+

WO2001066655A1 - Composition de revetement barriere produite a partir de silanes a fonction amino et de composes phenoliques - Google Patents

Composition de revetement barriere produite a partir de silanes a fonction amino et de composes phenoliques Download PDF

Info

Publication number
WO2001066655A1
WO2001066655A1 PCT/US2001/005573 US0105573W WO0166655A1 WO 2001066655 A1 WO2001066655 A1 WO 2001066655A1 US 0105573 W US0105573 W US 0105573W WO 0166655 A1 WO0166655 A1 WO 0166655A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
coating
substrate
composition
carbon atoms
Prior art date
Application number
PCT/US2001/005573
Other languages
English (en)
Inventor
Shrenik M. Nanavati
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 AU2001238615A priority Critical patent/AU2001238615A1/en
Publication of WO2001066655A1 publication Critical patent/WO2001066655A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C08J2483/00—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

Definitions

  • the present invention relates to coating compositions having barrier properties which are useful in packaging applications.
  • the coating compositions of this invention are formed by the reaction of amino functional silanes with phenolic compounds, and are particularly useful to reduce the diffusion of gases through organic polymer based packaging materials.
  • Organic polymers such as polypropylene and polyethylene terephthalate
  • Coating compositions containing silane compounds are known to improve the gas, oil, and flavor barrier performance of organic polymer film substrates, for example as described in PCT/BE98/00006, the corresponding US equivalent of which is US Serial No. 09/341253. Moreover, the adhesion of the coating to the film surface, as well as the improved barrier characteristics provided by the silane coating, are greatly enhanced by exposing the coated film to electron beam radiation.
  • U.S. Patent No. 5,434,007 teaches a silane resin coated on a plastic film, where the silane resin is composed of a monofunctional acrylate and an amino functional silane.
  • U.S. Patent Nos. 5,260,350 and 5,374,483 relate to a silicone coating composition which, when cured on a solid substrate either by ultraviolet or electron beam radiation, provides a transparent abrasion resistant coating firmly adhered thereon.
  • the silicone coating is prepared by reacting at least one multifunctional acrylate monomer with an amino-organofunctional silane, mixing the modified silane with at least one acrylic monomer and thereafter adding colloidal silica.
  • JP (Kokai) publication 7-18221 published on January 20, 1995 teaches a surface treatment composition for gas barrier comprising an amino functional silane and a compound having an aromatic ring or hydrogenated ring.
  • the present inventor has surprisingly discovered that the reaction products of an amino functional silane and a phenolic compound give excellent gas barrier properties at low to moderate relative humidity values, as well as excellent gas barrier properties at very high relative humidity values of 90% or more.
  • Coating compositions for improving barrier properties of organic polymer films based primarily on the reaction product of amino functional silanes and phenolic compounds heretofore are not known.
  • Amino functional silanes are commonly used as surface treatments of silicate based materials (such as glass or silica) to enhance the adhesion of a wide variety of organic polymers. Examples of the type of organic polymers reacted with amino functional silane treated silicate materials includes phenol-formaldehyde polymers.
  • the '690 teaches the necessity of mixing a phenolic compound in a phenol-formaldehyde resin to obtain a coating composition.
  • Silamines have been reacted with phenols to create curing agents for epoxide resins, as taught in US Patent No. 4,393,180.
  • these silamines differ from the amino functional silanes of the present invention in that they do not contain an alkoxy group and have not been suggested for improving the barrier properties of organic polymer films.
  • the present invention is directed to a composition, useful for improving the barrier properties of organic polymer films, prepared by reacting; (A) an amino functional silane and (B) a phenolic compound to form a reaction product.
