WO2005010076A2 - Aminofunctional silicone resins and emulsions containing them - Google Patents

Aminofunctional silicone resins and emulsions containing them Download PDF

Info

Publication number
WO2005010076A2
WO2005010076A2 PCT/US2004/021777 US2004021777W WO2005010076A2 WO 2005010076 A2 WO2005010076 A2 WO 2005010076A2 US 2004021777 W US2004021777 W US 2004021777W WO 2005010076 A2 WO2005010076 A2 WO 2005010076A2
Authority
WO
WIPO (PCT)
Prior art keywords
aminofunctional
aminofunctional silicone
units
sio
iii
Prior art date
Application number
PCT/US2004/021777
Other languages
French (fr)
Other versions
WO2005010076A3 (en
Inventor
Glenn Gordon
John Bernard Horstman
Donald Liles
Randall Schmidt
Gary Wieber
Gerald Lawrence Witucki
Original Assignee
Dow Corning Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Priority to DE602004008646T priority Critical patent/DE602004008646T2/en
Priority to JP2006520219A priority patent/JP4939215B2/en
Priority to US10/564,610 priority patent/US7501473B2/en
Priority to EP04756739A priority patent/EP1651703B1/en
Publication of WO2005010076A2 publication Critical patent/WO2005010076A2/en
Publication of WO2005010076A3 publication Critical patent/WO2005010076A3/en

Links

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/04—Preparations for care of the skin for chemically tanning the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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

