WO2021110739A1 - Composition de revêtement antiadhésif - Google Patents

Composition de revêtement antiadhésif Download PDF

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Publication number
WO2021110739A1
WO2021110739A1 PCT/EP2020/084254 EP2020084254W WO2021110739A1 WO 2021110739 A1 WO2021110739 A1 WO 2021110739A1 EP 2020084254 W EP2020084254 W EP 2020084254W WO 2021110739 A1 WO2021110739 A1 WO 2021110739A1
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Prior art keywords
nhr
release coating
coating composition
polymer
range
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PCT/EP2020/084254
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English (en)
Inventor
Xia MENG
Joerg Alexander DIMMER
Yuan Liu
Sukanya NUASAEN
Chu Shi WU
Li Wang
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Basf Se
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Priority to CN202080083516.0A priority Critical patent/CN114746521B/zh
Publication of WO2021110739A1 publication Critical patent/WO2021110739A1/fr

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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention is related to a release coating composition, a method for making such and its application as adhesives.
  • PSAs Pressure sensitive adhesives
  • the PSAs are typically coated onto a "backing” which includes many suitable substrates, such as films, foil, and paper.
  • the adhesive may be coated onto one or both sides of the backing.
  • the side of the backing coated with adhesive is referred to as the "adhesive-coated backing side".
  • the adhesive-coated backing is typically wound onto itself to form a roll. Therefore, it is advantageous for the adhesive layer to have a different affinity for one side of the tape than that of the opposite side of the tape.
  • Such differential affinity is typically achieved by two methods: the primer coating method and the release coating method.
  • the primer coating method only one side of the backing is coated. A primer layer that can strongly bond to the backing is applied first. Then, an adhesive that has a low affinity for the backing but a high affinity for the primer layer is coated onto the primer layer. Upon rolling, the adhesive adheres less strongly to the adhesive- free backing side.
  • both sides of the tape are coated: a release coating is applied to the adhesive-free side of the tape and an adhesive is applied to the other side of the tape.
  • the release coating has a strong affinity for the backing but a weak affinity for the adhesive. And, the release coating method is more flexible and can be used on various backings and in combination with different types of adhesives.
  • Release coating materials should also have the following characteristics. They should maintain low release-force so that the tape can be easily peeled off from the tape roll. In addition, it is desirable that the tape provides sufficient (high) re-adhesion after unwinding the role. After longer storage time (i.e. at higher temperature and higher humidity) tapes tend to provide lower re-adhesion than when tested directly after winding or after short storage times of the roll (also noted as “aging”).
  • the release coating materials shall have minimum “aging”. This “aging” of the adhesive can have different reasons. For example, the adhesive can show oxidative degradation in contact with air. Another important reason can be low molecular weight materials present in the release coating that tend to migrate into the adhesive layer.
  • water resistance is another a desirable property, especially when the adhesive material on the other side of the tape is water-based. Because water may penetrate the backing material. Since masking tapes are used to protect surfaces from false painting during a paint job and the paints used are very often water based, a sufficient water resistance is necessary to avoid water penetrating through the paper. Water penetration can then lead to a weakening of the bonding of the tape to the surface or even a false painting.
  • release agents including long chain alkyl carboxylic acids and esters, polyacrylates, polyurethanes, silicone polymers, fluorinated polymers and waxes. Many of the examples are discussed in “Release Coatings for Pressure Sensitive Adhesives,” Adhesion Science and Engineering — Surfaces, Chemistry, and Applications, pp. 535-71 (2002).
  • WO2015153484 discloses a polymer synthesized with monomers containing pendent groups that include at least two (thio)carbonyl groups and multiple additional heteroatoms.
  • the polymer can be used as a release coating or a release agent in a low adhesion backsize, either of which can be provided in VOC-free form and which exhibits excellent release performance even after aging under high humidity.
  • no water resistance data is provided.
  • the polymer is difficult to make and expensive, since special monomers are applied.
  • W02004085561 discloses a block-copolymers containing polysilsoxane blocks and polyoxyalkylene blocks.
  • the polymer has low release force. But, there is no data showing water resistance property. And, block co- polymers are usually difficult to make as well.
  • silicon material often migrates into the adhesives when they are in contact with adhesives and such migration will likely deteriorate the performance of the adhesive.
