WO2004085561A2 - Composition faiblement adhesive - Google Patents

Composition faiblement adhesive Download PDF

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Publication number
WO2004085561A2
WO2004085561A2 PCT/US2004/007550 US2004007550W WO2004085561A2 WO 2004085561 A2 WO2004085561 A2 WO 2004085561A2 US 2004007550 W US2004007550 W US 2004007550W WO 2004085561 A2 WO2004085561 A2 WO 2004085561A2
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WO
WIPO (PCT)
Prior art keywords
block
composition
copolymer
group
independently
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Application number
PCT/US2004/007550
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English (en)
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WO2004085561B1 (fr
WO2004085561A3 (fr
Inventor
Douglas Harper
Robin Righettini
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Omnova Solutions Inc.
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Publication of WO2004085561A2 publication Critical patent/WO2004085561A2/fr
Publication of WO2004085561A3 publication Critical patent/WO2004085561A3/fr
Publication of WO2004085561B1 publication Critical patent/WO2004085561B1/fr

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Classifications

    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer
    • C09J2453/005—Presence of block copolymer in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Definitions

  • the present invention relates to release coatings, coated products, and related methods that include block copolymers, particularly in adhesive and tape constructions.
  • PSA Pressure-sensitive adhesive
  • PSAs have a multitude of applications and different types of product embodiments such as masking tapes, labels, and bandages. PSAs adhere to many surfaces with no more than applied finger pressure. The adhesive is typically coated onto one or both sides of a substrate.
  • PSAs include, but are not limited to, natural rubber adhesives; butyl rubber; vinyl ether; acrylic; solvent-based rubber adhesives including cis-1 ,4-polyisoprene; block copolymer adhesives including SBS and SIS block copolymers; hot-melt block copolymers; synthetic rubbers including SBR; silicone based PSAs; and the like.
  • PSA tapes often are wound onto a roll.
  • a PSA product e.g., a label or a stamp
  • a release liner To provide such adhesion of a PSA to a non- adhesive coated surface, the non-adhesive coated surface is commonly coated with a release coating, also called a low adhesion backsize (LAB).
  • LAB low adhesion backsize
  • a release coating allows the adhesive layer to release from the non-adhesive surface but does not transfer to the adhesive layer during that process.
  • Release coatings may be applied to a substrate by various techniques including solvent and water coating techniques. Water-based compositions are especially preferred due to low odor, low flammability, and low toxicity.
  • the invention relates to release agents, liquid backsize compositions, and release coatings (i.e., LAB coatings) containing a block copolymer that includes a polysiloxane block and one or more polyoxyalkylene blocks.
  • Preferred block copolymers can have polyoxyalkylene blocks that include a non-hydroxyl terminal group, e.g., a polyoxyalkylene block terminal group can be alkyl, aryl, or a functional derivative of a carboxylic acid.
  • a polyoxyalkylene block can be "end-capped" to include a non- hydroxy terminal group, preferably an organic group that improves release properties of the block copolymer compared to the block copolymer with a terminal hydroxy group at the polyoxyalkylene block.
  • Particularly preferred terminal groups can include ester and carbamate groups such as alkyl esters, aryl esters such as benzoate esters, alkyl carbamates, and aryl carbamates.
  • Examples of preferred block copolymers include those of the formula:
  • each E preferably can be an end group that is not hydroxyl.
  • each E can be a terminal group that improves release performance of the block copolymer compared to the block copolymer having a hydroxyl terminal group.
  • terminal groups may include alkyl (e.g. C C 8 alkyl), aryl, and functional derivatives of carboxylic acid such as esters, amides, urethanes (carbamates), ureas, and carbonate esters.
  • Preferred E terminal groups include esters and carbamates, e.g., alkyl esters, aromatic esters, alkyl carbamates, and aromatic carbamates.
  • each L independently can be a linkage such as a single bond, a lower alkoxylene (e.g., a C 2 -C 5 alkoxylene), or a lower alkylene (e.g., a C 2 -C 5 alkylene); each R can be independently selected from the group consisting of alkyl or aryl groups, preferably methyl, ethyl, linear propyl, and linear butyl; each u can be from about 1 to about 50; each v can be from about 0 to about 50, e.g., from about 1 to about 50; each x can be from about 1 to about 50; and each y can be from about 1 to about 50.
