WO1999011683A1 - Compositions pour couches de colle a faible adherence - Google Patents

Compositions pour couches de colle a faible adherence Download PDF

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Publication number
WO1999011683A1
WO1999011683A1 PCT/US1998/017558 US9817558W WO9911683A1 WO 1999011683 A1 WO1999011683 A1 WO 1999011683A1 US 9817558 W US9817558 W US 9817558W WO 9911683 A1 WO9911683 A1 WO 9911683A1
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WO
WIPO (PCT)
Prior art keywords
silicone
low adhesion
component
polymer
adhesion backsize
Prior art date
Application number
PCT/US1998/017558
Other languages
English (en)
Inventor
David W. Stegink
Ramesh C. Kumar
Eric Baertich
Original Assignee
Minnesota Mining And Manufacturing Company
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 Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to AU93729/98A priority Critical patent/AU9372998A/en
Publication of WO1999011683A1 publication Critical patent/WO1999011683A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C09J2433/005—Presence of (meth)acrylic polymer 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule

Definitions

  • This invention relates to low adhesion backsize (LAB) coating compositions and more particularly to blended release agents.
  • a release agent is to reduce, control or moderate the force required to peel a pressure sensitive adhesive off an adherend that has been coated with a release agent. While the use of a release agent is useful to help reduce, control or moderate the peel force when unrolling a roll of tape, or removing an adhesive-coated article from a sheet or pad of sheets, the peel force must co-exist with the necessity of ink receptivity. Ink receptivity is desirable so that the adhesive-coated article may be printed or written upon.
  • release agents are known to those skilled in the art that provide control of the peel force of a pressure sensitive adhesive.
  • One variety for example, are acrylate -based polymer release agents.
  • a second variety being polymers based on fluorine-containing monomers, and a third variety based solely on silicone-containing monomers.
  • a typical example of the third variety would be crosslinked polydimethyl siloxane, herein referred to as PDMS.
  • PDMS crosslinked polydimethyl siloxane
  • Each of these various release agents provides a variety of properties over a spectrum of values. For example, a 100% PDMS release agent provides excellent release properties, that is, reduced peel force, but is generally considered to have little or no ink receptivity. At the other end of the spectrum are alkyl group containing (meth)acrylate based release agents that provide marginal release properties, but exhibit excellent ink receptivity (that is, writability).
  • blends of two components usually have properties intermediate between those of the individual components alone. Extending this to the situation where one component is of higher quality than another, one would expect that a blend of two or more components would have properties between the lowest quality and highest quality component, but still inferior to the properties of the best components.
  • release agents that display good performance against several measures at once are uncommon. Carrying this further; low viscosity, high solids, high efficiency, writable, printable, age stable, broad spectrum release agents are very rare indeed. When blending release agents, it is highly unlikely that improvements will occur in many parameters, if any of the parameters at once.
  • release agents that exhibit writability are generally not compatible with a broad range of adhesives. Most typically, they are compatible only with a narrow range of adhesive formulations, possibly only with one specific adhesive formulation.
  • a low adhesion backsize (LAB) coating composition comprising at least two components, wherein a first component is a silicone-containing acrylate polymer and a second component is either a silicone-containing polymer different than the first component, or an octadecyl acrylate containing polymer, or a mixture thereof.
  • LAB low adhesion backsize
  • a further aspect of the present invention is that when the second component is a silicone-containing polymer, then the first silicone-containing polymer contains silicone segments pendant to the polymer backbone.
  • the LAB coating compositions of this invention exhibit excellent and improved release properties when coated onto substrates. Improved release properties are quantified by laminating various adhesives to the LAB, and subsequently measuring the force required to peel the adhesive off the release agent. This test is referred to as Adhesion to Backsize or (ATB) and is typically measured against a reference adhesive tape.