  • WO2010012787 discloses a composition used to form a water-repellent and release coating for a flexible support made of paper or of polymer.
  • the composition comprises crosslinking polyorganosiloxanes (POSs) bearing oSi-H units and unsaturated, preferably oSi-Vi, vinyl-containing POSs, capable of reacting with the crosslinker by polyaddition, in the presence of platinum in order to form the crosslinked release coating on the flexible support.
  • POSs polyorganosiloxanes
  • unsaturated preferably oSi-Vi, vinyl-containing POSs
  • One objective of the present invention is to provide a release coating composition comprising:
  • silicone additive wherein the silicone additive is represented by formula (I) R 1 a R 2 bSiO(4-a-b)/2 formula (I), wherein R 1 is monovalent hydrocarbon moiety having 1 to 8 carbons;
  • R 2 is a group of the formula: -R 3 NH 2 , -R 3 NHR 4 NH 2 , -R 3 (NHR 4 ) g NH 2 , -R 3 NHR 5 , - R 3 NHR 4 NHR 5 , -R 3 (NHR 4 ) g NHR 5 , -R 3 NHR 4 NR 5 R 5 , -R 3 (NHR 4 ) g NR 5 R 5 - R 3 N(R 4 NH 2 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4
  • multi-functional compound 0.2-10 wt%, based on the total dry weight of the release coating composition, multi-functional compound, wherein the multi-functional compound is at least one selected from the group consisting of an isocyanate compound, an epoxy compound, an aziridine compound and a metal chelate compound.
  • Another objective of the present invention is to provide a process to make the release coating composition, comprising the abovementioned contents by blending them either at room temperature or at elevated temperature by stirring.
  • a third object objective of the present invention is to provide an adhesive article containing the release coating composition.
  • polymer or “polymers”, as used herein, includes both homopolymer(s), that is, polymers prepared from a single reactive compound, and copolymer(s), that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
  • copolymer that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
  • multi-functional compound means a compound containing at least two reactive moieties.
  • One objective of the present invention is to provide a release coating composition comprising:
  • silicone additive wherein the silicone additive is represented by formula (I) R 1 a R 2 bSiO(4-a-b)/2 formula (I), wherein R 1 is monovalent hydrocarbon moiety having 1 to 8 carbons;
  • R 2 is a group of the formula: -R 3 NH 2 , -R 3 NHR 4 NH 2 , -R 3 (NHR 4 ) g NH 2 , -R 3 NHR 5 , - R 3 NHR 4 NHR 5 , -R 3 (NHR 4 ) g NHR 5 , -R 3 NHR 4 NR 5 R 5 , -R 3 (NHR 4 ) g NR 5 R 5 - R 3 N(R 4 NH 2 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4
  • multi-functional compound 0.2-10 wt%, based on the total dry weight of the release coating composition, multi-functional compound, wherein the multi-functional compound is at least one selected from the group consisting of an epoxy compound, an isocyanate compound, an aziridine compound and a metal chelate compound.
  • the at least one hydrophobic monoethylenically unsaturated monomer a) may be selected from, but not limited to, (meth)acrylate monomers, (meth)acrylonitrile monomers, styrene monomers, vinyl alkanoate monomers, monoethylenically unsaturated di-and tricarboxylic ester monomers or any mixture thereof.
  • the (meth)acrylate monomers may be Ci-Ci9-alkyl (meth)acrylates, for example, but not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate (i.e.
  • the styrene monomers may be unsubstituted styrene or C1-C6-alkyl substituted styrenes, for example, but not limited to, styrene, a-methylstyrene, ortho-, meta- and para-methylstyrene, ortho-, meta- and para-ethylstyrene, o,p- dimethylstyrene, o,r-diethylstyrene, ispropylstyrene, o-methyl-p-isopropylstyrene or any mixture thereof.
  • the vinyl alkanoate monomers may be vinyl esters of C2-C11- alkanoic acids, for example, but not limited to, vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl versatate or a mixture thereof.
  • the monoethylenically unsaturated di-and tricarboxylic ester monomers may be full esters of monoethylenically unsaturated di-and tricarboxylic acids, for example, but not limited to, diethyl maleate, dimethyl fumarate, ethyl methyl itaconate, or any mixture thereof.
  • the hydrophobic monoethylenically unsaturated monomer a) may be methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, styrene, vinyl acetate or a mixture thereof.