  • Examples of useful terminal groups include alkyl and aryl groups, and functional derivatives of carboxylic acid, which include a carbonyl group (i.e., -C(O)-).
  • the carbonyl group may preferably be substituted with one or two groups such as -OR2, -NHR2, -N(R2) 2 , -O-, and -NH-, where each R2 can be any monofunctional organic group and is preferably an alkyl or an aryl group such as an alkyl (C-
  • Examples of terminal groups that are functional derivatives of a carboxylic acid include esters, amides, urethanes (also referred to as carbamates), ureas, and carbonate esters; e.g.: esters:
  • terminal groups can be prepared at the end of polyoxyalkylene groups that contain an active H by known methods such as, e.g., by reacting a Preferred block copolymer can include one polysiloxane block and one or more pendent polyoxyalkylene blocks, with each polyoxyalkylene block preferably being end-capped or otherwise terminated with an alkyl, aryl, or functional derivative of a carboxylic acid.
  • Each polyoxyalkylene block can itself be made up of random or repeating oxyalkylene units such as a polyoxyethylene or polyoxy- propylene block. Multiple homo- or co-polymeric polyoxyalkylene blocks can be attached to each other, such as when a homopolyoxyethylene block is attached to a homopolyoxypropylene block and connects to the polysiloxane block.
  • the block copolymer can be used as a release agent component of a liquid LAB composition, also referred to simply as a "backsize," and in their dried release coatings.
  • exemplary backsize compositions can be aqueous, e.g., water- based compositions such as aqueous emulsions, aqueous dispersions, aqueous solutions, etc.
  • the backsize may optionally contain organic solvent or be an organic solvent-based liquid composition such as an organic solvent-based solution, emulsion, or dispersion.
  • the aqueous backsize composition can contain no more than 50% organic solvent, based on the total amount of solvent, preferably less than 10 or less than 5% organic solvent based on total solvent.
  • the liquid backsize composition optionally can include other ingredients useful to prepare and coat the liquid backsize onto a substrate or to function in a dried release coating.
  • ingredients include film-forming polymers that allow the liquid backsize composition to be coated to a substrate as a preferably continuous film and that also, upon drying, function as a polymeric matrix to bind the block copolymer release agent to the substrate.
  • the film- forming polymer may optionally be crosslinkable or curable during or after drying.
  • the block copolymer can be coated as a release agent onto a substrate for use with products such as a release liner for PSA tape and label constructions, a release coating for a backside of a self-wound PSA tape, a release inter-liner for a PSA label or tape, or any other type of article that functions as a release surface.
  • products such as a release liner for PSA tape and label constructions, a release coating for a backside of a self-wound PSA tape, a release inter-liner for a PSA label or tape, or any other type of article that functions as a release surface.
  • the liquid backsize composition includes block copolymer that includes a polysiloxane block and an end-capped hydroxy-terminated polyoxyalkylene block.
  • the polyoxyalkylene block terminates with a group selected from an alkyl, an aryl, and a functional derivative of a carboxylic acid.
  • the backsize composition can be aqueous and include from 0.1 to 20 weight percent of a block copolymer that includes a polysiloxane block and polyoxyalkylene block.
  • aspects of the invention relate to a coated product in which a substrate is coated with release agent that includes the types of block copolymers just described; to block copolymer including a polysiloxane block and a polyoxyalkylene block terminated with a carbamate group; to a method of preparing an article that includes a release coating in which a substrate is coated with a liquid backsize composition including film-forming polymer and block copolymer including a polysiloxane block and an end-capped hydroxy-terminated polyoxyalkylene block; and to a method of preparing an article that includes a release coating in which a substrate is coated with an aqueous backsize composition including film-forming polymer and from 0.1 to 20 weight percent (by solids) of a block copolymer that includes a polysiloxane block and polyoxyalkylene block.
  • Backsize compositions (referring to coatable liquids) and release coatings (referring to dried coatings formed therefrom) contain as release agent a block copolymer that includes a polysiloxane and polyoxyalkylene blocks.
  • Preferred polyoxyalkylene blocks can include a terminal group that is not a hydroxyl meaning, for example, that a polyoxyalkylene block is an end-capped hydroxy- functional polyoxyalkylene block, or that a polyoxyalkylene block otherwise includes a non-hydroxyl terminal group such as an alkyl group, an aryl group, or a functional derivative of a carboxylic acid.