Definitions

  • This invention relates to new aminofunctional silicone resins which can be used to make tough, water, solvent and heat resistant hybrid materials with select organic materials.
  • the aminofunctional resins have higher aryl content, R2Si ⁇ 2/2 content and amine content than those known in the art.
  • Aminofunctional silicone resins are known in the art.
  • an aminofunctional silicone resin comprising the units (i) PhSiO3/2, (ii) R2SiO, and (iii) aminofunctional siloxy units selected from the group consisting essentially of a. H.2NRiSi ⁇ 3/2, b. Ri v HNRjiSi ⁇ 3/2,
  • U.S. Patent No. 4,988,778 is disclosed a stable polyamine-functional silane resin which is prepared by reacting: (i) an aminoalkoxysilane and (ii) a hydroxy- and amine- functional compound.
  • the aminoalkoxysilane is disclosed as being typically of the formula:
  • R is hydrogen, an alkyl group with no more than four carbon atoms, an aminoalkyl group, alkylaminoalkyl group or alkoxysilano alkyl group with no more than 6 carbon atoms in the alkyl group;
  • R is an alkylene having 1 to 6 carbon atoms, cycloalkylene or aryl group;
  • R ⁇ is an alkyl having 1 to 10 carbon atoms, cycloalkyl or aryl group;
  • R 3 is an lower alkyl group having 1 to about 4 carbon atoms;
  • aminoalkoxysilanes disclosed include aminoethyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aniinopropyldimethoxymethylsilane, aminopropyldiethoxymethylsilane, aminoethyl-gamma- aminopropyltrimethoxysilane, and iminobis(propyltrimethoxysilane).
  • the hydroxy and amine functional compound is disclosed as being an amino alcohol, amino polyalcohol, a polyamino alcohol or a polyamino polyalcohol.
  • R which are the same or different, each represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, or a hydrogen atom
  • R' each represent an amino-group-containing organic group
  • a is an integer of 0 to 3
  • m is an integer of 1 or more
  • n is an integer of 5 or more, provided that m+n is an integer of 2,000 or more, and dissolved in an organic solvent,
  • which film forming composition can give a smooth soft film that is excellent in water repellency, water resistance, touch, and durability in comparison with the conventional film forming compositions.
  • U.S. Patent No. 5,840,951 is disclosed organosilicon compounds containing reactive amino groups, their preparation and their use.
  • an aminofunctional silicone resin comprising the reaction product of an aminofunctional silane and a silicone resin having a formula selected from the group consisting of RSiO 3/2 (I), (RSiO 3 /2) w (R'R , 'SiO) x (Si ⁇ 4/ 2 ) y (II), and (RSiO3/2) w (R , R"SiO) x (SiO4/2) y (R 3 , "SiO) z (III) wherein R, R', R", and R'" are selected from the group consisting of alkyl, alkenyl, aryl, and alkylaryl radicals having from one to twenty carbon atoms; and w, x, y, and z are integers having a value of from zero to about one thousand with the proviso that the sum of w and y is at least one.
  • a hair treating composition comprising a mixture of a film forming material and a solvent for the film forming material, the film forming material being an aminofunctional silicone resin which is the reaction product obtained by directly combining a cyclic silylamine and a silicone resin, the silicone resin being a hydroxy derivative having a formula selected from the group consisting of RSiO 3/2 (I), (RSiO3/2) w (R'R"SiO) x (SiO4/2) y (II), and (RSi ⁇ 3/2) w (R , R"SiO) x (Si ⁇ 4/2) y (R3'"SiO 1 /2) z (III) wherein R, R', R", and R'" are selected from the group consisting of alkyl, alkenyl, aryl, and alkylaryl radicals having from one to twenty carbon atoms; x, y, and z are integers having
  • U.S. Patent No. 4,972,029 is disclosed thermally stable, crosslinked epoxy resins obtained by crosslinking an epoxy resin with a silicon compound containing a basic nitrogen which is bonded to silicon via carbon and to which at least 1 hydrogen atom is bonded directly to the nitrogen atom, and thereafter conditioning the crosslinked epoxy resin.
  • Cage structured aminofunctional silicone resins are disclosed in the journal article entitled "A Polyimide Nanocomposite from Octa(aminophenyl)silsesquioxane", R. Tamaki, J. Choi, and R.M.
  • this invention relates to an aminofunctional silicone resin comprising the units: (R 3 SiO 1/2 ) a (i)
  • the -NH- equivalent weight as used herein means the weight of material that contains one atomic weight of amine hydrogen.
  • the alkyl groups of R are illustrated by methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl with the alkyl group typically being methyl.
  • the aryl groups are illustrated by phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2- phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl with the aryl group typically being phenyl.
  • the aminofunctional hydrocarbon group is illustrated by groups having the formula -R ⁇ NHR ⁇ or -RINHR ⁇ NHR ⁇ wherein each R! is independently a divalent hydrocarbon radical having at least 2 carbon atoms and R ⁇ is hydrogen or an alkyl group.
  • Each R is typically an alkylene radical having from 2 to 20 carbon atoms, R is illustrated by -CH 2 CH 2 -, -CH 2 CH2CH 2 -, -CH 2 CHCH 3 -, -CH 2 CH2CH 2 CH 2 -
  • R 2 is an alkyl group it is typically methyl.
  • Typical aminofunctional hydrocarbon groups are -CH2CH2NH2,
  • -CH2CH2CH2NH2 -CH 2 CHCH 3 NH, -CH2CH2CH2NH2, -CH2CH2CH2CH2CH2NH2, -CH2CH 2 CH2CH2CH2NH2, -CH2CH2NHCH3, -CH2CH2CH2NHCH3, -CH2(CH 3 )CHCH2NHCH 3 , -CH2CH2CH2CH2NHCH3, -CH2CH2NHCH2CH2NH2,
  • aminofunctional silicone resins of this invention are illustrated by aminofunctional silicone resins comprising the units:
  • 10 to 30 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -NH- equivalent weight of the aminofunctional silicone resin is generally from 100 to 1500, alternatively from 100 to 1000, alternatively from 150 to 350, generally 20 to 50 weight percent of unit (ii) is present in the aminofunctional silicone resin, generally from 0 to 5 weight percent of unit (ii) are Me2Si ⁇ 2/2 units in the aminofunctional silicone resin, and generally from 50 to 75 weight percent of silicon-bonded R groups are silicon-bonded aryl groups.
  • the aminofunctional silicone resins of this invention were prepared by reaction of a cyclic silazane with a hydroxy-containing siloxane resin or by hydrolytic polycondensation of alkoxysilanes by one of two methods.
  • the hydrolysis of the non-aminofunctional alkoxysilanes was accomplished via catalysis with strong acid, followed by addition of the aminofunctional silanes and base-catalyzed equilibration of these species to yield the aminofunctional silicone resin.
  • the entire hydrolysis was run under base-catalyzed conditions with the aminofunctional alkoxysilane(s) present from the start.
  • the aminofunctional silicone resins of this invention can be manufactured by preparing a mixture of 45-60 wt% of aryltrialkoxysilane, arylalkyldialkoxysilane, ⁇ -aminoalkyltrialkoxysilane, ⁇ -aminoalkyldialkoxysilane and/or ⁇ - aminoalkylmonoalkoxysilaneoptionally dissolving the mixture in up to 35 wt% of an aromatic solvent. This mixture is then hydrolyzed with 1-20 wt% of deionized water, followed by distillative removal of the by-product alcohol.
  • the resulting product is then optionally reacted with up to 50 wt% of trialkylalkoxysilane, hexamethyldisilazane (HMDZ), ⁇ -aminoalkyldialkoxysilane, ⁇ -aminoalkylmonoalkoxysilane and/or dialkyldialkoxysilane, up to 35 wt% of additional solvent, and up to 20 wt% water can be added, a catalytic amount (to make 0-0.1 wt% KOH) of aqueous potassium hydroxide can then be optionally added and the water removed via azeotrope.
  • HMDZ hexamethyldisilazane
  • ⁇ -aminoalkyldialkoxysilane ⁇ -aminoalkylmonoalkoxysilane and/or dialkyldialkoxysilane
  • additional solvent up to 35 wt% of additional solvent
  • the hydroxide if added, is neutralized with aqueous HC1 or acetic acid, and water removed again via azeotrope. The mixture is then filtered and solvent removed to yield the aminofunctional silicone resin.
  • the aryl group is phenyl
  • the alkyl group is methyl
  • the alkoxy group is either methoxy or ethoxy
  • the amino group is the aminofunctional hydrocarbon group described above.
  • the aminofunctional silicone resins of this invention can also be manufactured by hydrolyzing 20-50 wt% of aryltrialkoxysilane and/or arylalkyldialkoxysilane, catalyzed by 0- 0.05 wt% with trifluoromethanesulfonic acid (TFMSA), with deionized water (0-10 wt%), followed by distillative removal of by-product alcohol.
  • TFMSA trifluoromethanesulfonic acid
  • HMDS hexamethyldisiloxane
  • 10 wt% water Up to 10 wt% water, and optionally up to 40 wt% toluene is added and the mixture heated to 50-60°C optionally followed by distillative removal of volatiles.
  • ⁇ -aminoalkyltrialkoxysilane APTES
  • ⁇ - aminoalkylmonoalkoxysilane or ⁇ -aminoalkyldialkoxyalkylsilane are added along with up to 10 wt% water, followed by distillative removal of alcohol.
  • Up to 40 wt% of toluene (if it was not added earlier) is added, up to 10 wt% of water, and optionally a catalytic amount (to make 0-0.1 wt% KOH) of 1.0 N aqueous potassium hydroxide is added and water removed via azeotrope.
  • the hydroxide was neutralized with 1.0 N aqueous HC1 or acetic acid, and water again removed via azeotrope. The mixture was filtered and solvent removed to yield the aminofunctional silicone resin.
  • the aryl group is phenyl
  • the alkyl group is methyl
  • the alkoxy group is either methoxy or ethoxy
  • the amino group is the aminofunctional hydrocarbon group described above.
  • the aminofunctional silicone resins of this invention can also be manufactured by preparing a mixture of aryltrialkoxysilane, arylalkyldialkoxysilane, and ⁇ -aminoalkyldialkoxyalkylsilane optionally dissolved in xylenes and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting product is then reacted with trialkylalkoxysilane, additional xylenes and additional water, followed by azeotropic removal of water. To a portion of this reaction mixture, additional xylene and colloidal silica dispersion are added and the water removed via azeotrope. The mixture is filtered and solvent removed to yield the silicone resin.
  • the aminofunctional silicone resins of this invention can also be manufactured by preparing a mixture of aryltrialkoxysilane and arylalkyldialkoxysilane optionally dissolved in xylenes and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting product is then reacted with cyclosilazane. The mixture is filtered and solvent removed to yield the silicone resin.
  • the aryl group is phenyl
  • the alkyl group is methyl
  • the alkoxy group is either methoxy or ethoxy
  • the amino group is the aminofunctional hydrocarbon group described above.
  • the aminofunctional silicone resins of this invention are useful in making tough, water, solvent, and heat resistant hybrid materials when used in combination with selected organic materials, particularly epoxy-containing organic materials.
  • the aminofunctional resins of this invention have the ability to flexibilize epoxy compounds while maintaining low CTE and solvent resistance.
  • This invention also relates to an emulsion composition comprising: (A) an aminofunctional silicone resin comprising the units: (R 3 SiO 1/2 ) a (i)
  • R is independently an alkyl group, an aryl group, or an aminofunctional hydrocarbon group
  • a has a value of less than 0.4
  • b has a value of greater than 0.15
  • c has a value of greater than zero to 0.7
  • d has a value of less than 0.2