  • the hydrophobic monomer may account for, based on the total weight of the polymer, at least 85 wt%, preferably at least 90 wt%, more preferably at least 95% by weight.
  • the at least one hydrophilic monoethylenically unsaturated monomer b) may be monoethylenically unsaturated monomers containing at least one functional group selected from, but not limited to, a group consisting of carboxyl, carboxylic anhydride, sulfonic acid, phosphoric acid, hydroxyl and amide.
  • the hydrophilic monoethylenically unsaturated monomer b) includes, but not limited to, monoethylenically unsaturated carboxylic acids, such as (meth)acrylic acid, itaconic acid, fumaric acid, citraconic acid, sorbic acid, cinnamic acid, glutaconic acid and maleic acid; monoethylenically unsaturated carboxylic anhydride, such as itaconic acid anhydride, fumaric acid anhydride, citraconic acid anhydride, sorbic acid anhydride, cinnamic acid anhydride, glutaconic acid anhydride and maleic acid anhydride; monoethylenically unsaturated amides, especially N-alkylolamides, such as (meth)acrylamide, N-methylol (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide; and hydroxyalkyl esters of monoethylenically unsaturated carboxylic acids, such as
  • acrylic acid, methacrylic acid, itaconic acid, acrylamide, methacrylamide or a mixture thereof is preferred as the at least one hydrophilic monoethylenically unsaturated monomer b).
  • the hydrophilic monomer may account for, based on the total weight of the polymer, at least 0.2 wt% and no more than 15 wt%, preferably at least 0.5 wt% and no more than 10 wt%, and more preferably at least 1 wt% and no more than 5 wt%.
  • the polymer may be synthesized with additional one or more crosslinking monomers c).
  • the crosslinking monomers can be chosen from di- or poly-isocyanates, polyaziridines, polycarbodiimide, polyoxazolines, glyoxals, triols, epoxy molecules, organic silanes, carbamates, diamines and triamines, hydrazides, carbodiimides and multi-ethylenically unsaturated monomers.
  • suitable crosslinking monomers include, but not limited to, glycidyl (meth)acrylate, N- methylol(meth)acrylamide, (isobutoxymethyl)acrylamide, vinyltrialkoxysilanes such as vinyltrimethoxysilane; alkylvinyldialkoxysilanes such as dimethoxymethylvinylsilane; (meth)acryloxyalkyltrialkoxysilanes such as (meth)acryloxyethyltrimethoxysilane, (3- acryloxypropyl)trimethoxysilane and (3-methacryloxypropyl)trimethoxysilane , allyl methacrylate, diallyl phthalate, 1,4-butylene glycol dimethacrylate, 1 ,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,4-butantediol diacrylate, divinyl benzene or any mixture thereof
  • the crosslinker can be added in an amount of, based on the total weight of the polymer, no more than 5 wt%, preferably no more than 3 wt%, and more preferably no more than 1 wt%.
  • the polymer may be synthesized with the presence of at least one chain transfer agent.
  • the chain transfer agent is frequently used to regulate the molecular weight of polymers.
  • the chain transfer agent may include compounds containing a thiol group, for example mercaptans, such as without limitation, ethyl mercaptan, n- propyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, t-butyl mercaptan, n-amyl mercaptan, isoamyl mercaptan, t-amyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, mercapto carboxylic acids and their esters, such as without limitation, 2-ethy
  • the chain transfer agent may be added in an amount of, based on the total weight of the polymer, no more than 5 wt%, preferably no more than 2 wt%, and more preferably no more than 1 wt%.
  • the polymer according to the present invention may have a weight-average molecular weight (Mw) in the range of 5,000 to 3,000,000, preferably from 10,000 to 100,000, more preferably from 15,000 to 80,000, as measured by Gel Permeation Chromatography (GPC) against polystyrene standard in tetrahydrofuran.
  • Mw weight-average molecular weight
  • the polymer according to the present invention may have a particle size in the range of 100 to 400 nm, preferably in the range of 150 to 350 nm, and more preferably in the range of 180 to 300 nm, as measured by Dynamic Light Scattering (DLS).