  • Non-hydroxyl terminal groups can improve release properties of the block copolymer.
  • Preferred terminal groups can include those that are functional derivatives of a carboxylic acid, such as alkyl or aryl carbamate and ester groups.
  • the polysiloxane-poly(alkoxyalkylene) block copolymer has two or more different blocks bound to one another, with at least one block being a polysiloxane block to which at least one polyoxyalkylene block is attached.
  • a polyoxyalkylene block may be a homopolymeric block of one type of polyoxyalkylene unit or a copolymeric block of two or more types of polyoxyalkylene units.
  • two or more separate blocks of different polyoxyalkylene homo- or co-polymers may be attached together.
  • a preferred block copolymer may include a polyoxyethylene block attached to a polysiloxane block through a linking group.
  • the polyoxyethylene block may terminate as described above, or may be further connected to a polyoxypropylene block, which may be terminated as described above with, e.g., a functional derivative of a carboxylic acid.
  • block copolymer e.g., to control release values, to improve printability, or to impart other desirable properties to a finished product.
  • the polysiloxane block can have repeat units of the formula:
  • each R independently can be a lower alkyl (e.g., an alkyl group having from one to about three carbon atoms) or aryl (e.g., phenyl or substituted phenyl).
  • a preferred polysiloxane block is polydimethylsiloxane (PDMS).
  • polyoxyalkylene blocks can include blocks of lower polyoxyalkylene homo- and co-polymers such as polyoxyethylene, polyoxypropylene, and copolymers of oxyethylene and oxypropylene units.
  • the polyoxyalkylene can be a polymerization product between an active hydrogen compound found attached to or pendent from a polysiloxane block, with cyclic ethers.
  • functionality bearing an active H atom include hydroxyl, amino, thiol and carboxyl groups.
  • cyclic ethers include alkylene oxides, (fluoro)oxetanes and their derivatives, and the furans (e.g., THF).
  • one or more polyoxyalkylene blocks can include a terminal group that improves release properties of the block copolymer compared to a terminal hydroxyl group, e.g., an end-capping group that is a reaction product of a polyoxyalkylene terminal hydroxyl group or similar. terminal hydroxyl group with a compound or sequence of compounds to form one of the described terminal groups.
  • An ester terminal group can be formed by condensation of an active H group (e.g., a terminal hydroxyl group of a polyoxyalkylene block) with a carboxylic acid such as acetic acid, propionic acid, benzoic acid, etc.
  • a carbamate terminal group may be formed by addition, at an active H group, of an alkyl or aryl isocyanate, e.g., methyl isocyanate, phenyl isocyanate, octadecyl isocyanate, etc.
  • Amides can be formed by reaction of an active H to an amine, followed by condensation of the amine to form an amide.
  • a particularly preferred block copolymer has the formula:
  • each E can independently be an end group that is preferably alkyl, aryl, or a functional derivative of a carboxylic acid such as an ester or a carbamate, e.g., an alkyl ester, an aromatic ester, an alkyl carbamate, or an aromatic carbamate; each L can independently be a divalent linkage such as a single bond, a lower alkoxylene (e.g., a C2-C5 alkoxy), or a lower alkylene (e.g., a C2-C5 alkylene); each R can independently be selected from alkyl or aryl groups, preferably methyl, ethyl, linear propyl, and linear butyl; each u, v, x and y independently can be of any values that, optionally in combination with other ingredients of a liquid backsize composition, allow the composition to be coated to a substrate and thereafter allow the coating to be dried and exhibit controlled release properties.
  • a carboxylic acid such as an ester or a
  • polysiloxane-poly(oxyalkylene) block copolymer that includes a terminal ester group at the end of a polyoxyalkylene block is illustrated by the formula:
  • R, x, y, u, and v are as defined, and R2 can preferably be an alkyl or an aryl group, e.g., a substituted or unsubstituted benzyl, or a C Ci8 alkyl.
  • polysiloxane-poly(oxyalkylene) block copolymer that includes a terminal carbamate group at the end of a polyoxyalkylene block is illustrated by the formula:
  • Block copolymer including a polysiloxane and polyoxyalkylene blocks can be prepared according to known methods. Exemplary block copolymers and their methods of preparation are described in U.S. Pat. No. 6,552,212, with the disclosures of such copolymers and their preparations being incorporated herein by reference. According to an exemplary method of preparing such a block copolymer, first is prepared a polysiloxane block that includes one or more active hydrogen- containing groups, preferably hydroxyl groups, to which one or more oxyalkylene blocks can be attached:
  • the backbone can be arranged such that the x and y groups are completely random or ordered. Randomness or order can depend on the methods and materials used to prepare the polymeric block.