  • the value of a + b + c + d l, with the provisos that 3 to 50 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii)
  • the -NH- equivalent weight of the aminofunctional silicone resin is from 100 to 1500, alternatively from 100 to 1000, alternatively from 150 to 350
  • the aminofunctional silicone resin is in the form of a neat liquid, solution, or meltable solid, greater than 20 weight percent of unit (ii) is present in the aminofunctional silicone resin, less than 10 weight percent
  • the aminofunctional silicone resin of Component (A) is as described above including preferred embodiments thereof.
  • the amount of Component (A) in the emulsion composition is typically from 25 to 75 weight percent, said weight percent being based on the total weight of the emulsion composition.
  • Component (B) is at least one surfactant.
  • the surfactant may be an anionic, cationic, nonionic, or amphoteric surfactant.
  • the surfactants may be employed separately or in combinations of two or more.
  • suitable anionic surfactants include alkali metal sulforicinates, sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent alcohol esters such as sodium oleylisethianate, amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride, sulfonated products of fatty acids nitriles such as palmitonitrile sulfonate, sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate, condensation products of naphthalene sulfonic acids with formaldehyde, sodium oct
  • Examples of cationic surfactants include various fatty acid amines and amides and their derivatives, and the salts of the fatty acid amines and amides.
  • aliphatic fatty acid amines examples include dodecylamine acetate, octadecylamine acetate, and acetates of the amines of tallow fatty acids, homologues of aromatic amines having fatty acids such as dodecylanalin, fatty amides derived from aliphatic diamines such as undecylimidazoline, fatty amides derived from aliphatic diamines such as undecylimidazoline, fatty amides derived from disubstituted amines such as oleylaminodiethylamine, derivatives of ethylene diamine, quaternary ammonium compounds and their salts which are exemplified by tallow trimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, didodecyldimethyl ammonium chloride, dihexadecyl ammonium chloride, alkyltrimethylammonium hydro
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants.
  • amphoteric surfactants examples include amino acid surfactants and betaine acid surfactants.
  • Typical commercially available surfactants include trimethylnonyl polyethylene glycol ethers and polyethylene glycol ether alcohols containing linear alkyl groups having from 11 to 15 such as 2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) (sold as Tergitol®TMN-6 by The Dow Chemical Company, Midland, MI), 2,6,8-trimethyl-4- nonyloxypolyethylene oxyethanol (10 EO) (sold as Tergitol®TMN-10 by The Dow Chemical Company, Midland, MI), alkylene-oxypolyethylene oxyethanol (C 11.15 secondary alkyl, 9 EO) (sold as Tergitol® 15-S-9 by The Dow Chemical Company, Midland, MI), alkylene- oxypolyethylene oxyethanol (C ⁇ 1.15 secondary alkyl, 15 EO) (sold as Tergitol®15-S
  • octylphenoxy polyethoxy ethanols having varying amounts of ethylene oxide units such as octylphenoxy polyethoxy ethanol (40 EO) (sold as Triton® X405 by Rohm and Haas Company, Philadelphia, Pa.), nonionic ethoxylated tridecyl ethers available from Emery Industries, Mauldin, S.C. under the general tradename Trycol, alkali metal salts of dialkyl sulfosuccinates available from American Cyanamid Company, Wayne, N. J.
  • Aerosol polyethoxylated quaternary ammonium salts and ethylene oxide condensation products of the primary fatty amines, available from Armak Company, Chicago, 111. under the tradenames Ethoquad, Ethomeen, or Arquad, and polyoxyalkylene glycol modified polysiloxanes. These preferred surfactants may also be obtained from other suppliers under different tradenames.
  • Surfactants useful in the invention also include those derived from silicone, sorbitan derivatives, and fatty alcohol derivatives. More specifically, suitable surfactants include, but are not limited to, sorbitan sesquioleate, sorbitan oleate, sorbitan isostearate; alkoxylated alcohols such as ethoxylated fatty alcohols including laureth-4, laureth-7, deceth-12, steareth- 10; hydroxylated derivatives of polymeric silicones, such as dimethicone copolyol; alkylated derivatives of hydroxylated polymeric silicones such as cetyl dimethicone copolyol; glyceryl esters such as polyglyceryl-4-isostearate; and mixtures thereof, especially mixtures of hydroxylated derivatives of polymeric silicones, alkylated derivatives of hydroxylated polymeric silicones and glyceryl esters, most especially mixtures of dimethicone copolyol
  • Component (B) is typically from 1 to 20 weight percent, said weight percent being based on the total weight of the emulsion composition.
  • Component (C) is water. Generally water is present at a level of from about 20 to 80 weight percent, said weight percent being based on the total weight of the emulsion composition.
  • the emulsion compositions of this invention can further comprise fragrances, preservatives, vitamins, ceramides, amino-acid derivatives, liposomes, polyols, such as glycerine and propylene glycol and botanicals (plant extracts) and additional conditioning agents such as quaternary polymers or silicone materials.
  • additives can include, but are not limited to the following depending on the use, glycols, vitamins A, vitamin C and vitamin E in their various forms, Pro-Nitamin B5, sunscreen agents (these include those which absorb ultraviolet light between about 290-320 nanometers (the UN-B region) and those which absorb ultraviolet light in the range of 320-400 (the UV-B region)), humectants, preservatives, such as known parabens, emollients, occlusive agents, and esters.
  • Other additives can include pigments especially when the emulsion is used as a make-up.
  • compositions according to the invention can also contain agents for artificially tanning and/or browning the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA).
  • self-tanning agents such as, for example, dihydroxyacetone (DHA).
  • DHA dihydroxyacetone
  • these optional ingredients can be present in the emulsion compositions of this invention up in an amount of up to 5 parts by weight per 100 parts by weight of emulsion composition, but typically are present in amount of from 0.1 to 1 part by weight per 100 parts by weight of emulsion composition.
  • the emulsion can be spray dried to form a resin/active composite particle.
  • the emulsion compositions of this invention may be prepared by mixing (or mechanically agitating) components (A)-(C), and any optional components, to form a homogenous mixture. This may be accomplished by any convenient mixing method known in the art exemplified by a spatula, mechanical stirrers, in-line mixing systems containing baffles and/or blades, powered in-line mixers, homogenizers, a drum roller, a three-roll mill, a sigma blade mixer, a bread dough mixer, and a two roll mill. The order of mixing is not considered critical.
  • Aminofunctional Silicone Resins A1-A9 were prepared in the following manner. A mixture of phenyltrimethoxysilane, phenylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane (APTES), and/or ⁇ -aminopropyldiethoxymethylsilane (APDEMS) was optionally dissolved in aromatic solvent and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol.
  • APTES ⁇ -aminopropyltriethoxysilane
  • APIDEMS ⁇ -aminopropyldiethoxymethylsilane
  • the resulting structure was optionally reacted with trimethylethoxysilane, hexamethyldisilazane (HMDZ), APDEMS and/or dimethyldimethoxysilane, additional solvent and additional water added, a catalytic amount of aqueous potassium hydroxide optionally added and the water removed via azeotrope.
  • the hydroxide, if added, was neutralized with aqueous HC1 or acetic acid, and water removed again via azeotrope.
  • the mixture was filtered and solvent removed to yield silicone resin product.
  • the amount of each ingredient is shown in Table 1 below.
  • the final aminofunctional silicone resin composition wt% phenyl (Ph), wt% R2SiO (D), wt% Me2SiO (D( ⁇ 2)), mole percent amino (-CH2CH2CH2NH2), wt% amine (-NH 2 ), and -NH- (Amine H) equivalent weight are shown in Table 2 below.
  • Aminofunctional Silicone Resins Bl- B6 were prepared in the following manner. Phenyltrimethoxysilane and or phenylmethyldimethoxysilane, catalyzed by trifluoromethanesulfonic acid (TFMSA), were hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. Hexamethyldisiloxane (HMDS) and additional water were added and the mixture heated to 50-60°C optionally followed by distillative removal of volatiles. ⁇ -Aminopropyltriethoxysilane (APTES) or ⁇ - aminopropyldiethoxymethylsilane (APDEMS) were added along with additional water, followed by distillative removal of alcohol.
  • TFMSA trifluoromethanesulfonic acid
  • HMDS Hexamethyldisiloxane
  • APTES ⁇ -Aminopropyltriethoxysilane
  • APIDEMS ⁇ - aminopropyldiethoxy
  • Aminofunctional Silicone Resin CI was prepared in the following manner. A mixture (amounts in Table 1) of phenyltrimethoxysilane, phenylmethyldimethoxysilane, and ⁇ -aminopropyldiethoxymethylsilane (APDEMS) was optionally dissolved in xylenes and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting structure was reacted with trimethylethoxysilane, additional xylenes and additional water, followed by azeotropic removal of water.
  • APDEMS ⁇ -aminopropyldiethoxymethylsilane
  • the final aminofunctional silicone resin composition wt% phenyl (Ph), wt% R2SiO (D), wt% Me2SiO (D(Me2)), mole percent amino (-CH2CH2CH2NH2), wt% amine (-NH2), and -NH- (Amine H) equivalent weight are shown in Table 2 below.
  • Aminofunctional Siloxane Resin El was prepared in the following manner: A mixture of 119.6g phenyltrimethoxysilane and 218.8g phenylmethyldimethoxysilane were hydrolyzed with 67.3g dilute aqueous HC1 (0.02 N), followed by distillative removal of byproduct methanol. The hydrolyzate was dissolved in 119.0g toluene followed by azeotropic removal of residual water and subsequently reacted with 34.4g cyclosilazane (1,1 ,2,4-
  • M denotes (C ⁇ .3)3SiO ⁇ /2
  • DPh denotes C 6 H 5 (CH 3 )Si ⁇ 2/2
  • T Ph denotes C ⁇ . ⁇ SiOy 2
  • T ⁇ h are as defined above, was weighed into a Hauschild (Hamm, Germany) Max 40 plastic cup followed by 0.9g of Tergitol® TMN-6 (2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) a nonionic surfactant from The Dow Chemical Company (Midland, MI)), l.Og Tergitol® 15-S-30 (alkylene-oxypolyethylene oxyethanol (Cn_i5 secondary alkyl, 30
  • EO a nonionic surfactant from The Dow Chemical Company (Midland, MI) and 2.0g of deionized water.
  • the cup was closed and placed into a Hauschild (Hamm, Germany) SpeedmixerTM DAC-150 laboratory mixing device. The cup and its contents were cycled in the mixer for 20 seconds. The cup was opened and the walls of the cup were scraped with a spatula. The cup and its contents were subjected to a second 20 second mixing cycle. Next 6g of Dl water was added and the cup was again subjected to a 20 second mixing cycle. An additional lOg of Dl water was added in increments of 5g followed by a 20 second mixing cycle after each addition. The emulsion that resulted was milky white in appearance with a slight bluish tint. The emulsion consisted of an approximately 60% by weight resin oil particle phase. Mean particle size was measured using a Microtrac® (Montgomeryville, PA)