  • DLS Dynamic Light Scattering
  • the silicone additive is represented by formula (I): R 1 a R 2 bSiO(4-a-b)/2 formula (I), wherein R 1 is monovalent hydrocarbon moiety having 1 to 8 carbons;
  • R 2 is a group of the formula: -R 3 NH 2 , -R 3 NHR 4 NH 2 , -R 3 (NHR 4 ) g NH 2 , -R 3 NHR 5 , -R 3 NHR 4 NHR 5 , - R 3 (NHR 4 ) g NHR 5 , -R 3 NHR 4 NR 5 R 5 , -R 3 (NHR 4 ) g NR 5 R 5 -R 3 N(R 4 NH 2 )(R 4 NH 2 ), -
  • R 1 is a substituted or unsubstituted monovalent hydrocarbon moiety having 1 to 8 carbon atoms and attached to the silicon atom in the molecule.
  • the hydrocarbon moiety include, but not limited to, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and octyl groups, cycloalkyl groups such as cyclopentyl and cyclohexyl groups, a phenyl group, and halogenated alkyl groups such as trifluoropropyl and nonafluorohexyl groups, with the methyl group being preferred.
  • R 2 is a group of the formula: -R 3 NH 2 , -R 3 NHR 4 NH 2 , -R 3 (NHR 4 ) g NH 2 , -R 3 NHR 5 , - R 3 NHR 4 NHR 5 , -R 3 (NHR 4 ) g NHR 5 , -R 3 NHR 4 NR 5 R 5 , -R 3 (NHR 4 ) g NR 5 R 5 R 3 N(R 4 NH 2 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4 NH 2 ), -R 3 N(R 4 NHR 5 )(R 4 NHR 5 ) or -
  • R 2 include, but not limited to, - (CH 2 ) 3 NH 2 , -(CH 2 ) 3 NH(CH 2 ) 2 NH 2 , -(CH 2 ) 3 NH(CH 2 ) 2 NH(CH 2 ) 2 NH 2 ,
  • g is a positive integer number in the range of 2 to 5, and more preferably g equals to 2.
  • the silicone additive is represented by formula (II) wherein R 6 and R 7 are identical or different alkyl group; R 8 has the same definition as R 2 in formula (I); m is an integer in the range of 8 to 3,000; n is an integer in the range of 1 to 1,000.
  • R 6 and R 7 can be independently -CH 3 or -CH 2 CH 3
  • R 8 is - CH 2 CH 2 NH 2 or -CH 2 CH 2 NHCH 2 CH 2 NH 2 ; preferably m is an integer in the range of 8 to 1,000 and n is an integer in the range of 1 to 250. More preferably, R 6 and R 7 are -CH 3
  • R 8 is -CH 2 CH 2 NHCH 2 CH 2 NH 2 ; m is an integer in the range of 8 to 200 and n is an integer in the range of 1 to 50.
  • the specific silicone additive may be obtained from commercial source, such as POLON-MF51 and POLON-MF14 from ShinEtsu Silicone emulsions or BLUESIL EMULSION 705 HV from Elkem.
  • the silicon additive may have an amine equivalent of no more than 10,000 g/mol and a viscosity in the range of 500 mm 2 /s to 20,000 mm 2 /s.
  • the silicon additive may have an amine equivalent of no more than 5,000 g/mol and a viscosity in the range of 1,000 mm 2 /s to 15,000 mm 2 /s.
  • the silicon additive may have an amine equivalent of no more than 3,000 g/mol and a viscosity in the range of 1,000 mm 2 /s to 10,000 mm 2 /s.
  • the silicon additive may be added in amount of 0.1-10 wt%, based on the total dry weight of the release coating composition.
  • the silicon additive may be added in amount of 0.8-8 wt%, based on the total dry weight of the release coating composition. More preferably, the silicon additive may be added in amount of 1-5 wt%, based on the total dry weight of the release coating composition.
  • the multi-functional compound C) generally serves the function of crosslinking. It is at least one selected from the group consisting of an epoxy compound, an isocyanate compound, an aziridine compound and a metal chelate compound.
  • Suitable examples of the epoxy compound include, but not limited to, those that contain glycidyl or epoxidized compounds having at least two epoxy groups.
  • glycidyl-containing compounds include aliphatic diglycidyls such as an alkyl diglycidyl ether or an alkyl diglycidyl ester, or aromatic diglycidyls such as bisphenol diglycidyl ether.