  • Adhesion to Backsize Adhesion to Backsize
  • an improved low adhesion backsize coating is obtainable according to the following steps:
  • a low adhesion backsize coating composition comprising at least two components, wherein the first component is a silicone containing acrylate polymer and a second component is a silicone-containing polymer different than the first component, or an octadecyl acrylate containing polymer or a mixture thereof,
  • drying the coated substrate wherein the drying process includes heated metal drying rolls, steam treatment or radio frequency drying.
  • the unique LAB coating compositions of this invention are more efficient in that less LAB need be applied to obtain equivalent release levels than any LAB component alone. Furthermore, at equivalent coat weights, the blended LAB compositions will have better release levels than any LAB component alone.
  • writability of blends were simply intermediate between the two components.
  • one property of a blend might have been better than the corresponding property of an individual component, but this improvement would have been obtained at the expense of another property.
  • writability of a blend might be better than the writability of the worst of the blend components alone, but the blend would also exhibit release values worse than the best component alone. This is typically the tradeoff seen when trying to improve the writability of a promising release agent.
  • the blended LAB coating compositions of the present invention unexpectedly exhibit excellent release and excellent writability. In most cases, writability of the blends was very close to that of the best of the components alone. In some cases writability was better than that of either component.
  • compositions known to those skilled in the art the unacceptably high viscosity of an otherwise promising release agent might be reduced by blending it with a low viscosity release agent.
  • these compositions would reach the goal of reduced viscosity at the expense of other beneficial properties.
  • a reduction in viscosity is associated by a reduction in percent solids, or by worsened release or worsened writability.
  • release agents it is highly desirable for release agents to have excellent release properties along with excellent ink receptivity. It is even more desirable to obtain other beneficial properties such as good handleability, low cost, low tendency to foam, low viscosity and good aging properties along with the first two features. Such release agents are not known in the art. In general, release agents that deliver writability are not capable of providing extremely low release levels, for example
  • compositions of this invention possess reduced viscosity (compared to the most viscous component) without an associated reduction in percent solids. This is particularly useful because it allows one to coat the compositions at higher solids levels than previously possible. Coating methods such as gravure coating favor low viscosity materials and previously the only means to obtain this was dilution. In addition, viscous materials tend to capture entrained air when mixed, and this leads to foam formation. Compositions with reduced viscosity materials are less likely to physically entrap air because the air bubbles escape more quickly, and thus they are much less likely to cause foaming problems. As used in this application:
  • waterborne means that the polymeric base of the release agent is dissolved, dispersed, suspended or similarly carried in a vehicle consisting primarily of water.
  • a low adhesion backsize (LAB) coating composition comprising at least two components, wherein a first component is a silicone-containing acrylate polymer and a second component is either a silicone-containing polymer different than the first component, or an octadecyl acrylate containing polymer, or a mixture thereof.
  • a further aspect of the present invention is that when the second component is a silicone-containing polymer, the first silicone-containing polymer contains silicone segments pendant to the polymer backbone.
  • LAB coating compositions of the present invention exhibit improved release properties as measured by adhesion to backsize (ATB) and as measured by ATB using with other challenging adhesives. Unexpectedly, the improvements demonstrated by the unique LAB coating compositions of this invention permit the use of less LAB to obtain any given release level.
  • writability was simply intermediate between the different components. In a few cases, one property of the blend might have been better than that property of a single component. For example, writability of a blend was better than either component alone.
  • the present invention provides a release coating composition that exhibits improved properties with respect to writability and peel force. Theoretically, it is expected a blend would exhibit the writability of component A (poor release) and the release characteristic of component B (poor writability). However, when blended, the LAB coating compositions of the present invention unexpectedly have excellent release and excellent writability.
  • blends also gave significantly reduced viscosity. This is particularly useful because it allows preparation of coating compositions at higher solids levels.
  • Representative component polymers for the blends of this invention include:
  • octadecyl acrylate-containing polymers would be a tetrapolymer of octadecyl acrylate, methyl acrylate, acrylic acid and acrylonitrile.