  • a polysiloxane polymer or copolymer may be prepared by ring opening reactions of cyclic siloxanes.
  • the use of a cyclic siloxane tetrapolymer to prepare a copolymer or block copolymer results in arrangements of repeating groups of four -SiO(R) 2 - units.
  • the use of other monomers may result in repeating groups of different lengths.
  • R3 can be an active hydrogen-containing group such as a group that contains a hydroxyl, amino, thiol or a carboxyl group.
  • the active hydrogen can be included on an alkylene, preferably a C 2 -C 5 alkylene.
  • R3 can take the form of a hydroxyalkyl, an amino-alkyl, a thio-alkyl, or carboxyl-substituted alkyl.
  • a preferred active hydrogen can be part of a hydroxyl group, meaning that R3 can preferably be a hydroxyalkyl group, preferably a linear hydroxyalkyl group such as a C 2 -C 5 hydroxyalkyl, e.g., -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, etc.
  • Such polysiloxane polymers can include hydroxy-functional oligomeric and high molecular weight homopolymers and copolymers containing residues such as dimethyl siloxane, diethyl siloxane, methyl phenyl siloxane, vinyl methyl siloxane and methyl 3,3,3-trifluoro-n-propyl siloxane.
  • a block copolymer can be prepared by attaching a polyoxyalkylene block at the active hydrogen group, e.g., by alkoxylation of a hydroxyl group(s).
  • the number of alkoxy units reacted with the polysiloxane can be an amount that results in one or more polyoxyalkylene blocks useful as a release agent.
  • alkoxylene groups of the polyoxyalkylene can be ethylene oxide and/or, propylene oxide.
  • Exemplary (hydroxy-terminated) polyoxyalkylene groups are represented by the following structure: -(R5) p -O-(R6O) u (R7O) v -H wherein R5 may be a C 1 -C 10 alkyl group; p is a number from 1 to 10; R6 is a C 2 - C- 12 alkylene group, e.g., 2 or 3 carbon atoms; u is a number from 1 to 50, e.g., from 1 to 20; R7 is a C 2 -C 2 0 alkylene group, e.g., 2 or 3 carbon atoms; and v is a number from 0 to 50, e.g., from 1 to 50 or from 1 to 20.
  • An example of a reaction to add a polyoxyethylene block, polyoxypropylene block, or a copolymer polyoxyethylene-polyoxypropylene block, to an active-hydrogen-functional polysiloxane backbone is:
  • This reaction product can be a block copolymer including a polysiloxane block and a polyoxyalkylene block(s), as shown, wherein the polyoxyalkylene block(s) include terminal hydroxyl groups (i.e., E is hydrogen).
  • Each R independently can be the same or different, and, in preferred embodiments each R can be methyl.
  • the polyoxyalkylene block can be a hydroxy-terminated polyether group, preferably a hydroxy terminated co-polyether group wherein one polyether block includes ethylene oxide units and the other includes propylene oxide units.
  • polyether polysiloxane copolyol can be of the following formula, wherein each R is a methyl group:
  • u, x, and y are each independently an integer of 1 or greater (e.g., 1 to 50), and v can be 0 or 1 or greater (e.g., 0 to 50).
  • Hydroxy-terminated polyether polysiloxane copolyols can be referred to based on a CTFA name of dimethicone copolyol, and are also known as silicone glycol copolymer or polysiloxane polyether copolymers.
  • Exemplary hydroxy- terminated polyether polysiloxane copolyols include SILWETTM L-7200, L-7210, L-7230, L-7604, L-7608, L-7614 and L-7657 silicone glycol copolymers.
  • SILWETTM L-7200, L-7210 and L- 7230 surfactants are alkyl pendent polyether-modified silicone copolymers, namely hydroxy-terminated copolymers.
  • Other commercially available materials include Dow CorningTM 190 and 193 surfactants (Dow Corning; Midland, Michigan) and ABILTM B8842, 8843, 8847, 88183, etc., polyethers siloxanes (Goldschmidt Chem Co.; Hopewell, Virginia).