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
  • Colloid Chemistry (AREA)

Abstract

This invention relates to aminofunctional silicone resins having high aryl content, R2Si02/2 content and amine content. The aminofunctional silicone resins of this invention are useful in making tough, water, solvent, and heat resistant hybrid materials when used in combination with selected organic materials, particularly epoxy-containing organic materials. The aminofunctional resins of this invention have the ability to flexibilize epoxy compounds while maintaining low CTE and solvent resistance. This invention also relates to emulsion compositions containing the above described arninofunctional silicone resins.

Description

AMINOFUNCTIONAL SILICONE RESINS AND EMULSIONS CONTAINING THEM
DESCRIPTION
[0001] This invention relates to new aminofunctional silicone resins which can be used to make tough, water, solvent and heat resistant hybrid materials with select organic materials. The aminofunctional resins have higher aryl content, R2Siθ2/2 content and amine content than those known in the art. Aminofunctional silicone resins are known in the art. For example, in U.S. Patent No. 5,262,507 is disclosed an aminofunctional silicone resin comprising the units (i) PhSiO3/2, (ii) R2SiO, and (iii) aminofunctional siloxy units selected from the group consisting essentially of a. H.2NRiSiθ3/2, b. RivHNRjiSiθ3/2,
c. (RivHNRii)3_y(Rv)ySiOι/2, d. (H2NRϋ)3_x(Rv)xSiOι/2 and, e. mixtures of a, b, c, and d, wherein Ph is the phenyl radical; each R is independently selected from phenyl and alkyl groups of 1 to 3 carbon atoms with the proviso that when R in (ii) is an alkyl radical in each case, there can be no more than 10 weight percent of (ii) in the silicone resin and with the further proviso that when one R in (ii) is an alkyl radical and one R in (ii) is a phenyl radical on the same silicon atom, there can be no more than 15 weight percent of (ii) present in the silicone resin; R[ is a divalent hydrocarbon radical selected from alkylene, arylene, alkarylene, and aralkylene having 1 to 10 carbon atoms, and -RjiNHRjϋ-, wherein R^ and Rjϋ are each independently selected from alkylene, arylene, alkarylene and aralkylene of 1 to 10 carbon atoms; each of x and y have a value of 0, 1 , or 2; Rjv is selected from methyl, ethyl, propyl or phenyl; Rv is selected from methyl and phenyl, and the aminofunctional silicone resin has an --NH-- equivalent in the range of 350 to 1000.
[0002] In U.S. Patent No. 4,988,778 is disclosed a stable polyamine-functional silane resin which is prepared by reacting: (i) an aminoalkoxysilane and (ii) a hydroxy- and amine- functional compound. The aminoalkoxysilane is disclosed as being typically of the formula:
RNHR1Si(R2)m(OR3)n wherein R is hydrogen, an alkyl group with no more than four carbon atoms, an aminoalkyl group, alkylaminoalkyl group or alkoxysilano alkyl group with no more than 6 carbon atoms in the alkyl group; R is an alkylene having 1 to 6 carbon atoms, cycloalkylene or aryl group; R^ is an alkyl having 1 to 10 carbon atoms, cycloalkyl or aryl group; R3 is an lower alkyl group having 1 to about 4 carbon atoms; m is 0 or 1; n is 3 to 2; and m+n=3. Some specific aminoalkoxysilanes disclosed include aminoethyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aniinopropyldimethoxymethylsilane, aminopropyldiethoxymethylsilane, aminoethyl-gamma- aminopropyltrimethoxysilane, and iminobis(propyltrimethoxysilane). The hydroxy and amine functional compound is disclosed as being an amino alcohol, amino polyalcohol, a polyamino alcohol or a polyamino polyalcohol.
[0003] In U.S. Patent No. 5,110,891 is disclosed an aminofunctional organosilicon compound of the formula R3SiO[R2SiO]x[RQ1SiO]y[RQSiO]zSiR3 wherein R denotes an alkyl group of one to four carbons, OH, an alkoxy group or a phenyl group with the proviso that at least fifty percent of the total R groups are methyl; Q denotes an amine functional substituent of the formula —R^Z, wherein R^ is a divalent alkylene radical of three to six carbon atoms and Z is a monovalent radical selected from the group consisting -NR 3, -NR3(CH2)nNR23, and -NR3(CH2)nN(R3)(C=O)R4 wherein R3 denotes hydrogen or an alkyl group of one to four carbons, R4 denotes an alkyl group of one to four carbons and n is an integer from two to six; x, y and z are integers the sum of which is within the range of about twenty-five to about eight hundred; 4 is at least one; and Ql denotes an amine functional substituent as defined above additionally including a carbon bonded silicon atom having at least one silicon-bonded hydrolyzable group. [0004] In U.S. Patent No. 5,489,482 is disclosed a film forming composition, comprising an amine-modified highly polymerized polysiloxane represented by the general formula (1):
RaR'3_aSiO(R2SiO)m(RR'SiO)nSiRaR'3_a wherein R, which are the same or different, each represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, or a hydrogen atom, R' each represent an amino-group-containing organic group, a is an integer of 0 to 3, m is an integer of 1 or more, and n is an integer of 5 or more, provided that m+n is an integer of 2,000 or more, and dissolved in an organic solvent, which film forming composition can give a smooth soft film that is excellent in water repellency, water resistance, touch, and durability in comparison with the conventional film forming compositions. [0005] In U.S. Patent No. 5,840,951 is disclosed organosilicon compounds containing reactive amino groups, their preparation and their use.
[0006] In U.S. Patent No. 3,890,269 is disclosed a process for preparing aminofunctional organopolysiloxanes which comprises equilibrating a mixture containing organopolysiloxane and an aminofunctional silane or siloxane in the presence of a catalyst.
[0007] In U.S. Patent No. 5, 152,984 is disclosed an aminofunctional silicone resin comprising the reaction product of an aminofunctional silane and a silicone resin having a formula selected from the group consisting of RSiO3/2 (I), (RSiO3/2)w(R'R,'SiO)x(Siθ4/2)y (II), and (RSiO3/2)w(R,R"SiO)x(SiO4/2)y(R3 ,"SiO)z (III) wherein R, R', R", and R'" are selected from the group consisting of alkyl, alkenyl, aryl, and alkylaryl radicals having from one to twenty carbon atoms; and w, x, y, and z are integers having a value of from zero to about one thousand with the proviso that the sum of w and y is at least one.
[0008] In U.S. Patent No. 5,126,126 is disclosed a hair treating composition comprising a mixture of a film forming material and a solvent for the film forming material, the film forming material being an aminofunctional silicone resin which is the reaction product obtained by directly combining a cyclic silylamine and a silicone resin, the silicone resin being a hydroxy derivative having a formula selected from the group consisting of RSiO3/2 (I), (RSiO3/2)w(R'R"SiO)x(SiO4/2)y (II), and (RSiθ3/2)w(R,R"SiO)x(Siθ4/2)y(R3'"SiO1/2)z (III) wherein R, R', R", and R'" are selected from the group consisting of alkyl, alkenyl, aryl, and alkylaryl radicals having from one to twenty carbon atoms; x, y, and z are integers having a value of from zero to about one thousand and w is an integer having a value of from one to about one thousand.
[0009] In U.S. Patent No. 4,972,029 is disclosed thermally stable, crosslinked epoxy resins obtained by crosslinking an epoxy resin with a silicon compound containing a basic nitrogen which is bonded to silicon via carbon and to which at least 1 hydrogen atom is bonded directly to the nitrogen atom, and thereafter conditioning the crosslinked epoxy resin. [0010] Cage structured aminofunctional silicone resins are disclosed in the journal article entitled "A Polyimide Nanocomposite from Octa(aminophenyl)silsesquioxane", R. Tamaki, J. Choi, and R.M. Laine, Chemical Materials, Nolume 15, pages 793-797 (2003) and in the journal article entitled "Silicone/Amine Resin Hybrid Materials as Abrasion Resistant Coatings", C. Li and G. Wilkes, Chemical Materials, Nolume 13, pages 3663-3668 (2001).
[0011] When silicone resins are added to epoxy compounds at high loadings the glass transition temperature of the hybrid material is within the use range and it is accompanied by a large drop in modulus which hinders the reliability of devices based on these materials. Epoxy compounds are brittle and need to be toughened for use in many applications however when linear siloxanes are added to provide greater flexibility the material loses its solvent resistance. Hence there is a need for a material that flexibilizes epoxies while maintaining low CTE and solvent resistance. Thus there is a need for amino-functional resins with high R2SiO content >15 mol%, and high amine content.
[0012] Thus this invention relates to an aminofunctional silicone resin comprising the units: (R3SiO1/2)a (i)
(R2SiO2/2)b (ϋ) (RSiO3/2)c (iii) and
(SiO4/2)d ( ) wherein R is independently an alkyl group, an aryl group, or an aminofunctional hydrocarbon group, a has a value of less than 0.4, b has a value of greater than 0.15, c has a value of greater than zero to 0.7, d has a value of less than 0.2, the value ofa + b + c + d = l, with the provisos that 3 to 50 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -ΝH- equivalent weight of the aminofunctional silicone resin is from 100 to 1500, alternatively from 100 to 1000, alternatively 150 to 350, the aminofunctional silicone resin is in the form of a neat liquid, solution, or meltable solid, greater than 20 weight percent of unit (ii) is present in the aminofunctional silicone resin, less than 10 weight percent of unit (ii) are Me2Siθ2/2 units in the aminofunctional silicone resin, and greater than 50 weight percent of silicon-bonded R groups are silicon-bonded aryl groups. [0013] The -NH- equivalent weight as used herein means the weight of material that contains one atomic weight of amine hydrogen. [0014] The alkyl groups of R are illustrated by methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl with the alkyl group typically being methyl. The aryl groups are illustrated by phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2- phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl with the aryl group typically being phenyl. The aminofunctional hydrocarbon group is illustrated by groups having the formula -R^NHR^ or -RINHR^NHR^ wherein each R! is independently a divalent hydrocarbon radical having at least 2 carbon atoms and R^ is hydrogen or an alkyl group. Each R is typically an alkylene radical having from 2 to 20 carbon atoms, R is illustrated by -CH2CH2-, -CH2CH2CH2-, -CH2CHCH3-, -CH2CH2CH2CH2-
-CH2CH(CH3)CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH(CH2CH3)CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2-, and
-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-. The alkyl groups R2 are as illustrated above for R. When R2 is an alkyl group it is typically methyl.
[0015] Typical aminofunctional hydrocarbon groups are -CH2CH2NH2,
-CH2CH2CH2NH2, -CH2CHCH3NH, -CH2CH2CH2CH2NH2, -CH2CH2CH2CH2CH2NH2, -CH2CH2CH2CH2CH2CH2NH2, -CH2CH2NHCH3, -CH2CH2CH2NHCH3, -CH2(CH3)CHCH2NHCH3, -CH2CH2CH2CH2NHCH3, -CH2CH2NHCH2CH2NH2,
-CH2CH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2CH2NHCH2CH2CH2CH2NH2, -CH2CH2NHCH2CH2NHCH3, -CH2CH2CH2NHCH2CH2CH2NHCH3, -CH2CH2CH2CH2NHCH2CH2CH2CH2NHCH3, and -CH2CH2NHCH2CH2NHCH2CH2CH2CH3. [0016] The aminofunctional silicone resins of this invention are illustrated by aminofunctional silicone resins comprising the units:
Figure imgf000006_0001
(ii) (C6H5(CH3)SiO2/2)b
(iii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2 (iv) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) (C6H5(CH3)SiO2/2)b