  • silicone-containing acrylate polymers with pendant silicone segments is a silicone grafted tetrapolymer of methyl acrylate, acrylic acid, NVP and SiMac. Methyl Acrylate 10-45%
  • ODA means octadecyl acrylate
  • NDP means N-vinyl pyrollidone, an ethylenically unsaturated cyclic amine.
  • SiMac refers to a free-radically polymerizable methacrylate functional silicone macromonomer having a number average molecular weight in the range of 10,000.
  • MFS means mercapto-functional polydimethyl siloxane, having a number average molecular weight in the range of 8,000 and containing 4-5% mercaptan functionality on a molar basis.
  • MFS monomers and MFS analogs are commercially available from Shin Etsu (Japan), KF-2001 being one such suitable grade.
  • SiMac and SiMac- analogs are commercially available from Shin Etsu and from 3M.
  • Blended LABs of the present invention can be used as release coatings for any article having a substrate and at least one layer of adhesive coated thereon.
  • LABs of the present invention can be used in the construction of repositionable notes, such as Post-it® Notes, flags, such as Post-it® Flags, roll tape, such as ScotchTM MagicTM Tape.
  • Other articles would include signage, pads of tape, and the like.
  • the construction of such articles at the minimum comprise a release layer coated on one surface of a substrate, the substrate and at least one coating of an adhesive coated on the other surface of the substrate.
  • blended LABs of the present invention can be used as release coatings for articles, such as release liners and are useful in making indicia receptive release liner material compatible with a wide variety of adhesives.
  • Such an article would consist primarily of a substrate and a layer of low adhesion backsize coating thereon.
  • Case 1 is for a blend of one ODA-containing acrylate polymer and one silicone acrylate co-polymer.
  • the silicone-containing acrylate polymer can contain backbone silicone segments, although silicone segments pendant to the polymer backbone are preferred.
  • Case 2 is for a blend of two different silicone acrylate co-polymers.
  • at least one of the polymers contains silicone segments pendant to the polymer backbone.
  • Case 3 is for a blend of two separate silicone acrylate copolymers and a third ODA containing acrylate polymer.
  • at least one of the polymers contains silicone segments pendant to the polymer backbone.
  • the blend ratios of the first component to the second component are in range of 1 :99 to 99: 1, wherein if the second component is a mixture itself, the mixture of the second component and the third component is in the range of 1 :99 to 99:1.
  • Preparation methods for these blends, and for the three constituent polymers are similar.
  • the following preparation methods are illustrative of a method for preparing the constituent polymers and the corresponding blends. Methods other than those described can be used provided they produce the copolymer of interest. Furthermore, the exact amounts are only indicative of a specific example, similar ratios can also be construed from these illustrative preparation descriptions.
  • polymers of the type used in the blends of this invention are solution polymerized at approximately 25-40% solids in organic solvents, such as ethyl acetate using conventional free-radical methods. The solvent/polymer solution is then dispersed in water by neutralization of the acid moieties with an organic or inorganic amine, following by removal of the organic solvent by vacuum stripping.
  • all of the blends of this invention are of suitable viscosity for coating with a slot die, by direct gravure, or by roll coating.
  • the preferred slot die for applying these LAB blends has a 14.6 cm wide x 0.038 cm deep orifice slot through which the material is extruded onto a backing.
  • the die has approximately a 0.16 cm smoothing land following the orifice.
  • This coating die is suitable for application levels between 4 and 10 wet grams wet/sq meter.
  • the solids level of the LAB blend will need to be adjusted appropriately so as to coincide with a wet coat weight of at least 4 g/sq meter and no more than 10 g/sq meter.
  • coat weights range between 0.05 and 1.72 dry grams/sq meter.
  • coat weights ranging between 0.21 and 1.0 dry grams/sq meter are more preferred. Most preferred are coat weights ranging between 0.5-0.9 dry grams/sq meter. In the following examples, a variety of coat weights were often coated so that the effect of coat weight on release could be assessed.