  • the composition should be free of phenol-formaldehyde resole resin.
  • the composition can be cured by further heating in the presence of moisture.
  • the present invention also teaches a method for preparing substrates with improved barrier properties by coating a variety of substrates used in packaging applications with the inventive compositions.
  • the substrates prepared by the method of the present invention show improved resistance of the substrate to transmission of gases and aromas there through.
  • a 30 micrometers uncoated biaxially oriented, corona treated polypropylene film is generally found to have a permeability to oxygen of 1200 cc/m /day as measured according to ASTM D3985-81 at 90%) relative humidity.
  • the oxygen transmission rate of the same film is reduced to less than lcc/m /day as measured at 90% relative humidity.
  • the terminology "improved barrier" refers to a coating which can reduce oxygen transmission rate of the aforementioned un-coated polypropylene film from
  • R is independently a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms
  • R is independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylalkyl group, an acryl group, a methacryl group, or an alkylaryl group
  • R is independently selected from the group consisting of, linear or branched alkylene groups having from 1 to 12 carbon atoms, arylene groups having from 6 to 12 carbon atoms, and linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group
  • amino functional silanes useful for the present invention are N-(2- aminoethyl)-3-aminopropyltrimethoxy silane, and aminopropyltriethoxysilane, and blends thereof.
  • amino functional silane has the general formula;
  • R is a monovalent radical independently selected from the group consisting of hydrogen atoms; acryl, methacryl, alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isobutyl, hexyl, octyl, decyl, dodecyl and octadecyl; substituted alkyl having 1 to 18 carbon atoms, such as 3-chloropropyl and 3,3,3-trifluoropropyl; aryl having 6 to 16 carbon atoms, such as phenyl and naphthyl; substituted aryl having 6 to 30 carbon atoms, such as chlorophenyl, chlorotolyl and dichloroxylyl; arylalkyl having 7 to 9 carbon atoms, such as benzyl, phenethyl and 3-phenylpropyl; and alkylaryl having 7 to 16 carbon atoms, such as tolyl, xy
  • R can also be an alkylene linking group which links two different nitrogen atoms together, thus forming a cyclic aminosilane.
  • the alkylene linking group can also be an arylene group which is connected to the same nitrogen atom.
  • the alkylene linking group will have at least 2 carbon atoms and as many as 12 carbon atoms.
  • R is an organic connecting group which provides a separation of at least one carbon atom between the nitrogen atoms or the nitrogen and silicon atoms.
  • R can be an alkylene group having at least 1 carbon atom or an arylene group having at least 6 carbon atoms.
  • R is selected from the group consisting of methylene, ethylene, propylene, butylene, isobutylene, trimethylene, tetramethylene, and hexamethylene.
  • R can contain polar groups such as, linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group.
  • polar groups such as, linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group.
  • polar groups such as, linear or branched hydrocarbon groups having from 1 to 16 carbon atoms and at least one alcohol, alcohol ether, ester, amide, urea, thiourea or polyether group.
  • Examples of specific amine-containing groups include such structures as - CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 N(H)CH 2 CH 2 NH 2 , - CH 2 CH 2 CH 2 N(H)CH 2 CH 2 N(H)CH 2 CH 2 NH 2 , -CH CH 2 CH 2 CH 2 NH 2 , - CH 2 CH 2 CH 2 CH 2 NH 2 , -CH 2 CH 2 CH 2 N(H)Me, -CH 2 NHCH CH 2 NH 2 , -
  • amino functional silane can mean a single species of the formula described above, such as N-(2-aminoethyl)-3-aminopropyltrimethoxy silane, or it can mean mixtures of one or more species of amino functional silanes, such as N-(2-aminoethyl)-3- aminopropyltrimethoxy silane and aminopropyltriethoxysilane.
  • amino functional silanes can be prepared by methods known to those skilled in the art, and which are amply described in the chemical literature.
  • Component B) of our composition is a phenolic compound.
  • phenolic compounds to be any compound having a structure with at least one hydroxy group substituent on an aromatic ring.