  • preferred block copolymers include a group terminal to the polyoxyalkylene block that is not a hydroxyl group and that is preferably an alkyl, an aryl, or a functional derivative of a carboxylic acid.
  • these terminal groups can be placed at the end of a polyoxyalkylene block by reaction of the terminal hydroxyl group of the polyoxyalkylene block, e.g., by an end- capping reaction that converts the terminal hydroxyl group to a more desirable terminal group.
  • an ester terminal group can be formed. Following is a single example of such a reaction, wherein the variables are as defined above:
  • a benzoic acid compound can be reacted with a hydroxy-terminated polyether polysiloxane copolyol to produce a benzoate ester-terminated polyoxyalkylene-polysiloxane block copolymer.
  • the benzoic acid can be reacted with the hydroxy terminated polyether polysiloxane copolyol in stoichiometric amounts or with a excess benzoic acid.
  • starting materials may be used in amounts corresponding to from 1 :1 benzoic acid to copolyol, e.g., from 1 :0.8, but can go as low as 1 :0.5.
  • a catalyst can be present during the reaction, such as stannous oxalate, methane sulfonic acid, and the like.
  • Exemplary benzoate esters include FINSOLVTM SLB- 101 dimethicone PEG/PPG-20/23 benzoate and SLB-201 dimethicone PEG-8 benzoate (both from Finetex, Inc,; Elmwood Park, New Jersey).
  • a specific embodiment of a benzoate ester of a hydroxy terminated polyether polysiloxane copolyols can be reacted in accordance with the following equation to produce a benzoate ester-terminated polyoxyalkylene group- containing block copolymer.
  • block copolymers that include non-hydroxyl terminal groups can be prepared by methods generally mentioned herein or known to the ordinarily skilled artisan, e.g., to produce polysiloxane-polyoxyalkylene block copolymers that include alkyl or aryl polyoxyalkylene terminal groups, or polyoxyalkylene terminal groups that are functional derivatives of carboxylic acids.
  • the block copolymer can be used as a release agent, typically by preparing a liquid backsize composition, optionally with other ingredients, for coating onto a substrate to form a release coating or LAB coating.
  • Coatable backsize composition may be aqueous or organic-solvent based, with useful liquid compositions including solutions, dispersions, and emulsion that contain, as water and/or organic solvent.
  • One ingredient that can be especially useful in forming liquid backsize compositions is a film-forming polymer.
  • Film-forming polymers can include natural and synthetic polymeric ingredients and are capable of forming a film on application to a substrate.
  • Preferred film forming polymers generally allow coating and processing of a liquid backsize composition to a dried, coated release coating, by providing film-forming properties and preferably, upon drying, placing release agent (block copolymer, or at least portions of polysiloxane blocks) at a surface of a coated substrate. While not wishing to be bound by theory, most preferably, upon drying and optional crosslinking of the film forming polymer, at least a portion of the block copolymer can become situated at a surface to provide release properties, while the film-forming polymer provides mechanical properties that secure the block copolymer to the substrate.
  • release agent block copolymer, or at least portions of polysiloxane blocks
  • Film-forming polymers may be prepared into a liquid composition by emulsifying, dispersing, or dissolving the polymer in a preferably predominately aqueous medium from which the film forming polymer, in combination with the block copolymer as a release agent, may be coaled to a substrate to form a film and coating upon evaporation of solvent.
  • Examples of useful film-forming polymers may include vinyl acetate homo- and co-polymer latices, styrene-butadiene copolymer latices, styrene-butadiene-acrylonitrile copolymer latices, homo- and co-polymer latices of (meth)acrylic esters, melamine-formaldehyde compositions; carboxylaled vinyl acetate ethylene copolymer latices; poly(vinyl butyral) and poly(vinyl acetal) dispersions; water reducible alkyd resins; polyacrylamides; poly(vinyl alcohol); poly((meth)acrylic acid); poly(ethylene oxide); copolymers of these; gums such as guar gum and gum arabic.
  • Preferred film-forming polymer may include poly(vinyl acetate) homo- and co-polymers, (co)polymers of the esters of (meth)acrylic acid, copolymers of styrene and butadiene, and terpolymers of styrene, butadiene, and acrylonitrile.
  • water soluble film forming polymers include water soluble film forming polymers.
