein the organopolysiloxane (A) containing groups which are capable of condensation is one of the formula RO-[SiR1 2O]n-R (I) in which R is identical or different and is a hydrogen atom or alkyl radical having 1 to 6 carbon atom(s), R1 is an identical or different hydrocarbon radical having 1 to 18 carbon atom(s), which is optionally substituted by a halogen atom, amino group, ether group, ester group, epoxide group, mercapto group, cyano group or a (poly)glycol radical, the latter being built up from oxyethylene and/or oxypropylene units, and n is an integer of at least 30.
5. An aqueous dispersion as claimed in claim 1, wherein the organopolysiloxane resin (C) is one of units of the formula in which R2 is an identical or different hydrocarbon radical having 1 to 18 carbon atom(s), which is optionally substituted by a halogen atom, amino group, ether group, ester group, epoxide group, mercapto group, cyano group or (poly)glycol radical, the latter being built up from oxyethylene and/or oxypropylene units, and a is a number having an average value between 0.5 and 1.95.
6. An aqueous dispersion as claimed claim 5, wherein the organopolysiloxane resin (C) has a molecular weight Mw of not more than 10,000.
7. An aqueous dispersion as claimed in claim 5, wherein the organopolysiloxane resin (C) is one of the formula [CH3SiO3/2]0.6-0.8 [(CH3)2SiO]0.2-0.4 having an average molecular weight Mw between 500 and 6,000.
8. An aqueous dispersion as claimed claim 1, wherein the organopolysiloxane resin (C) is present in amounts of 0.1 to 100 parts by weight, based on 100 parts by weight of organopolysiloxane (A) containing groups which are capable of condensation.
9. An aqueous dispersion as claimed in claim 1, wherein component (D) is an organosilicon compound having at least one organic radical containing basic nitrogen, of units of the formula in which R4 is identical or different and is a monovalent organic radical which is free from basic nitrogen, R5 is identical or different and is a hydrogen atom,alkyl radical, alkali metal cation or ammonium or phosphonium group Y is identical or different and is a monovalent SiC-bonded radical with basic nitrogen, b is 0, 1, 2 or 3, c is 0, 1, 2, 3 or 4 and d is 0, 1, 2 or 3, with the proviso that the sum of b, c and d is less than or equal to 4 and at least one radical Y
is present per molecule.
is present per molecule.
10. A process for the preparation of an aqueous dispersion as claimed in claim 1, which comprises dissolving the organopolysiloxane resin (C) in the organopolysiloxane (A) containing groups which are capable of condensation and emulsifying the solution with polyvinyl alcohol (E) and water and, optionally, other components.
11. A process for the preparation of an aqueous dispersion as claimed in claim 10, wherein water is added first in small portions and later in larger portions and the components are mixed homogeneously, where the volume ratio of small portions to larger portions is 1:2 to 1:20, the number of small portions is 2 to 20 and the number of larger portions is 2 to 20.
12. A method of treating textiles, comprising applying the aqueous dispersion of claim 1 to said textile.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19514665A DE19514665A1 (en) | 1995-04-20 | 1995-04-20 | Aqueous dispersions of organopolysiloxanes |
| DE19514665.4 | 1995-04-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2171168A1 CA2171168A1 (en) | 1996-10-21 |
| CA2171168C true CA2171168C (en) | 1999-12-07 |
Family
ID=7760029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002171168A Expired - Fee Related CA2171168C (en) | 1995-04-20 | 1996-03-06 | Aqueous dispersions of organopolysiloxanes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0738747A1 (en) |
| JP (1) | JPH08291255A (en) |
| KR (1) | KR960037772A (en) |
| BR (1) | BR9601998A (en) |
| CA (1) | CA2171168C (en) |
| DE (1) | DE19514665A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19744612A1 (en) * | 1997-10-09 | 1999-04-15 | Wacker Chemie Gmbh | Emulsions of organosilicon compounds for the hydrophobization of building materials |