  • the inventor believes any phenolic compound will suffice for reaction with the amino functional silanes described above to form the compositions of this present invention. While not to be bound by any theory, the inventor believes the hydroxy group of the phenolic compound reacts with the alkoxy group of the amino functional silane, liberating alcohol (corresponding to the alkoxy group on the amino functional silane) and forming a complex.
  • the complex unexpectedly provides unique physical properties that make them useful in the preparation of barrier coatings.
  • the phenolic compounds of this invention may be further substituted with a variety of chemical groups, such as hydrogen, alkyl, aryl, hydroxy, carboxylic acids, esters, thio, amino, amide, or nitro groups.
  • the phenolic compound has two or more hydroxy substituents on its aromatic ring structure.
  • the phenolic compounds may have one or several aromatic rings in its structure.
  • the polycyclic aromatic structure is preferably chosen from the group consisting of naphthyl, anthryl, and phenanthryl derivatives.
  • Preferred embodiments of a polycyclic aromatic phenolic compound are 1, 5 dihydroxynaphthalene and 2, 7 dihydroxynaphthalene.
  • the phenolic compound has one aromatic ring and contains several hydroxy substituents.
  • a specific preferred embodiment is when the phenolic compound is 1, 2, 3, -trihydroxybenzene, commonly know as pyrogallol.
  • the components (A) and (B) of the present invention can be reacted together in a solvent.
  • the solvent must wet the substrate and should not extend the drying time of the coating beyond what is commercially acceptable.
  • the amount of solvent can range from about 1% to about 99%) .
  • the solvent is present from about 5 to about 95 parts by weight of the total composition, and most preferably is present from about 70 to about 80 parts by weight of the total composition.
  • alcohols serve as suitable solvents.
  • Preferred solvents are methanol, ethanol, n-propanol, isopropanol, butanol, and l-methoxy-2-propanol (available as
  • the coating can be applied in any desired amount, however, it is preferred that the coating be applied in a thickness ranging from 0.05 micrometers to 15 micrometers, the preferred coating thickness range being from about 0.5 to about 7 micrometers. Coating thickness can be determined by Scanning Electron Microscopy or by the use of a profiler (Tencor P-1 Long Scan Profilometer, Tencor Instruments, Santa Clara, CA).
  • the coating can be applied to the substrate by any conventional method, such as spray coating, roll coating, slot coating, meniscus coating, immersion coating, and direct, offset, and reverse gravure coating.
  • the coating can be disposed on a wide variety of substrates, including, but not limited to polyolefins, such as oriented polypropylene (OPP), cast polypropylene, polyethylene and polyethylene copolymers, polystyrene, polyesters, such as polyethylene terephthalate (PET), or polyethylene naphthalate (PEN), polyolefin copolymers, such as ethylene vinyl acetate, ethylene acrylic acid and ethylene vinyl alcohol (EVOH), polyvinylalcohol and copolymers thereof, polyamides, such as nylon, and nylon MXD6, polyimides, polyacrylonitrile, polyvinylchloride, polyvinyl dichloride, polyvinylidene chloride, and polyacrylates, ionomers, polysaccharides, such as regenerated cellulose, and silicone, such as rubbers or sealants, other natural or synthetic rubbers, glassine or clay coated paper, paper board or craft paper, and metallized polymer films and vapor deposited metal
  • the aforesaid substrates are likely to be in the form of a film or sheet, though this is not obligatory.
  • the substrate may be a copolymer, a laminate, a coextruded, a blend, a coating or a combination of any of the substrates listed above according to the compatibility of the materials with each other.
  • the substrate may be in the form of a rigid container made from materials such as polyethylene, polypropylene, polystyrene, polyamides, PET, EVOH, or laminates containing such materials.
  • compositions of the present invention can be used for a wide variety of packaging containers, such as pouches, tubes, bottles, vials, bag-in-boxes, stand-up pouches, gable top cartons, thermo-formed trays, brick-packs, boxes, cigarette packs and the like.