  • Water soluble film forming polymers include unmodified starch; oxidized starch; enzyme-converted starch; starches having functional groups such as hydroxyl, carbonyl, amido, and amino groups; proteins such as casein; latices such as styrene-butadiene resin; and the like.
  • Methods of preparation of solvent-based or aqueous solutions, dispersions, emulsions, or latices, of film forming polymers, are known, and examples of film-forming polymer compositions are commercially available.
  • a liquid backsize composition may be prepared by combining to any one of a solvent (water, organic solvent, or a mixture) or a liquid film forming polymer composition with polysiloxane-poly(oxyalkylene) block copolymer.
  • the relative amounts of block copolymer and solvent and optional film forming polymer can be any relative amounts useful to allow the liquid composition to be coated to a substrate and dried to provide a coating with release properties.
  • Mixing may be required to combine the block copolymer into an aqueous or organic solvent- based liquid solution, emulsion, or dispersion.
  • An aqueous backsize composition containing block copolymer dissolved or dispersed in an aqueous solution, dispersion, or emulsion, etc. can also contain film-forming polymer.
  • Such an aqueous dispersion or solution may include from about 0.1 to about 55 weight percent solids, e.g., from 1 to 40 weight percent solids, water, and less than 50%, e.g., less than 10% or less than 5% organic solvent.
  • a preferred aqueous backsize composition may contain from 35 to about 54.9 pbw film- forming polymer and from about 0.1 to about 20 pbw block copolymer.
  • a liquid backsize composition can be an organic solvent-based solution, dispersion, or emulsion, e.g., a solution including block copolymer described herein dissolved in organic solvent.
  • useful organic solvents include such common solvents as ethanol, methanol, isopropyl alcohol, MEK, etc., or combinations of two or more of these.
  • An organic solvent- based solution can include any desired amount of dissolved block copolymer, e.g., from 0.1 weight percent up to a useful or soluble limit, such as from 0.1 to 5 or 0.1 to 1 weight percent.
  • the solution may or may not include film-forming polymer, and may specifically exclude film-forming polymer such as in applications designed to coat only a light amount of block copolymer to a substrate.
  • a liquid backsize composition can be prepared as an aqueous solution of block copolymer in water, optionally in combination with some amount of organic solvent.
  • Block copolymer may be dissolved in water or a mixture of water and solvent in any useful amount, e.g., from 0.1 weight percent up to a useful or soluble limit, such as from 0.1 to 5 or 0.1 to 1 weight percent.
  • the solution may or may not include film-forming polymer, and may specifically exclude film-forming polymer as noted in the preceding paragraph.
  • Other ingredients may be included in the liquid backsize composition.
  • useful ingredients include one or more of organic solvent, emulsifier, surfactant, dispersant, thickener, defoamer, biocide, pigment, pigment dispersing agent, fillers, buffers, coalescents, heat stabilizers, wetting agents, dyes, coupling agents, ultraviolet light absorbers, colorants, preservatives, antifoaming agents, catalyst, etc., as desired or needed.
  • aqueous backsize compositions do not require added organic solvent, and aqueous liquid backsize compositions include less than 50% by weight organic solvent based on the total amount of solvent.
  • an aqueous composition can include even lower amounts of organic solvent, such as below 20 weight percent, e.g., less than 10% or less than 5%, based on the total amount of water plus any organic solvent.
  • Certain raw materials of a liquid backsize composition may include small amounts of residual organic solvent due to their manufacture processing histories. This amount can be included in an aqueous backsize composition of the invention.
  • an aqueous backsize composition can be prepared by combining water or aqueous film-forming polymer composition such as a dispersion, solution, or emulsion, preferably that contains substantially no organic solvent, with block copolymer as described.
  • aqueous film-forming polymer composition such as a dispersion, solution, or emulsion, preferably that contains substantially no organic solvent, with block copolymer as described.
  • a liquid backsize composition can be applied to a backing using conventional methods such as knife coating, roller coating, gravure, wire-wound rod, reverse roll, air-knife, blade, and print coating. After being applied to a backing, it may be dried.
  • the wet and dry coating weights of a coated backsize composition can be any coating weight useful to allow coating and processing of the liquid backsize composition to a dried release coating.