  • polymers of the type used in the blends of this invention are solution polymerized at approximately 25-40% solids in organic solvents, such as ethyl acetate using conventional free-radical methods.
  • organic solvents such as ethyl acetate
  • the solvent/polymer solution is then dispersed in water by neutralization of the acid moieties with an organic or inorganic amine, following by removal of the organic solvent by vacuum stripping.
  • ODA-containing acrylate polymer (Polymer 1) An amber-colored quart bottle was charged with 102 grams of octadecylacylate (ODA) (50% solids in ethyl acetate), 1 1 grams of methyl acrylate (MA), 25 grams of acrylonitrile (AN), 13 grams of acrylic acid (AA), 0.5 grams of 2,2' -azobisisobutyronitrile (AIBN) and 182 grams of ethyl acetate. The resulting mixture was purged with nitrogen for 3 minutes at 1 L/min, after which the bottle was sealed. The sealed bottle containing the solution was tumbled in a constant temperature bath for 48 hours at 65°C.
  • ODA octadecylacylate
  • MA methyl acrylate
  • AN acrylonitrile
  • AIBN 2,2' -azobisisobutyronitrile
  • a 16 oz. amber glass reaction bottle was charged with 39.1 grams of methyl acrylate (MA), 30.4 grams of N-vinyl pyrollidone (NVP), 43 grams of acrylic acid (AA), 26.1 grams of 10,000 MW silicone macromer (SiMac), 2.5 grams of 2,2'- azobisisobutyronitrile (AIBN) and 150 grams of methyl ethyl ketone (MEK).
  • MA methyl acrylate
  • NDP N-vinyl pyrollidone
  • AA acrylic acid
  • SiMac acrylic acid
  • AIBN 2,2'- azobisisobutyronitrile
  • MEK methyl ethyl ketone
  • a 16 oz. amber glass reaction bottle was charged with 50 grams of methyl acrylate (MA), 20 grams of methyl methacrylate (MMA), 5 grams of methacrylic acid (MAA), 25 grams of mercaptofunctional silicone, 0.25 grams of 2,2 '-azobisisobutyronitrile (AIBN) and 150 grams of methyl ethyl ketone (MEK).
  • MA methyl acrylate
  • MAA methacrylic acid
  • AIBN 2,2 '-azobisisobutyronitrile
  • MEK methyl ethyl ketone
  • Polymer 1 was a thin liquid with a viscosity of 10 cps. After the two components had been mixed gently for a few minutes, the blend was thoroughly combined using an air mixer turning at about 200 rpm. The result was 2000 grams of a uniform mixture at 10.0% solids, with a viscosity of 1320 cps. To verify homogeneity, a sample was spun in a ultracentrifuge at 10,000 rpm for 15 minutes.
  • a milky viscous solution was obtained .
  • Solids, pH and viscosity of the blend are 12.5%, 8.0 and 4600 cps respectively.
  • Case 3 Blend Preparation of a Case 3 blend containing 50% Polymer 1, 25% Polymer 2 and 25% Polymer 3, with the percentages based on the solids content of the constituent components.
  • Polymer 2 is a gelatinous liquid with a viscosity of 3450 cps.
  • Polymer 1 was a thin liquid with a viscosity of 10 cps.
  • 286 grams of Polymer 3 at 20% solids was combined with Polymer 1 briefly, then that mixture was combined with the 571 grams of Polymer 2 already in the first container.
  • Polymer 3 was a thin liquid with a viscosity of 55 cps. After the two components had been mixed gently for a few minutes, the blend was thoroughly combined using an air mixer turning at about 200 rpm. The result was 2000 grams of a uniform mixture at 11.4% solids, with a viscosity of 450 cps. To verify homogeneity, a sample was spun in a centrifuge at 10,000 ⁇ m for 15 minutes. No phase separation was visible.