(ii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2 (iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) ((CH3)3SiO1/2)a
(ii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2
(iii) (RSiO3/2)c where R = -CH2CH2CH2NH2 (iv) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) ((CH3)3SiOι/2)a
(ii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2
(iii) (C6H5SiO3/2)c aminofunctional silicone resin comprising the units
(i) ((CH3)3SiO1/2)a
(ii) (CH3)2SiO2/2)b
(iii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2 (iv) (C6H5SiO3/2)c aminofunctional silicone resin comprising the units:
(i) ((CH3)2RSiO1/2)a where R = -CH2(CH3)CHCH2NHCH3
(ii) (CH3)2SiO2/2)b (iii) (C6H5(CH3)SiO2/2)b (iv) (C6H5SiO3/2)c aminofunctional silicone resins comprising the units:
(i) ((CH3)2RSiO1/2)a where R = -CH2(CH3)CHCH2NHCH3
(ii) (C6H5(CH3)SiO2/2)b
(iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units: (i) ((CH3)RSiO2/2)b where R = -CH2(CH3)CHCH2NHCH3 (ii) (C6H5(CH3)Siθ2/2)b (iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units: (i) ((CH3)2RSiO1/2)a where R = -CH2(CH3)CHCH2NHCH3
(ii) (C6H5(CH3)SiO2/2)b
(iii) (SiO4/2)d, and aminofunctional silicone resins comprising the units:
Figure imgf000008_0001
(ii) (C6H5(CH3)SiO2/2)b
(iii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2
(iv) (C6H5SiO3/2)c
(v) (SiO4/2)d wherein a, b, c, and d are as defined above. [0017] In the aminofunctional silicone resin a has a typical value of 0.1 to 0.3, b has a typical value of 0.2 to 0.4, c has a typical value of 0.2 to 0.5, d has a typical value of 0. Generally, 10 to 30 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -NH- equivalent weight of the aminofunctional silicone resin is generally from 100 to 1500, alternatively from 100 to 1000, alternatively from 150 to 350, generally 20 to 50 weight percent of unit (ii) is present in the aminofunctional silicone resin, generally from 0 to 5 weight percent of unit (ii) are Me2Siθ2/2 units in the aminofunctional silicone resin, and generally from 50 to 75 weight percent of silicon-bonded R groups are silicon-bonded aryl groups. [0018] Generally, the aminofunctional silicone resins of this invention were prepared by reaction of a cyclic silazane with a hydroxy-containing siloxane resin or by hydrolytic polycondensation of alkoxysilanes by one of two methods. In some cases, the hydrolysis of the non-aminofunctional alkoxysilanes was accomplished via catalysis with strong acid, followed by addition of the aminofunctional silanes and base-catalyzed equilibration of these species to yield the aminofunctional silicone resin. In other cases, the entire hydrolysis was run under base-catalyzed conditions with the aminofunctional alkoxysilane(s) present from the start. In both cases, the hydrolysis was followed by distillative removal of by-product alcohol, filtration and removal of solvent to provide the product. [0019] More specifically the aminofunctional silicone resins of this invention can be manufactured by preparing a mixture of 45-60 wt% of aryltrialkoxysilane, arylalkyldialkoxysilane, γ-aminoalkyltrialkoxysilane, γ-aminoalkyldialkoxysilane and/or γ- aminoalkylmonoalkoxysilaneoptionally dissolving the mixture in up to 35 wt% of an aromatic solvent. This mixture is then hydrolyzed with 1-20 wt% of deionized water, followed by distillative removal of the by-product alcohol. The resulting product is then optionally reacted with up to 50 wt% of trialkylalkoxysilane, hexamethyldisilazane (HMDZ), γ-aminoalkyldialkoxysilane, γ-aminoalkylmonoalkoxysilane and/or dialkyldialkoxysilane, up to 35 wt% of additional solvent, and up to 20 wt% water can be added, a catalytic amount (to make 0-0.1 wt% KOH) of aqueous potassium hydroxide can then be optionally added and the water removed via azeotrope. The hydroxide, if added, is neutralized with aqueous HC1 or acetic acid, and water removed again via azeotrope. The mixture is then filtered and solvent removed to yield the aminofunctional silicone resin. Typically the aryl group is phenyl, the alkyl group is methyl, the alkoxy group is either methoxy or ethoxy, and the amino group is the aminofunctional hydrocarbon group described above. The aminofunctional silicone resins of this invention can also be manufactured by hydrolyzing 20-50 wt% of aryltrialkoxysilane and/or arylalkyldialkoxysilane, catalyzed by 0- 0.05 wt% with trifluoromethanesulfonic acid (TFMSA), with deionized water (0-10 wt%), followed by distillative removal of by-product alcohol. Up to 35 wt% of hexamethyldisiloxane (HMDS), up to 10 wt% water, and optionally up to 40 wt% toluene is added and the mixture heated to 50-60°C optionally followed by distillative removal of volatiles. Up to 20 wt% of γ-aminoalkyltrialkoxysilane (APTES), γ- aminoalkylmonoalkoxysilane or γ-aminoalkyldialkoxyalkylsilane are added along with up to 10 wt% water, followed by distillative removal of alcohol. Up to 40 wt% of toluene (if it was not added earlier) is added, up to 10 wt% of water, and optionally a catalytic amount (to make 0-0.1 wt% KOH) of 1.0 N aqueous potassium hydroxide is added and water removed via azeotrope. If added, the hydroxide was neutralized with 1.0 N aqueous HC1 or acetic acid, and water again removed via azeotrope. The mixture was filtered and solvent removed to yield the aminofunctional silicone resin. Typically the aryl group is phenyl, the alkyl group is methyl, the alkoxy group is either methoxy or ethoxy, and the amino group is the aminofunctional hydrocarbon group described above.
[0020] The aminofunctional silicone resins of this invention can also be manufactured by preparing a mixture of aryltrialkoxysilane, arylalkyldialkoxysilane, and γ-aminoalkyldialkoxyalkylsilane optionally dissolved in xylenes and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting product is then reacted with trialkylalkoxysilane, additional xylenes and additional water, followed by azeotropic removal of water. To a portion of this reaction mixture, additional xylene and colloidal silica dispersion are added and the water removed via azeotrope. The mixture is filtered and solvent removed to yield the silicone resin. Typically the aryl group is phenyl, the alkyl group is methyl, the alkoxy group is either methoxy or ethoxy, and the amino group is the aminofunctional hydrocarbon group described above. [0021] The aminofunctional silicone resins of this invention can also be manufactured by preparing a mixture of aryltrialkoxysilane and arylalkyldialkoxysilane optionally dissolved in xylenes and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting product is then reacted with cyclosilazane. The mixture is filtered and solvent removed to yield the silicone resin. Typically the aryl group is phenyl, the alkyl group is methyl, the alkoxy group is either methoxy or ethoxy, and the amino group is the aminofunctional hydrocarbon group described above. [0022] The aminofunctional silicone resins of this invention are useful in making tough, water, solvent, and heat resistant hybrid materials when used in combination with selected organic materials, particularly epoxy-containing organic materials. The aminofunctional resins of this invention have the ability to flexibilize epoxy compounds while maintaining low CTE and solvent resistance. [0023] This invention also relates to an emulsion composition comprising: (A) an aminofunctional silicone resin comprising the units: (R3SiO1/2)a (i)
(R2SiO2/2)b (ϋ) (RSiO3/2)c (ϋi) and (SiO4/2)d (iv) wherein R is independently an alkyl group, an aryl group, or an aminofunctional hydrocarbon group, a has a value of less than 0.4, b has a value of greater than 0.15, c has a value of greater than zero to 0.7, d has a value of less than 0.2, the value of a + b + c + d = l, with the provisos that 3 to 50 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -NH- equivalent weight of the aminofunctional silicone resin is from 100 to 1500, alternatively from 100 to 1000, alternatively from 150 to 350, the aminofunctional silicone resin is in the form of a neat liquid, solution, or meltable solid, greater than 20 weight percent of unit (ii) is present in the aminofunctional silicone resin, less than 10 weight percent of unit (ii) are Me2Siθ2/2 units in the aminofunctional silicone resin, and greater than 50 weight percent of silicon-bonded R groups are silicon-bonded aryl groups; (B) at least one surfactant; and (C) water.
[0024] The aminofunctional silicone resin of Component (A) is as described above including preferred embodiments thereof. The amount of Component (A) in the emulsion composition is typically from 25 to 75 weight percent, said weight percent being based on the total weight of the emulsion composition.
[0025] Component (B) is at least one surfactant. The surfactant may be an anionic, cationic, nonionic, or amphoteric surfactant. The surfactants may be employed separately or in combinations of two or more. Examples of suitable anionic surfactants include alkali metal sulforicinates, sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent alcohol esters such as sodium oleylisethianate, amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride, sulfonated products of fatty acids nitriles such as palmitonitrile sulfonate, sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate, condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate or triethanol amine lauryl sulfate, ether sulfates having alkyl groups of 8 or more carbon atoms such as sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium alkyl aryl ether sulfates, and ammonium alkyl aryl ether sulfates, alkylarylsulfonates having 1 or more alkyl groups of 8 or more carbon atoms, alkylbenzenesulfonic acid alkali metal salts exemplified by hexylbenzenesulfonic acid sodium salt, octylbenzenesulfomc acid sodium salt, decylbenzenesulfonic acid sodium salt, dodecylbenzenesulfonic acid sodium salt, cetylbenzenesulfonic acid sodium salt, and myristylbenzenesulfonic acid sodium salt, sulfuric esters of polyoxyethylene alkyl ether including CH3(CH2)6CH2O(C2H4O)2SO3H,
CH3(CH2)7CH2θ(C2H4θ)3.5SO3H, CH3(CH2)8CH2θ(C2H4θ)8Sθ3H,
CH3(CH2)i9CH2O(C2H4O)4SO3H, and CH3(CH2)ιoCH2θ(C2H4θ)6SO3H, sodium salts, potassium salts, and amine salts of alkylnaphthylsulfonic acid. [0026] Examples of cationic surfactants include various fatty acid amines and amides and their derivatives, and the salts of the fatty acid amines and amides. Examples of aliphatic fatty acid amines include dodecylamine acetate, octadecylamine acetate, and acetates of the amines of tallow fatty acids, homologues of aromatic amines having fatty acids such as dodecylanalin, fatty amides derived from aliphatic diamines such as undecylimidazoline, fatty amides derived from aliphatic diamines such as undecylimidazoline, fatty amides derived from disubstituted amines such as oleylaminodiethylamine, derivatives of ethylene diamine, quaternary ammonium compounds and their salts which are exemplified by tallow trimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, didodecyldimethyl ammonium chloride, dihexadecyl ammonium chloride, alkyltrimethylammonium hydroxides such as octylfrimethylammonium hydroxide, dodecy methylammonium hydroxide, or hexadecyltrimethylammonium hydroxide, dialkyldimethylammonium hydroxides such as octyldimethylammonium hydroxide, decyldimethylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctadecyldimemylammonium hydroxide, tallow trimethylammonium hydroxide, coconut oil, trimethylammonium hydroxide, methylpolyoxyethylene cocoammonium chloride, and dipalmityl hydroxyethylammomum methosulfate, amide derivatives of amino alcohols such as beta-hydroxylethylstearylamide, and amine salts of long chain fatty acids.
[0027] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants.