  • Specific wet and dry coating weights may vary widely depending on a number of considerations including the type of release coating desired, e.g., release value; the type of substrate; the composition of the liquid backsize composition, such as the relative amounts of film- forming polymer and release agent, and their individual chemical compositions; the type of adhesive or other product to be used with the release coating; and even the equipment and conditions used to prepare the liquid or dried coating.
  • the ordinarily skilled artisan can identify useful wet and dry coating weights for applying different embodiments of liquid backsize compositions to substrates.
  • liquid backsize composition can be cured (i.e., crosslinked) either during or following coating or drying. Whether a backsize composition can be cured often can depend on the formulation, particularly the type of film forming polymer used in the backsize composition. Curable film- forming polymers are known in the release coating arts. Examples include polymers that crosslink by addition or condensation reactions, with one particularly preferred mechanism being reaction of methylol functionalities with active hydrogen functionalities.
  • useful substrates include, but are not limited to, films, foil, paper, nonwovens, wovens and composites thereof. They may be porous or smooth.
  • the base film or sheet of PSA tape or contact sheet, and the base sheet of the protecting cover sheet are not particularly limited, and include, for example, thermoplastic films and sheets made of polyethylene, polypropylene, polyester such as polyethylene terephthalate, and cellophane, i.e., cellulose acetate; papers such as saturated paper, woodfree paper, Kraft paper, crepe paper and glassine paper; seal-coated papers such as impregnated paper and plastic- coated paper; and cloths.
  • the coated surface of plastic film or sheet may be surface-treated by a conventional surface-treating procedure such as corona discharge or plasma treatment.
  • One embodiment of the invention is a PSA tape including a backing (i.e., substrate) having an adhesive-coated side and a release-coated side.
  • the backing is wound onto itself so that the adhesive-coated backing side is placed in physical contact with the release-coated backing side.
  • a coated product according to the invention can be a release liner, comprising a desired backing and one surface coated with a release coating as described above.
  • one or both sides of a backing can be coated with adhesive (double adhesive-coated backing), and a separate release liner coated on one or both sides with a release coating, can be used to contact one or both sides of the adhesive-coated backing sides.
  • Example 1 a mixture containing 77.5 g 30% polyacrylamide, 15 g water, and 7.5 g FinsolvTM SLB-101 was prepared by stirring.
  • Example 2 a mixture containing 92.5 g 42% enzyme-converted starch and 7.5 g FinsolvTM SLB-101 was prepared by stirring. These were coated onto N2A Lenita cards using a #6 Mayer rod and allowed to dry at 60°C for one minute.
  • Adhesion to backing was measured using Pressure Sensitive Tape Council test method PSTC-4B and a 3MTM 234 masking tape (3M Co., St. Paul, Minnesota).
  • PSTC-4B Pressure Sensitive Tape Council test method
  • 3MTM 234 masking tape 3M Co., St. Paul, Minnesota.
  • the measured force to disbond for the uncoated paper was 510 g (18 oz.), as compared to 25.5 g (0.9 oz.) and 14.2 g (0.5 oz.) for the coated sheets of Examples 1 and 2, respectively.
  • Example 3 Solvent-based Coating A mixture containing 17 g poly(vinyl butyral), 3 g FinsolvTM SLB-101 , 48 g toluene, and 32 g 95% ethanol was prepared by simple stirring with a wooden tongue blade. This yielded a clear viscous solution which was coated onto a N2A Lenita card using a #0 Mayer rod, and allowed to dry at room temperature. Adhesion to backing (ATB) was measured as in Examples 1-2. The measured force to disbond for the uncoated paper was 510 g (18 oz.), as compared to 17.0 g (0.6 oz.) for the coated sheet.
  • Examples 4-5 Carbamate A 100 mL three necked 14/20 round bottom flask was fitted with a magnetic stirrer, heating mantle, N 2 inlet, condenser, and a bubbler to observe the N 2 flow.
  • Example 4 into the flask was placed 39.9 g SilwetTM hydroxy-functional block copolymer and 10 g phenyl isocyanate.
  • Example 5 into the flask was placed 16.07 g SilwetTM L-7230 hydroxy-functional block copolymer and 10 g phenyl isocyanate.