  • glycidyl and epoxide compounds include without limitation, bisphenol A diglycidyl ether, bisphenol A ethoxylate diglycidyl ether, bisphenol A propoxylate diglycidyl ether, bisphenol F diglycidyl ether, bisphenol F ethoxylate diglycidyl ether, bisphenol F propoxylate diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol) diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, diglycidyl 1, 2,
  • isocyanate compound examples include, but not limited to, aliphatic polyisocyanates such as 1 ,2-ethylene diisocyanate, 1 ,4-butylene diisocyanate, 1,6- hexamethylene diisocyanate, etc.; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.; aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, xylylene diisocyanate, etc.
  • aliphatic polyisocyanates such as 1 ,2-ethylene diisocyanate, 1 ,4-butylene diisocyanate, 1,6- hexamethylene diisocyanate, etc
  • aziridine compound examples include, but not limited to, N,N'-toluene-2,4-bis(1- aziridinecarboxide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxide), triethylene melamine, bisisoprothaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, etc.
  • Examples of the metal chelate compound may be the one in which a multivalent metal element such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and vanadium is coordinated with acetylacetone or ethyl acetoacetate.
  • a multivalent metal element such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and vanadium is coordinated with acetylacetone or ethyl acetoacetate.
  • the multi-functional compound may be trimethylolpropane triglycidyl ether, or trimethyllethane trigycidyl ether.
  • the multi-functional compound may be presented in an amount of, based on the total weight of the release coating composition, at least 0.2 wt% and no more than 10 wt%, preferably at least 0.5 wt% and no more than 10 wt%, and more preferably at least 1 wt% and no more than 5 wt%.
  • the release coating compositions of the present invention further include from about 1 wt% to about 15 wt%, based on the total weight of the release coating composition, a release promoting additive.
  • release promoting additives include, but are not limited to, anionic surfactants, cationic surfactants, zwitter-ionic surfactants, non-ionic surfactants, and mixtures thereof.
  • these surfactants contain C8-C22 alkyl chains, C8-C22 alkyl substituted aryls, silicon atoms, fluorine atoms, and combinations thereof, as described in “Handbook of Pressure-Sensitive Adhesive Technology,” ed. D.
  • Non-limiting examples of useful release promoting additives include N-alkyl sulfosuccinamates, dialkyl sulfosuccinates, alkyl sulfates and sulfonates, alkyl-polyalkyleneoxidesulfates, alkyl- aryl-polyalkyleneoxidesulfates, alkyl-aryl-sulfonates, alkylpolyalkyleneoxides, alkyl- aryl-polyalkyleneoxides, block copolymers of alkyloxides, and mixtures thereof.
  • release promoting additives useful herein include, but are not limited to, Aerosol A-22 (manufactured by Cytec Industries Inc., located in West Paterson, N.J.), lconol OP40 and Pluronic 62 (both manufactured by BASF Corporation, Mount Olive, N.J.), Ammonyx SO (manufactured by Stepan Company, Northfield, III.) and mixtures thereof.
  • pH modifiers such as ammonium hydroxide, sodium hydroxide, and so on may be used to adjust the pH of the latex depending on the application.
  • Coalescing agents may be admixed with the latex in order to ensure adequate coverage of a coating thereof onto a substrate.
  • Useful coalescing agents include but are not limited to N-methyl pyrrolidone, the CarbitolTM series of poly(ethylene glycol) alkyl ethers (available from Union Carbide), and mixtures thereof.
  • Rheology modifiers may be added as well to improve the theological properties of the latex.
  • Useful rheology modifiers include but are not limited to Kelzan ® series (available from Kelco), hydroxyethyl cellulose, UCAR ® Polyphobe series (available from Union Carbide), and mixtures thereof. Defoamers can also be added in the applications in which foam is generated. Useful defoamers include but are not limited to: Surfynol ® series (available from Air Products), Antifoam H-10 Emulsion (available from Dow Corning), and mixtures thereof. In addition, other optional adjuvants may be added, such as colorants, fillers, stabilizers, etc.
  • Another objective of the present invention is to provide a process to make the release coating composition.
  • the polymer according to the present invention may be prepared by a single-stage or a multi-stage polymerization process.
  • all the monomers are polymerized in one stage.
  • the process includes at least two stages: polymerization of the first-stage monomers resulting the first-stage polymer and subsequent the second-stage monomers resulting the second stage polymer.