  • the present invention is not limited to just packaging applications, and may be used in any application wherein gas, or aroma barrier properties are desired, such as tires, buoyancy aides, inflatable devices generally, etc.
  • any of the foregoing substrates may have a primer or primers applied thereon.
  • the primers are applied to the substrates by methods known in the art such as spray coating, roll coating, slot coating, meniscus coating, immersion coating, and indirect, offset, and reverse gravure coating.
  • Suitable primers include, but are not limited to carbodiimide, polyethylenimine, and silanes, such as N-(2-aminoethyl)-3-aminopropyltrimethoxy silane and aminopropyltriethoxysilane.
  • compositions of the present invention will form films at ambient conditions, optimum results are achieved by heat curing. Generally, the higher the temperature, the faster the coating will solidify.
  • the upper limit to the heating is the temperature at which the substrate will undergo unacceptable distortion. Also, heating will accelerate the rate of hydrolysis of silicon/alkoxy groups and also the rate of condensation of the silicon bonded alkoxy groups with silicon bonded hydroxy groups to form silicon-oxygen-silicon groups.
  • the composition may be dried at room temperature or in an oven at temperatures up to about 140°C, with temperatures of from about 60°C to about 120°C being preferred and temperatures of about 60°C to about 80°C being most preferred. Heating time is temperature and solvent dependent and the coating will reach tack free time in 1 to 10 seconds.
  • the heating step serves to evaporate the solvent when used and accelerate the condensation reaction between Si-OH groups and SiOH/SiOR groups.
  • Various optional additives can be added to the composition to improve various properties. These additives may be added as desired and in any amount as long as they do not reduce the performance of the barrier coatings as illustrated herein. Examples of additives include additional additives as earlier described, antiblock and slip aides such as stearamide, oleamide or polar additives, such as epoxides, polyols, glycidols or polyamines, such as polyethylenimine, and other silanes may be added.
  • Wetting agents such as a polyethoxylated alkyl phenols may also be added.
  • compositions of the present invention are phenol- formaldehyde resins.
  • the solvent employed in all examples was methanol, used as obtained from Fisher.
  • the trimethoxysilylpropyl amine used was obtained as Siquest Al 110 from Witco/OSi, (Greenwich,
  • the N-(2 -amino ethyl)gamma aminopropyl trimethoxysilane used was Dow Corning ® Z6020 (Midland, MI).
  • the pentaerythritol tetraacrylate (PETA, SR 295) was obtained from Sartomer, (Exton, PA).
  • the photoinitiator was Darocur 1173 [titanium bis(ethyl-3- oxobutanoato-O ,O )bis(2-propanolato)-]from CIBA additives (CIBA Additives Division, Tarrytown, NY). All phenolic compounds, and 1,4 cyclohexanediol, were obtained and used as received from the Aldrich Chemical Company (Milwaukee, WI).
  • the coating solutions were applied to either polypropylene or polyethylene terephthalate plastic substrates utilizing a laboratory drawdown rod (from UV Supply Processes, Inc., Chicago, IL).
  • the coated films were then dried and cured in an oven at 60°C for 10 minutes.
  • the oxygen permeability values for each film were measured and recorded in units of cc/square meter per 24 hours (day), "dry” values being measured at 0%> relative humidity and "wet” values at 90% relative humidity utilizing MOCON Oxtran 2/20 Series.
  • the MOCON instruments were obtained from Modern Controls Corporation. Coating thickness was determined by the use of a profiler (Tencor P-1 Long Scan Profilometer, Tencor Instruments, Santa Clara, CA).
  • the polypropylene substrate was corona treated 30 micrometer thick oriented polypropylene film (hereafter referred to as OPP), obtained from UCB Films (product T217/30).
  • OPP corona treated 30 micrometer thick oriented polypropylene film
  • the polyethylene terephthlate (hereafter referred to as PET) film substrate was 48 gauge DuPont Mylar LBT2.
  • PET polyethylene terephthlate
  • the PET base film had a permeability of 144 cc/m /day under dry conditions and 123 cc/m /day under wet conditions.