[0028] Examples of the amphoteric surfactants that can be used include amino acid surfactants and betaine acid surfactants. [0029] Typical commercially available surfactants include trimethylnonyl polyethylene glycol ethers and polyethylene glycol ether alcohols containing linear alkyl groups having from 11 to 15 such as 2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) (sold as Tergitol®TMN-6 by The Dow Chemical Company, Midland, MI), 2,6,8-trimethyl-4- nonyloxypolyethylene oxyethanol (10 EO) (sold as Tergitol®TMN-10 by The Dow Chemical Company, Midland, MI), alkylene-oxypolyethylene oxyethanol (C 11.15 secondary alkyl, 9 EO) (sold as Tergitol® 15-S-9 by The Dow Chemical Company, Midland, MI), alkylene- oxypolyethylene oxyethanol (C\ 1.15 secondary alkyl, 15 EO) (sold as Tergitol®15-S-15 by
The Dow Chemical Company, Midland, MI), octylphenoxy polyethoxy ethanols having varying amounts of ethylene oxide units such as octylphenoxy polyethoxy ethanol (40 EO) (sold as Triton® X405 by Rohm and Haas Company, Philadelphia, Pa.), nonionic ethoxylated tridecyl ethers available from Emery Industries, Mauldin, S.C. under the general tradename Trycol, alkali metal salts of dialkyl sulfosuccinates available from American Cyanamid Company, Wayne, N. J. under the general tradename Aerosol, polyethoxylated quaternary ammonium salts and ethylene oxide condensation products of the primary fatty amines, available from Armak Company, Chicago, 111. under the tradenames Ethoquad, Ethomeen, or Arquad, and polyoxyalkylene glycol modified polysiloxanes. These preferred surfactants may also be obtained from other suppliers under different tradenames.
[0030] Surfactants useful in the invention also include those derived from silicone, sorbitan derivatives, and fatty alcohol derivatives. More specifically, suitable surfactants include, but are not limited to, sorbitan sesquioleate, sorbitan oleate, sorbitan isostearate; alkoxylated alcohols such as ethoxylated fatty alcohols including laureth-4, laureth-7, deceth-12, steareth- 10; hydroxylated derivatives of polymeric silicones, such as dimethicone copolyol; alkylated derivatives of hydroxylated polymeric silicones such as cetyl dimethicone copolyol; glyceryl esters such as polyglyceryl-4-isostearate; and mixtures thereof, especially mixtures of hydroxylated derivatives of polymeric silicones, alkylated derivatives of hydroxylated polymeric silicones and glyceryl esters, most especially mixtures of dimethicone copolyol, cetyl dimethicone copolyol and polyglyceryl-4-isostearate. Most preferred is a mixture of such surfactants, i.e. a dimethicone copolyol, sorbitan sesquioleate and laureth-7. [0031] The amount of Component (B) in the emulsion composition is typically from 1 to 20 weight percent, said weight percent being based on the total weight of the emulsion composition. [0032] Component (C) is water. Generally water is present at a level of from about 20 to 80 weight percent, said weight percent being based on the total weight of the emulsion composition.
[0033] The emulsion compositions of this invention can further comprise fragrances, preservatives, vitamins, ceramides, amino-acid derivatives, liposomes, polyols, such as glycerine and propylene glycol and botanicals (plant extracts) and additional conditioning agents such as quaternary polymers or silicone materials. Other additives can include, but are not limited to the following depending on the use, glycols, vitamins A, vitamin C and vitamin E in their various forms, Pro-Nitamin B5, sunscreen agents (these include those which absorb ultraviolet light between about 290-320 nanometers (the UN-B region) and those which absorb ultraviolet light in the range of 320-400 (the UV-B region)), humectants, preservatives, such as known parabens, emollients, occlusive agents, and esters. Other additives can include pigments especially when the emulsion is used as a make-up. [0034] The compositions according to the invention can also contain agents for artificially tanning and/or browning the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA). These optional ingredients can be present in the emulsion compositions of this invention up in an amount of up to 5 parts by weight per 100 parts by weight of emulsion composition, but typically are present in amount of from 0.1 to 1 part by weight per 100 parts by weight of emulsion composition. Also the emulsion can be spray dried to form a resin/active composite particle.
[0035] The emulsion compositions of this invention may be prepared by mixing (or mechanically agitating) components (A)-(C), and any optional components, to form a homogenous mixture. This may be accomplished by any convenient mixing method known in the art exemplified by a spatula, mechanical stirrers, in-line mixing systems containing baffles and/or blades, powered in-line mixers, homogenizers, a drum roller, a three-roll mill, a sigma blade mixer, a bread dough mixer, and a two roll mill. The order of mixing is not considered critical. EXAMPLES
EXAMPLE 1
[0036] Aminofunctional Silicone Resins A1-A9 were prepared in the following manner. A mixture of phenyltrimethoxysilane, phenylmethyldimethoxysilane, γ-aminopropyltriethoxysilane (APTES), and/or γ-aminopropyldiethoxymethylsilane (APDEMS) was optionally dissolved in aromatic solvent and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting structure was optionally reacted with trimethylethoxysilane, hexamethyldisilazane (HMDZ), APDEMS and/or dimethyldimethoxysilane, additional solvent and additional water added, a catalytic amount of aqueous potassium hydroxide optionally added and the water removed via azeotrope. The hydroxide, if added, was neutralized with aqueous HC1 or acetic acid, and water removed again via azeotrope. The mixture was filtered and solvent removed to yield silicone resin product. The amount of each ingredient is shown in Table 1 below. The final aminofunctional silicone resin composition, wt% phenyl (Ph), wt% R2SiO (D), wt% Me2SiO (D( β2)), mole percent amino (-CH2CH2CH2NH2), wt% amine (-NH2), and -NH- (Amine H) equivalent weight are shown in Table 2 below.
[0037] Aminofunctional Silicone Resins Bl- B6 were prepared in the following manner. Phenyltrimethoxysilane and or phenylmethyldimethoxysilane, catalyzed by trifluoromethanesulfonic acid (TFMSA), were hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. Hexamethyldisiloxane (HMDS) and additional water were added and the mixture heated to 50-60°C optionally followed by distillative removal of volatiles. γ-Aminopropyltriethoxysilane (APTES) or γ- aminopropyldiethoxymethylsilane (APDEMS) were added along with additional water, followed by distillative removal of alcohol. Toluene, additional water and optionally a catalytic amount of 1.0 N aqueous potassium hydroxide were added and water removed via azeotrope. If added the hydroxide was neutralized with 1.0 N aqueous HC1, and water again removed via azeotrope. The mixture was filtered and solvent removed. The amount of each ingredient is shown in Table 1 below. The final aminofunctional silicone resin composition, wt% phenyl (Ph), wt% R2SiO (D), wt% Me2SiO (D(Me2)), mole percent amino (-CH2CH2CH2NH2), wt% amine (-NH2), and -NH- (Amine H) equivalent weight are shown in Table 2 below.
[0038] Aminofunctional Silicone Resin CI was prepared in the following manner. A mixture (amounts in Table 1) of phenyltrimethoxysilane, phenylmethyldimethoxysilane, and γ-aminopropyldiethoxymethylsilane (APDEMS) was optionally dissolved in xylenes and hydrolyzed with deionized water, followed by distillative removal of by-product alcohol. The resulting structure was reacted with trimethylethoxysilane, additional xylenes and additional water, followed by azeotropic removal of water. To a 177.0 gram portion of this reaction mixture, 19.3 grams of additional xylenes and 48.5 grams of colloidal silica dispersion (Ludox® HS-40-220 m^/gm Grace Davison (Columbia, MD)) were added and the water removed via azeotrope. The mixture was filtered and solvent removed to yield 110.6 grams of silicone resin product. The amount of each ingredient is shown in Table 1 below. The final aminofunctional silicone resin composition, wt% phenyl (Ph), wt% R2SiO (D), wt% Me2SiO (D(Me2)), mole percent amino (-CH2CH2CH2NH2), wt% amine (-NH2), and -NH- (Amine H) equivalent weight are shown in Table 2 below.
[0039] Aminofunctional Siloxane Resin El was prepared in the following manner: A mixture of 119.6g phenyltrimethoxysilane and 218.8g phenylmethyldimethoxysilane were hydrolyzed with 67.3g dilute aqueous HC1 (0.02 N), followed by distillative removal of byproduct methanol. The hydrolyzate was dissolved in 119.0g toluene followed by azeotropic removal of residual water and subsequently reacted with 34.4g cyclosilazane (1,1 ,2,4-
Tetramethyl-l-sila-2-azacyclopentane). 5.1g dilute aqueous KOH (1.0 N) was added and the mixture heated to reflux for three hours. The mixture was neutralized with 5.2g aqueous HC1 (1.0 N) dried via azeotropic distillation, filtered and solvent removed to yield 265. lg of the silicone resin El
Figure imgf000017_0001
Figure imgf000018_0001
In Table 2 above: # molar mass of phenyl in the composition divided by the molar mass of all resin R groups in the composition
*based on the molar mass of the designated group divided by the molar mass of the composition M denotes (CΗ.3)3SiOι/2 MNH denotes (CH3)2RSiOι / where R = -CH2(CH3)CHCH2NHCH3
D denotes (CH3)2SiO2/2
DPh denotes C6H5(CH3)Siθ2/2
DNH2 denotes(CH3)RSiO2/2 where R = -CH2CH2CH2NH2
TPh denotes C^Η.ζSiOy2 T H2 denotes RSiO /2 where R = -CH2CH2CH2NH2
Q denotes Siθ4/2 EXAMPLE 2
[0040] 30.0g of aminofunctional silicone resin B4 prepared and described above comprising the units MQ.299 D^n0.101 DNEEO.099 TPn 0.497 wherein M, D^h, DNH25 ^
T^h are as defined above, was weighed into a Hauschild (Hamm, Germany) Max 40 plastic cup followed by 0.9g of Tergitol® TMN-6 (2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) a nonionic surfactant from The Dow Chemical Company (Midland, MI)), l.Og Tergitol® 15-S-30 (alkylene-oxypolyethylene oxyethanol (Cn_i5 secondary alkyl, 30
EO) a nonionic surfactant from The Dow Chemical Company (Midland, MI) and 2.0g of deionized water. The cup was closed and placed into a Hauschild (Hamm, Germany) SpeedmixerTM DAC-150 laboratory mixing device. The cup and its contents were cycled in the mixer for 20 seconds. The cup was opened and the walls of the cup were scraped with a spatula. The cup and its contents were subjected to a second 20 second mixing cycle. Next 6g of Dl water was added and the cup was again subjected to a 20 second mixing cycle. An additional lOg of Dl water was added in increments of 5g followed by a 20 second mixing cycle after each addition. The emulsion that resulted was milky white in appearance with a slight bluish tint. The emulsion consisted of an approximately 60% by weight resin oil particle phase. Mean particle size was measured using a Microtrac® (Montgomeryville, PA)
UPA150 instrument and had the following properties: D(v, 0.5) = 0.2766 um, D(v, 0.9) =
0.3467 um
Example 3
[0041] 1.02g of amino functional siloxane resin El was weighed into a glass vial followed by the addition of 5.68g of DER® 331 and 3.35g Nersamine® C-30. The ingredients were mixed thoroughly with a wooden stir rod resulting in a clear and colorless mixture containing 10% by weight of siloxane resin El and stoichiometric ratio of amine to epoxy. Six mil drawdowns were made onto Chromated aluminum panels (AL-39 from Q-Panel Inc. Cleveland, OH) and the panels were exposed to a nitrogen purged oven for one hour at 100°C and one hour at 150°C. The cured film was clear and colorless and had increased flexibility (4) compared to a control sample (6) with no siloxane resin added as measured by T Bend Flex Test (ASTM D4145).