  • Multi-stage polymerization techniques well known in the art may be used for preparing the aqueous multi-stage copolymer dispersion according to the present invention, such as the process disclosed in US2728804A, US20170096575A1, US20170355802A1, etc.
  • the polymer may be synthesized according to the method described in WO2011154920.
  • a first polymer dispersed in water is prepared by free-radical emulsion polymerization with first-stage ethylenically unsaturated, free-radically polymerizable monomer composition.
  • a polymer dispersion is prepared in aqueous medium in the presence of the first polymer by free-radical emulsion polymerization of a second-stage monomer composition, which is different from the first-stage monomer composition.
  • the monomers of the first-stage monomer composition comprise at least one monomer having at least one acid group, in an amount of at least 0.1 part by weight, based on the total amount of monomers of the first and second-stages.
  • the acid groups of the first polymer are neutralized to an extent such that the pH of the polymer dispersion at the end of the second stage is greater than 5, preferably greater than or equal to 5.5.
  • the principle of the process is based on the preferably seed-controlled formation of small polymer particles in aqueous dispersion in a first polymerization stage by free- radical polymerization of a first-stage monomer composition comprising at least one ethylenically unsaturated monomer having at least one acid group.
  • the acid groups of the first polymer are neutralized only during the polymerization of the second stage.
  • the second polymer is formed under the “protection” of the polymer particles formed in the first stage.
  • the process is called “protective colloidal polymerization”. More specifically, in a first stage polymerization, a first polymer dispersed in water is prepared by free-radical emulsion polymerization.
  • the first polymer is prepared from a first reactant composition comprising ethylenically unsaturated, free-radically polymerizable monomers, where the monomers of the first stage comprise at least one monomer having at least one acid group, in an amount of at least 0.1 part by weight, based on the total amount of monomers of the first and second stages.
  • a polymer dispersion is prepared in aqueous medium in the presence of the first polymer by free-radical emulsion polymerization of a second reactant composition, which is different from the first composition and comprises ethylenically unsaturated, free-radically polymerizable monomers.
  • the acid groups of the first polymer are only neutralized during the polymerization of the second stage by means of adding neutralizing agent in parallel to the feeding of the second reactant composition.
  • polymerization of the first stage takes place at a pH of less than 5 and, during the polymerization of the second stage, the acid groups of the first polymer are neutralized to an extent such that the pH of the polymer dispersion at the end of the second stage is greater than 5.
  • the weight ratio of monomers containing acid groups to monomers without acid groups in the monomer mixture of the first polymerization stage is preferably in the range from 0.5:99.5 to 30:70, preferably from 1 :99 to 20:80 or from 5:95 to 15:85.
  • the weight ratio of the amount of the monomers used in the first stage to the amount of the monomers used in the second stage is preferably from 5:95 to 50:50, more preferably from 5:95 to 40:60 and most preferably from 10:90 to 30:70.
  • the amount of emulsifier shall be, based on the total weight of the polymer emulsion, less than 1 wt%, preferably less than 0.5 wt%, more preferably less than 0.3 wt% and most preferably less than 0.2 wt%.
  • the release coating composition may be formulated according many methods known to the skilled person in the art.
  • the resulted polymer may be formulated with the silicone additive, the multi-function compound and other additive, if presented, by mixing in a mixer.
  • a third objective of the present invention is to provide an adhesive article containing the release coating composition.
  • the release coating composition according to the present invention may be used many solid substrates, such as a sheet, a fiber or a shaped object.
  • the release coating composition according to the present invention may be applied on substrates that are typically used for pressure-sensitive adhesives.
  • substrates include, but are not limited to, paper, metal sheets and foils, nonwoven fabrics, cellophane, films of thermoplastic resins such as polyesters, polyamides, polyolefins, polycarbonates, polyvinyl chloride, and acetate films.
  • the desired concentration of the release coating composition depends on the specific application.
  • the release coating composition may be diluted with water to a lower concentration or concentrated by evaporating some water.
  • the release coating composition may be applied to a suitable substrate by means of conventional coating techniques such as wire-wound rod, direct gravure, offset gravure, reverse roll, chute or slot die, air-knife and trailing blade coating.
  • conventional coating techniques such as wire-wound rod, direct gravure, offset gravure, reverse roll, chute or slot die, air-knife and trailing blade coating.
  • the resultant coatings provide effective release for a wide variety of conventional pressure-sensitive adhesives, such as natural rubber-based, acrylic and other synthetic elastomeric materials.