  • Example 3 A solution of 3 g of Z6020 and 7 g of methanol was prepared and this was coated on the substrate by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 21.7 cc dry and 1339 cc wet and the coating thickness was found to be 1.9 micrometers.
  • Example 3 A 1 1 10/pyrogallol (90- 1 wt) on OPP
  • a solution of 2.1 g of Al 110 and 7 g of methanol was prepared and 0.9 g of pyrogallol was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 157.4 cc dry and 0.3cc wet and the coating thickness was found to be 1.47 micrometers.
  • a solution of 2.1 g of Z6020 and 7g of methanol was prepared and 0.9 g of pyrogallol was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be
  • OTR is oxygen transmission rate or oxygen gas permeability
  • TtlPt T-/P- + Tc/Pc
  • T refers to the thickness, in micrometers
  • P to the permeability coefficient of the composite (Tt, Pt), substrate Ts, Ps), & coating (Tc, Pc).
  • the substrate OPP was measured to be 30 micrometers thick and have an OTR of 1 191 cc/m 2 /day at 0%RH. 3: same as 2 except that the permeability was measured to be I238cc/m /day as measured at 90%RH 4: Permeability expected is that provided by the base film OPP itself .
  • Example 7 various phenolic compounds were combined with amino functional silanes and coated on OPP.
  • hydroquinone was added to Silquest Al 1 10 in the weight ratio indicated.
  • Examples 8-11 dihydroxynaphthalenes were added to Silquest Al 110 in different weight ratios as indicated.
  • hydroquinone was added to Z6020 in the weight ratio indicated.
  • Example 13 1 ,5-dihydroxynaphthalene was added to Z6020 in the weight ratio indicated.
  • a solution of 2.1 g of Al 170 and 7 g of methanol was prepared and 0.9 g of hydroquinone was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 144.7 cc dry and 65.2 cc wet and the coating thickness was found to be 6.9 micrometers.
  • a solution of 2.1 g of Al 170 and 7g of methanol was prepared and 0.9 g of 1,5- dihydroxynaphthalene was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 78.5 cc dry and 1.2 cc wet and the coating thickness was found to be 5.8 micrometers.
  • Example 9 A 1 1 1 /1 -HihyHrovynaphthalene (5Q-50wr) on OPP A solution of 1.5 g of Al 170 and 7 g of methanol was prepared and 1.5 g of 1,5- dihydroxynaphthalene was added with stirring.
  • a solution of 2.1 g of Al 170 and 7 g of methanol was prepared and 0.9 g of 2,7- dihydroxynaphthalene was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 47 cc dry and 2.1 cc wet and the coating thickness was found to be 7.7 micrometers.
  • a solution of 1.5 g of Al 170 and 7g of methanol was prepared and 1.5 g of 2,7- dihydroxynaphthalene was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 50.1 cc dry and 1.6 cc wet and the coating thickness was found to be 3.8 micrometers.
  • Example 12 - 76070 hyHroq ⁇ nnone (70 30wt) on OPP
  • Example 13 - 76070/1 5- ihydro ⁇ ynaphthal ne (7Q-30wt) on OPP
  • a solution of 2.1 g of Z6020 and 7 g of methanol was prepared and 0.9 g of 1,5- dihydroxynaphthalene was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 13.6 cc dry and 20 cc wet and the coating thickness was found to be 4.2 micrometers.
  • OTR is oxygen transmission rate or oxygen gas permeability
  • the substrate OPP was measured to be 30 micrometers thick and have an OTR of 1 191 cc/m /day at 0%RH. same as 2 except that the permeability was measured to be 1238cc/m 2 /,day as measured at 90%RH Permeability expected is that provided by the base film OPP itself DHN is dihydroxynaphthalene
  • Example 14 a solution of Z6020 reacted with 1,5-dihydroxynaphthalene (in 70:30wt) in methanol was evaluated on PET.
  • a solution of 2.14 kg of Z6020 and 11.9 kg of methanol was prepared, then 0.9 kg of 1,5- dihydroxynaphthalene was added with stirring. This was coated on the substrate after 2 hours of mixing by the use of a # 14 drawdown rod. After coating, drying and curing, the permeability was determined to be 6.2 cc dry and 26 cc wet and the coating thickness was found to be 0.37 micrometers.
  • OTR is oxygen transmission rate or oxygen gas permeability
  • T//P* T-/P-- + Tc/Pc
  • T refers to the thickness, in micrometers
  • P to the permeability coefficient of the composite (Tt, Pt), substrate C s, Ps), & coating (Tc, Pc).
  • the substrate PET was measured to be 12 micrometers thick and have an OTR of 144cc/m 2 /day as measured at 0%RH.
  • DHN is dihydroxynaphthalene