Claims

CLAIMS 1. An aminofunctional silicone resin comprising the units:
Figure imgf000020_0001
(R2SiO2/2)b (ϋ) (RSiO3/2)c (iii) and
(SiO4/2)d (iv) wherein R is independently an alkyl group, an aryl group, or an aminofunctional hydrocarbon group, a has a value of less than 0.4, b has a value of greater than 0.15, c has a value of greater than zero to 0.7, d has a value of less than 0.2, the value ofa + b + c + d = l, with the provisos that 3 to 50 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -NH- equivalent weight of the aminofunctional silicone resin is from 100 to 1500, the aminofunctional silicone resin is in the form of a neat liquid, solution, or meltable solid, greater than 20 weight percent of unit (ii) is present in the aminofunctional silicone resin, less than 10 weight percent of unit (ii) are Me2Siθ2/2 units in the aminofunctional silicone resin, and greater than 50 weight percent of silicon-bonded R groups are silicon-bonded aryl groups.
2. An aminofunctional silicone resin comprising the units: (R3SiOi/2)a (i)
(R2SiO2/2)b (ϋ) (RSiO3/2)c (ϋi) and (SiO4/2)d (iv) wherein R is independently an alkyl group, an aryl group, or an aminofunctional hydrocarbon group, a has a value of less than 0.4, b has a value of greater than 0.15, c has a value of greater than zero to 0.7, d has a value of less than 0.2, the value ofa + b + c + d = l, with the provisos that 3 to 50 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -NH- equivalent weight of the aminofunctional silicone resin is from 100 to 1000, the aminofunctional silicone resin is in the form of a neat liquid, solution, or meltable solid, greater than 20 weight percent of unit (ii) is present in the aminofunctional silicone resin, less than 10 weight percent of unit (ii) are Me2Siθ2/2 units in the aminofunctional silicone resin, and greater than 50 weight percent of silicon-bonded R groups are silicon-bonded aryl groups.
3. An aminofunctional silicone resin according to Claim 1 or 2 wherein R is independently selected from methyl, phenyl, or an aminofunctional hydrocarbon group having the formula R^NHR2 or -R^NHRINHR2 wherein each R is independently a divalent hydrocarbon radical having at least 2 carbon atoms and R2 is hydrogen or an alkyl group.
4. An aminofunctional silicone resin according to any of Claims 1 - 3 wherein the aminofunctional hydrocarbon groups are selected from -CH2CH2NH2,
-CH2CH2CH2NH2, -CH2CHCH3NH, -CH2CH2CH2CH2NH2, -CH2CH2CH2CH2CH2NH2, -CH2CH2CH2CH2CH2CH2NH2, -CH2CH2NHCH3, -CH2CH2CH2NHCH3, -CH2(CH3)CHCH2NHCH3, -CH2CH2CH2CH2NHCH3, -CH2CH2NHCH2CH2NH2,
-CH2CH2CH2 HCH2CH2CH2 H2, -CH2CH2CH2CH2NHCH2CH2CH2CH2NH2, -CH2CH2NHCH2CH2NHCH3, -CH2CH2CH2NHCH2CH2CH2NHCH3, -CH2CH2CH2CH2NHCH2CH2CH2CH2NHCH3, and -CH2CH2NHCH2CH2NHCH2CH2CH2CH3.-
5. An aminofunctional resin according to Claim 1 or 2 wherein the aminofunctional silicone resin is selected from aminofunctional silicone resins comprising the units:
(i) ((CH3)3SiO1/2)a (ii) (C6H5(CH3)SiO2/2)b
(iii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2
(iv) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) (C6H5(CH3)Siθ2/2)b (ii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2
(iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
Figure imgf000023_0001
(ii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2 (iii) (RSiO3/2)c where R = -CH2CH2CH2NH2
(iv) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units: ,
Figure imgf000023_0002
(ii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2 (iii) (C6H5SiO3/2)c or aminofunctional silicone resins comprising the units:
Figure imgf000023_0003
(ii) (C6H5(CH3)SiO2/2)b (iii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2 (iv) (C6H5SiO3/2)c
(v) (SiO4/2)d wherein a, b, c, and d are as defined above.
6. An aminofunctional resin according to Claim l or 2 wherein the aminofunctional silicone resin is selected from aminofunctional silicone resins comprising the units:
Figure imgf000024_0001
(ii) (C6H5(CH3)SiO2/2)b
(iii) ((CH3)RSiO /2)b where R = -CH2CH2CH2NH2
(iv) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) (C6H5(CH3)SiO2/2)b (ii) ((CH )RSiO2/2)b where R = -CH2CH2CH2NH2
(iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) ((CH3)3SiOι/2)a
(ii) ((CH3)RSiO2/ )b where R = -CH2CH2CH2NH2 (iii) (RSiO3/2)c where R = -CH2CH2CH2NH2
(iv) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) ((CH3)3SiOι/2)a
(ii) ((CH )RSiO2/2)b where R = -CH2CH2CH2NH2 (iii) (C6H5SiO3/2)c aminofunctional silicone resin comprising the units
Figure imgf000024_0002
(ii) (CH3)2SiO2/2)b
(iii) ((CH3)RSiO /2)b where R = -CH2CH2CH2NH2 (iv) (C6H5SiO3/2)c aminofunctional silicone resin comprising the units:
(i) ((CH3)2RSiOι/2)a where R = -CH2(CH3)CHCH2NHCH3
(ii) (CH3)2SiO2/2)b (iii) (C6H5(CH3)SiO2/2)b (iv) (C6H5Siθ3/2)c aminofunctional silicone resins comprising the units:
(i) ((CH3)2RSiOi 2)a where R = -CH2(CH3)CHCH2NHCH3
(ii) (C6H5(CH3)Siθ2/2)b
(iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units:
(i) ((CH3)RSiO2/2)b where R = -CH2(CH3)CHCH2NHCH3
(ii) (C6H5(CH3)SiO2/2)b
(iii) (C6H5SiO3/2)c , aminofunctional silicone resins comprising the units: (i) ((CH3)2RSiOι/2)a where R = -CH2(CH3)CHCH2NHCH3
(ii) (C6H5(CH3)SiO2/2)b
(iii) (Siθ4/2)d, or aminofunctional silicone resins comprising the units:
Figure imgf000025_0001
(ii) (C6H5(CH3)Siθ2/2)b
(iii) ((CH3)RSiO2/2)b where R = -CH2CH2CH2NH2
(iv) (C6H5SiO3/2)c
(v) (SiO4/2)d wherein a, b, c, and d are as defined above.
7. An emulsion composition comprising:
(A) an aminofunctional silicone resin of any of claims 1-6;
(B) at least one surfactant; and
(C) water.
8. An emulsion composition according to Claim 7 wherein a has a value of 0.1 to 0.3, b has a value of 0.2 to 0.4, c has a value of 0.2 to 0.5, d has a value of 0, 10 to 30 mole percent of silicon atoms contain aminofunctional hydrocarbon groups in units (i), (ii) or (iii), the -NH- equivalent weight of the aminofunctional silicone resin is from 150 to 350, 20 to 50 weight percent of unit (ii) is present in the aminofunctional silicone resin, 0 to 5 weight percent of unit (ii) are Me2Siθ2/2 units in the aminofunctional silicone resin, and from 50 to 75 weight percent of silicon-bonded R groups are silicon-bonded aryl groups.
9. An emulsion composition according to Claim 7 or 8 wherein the surfactant is selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, or a combination thereof.
10. An emulsion composition according to any of Claims 7-9, wherein the emulsion composition further comprises at least one ingredient selected from fragrances, preservatives, vitamins, ceramides, amino-acid derivatives, liposomes, polyols, botanicals, conditioning agents, glycols, vitamin A, vitamin C, vitamin E, Pro-Vitamin B5, sunscreen agents, humectants, preservatives, emollients, occlusive agents, esters, pigments, or self-tanning agents. 11 An emulsion composition according to any of Claims 8-10, wherein the emulsion is in the form of spray-dried composite particles.
PCT/US2004/021777 2003-07-16 2004-07-07 Aminofunctional silicone resins and emulsions containing them WO2005010076A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE602004008646T DE602004008646T2 (en) 2003-07-16 2004-07-07 AMINO FUNCTIONAL SILICONE RESINS AND THESE EMULSIONS CONTAINING
JP2006520219A JP4939215B2 (en) 2003-07-16 2004-07-07 Amino-functional silicone resins and emulsions containing them
US10/564,610 US7501473B2 (en) 2003-07-16 2004-07-07 Aminofunctional silicone resins and emulsions containing them
EP04756739A EP1651703B1 (en) 2003-07-16 2004-07-07 Aminofunctional silicone resins and emulsions containing them

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48769803P 2003-07-16 2003-07-16
US60/487,698 2003-07-16

Publications (2)

Publication Number Publication Date
WO2005010076A2 true WO2005010076A2 (en) 2005-02-03
WO2005010076A3 WO2005010076A3 (en) 2005-11-17

Family

ID=34102714

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/021777 WO2005010076A2 (en) 2003-07-16 2004-07-07 Aminofunctional silicone resins and emulsions containing them

Country Status (7)

Country Link
US (1) US7501473B2 (en)
EP (1) EP1651703B1 (en)
JP (1) JP4939215B2 (en)
CN (1) CN100404589C (en)
AT (1) ATE371692T1 (en)
DE (1) DE602004008646T2 (en)
WO (1) WO2005010076A2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008088492A1 (en) 2006-12-20 2008-07-24 Dow Corning Corporatrion Blocked isocyanate silicone resins
WO2010125180A2 (en) * 2009-04-30 2010-11-04 Ewald Dörken Ag Method for the production of a binder for coating conductive surfaces
CN102040842A (en) * 2010-10-28 2011-05-04 华南理工大学 Autocatalytic crosslinking type organic silicon-epoxy composite material and preparation method thereof
US8101702B2 (en) 2007-01-12 2012-01-24 Dow Corning Corporation Silicone-containing composition
CN103333339A (en) * 2013-06-04 2013-10-02 黄山市强力化工有限公司 Method for preparing hydroxyl-terminated phenyl amino polyether modified silicone oil