  • This invention provides a coated sheet material wherein the release coating is on one side of the sheet and the adhesive is on the other side.
  • the invention further provides a coated sheet material wherein the adhesive is a normally tacky and pressure sensitive adhesive, for example, cured hot melts, tacky pressure sensitive adhesives, post-curable adhesives, and microsphere adhesives and coatings.
  • the invention also provides a stack of superimposed sheets of coated sheet material, the pressure- sensitive adhesive on each sheet being in contact with the release coating on an immediately adjacent sheet.
  • Disponil ® FES 77 from BASF, Fatty alcohol polyglycol ether sulphate, sodium salt.
  • Golpanol ® VS from BASF, sodium vinyl sulfonate.
  • Aerosol ® 22 from Solvay, Tetrasodium N-(1,2-dicarboxyethyl)-N octadecyl sulfosuccinamate.
  • TTG trimethylolpropane triglycidyl ether.
  • ERISYSTM GE31 from CVC Thermoset Specialties, triglycidyl ether of trimethylolethane, (hereinafter noted as GE31).
  • Bayhydur ® BL2867 from Covestro, reactive, blocked, aliphatic polyisocyanate, (hereinafter noted as BL2867).
  • BLUESIL EMULSION 705 HV from Elkem, CAS No. 71750-79-3, (hereinafter noted as 705 HV).
  • TWEEN ® 80 from Sigma-Aldrich, CAS No. 9005-65-6.
  • the weight average molecular weight was measured by Gel Permeation Chromatography (GPC) against polystyrene standard in THF.
  • the average particle diameter as referred herein relates to the Z average particle diameter as determined by means dynamic light scattering (DLS).
  • the measurement method is described in the ISO 13321 : 1996 standard.
  • a sample of the aqueous polymer latex will be diluted and the dilution will be analysed.
  • the aqueous dilution may have a polymer concentration in the range from 0.001 to 0.5 % by weight, depending on the particle size. For most purposes, a proper concentration will be 0.01 % by weight. However, higher or lower concentrations may be used to achieve an optimum signal/noise ratio.
  • the dilution can be achieved by addition of the polymer latex to water or an aqueous solution of a surfactant in order to avoid flocculation.
  • a surfactant in order to avoid flocculation.
  • dilution is performed by using a 0.1 % by weight aqueous solution of a non-ionic emulsifier, e.g. an ethoxylated C16/C18 alkanol (degree of ethoxylation of 18), as a diluent.
  • a non-ionic emulsifier e.g. an ethoxylated C16/C18 alkanol (degree of ethoxylation of 18
  • measurement temperature 20.0°C measurement time 120 seconds (6 cycles each of 20 s); scattering angle 173°; wavelength laser 633 nm (HeNe); refractive index of medium 1 .332 (aqueous); viscosity 0.9546 mPa-s.
  • the measurement gives an average value of the second order cumulant analysis (mean of fits), i.e. Z average.
  • the "mean of fits" is an average, intensity-weighted hydrodynamic particle diameter in nm.
  • a solution containing 40.5g t-butyl hydroperoxide aqueous solution (5 wt%) and 57.8g sodium bisulfite aqueous solution (3.5 wt%) were fed into the reactor from a different neck in 35min.
  • the reaction mixture was allowed to reach room temperature.
  • the solid content of D2 was controlled to be 51 wt% by adjusting the amount of water and the particle size measured by DLS is 280 nm.
  • the release coating formulations were obtained by mixing the components one by one under stirring.
  • the composition of each coating formulations are listed in Table 1.
  • RF(age) refers to the specimen stored at condition (II).
  • the tapes were peeled-off from the coated paper after different storage conditions to measure the release forces are used to the measure the Re-adhesion (RA). They are re-applied with adhesive side onto stainless steel panels and rolled onto the panel using a 1kg roller, rolling back and forth for 3 cycles. After 20 min dwell time the peel- resistance is measured at 180° and 300mm/min (in accordance to FINAT FTM1). The obtained values are the Re-adhesions (RA).
  • RA(ini) refers to the tape removed from the specimen stored at condition (I) and RA(age) refers to the tape removed from the specimen stored at condition (II)
  • WPT Water Penetration Time
  • release coating formulations produced with the addition of both amino silicon additives and multi functional compounds according to the present invention can have a balance performance between high water resistance (i.e. longer WPT time) and low release force (RF) after aging.