  • barrier coating compositions prepared from amino functional silanes and monohydroxy-benzene and monohydroxy-naphthalene were evaluated on OPP.
  • monohydroxy- containing aromatics were added to Silquest Al 110 in different weight ratios as indicated.
  • monohydroxy- containing aromatics were added to Z6020 in different weight ratios as indicated.
  • OTR is oxygen transmission rate or oxygen gas permeability
  • the substrate OPP was measured to be 30 micrometers thick and have an OTR of 1 191 cc/m 2 /day at 0%RH.
  • a solution of 2.1 g of Z6020 and 7 g of methanol was prepared and 0.9 g of 1,4- cyclohexanediol was added with stirring. This was coated on the substrate after 1 hour of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 261.7 cc dry and 1303.3 cc wet and the coating thickness was found to be 1.27 micrometers.
  • OTR is oxygen transmission rate or oxygen gas permeability
  • Examples 22-24 were conducted to further demonstrate the unexpected improvements in barrier properties obtained for the reaction product species from amino functional silanes with phenolic compounds.
  • pyrogallol was added to pentaerythritol tetraacrylate (PET A) in the weight ratios as indicated.
  • PET A pentaerythritol tetraacrylate
  • Pyrogallol is a solid, and cannot be cast into a film alone. Thus, the pyrogallol had to be cast via a coating matrix that would not react or interact with the pyrogallol.
  • An acrylate coating composition was prepared from pentaerythritol tetraacrylate (PETA, SR 295) with and without pyrogallol, and cured with a photoinitiator (Darocur 1173 from CIBA additives) on OPP, for this purpose.
  • PETA pentaerythritol tetraacrylate
  • Darocur 1173 from CIBA additives
  • Example 22 ⁇ PF.TA alone on OPP
  • a solution of 3 g of PETA and 7 g of methanol was prepared and 0.1 g of Darocur 1173 was added 5 minutes prior to coating with stirring. This was coated on the substrate after 30 minutes of mixing by the use of a # 18 drawdown rod.
  • a solution of 2.7 g of PETA and 7 g of methanol was prepared and 0.3 g pyrogallol was added with stirring. After 1 hour , 0.1 g of Darocur 1173 was added and the mixture was coated on the substrate after an additional 30 minutes of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 1164 cc dry and 348 cc wet and the coating thickness was found to be 0.93 micrometers.
  • a solution of 2.1 g of PETA and 7 g of methanol was prepared and 0.9 g pyrogallol was added with stirring. After 1 hour , 0.1 g of Darocur 1173 was added and the mixture was coated on the substrate after an additional 30 minutes of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 553.7 cc dry and 912.5 cc wet and the coating thickness was found to be 4.7 micrometers..
  • OTR is oxygen transmission rate or oxygen gas permeability
  • the substrate OPP was measured to be 30 micrometers thick and have an OTR of 1191 cc/m 2 /day at 0%RH.
  • Examples 25-29 pyrogallol was added to various non-amine functional silanes in the weight ratios as indicated. These experiments were conducted as controls to show the necessity of using an amino functional silane to create the compositions of the present invention. All non-amine functional silanes used were commercial products of Dow Corning Corporation.
  • Example 25 glycidoxypropyltrimethoxy silane/pyrogallol (70-30 wt) on OPP
  • a solution of 2.1 g of methyltrimethoxy silane and 7 g of methanol was prepared and 0.9 g of pyrogallol was added with stirring. After 20 minutes, 0.2 g of Tyzor DC was added. This mixture was coated on the substrate after 10 minutes of mixing by the use of a # 18 drawdown rod. After coating, drying and curing, the permeability was determined to be 1197.9 cc dry and 1322 cc wet and the coating thickness was found to be 0.9 micrometers.
  • Example 27 his(trimethoxysilylethyl)henzene /pyrogallol (70:30 wt) on OPP
  • OTR is oxygen transmission rate or oxygen gas permeability
  • the substrate OPP was measured to be 30 micrometers thick and have an OTR of 1191 cc/m /day at 0%RH. same as 2 except that the permeability was measured to be 1238cc/m /day as measured at 90%RH
  • GTMS is glycidoxypropyltrimethoxy silane
  • MTMS is methyltrimethoxy silane
  • TMSB is bis(trimethoxysilylethyl)benzene
  • VTMS vinyltrimethoxy silane
  • iBTMS is isobutyltrimethoxy silane
  • Permeability expected is that provided by the base film OPP itself