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004014217A1 (en) * 2004-03-23 2005-10-13 Wacker-Chemie Gmbh Crosslinkable compositions based on organosilicon compounds
US7705090B2 (en) * 2004-08-20 2010-04-27 Chevron Oronite Company Llc Method for preparing polyolefins containing a high percentage of exo-olefin chain ends
JP2012525484A (en) * 2009-04-30 2012-10-22 ダウ グローバル テクノロジーズ エルエルシー Reactive inorganic cluster
EP2431421B1 (en) * 2010-09-20 2013-11-06 Wacker Chemie AG Aqueous mixtures comprising aminoalkyl-containing polyorganosiloxanes and silicone resins
EP2785909B1 (en) 2011-11-29 2022-04-06 Dow Silicones Corporation Aminofunctional silicone emulsions
US8987180B2 (en) * 2012-12-18 2015-03-24 Kimberly-Clark Worldwide, Inc. Wet wipes including silicone reactive amino containing dimethicone copolyols
CN109071820B (en) * 2016-05-10 2021-08-17 美国陶氏有机硅公司 Silicone block copolymers with amino-functional end-capping groups and methods of making and using the same
US11607376B2 (en) 2017-05-27 2023-03-21 Wacker Chemie Ag Oil-in-water microemulsions and the preparation thereof
CN108342085A (en) * 2018-03-21 2018-07-31 东莞市正安有机硅科技有限公司 A kind of heat safe silicon compounded rubber stock and preparation method thereof
CN112368347B (en) 2018-07-19 2022-04-08 陶氏环球技术有限责任公司 Weather-resistant and durable coating composition
MX2020013819A (en) 2018-07-19 2021-03-09 Dow Global Technologies Llc Weatherable and durable coating compositions.
CN115397889A (en) * 2020-04-21 2022-11-25 劲量汽车有限公司 Water-based silicone combination surface modification composition and method of use thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5126126A (en) * 1990-11-20 1992-06-30 Dow Corning Corporation Hair fixatives
US5262507A (en) * 1990-09-11 1993-11-16 Dow Corning Corporation High modulus silicones as toughening agents for epoxy resins

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166527A (en) 1960-10-03 1965-01-19 Union Carbide Corp Anti-corrosion, amino-organosiliconepoxy finishing compositions
US3890269A (en) 1972-08-11 1975-06-17 Stauffer Chemical Co Process for preparing aminofunctional polysiloxane polymers
JPS52147657A (en) 1976-06-02 1977-12-08 Toray Silicone Co Ltd Curable organopolysiloxane compositions
US4125510A (en) 1977-03-01 1978-11-14 Dow Corning Corporation Method of improving crack resistance of siloxane molding compositions
DE2730744A1 (en) 1977-07-07 1979-05-03 Bayer Ag ORGANOPOLYSILOXANE COMPOSITIONS MODIFIED WITH POLYURETHANE
US4234697A (en) 1979-01-18 1980-11-18 Dow Corning Corporation Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom
CA1235245A (en) 1984-12-26 1988-04-12 Toshifumi Hirose Curable resinous composition comprising epoxy resin and silicon-containing elastomeric polymer
JPS6245667A (en) 1985-08-22 1987-02-27 Shin Etsu Chem Co Ltd Paint composition
US4661577A (en) * 1985-10-01 1987-04-28 General Electric Company Aminofunctional polysiloxanes
DE3689022T2 (en) 1985-10-07 1994-04-21 Shinetsu Chemical Co Epoxy resin composition.
US4795680A (en) 1986-05-09 1989-01-03 General Electric Company Polyimide-siloxanes, method of making and use
DE3709045A1 (en) 1987-03-19 1988-09-29 Wacker Chemie Gmbh METHOD FOR PRODUCING PAINTS EXPOSED TO WEATHERING
DE3813719A1 (en) 1988-04-22 1989-11-02 Wacker Chemie Gmbh METHOD FOR PRODUCING HEAT-RESISTANT, CROSS-LINKED EPOXY RESINS
US4935482A (en) 1989-01-03 1990-06-19 Dow Corning Corporation Polysiloxane-polyurea block copolymers
US5102960A (en) 1989-09-11 1992-04-07 Bayer Aktiengesellschaft Silicon-epoxy resin composition
US4988778A (en) 1990-01-18 1991-01-29 Ppg Industries, Inc. Polyamine-functional silane resin
JP2661328B2 (en) 1990-05-18 1997-10-08 信越化学工業株式会社 Flame-retardant coating material and workpiece coated with the coating material
US5013577A (en) 1990-08-22 1991-05-07 Dow Corning Corporation Siloxane soluble (CH3)3 SIO1/2 /SIO2 (M/Q) resins with amine and amide organofunctionality
US5135993A (en) 1990-09-11 1992-08-04 Dow Corning Corporation High modulus silicones as toughening agents for epoxy resins
US5431765A (en) 1994-06-20 1995-07-11 Toray Industries Preparing epoxy resin/aminopolysiloxane/aromatic oligomer composite
US5152984A (en) 1990-11-20 1992-10-06 Dow Corning Corporation Hair fixatives
CA2034851A1 (en) 1991-01-24 1992-07-25 Chak-Kai Yip Amine functional silane modified epoxy resin composition and weatherstrip coatings made therefrom
US5110891A (en) 1991-04-11 1992-05-05 Dow Corning Corporation Amine functional siloxanes
US5290882A (en) 1991-08-13 1994-03-01 Shin-Etsu Chemical Co., Ltd. Thermosetting resin compositions
JP3363484B2 (en) * 1992-03-13 2003-01-08 東レ・ダウコーニング・シリコーン株式会社 Curable resin composition
DE4211256A1 (en) 1992-04-03 1993-10-07 Wacker Chemie Gmbh Crosslinkable composition based on aminosilicone
EP0620242B1 (en) 1993-04-15 1998-08-19 Dow Corning Toray Silicone Company, Limited Epoxy group-containing silicone resin and compositions based thereon
US5952439A (en) 1993-04-15 1999-09-14 Dow Corning Toray Silicone Co., Ltd. Epoxy group-containing silicone resin and compositions based thereon
US5804616A (en) 1993-05-19 1998-09-08 Ameron International Corporation Epoxy-polysiloxane polymer composition
JP3095330B2 (en) 1993-11-10 2000-10-03 信越化学工業株式会社 Film-forming composition
JP3147677B2 (en) 1994-09-30 2001-03-19 株式会社村田製作所 Liquid epoxy resin composition
US5840806A (en) 1995-05-09 1998-11-24 Dainippon Ink And Chemicals, Inc. Curable resin compositions
DE19638125A1 (en) 1996-09-18 1998-03-19 Wacker Chemie Gmbh Organosilicon compounds containing amino groups, their preparation and use
JP4420548B2 (en) * 2000-09-28 2010-02-24 旭化成ケミカルズ株式会社 Polyphenylene ether resin composition
PL1651704T3 (en) * 2003-07-16 2012-01-31 Dow Corning Coating compositions containing aminofunctional silicone resins
WO2005010115A1 (en) * 2003-07-16 2005-02-03 Dow Corning Corporation Coating compositions comprising epoxy resins and aminofunctional silicone resins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262507A (en) * 1990-09-11 1993-11-16 Dow Corning Corporation High modulus silicones as toughening agents for epoxy resins
US5126126A (en) * 1990-11-20 1992-06-30 Dow Corning Corporation Hair fixatives

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008088492A1 (en) 2006-12-20 2008-07-24 Dow Corning Corporatrion Blocked isocyanate silicone resins
US8101702B2 (en) 2007-01-12 2012-01-24 Dow Corning Corporation Silicone-containing composition
WO2010125180A2 (en) * 2009-04-30 2010-11-04 Ewald Dörken Ag Method for the production of a binder for coating conductive surfaces
WO2010125180A3 (en) * 2009-04-30 2011-01-13 Ewald Dörken Ag Method for the production of a binder for coating conductive surfaces
CN102040842A (en) * 2010-10-28 2011-05-04 华南理工大学 Autocatalytic crosslinking type organic silicon-epoxy composite material and preparation method thereof
CN103333339A (en) * 2013-06-04 2013-10-02 黄山市强力化工有限公司 Method for preparing hydroxyl-terminated phenyl amino polyether modified silicone oil

Also Published As

Publication number Publication date
CN100404589C (en) 2008-07-23
ATE371692T1 (en) 2007-09-15
DE602004008646D1 (en) 2007-10-11
DE602004008646T2 (en) 2008-06-12
EP1651703A2 (en) 2006-05-03
US7501473B2 (en) 2009-03-10
WO2005010076A3 (en) 2005-11-17
US20070104674A1 (en) 2007-05-10
EP1651703B1 (en) 2007-08-29
JP4939215B2 (en) 2012-05-23
JP2007525559A (en) 2007-09-06
CN1823115A (en) 2006-08-23

Similar Documents

Publication Publication Date Title
EP1651734A1 (en) Coating compositions comprising epoxy resins and aminofunctional silicone resins
US7501473B2 (en) Aminofunctional silicone resins and emulsions containing them
JP2007523964A6 (en) Coating composition comprising an epoxy resin and an amino-functional silicone resin
US6248855B1 (en) Method of making silicone-in-water emulsions
US6475974B1 (en) Mechanical microemulsions of blended silicones
EP1426398B1 (en) Method of making emulsion containing quaternary ammonium functional silanes and siloxanes
EP1718799A1 (en) Treating textiles with emulsions containing silicone resins
JP2849044B2 (en) Film-forming silicone emulsion composition
JP2007525559A5 (en)
JP5954255B2 (en) Curable silicone emulsion composition
EP1625132B1 (en) Method of preparing emulsions containing elastomeric silanes and siloxanes having quaternary ammonium groups
EP0640670B1 (en) Film-forming silicone emulsion composition
EP3653680B1 (en) Silicone emulsion composition for forming rubber coating film, and method for manufacturing same
US7858697B2 (en) Carbinol functional silicone resins
JP7249442B2 (en) Aminosilicone polymer, silicone emulsion containing the same, and method for producing the same
US20110201751A1 (en) Film Forming Silicone Emulsions
KR20080031625A (en) Particle dispersion
WO2009120424A1 (en) A method of reducing dust and dirt settlement

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480020348.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007104674

Country of ref document: US

Ref document number: 10564610

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2006520219

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2004756739

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2004756739

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 10564610

Country of ref document: US

WWG Wipo information: grant in national office

Ref document number: 2004756739

Country of ref document: EP