  • the release coating formulations can also have high re-adhesion either after 24hrs (RAini) and after aging RA(age).
  • RAini a traditional polymer dispersion, other than a dispersion synthesized with “protective colloidal polymerization” method, is used, both the water resistance and release force properties are insufficient.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement antiadhésif, un procédé de fabrication de celle-ci et son application dans un article adhésif tel que des bandes de masquage. Une composition de revêtement antiadhésif selon l'invention présente des performances équilibrées entre une résistance élevée à l'eau (c'est-à-dire un temps WPT plus long), une faible force de libération (RF) après vieillissement, une réadhérence élevée soit après 24 heures (RAini) et/ou après vieillissement RA (âge).
PCT/EP2020/084254 2019-12-06 2020-12-02 Composition de revêtement antiadhésif WO2021110739A1 (fr)

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EP0189978A1 (fr) * 1985-01-10 1986-08-06 United Merchants and Manufacturers, Inc. Compositions de revêtement anti-adhésives à base aqueuse
WO1997035930A1 (fr) * 1996-03-26 1997-10-02 Minnesota Mining And Manufacturing Company Compositions a polymerisation radicalaire pouvant former un revetment a l'aide d'un procede electrostatique
WO2001014150A1 (fr) * 1999-08-24 2001-03-01 3M Innovative Properties Company Revetement de decollement permettant l'impression numerique et construction de formule utilisant ce revetement
WO2004085561A2 (fr) 2003-03-21 2004-10-07 Omnova Solutions Inc. Composition faiblement adhesive
WO2010012787A2 (fr) 2008-07-30 2010-02-04 Bluestar Silicones France Sas Composition silicone d'enduction d'un support flexible destine a former un revetement reticule ayant un accrochage, une resistance mecanique et une reactivite accrus
WO2011154920A1 (fr) 2010-06-11 2011-12-15 Basf Se Préparation en plusieurs étapes de dispersions aqueuses de polymères pour la production de films composites
WO2015153484A1 (fr) 2014-03-30 2015-10-08 Omnova Solutions Inc. Polymères à faible teneur en cov présentant des propriétés anti-adhésives
US20170096575A1 (en) 2014-06-20 2017-04-06 Rohm And Haas Company Multi-stage latex polymers, process of making the same, and coating compositions made thereof
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US2728804A (en) 1952-11-01 1955-12-27 Exxon Research Engineering Co Multi-stage polymerization process
EP0189978A1 (fr) * 1985-01-10 1986-08-06 United Merchants and Manufacturers, Inc. Compositions de revêtement anti-adhésives à base aqueuse
WO1997035930A1 (fr) * 1996-03-26 1997-10-02 Minnesota Mining And Manufacturing Company Compositions a polymerisation radicalaire pouvant former un revetment a l'aide d'un procede electrostatique
WO2001014150A1 (fr) * 1999-08-24 2001-03-01 3M Innovative Properties Company Revetement de decollement permettant l'impression numerique et construction de formule utilisant ce revetement
WO2004085561A2 (fr) 2003-03-21 2004-10-07 Omnova Solutions Inc. Composition faiblement adhesive
WO2010012787A2 (fr) 2008-07-30 2010-02-04 Bluestar Silicones France Sas Composition silicone d'enduction d'un support flexible destine a former un revetement reticule ayant un accrochage, une resistance mecanique et une reactivite accrus
WO2011154920A1 (fr) 2010-06-11 2011-12-15 Basf Se Préparation en plusieurs étapes de dispersions aqueuses de polymères pour la production de films composites
WO2015153484A1 (fr) 2014-03-30 2015-10-08 Omnova Solutions Inc. Polymères à faible teneur en cov présentant des propriétés anti-adhésives
US20170096575A1 (en) 2014-06-20 2017-04-06 Rohm And Haas Company Multi-stage latex polymers, process of making the same, and coating compositions made thereof
US20170355802A1 (en) 2014-11-24 2017-12-14 Arkema France Process of manufacturing a multistage polymer, its composition, its use and composition comprising it

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"Release Coatings for Pressure Sensitive Adhesives", ADHESION SCIENCE AND ENGINEERING-SURFACES, CHEMISTRY, AND APPLICATIONS, 2002, pages 535 - 71
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