  • Example 6 Release agents shown in the following table each were diluted to 25% solids with water and added to SuncrylTM 129 vinyl acrylic emulsion polymer (OMNOVA Solutions Inc., Chester, South Carolina) with gentle stirring to prepare a liquid backsize. Test backsizes were applied using a #0 Meyer rod to saturated Kraft paper, and dried for 25 seconds at 177°C (350°F). ATB was measured using Pressure Sensitive Tape Council test method PSTC-4B. A 2.56 cm x 2.56 cm x 2.56 cm (1x1 1 inch) steel bar was used for 10 minutes at 82°C (180°F) to adhere the coated substrate to 3MTM 234 tape. Rolling ball tack was measured by Pressure Sensitive Tape Council test PSTC-6. (Results in the ATB test are highly dependent on the specific lot of masking tape used, so experimental evaluations are presented separately).
  • Example 7 SequabondTM DW1 emulsified poly(vinyl acetate) copolymer (OMNOVA Solutions), was combined with release agents (shown in the table below) and evaluated using the procedure described in Example 6.

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  • Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne des agents et des revêtements anti-adhésifs contenant des copolymères séquencés qui comprennent une séquence polysiloxane et une séquence polyoxyalkylène ainsi que des procédés et des produits tels que, par exemple, des bandes PSA.
PCT/US2004/007550 2003-03-21 2004-03-11 Composition faiblement adhesive WO2004085561A2 (fr)

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US45644703P 2003-03-21 2003-03-21
US60/456,447 2003-03-21

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007063165A1 (fr) * 2005-12-01 2007-06-07 Upm-Kymmene Oyj Materiaux fibreux impermeable nanostructure
WO2021110739A1 (fr) 2019-12-06 2021-06-10 Basf Se Composition de revêtement antiadhésif
WO2021255544A1 (fr) * 2020-06-17 2021-12-23 3M Innovative Properties Company Revêtements antiadhésifs et articles les comprenant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1795557A1 (de) * 1961-05-27 1972-03-30 Goldschmidt Ag Th Verfahren zur Herstellung von Polyalkylkieselsaeureestern mit einer dem statistischen Gleichgewicht angenaeherten Polymerenverteilung
US4263250A (en) * 1978-10-16 1981-04-21 Th. Goldschmidt Ag Lubricant and release agent for molded rubber articles
EP0329279A2 (fr) * 1988-01-22 1989-08-23 Minnesota Mining And Manufacturing Company Composition pour revêtement de séparation à base de silicones
EP0329167A2 (fr) * 1988-02-18 1989-08-23 Toray Silicone Company, Limited Composition anti-adhésive
EP0606532A1 (fr) * 1992-12-14 1994-07-20 Andrew A. Shores Solution de revêtement aqueuse contenant un polyélectrolyte à base d'un polysiloxane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1795557A1 (de) * 1961-05-27 1972-03-30 Goldschmidt Ag Th Verfahren zur Herstellung von Polyalkylkieselsaeureestern mit einer dem statistischen Gleichgewicht angenaeherten Polymerenverteilung
US4263250A (en) * 1978-10-16 1981-04-21 Th. Goldschmidt Ag Lubricant and release agent for molded rubber articles
EP0329279A2 (fr) * 1988-01-22 1989-08-23 Minnesota Mining And Manufacturing Company Composition pour revêtement de séparation à base de silicones
EP0329167A2 (fr) * 1988-02-18 1989-08-23 Toray Silicone Company, Limited Composition anti-adhésive
EP0606532A1 (fr) * 1992-12-14 1994-07-20 Andrew A. Shores Solution de revêtement aqueuse contenant un polyélectrolyte à base d'un polysiloxane

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007063165A1 (fr) * 2005-12-01 2007-06-07 Upm-Kymmene Oyj Materiaux fibreux impermeable nanostructure
GB2446999A (en) * 2005-12-01 2008-08-27 Upm Kymmene Oyj Nanostructured repellent fibrous material
GB2446999B (en) * 2005-12-01 2011-06-15 Upm Kymmene Oyj Nanostructured release paper
CN101341298B (zh) * 2005-12-01 2013-11-27 芬欧汇川集团 纳米结构化的排斥性纤维材料
WO2021110739A1 (fr) 2019-12-06 2021-06-10 Basf Se Composition de revêtement antiadhésif
WO2021255544A1 (fr) * 2020-06-17 2021-12-23 3M Innovative Properties Company Revêtements antiadhésifs et articles les comprenant

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WO2004085561A3 (fr) 2005-01-20

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