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

Les produits issus d'une réaction entre des silanes à fonction amino et des compositions phénoliques permettent d'obtenir des compositions de revêtement barrière améliorées. Ces compositions sont particulièrement utiles pour réduire la diffusion de gaz à travers des matières d'emballage en polymère organique, tel que du polypropylène, y compris dans des conditions d'humidité relative élevée.
PCT/US2001/005573 2000-03-03 2001-02-21 Composition de revetement barriere produite a partir de silanes a fonction amino et de composes phenoliques WO2001066655A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001238615A AU2001238615A1 (en) 2000-03-03 2001-02-21 Barrier coating compositions from amino functional silanes and phenolic compounds

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US51873900A 2000-03-03 2000-03-03
US09/518,739 2000-03-03

Publications (1)

Publication Number Publication Date
WO2001066655A1 true WO2001066655A1 (fr) 2001-09-13

Family

ID=24065272

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/005573 WO2001066655A1 (fr) 2000-03-03 2001-02-21 Composition de revetement barriere produite a partir de silanes a fonction amino et de composes phenoliques

Country Status (2)

Country Link
AU (1) AU2001238615A1 (fr)
WO (1) WO2001066655A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005040294A1 (fr) * 2003-10-21 2005-05-06 Degussa Ag Composition pour la production d'une couche barriere de gaz
US7208039B2 (en) 2001-09-07 2007-04-24 Imerys Pigments, Inc. Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness
US7413601B2 (en) 2000-08-17 2008-08-19 Imerys Pigments, Inc. Kaolin products and their use
US7442281B2 (en) 2000-08-17 2008-10-28 Imerys Minerals Limited Kaolin products and their production
DE102018108587A1 (de) 2018-04-11 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Barriereschichten sowie Zusammensetzungen für deren Herstellung
WO2019197454A1 (fr) 2018-04-11 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Couches barrières et compositions pour leur production

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341494A (en) * 1964-03-12 1967-09-12 Monsanto Chemicals Silicon-containing polymers and their production
EP0476202A1 (fr) * 1989-04-12 1992-03-25 E.G. Technology Partners, L.P. Revêtement barrière pour films polymères
EP0624464A1 (fr) * 1993-05-14 1994-11-17 Dow Corning Corporation Feuille barrière pour emballage
EP0671450A1 (fr) * 1993-09-29 1995-09-13 Nippon Shokubai Co., Ltd. Composition de traitement de surface et moulage en resine a surface traitee
JPH08165365A (ja) * 1994-12-13 1996-06-25 Nippon Shokubai Co Ltd ガスバリア性積層体
EP0875532A1 (fr) * 1997-04-30 1998-11-04 J.M. Huber Corporation Produit d'argile traitée, procédé de fabrication et utilisation et produits obtenus