| US6294608B1 (en) | 1995-05-11 | 2001-09-25 | Wacker-Chemie Gmbh | Emulsions of organosilicon compounds for imparting water repellency to building materials |
| FR2771098B1 (en) * | 1997-11-18 | 2004-08-13 | Rhodia Chimie Sa | AQUEOUS SILICONE DISPERSIONS, PARTICULARLY PAINT FORMULATIONS COMPRISING SAME AND ONE OF THEIR PREPARATION METHODS |
| DE19937477A1 (en) | 1999-08-07 | 2001-02-08 | Ciba Sc Pfersee Gmbh | Compositions containing silicone for the treatment of wool materials |
| DE10016610A1 (en) | 2000-04-04 | 2001-10-11 | Ciba Sc Pfersee Gmbh | Composition containing silicone for the treatment of woolen materials |
| DE102006003493A1 (en) * | 2006-01-25 | 2007-08-09 | Gabriele Wiegand | Method for producing knitted fabric, particularly synthetic fibers extended to return flexibly to its initial shape involves subjecting thermal treatment and expose it to mold pressure in transfer press |
| CN101541889B (en) * | 2006-11-29 | 2012-02-08 | 陶氏康宁公司 | Aqueous emulsions of silicone resins |
| JP5970154B2 (en) | 2007-03-21 | 2016-08-17 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Aqueous dispersion and method of using it for production of sheet-like substrate |
| EP2247443B1 (en) | 2008-02-27 | 2018-08-22 | Basf Se | Multi-layer composite materials comprising a plastic or metal foil, corresponding method of production and use thereof |
| DE102008000419A1 (en) * | 2008-02-27 | 2009-09-03 | Basf Se | Multilayer composites comprising a fabric, process for their preparation and their use |
| WO2009106498A1 (en) | 2008-02-27 | 2009-09-03 | Basf Se | Multi-layer composite materials comprising a foam layer, corresponding method of production and use thereof |
| US9375904B2 (en) | 2008-02-27 | 2016-06-28 | Basf Se | Multi-layer composite materials comprising a cellulose-containing layer, corresponding method of production and use thereof |
| CN102056737A (en) | 2008-06-09 | 2011-05-11 | 巴斯夫欧洲公司 | Multilayer composite materials which comprise a plastics foil permeable to water vapour, method for production of the same and use of the same |
| DE102009001121A1 (en) | 2009-02-24 | 2010-08-26 | Basf Se | Multi-layer composite material, useful for manufacture of decorative material and automotive interior parts, comprises substrate, connecting layer and polyurethane layer having capillaries that extend over its entire thickness |
| CH702731A1 (en) | 2010-02-25 | 2011-08-31 | Biwi Sa | A method of manufacturing a part comprising an elastomer coating and said workpiece obtained. |
| KR20130124519A (en) | 2010-12-03 | 2013-11-14 | 바스프 에스이 | Method for producing multi-layer composite bodies |
| WO2022248558A1 (en) | 2021-05-27 | 2022-12-01 | Basf Se | Multilayered composite material comprising foamed granules |
| WO2023208987A1 (en) | 2022-04-27 | 2023-11-02 | Basf Se | Local compaction of e-tpu particle foam material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3932025A1 (en) * | 1989-09-26 | 1991-04-04 | Wacker Chemie Gmbh | WAESSED DISPERSIONS OF ORGANOPOLYSILOXANES |
| DE4217561A1 (en) * | 1992-05-27 | 1993-12-02 | Wacker Chemie Gmbh | Aqueous dispersions of organopolysiloxanes |
-
1995
- 1995-04-20 DE DE19514665A patent/DE19514665A1/en not_active Withdrawn
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1996
- 1996-03-06 CA CA002171168A patent/CA2171168C/en not_active Expired - Fee Related
- 1996-04-17 KR KR1019960011672A patent/KR960037772A/en not_active Application Discontinuation
- 1996-04-18 JP JP8097012A patent/JPH08291255A/en active Pending
- 1996-04-18 EP EP96106091A patent/EP0738747A1/en not_active Ceased
- 1996-04-19 BR BR9601998A patent/BR9601998A/en not_active Application Discontinuation
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| Publication number | Publication date |
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| DE19514665A1 (en) | 1996-10-24 |
| CA2171168A1 (en) | 1996-10-21 |
| BR9601998A (en) | 1998-10-06 |
| KR960037772A (en) | 1996-11-19 |
| EP0738747A1 (en) | 1996-10-23 |
| JPH08291255A (en) | 1996-11-05 |
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