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3341494A (en) * 1964-03-12 1967-09-12 Monsanto Chemicals Silicon-containing polymers and their production
EP0476202A1 (fr) * 1989-04-12 1992-03-25 E.G. Technology Partners, L.P. Revêtement barrière pour films polymères
EP0624464A1 (fr) * 1993-05-14 1994-11-17 Dow Corning Corporation Feuille barrière pour emballage
EP0671450A1 (fr) * 1993-09-29 1995-09-13 Nippon Shokubai Co., Ltd. Composition de traitement de surface et moulage en resine a surface traitee
JPH08165365A (ja) * 1994-12-13 1996-06-25 Nippon Shokubai Co Ltd ガスバリア性積層体
EP0875532A1 (fr) * 1997-04-30 1998-11-04 J.M. Huber Corporation Produit d'argile traitée, procédé de fabrication et utilisation et produits obtenus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 10 31 October 1996 (1996-10-31) *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7413601B2 (en) 2000-08-17 2008-08-19 Imerys Pigments, Inc. Kaolin products and their use
US7442281B2 (en) 2000-08-17 2008-10-28 Imerys Minerals Limited Kaolin products and their production
US7208039B2 (en) 2001-09-07 2007-04-24 Imerys Pigments, Inc. Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness
US7214264B2 (en) 2001-09-07 2007-05-08 Imerys Pigments, Inc. Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness
US7226005B2 (en) 2001-09-07 2007-06-05 Imerys Pigments, Inc. Hyperplaty clays and their use in paper coating and filling, methods for making same, and paper products having improved brightness
WO2005040294A1 (fr) * 2003-10-21 2005-05-06 Degussa Ag Composition pour la production d'une couche barriere de gaz
DE10362060B4 (de) * 2003-10-21 2009-07-09 Altana Coatings & Sealants Gmbh Verpackungsmaterial mit einer Barriereschicht für Gase
DE102018108587A1 (de) 2018-04-11 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Barriereschichten sowie Zusammensetzungen für deren Herstellung
WO2019197454A1 (fr) 2018-04-11 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Couches barrières et compositions pour leur production
DE102018108588A1 (de) 2018-04-11 2019-10-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Barriereschichten sowie Zusammensetzungen für deren Herstellung
DE102018108588B4 (de) 2018-04-11 2024-07-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Zusammensetzung, daraus erhaltene Barrierebeschichtung und Verfahren zur Herstellung der Barrierebeschichtung sowie Verwendung der Zusammensetzung

Also Published As

Publication number Publication date
AU2001238615A1 (en) 2001-09-17

Similar Documents

Publication Publication Date Title
CN101367939B (zh) 用于环氧官能有机硅烷的可控水解和缩合以及其与其它有机官能烷氧基硅烷的共缩合的方法
US6686008B1 (en) Silicone/multifunctional acrylate barrier coatings
US6436498B1 (en) Reactive silicone/alkyleneimine barrier laminating adhesives having bis-silane additives
EP1263889A1 (fr) Revetements isolants comprenant des bis-silanes
JP2001514674A (ja) アルキレンイミン／有機バリヤコーティング製造方法とその応用
US6514584B1 (en) Silicone containing laminate adhesive
AU728150B2 (en) Silicone containing laminate adhesive
CA2401395C (fr) Revetements d'isolement dans lesquels des polyacides sont utilises
JP4863024B2 (ja) ガスバリア膜形成用組成物、ガスバリア性積層体及びそれを用いた成形体
JP2742369B2 (ja) ガスバリア用表面処理用組成物および表面処理樹脂成形体
JP3851354B2 (ja) 反応性シリコーン／アルキレンイミンバリヤ積層接着剤とその応用分野
US6423416B1 (en) Barrier coating compositions from bis-aminosilanes and phenolic compounds
JP2009154449A (ja) バリア性フィルム
WO2001066655A1 (fr) Composition de revetement barriere produite a partir de silanes a fonction amino et de composes phenoliques
WO2001066656A2 (fr) Revetements isolants a base de bis-silanes, d'acrylates multifonctionnels et d'acides ethyleniquement insatures
ES2247071T3 (es) Revestimiento alquilemilina/barrera organica que tienen aditivos de bis-silano.
JP2000086765A (ja) 有機ケイ素組成物
WO2001066662A2 (fr) Adhesif lamine possedant des bis-silanes, des acrylates multifonctionnels et des acides ethyleniquement insatures
GB2367556A (en) Polysiloxane barrier coating composition
JP2007098677A (ja) ガスバリアフィルム
JP7447893B2 (ja) バリア材形成用組成物、バリア材及びその製造方法、並びに製品及びその製造方法
GB2360525A (en) Barrier coatings
CN116285475A (zh) 一种疏水二氧化硅及其制备方法
KR20000008569A (ko) 코팅용액 화합물 및 이를 포함하는 코팅제품
JP2002321327A (ja) ガラスコーティングポリオレフィン及びそれを用いて製造した成型品

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE 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 NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

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

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载