  • the 3-roll coater applied between 4.3 and 6.5 wet g/m 2 to a 15.2 cm wide web of 75 g/m 2 wood-free paper. It should be noted that the coat weight that results from this type of coater is affected partly by the viscosity of the blend and partly by the pan roll speed. Coating speed was 274 m/min. This corresponds to a dry coat weight of 0.34-0.52 dry g/m 2 .
  • Drying Method 1 The web, having been previously coated with LAB using Coating Method 1 and remaining wet, is dried on two, 120°C, 17.8 cm diameter stainless steel heated cans at a speed of roughly 2.4 meters/minute, such that the final moisture content after drying is preferably in the range of 4-6% as measured gravimetrically. Drying Method 2
  • the web having been previously coated with LAB using Coating Method 1 and remaining wet, was dried using three forced air blowers. Each blower had a
  • the web was coated with LAB at a line speed 274 meters/minute using Coating Method 2 and was dried using 4 ampere radio-frequency oven roughly 6 meters in total length.
  • This oven was manufactured by Radio Frequency Co ⁇ oration (Willis, MA). This rf oven has an airflow of 15-20 cubic meters/minute of 24°C air moving across the web.
  • the moisture content after drying should preferably be in the range of 4-6% as measured gravimetrically.
  • Reference tapes were generated by the following method.
  • the adhesive of interest was coated at 6.7 dry grams/sq meter using an appropriate slot die or similar coating method at a speed of 15.2 meters/minute onto a web of 75 gram sq meter wood-free paper approximately 95 micrometers thick.
  • the adhesive was coated from water.
  • Two “reference” tapes were prepared (referred to hereinafter as "Reference Tape A” and “Reference Tape B”:
  • Reference Tape A was made using the following adhesive:
  • Stepanol AM-V (10% solution in water)
  • an alkyl sulfate commercially available from Stepan Co. Northfield, IL
  • Rohm & Haas, Co. 16.50 gms Stepanol AM-V (10% solution in water)
  • HEM A hydroxyethyl methacrylate
  • NVP N- vinyl pyrollidone
  • the agitation in the flask is increased to 360 ⁇ m and the IOA mixture is added to the flask.
  • Heat is applied via IR lamps to bring the contents to 42°C. It takes ten minutes to rise to this temperature. After approximately sixty minutes an exotherm begins, rising to a peak temperature of 75°C in fifty-five minutes.
  • the batch is cured at 75 °C for six hours and the nitrogen purge is replaced with a nitrogen pad. After cooling the product is filtered through one layer of cheesecloth.
  • the sample had a particle size from 35 to 45 micrometers.
  • Carbotac 26222 (51 % solids in water) (an acrylic resin commercially available from B.F. Goodrich, Akron, OH)
  • Kelzan S (a Xanthan gum commercially available from
  • Adhesive A A reference tape made using Adhesive A was prepared as follows:
  • Adhesive A was applied with a slot die onto 70 g/m" wood-free paper at 0.6 g/sq ft dry weight. Drying was accomplished on 120°C hot cans. This coat weight resulted in an adhesion level of roughly 47 g/cm as measured by 90 degree peel adhesion to polyester film. Test results generated with this reference tape are referred to as "ATB-Adhesive A.”
  • Reference Tape B was made using the following adhesive:
  • the agitation in the flask is increased to 340 ⁇ m and the IOA mixture is added to the flask. Heat is applied via IR lamps to bring the contents to 50°C. It takes fifteen minutes to rise to this temperature. After approximately ten minutes an exotherm begins, rising to a peak temperature of 76°C in eight minutes. The batch is allowed to cool back to 50°C and the nitrogen purge is replaced with a nitrogen pad. The flask is held at this temperature for a total heat time of 22 hours. After cooling the product is filtered through one layer of cheesecloth. The sample had a particle size from 40 to 60 micrometers. To the resultant suspension the following components were added:
  • Adhesive B A reference tape made using Adhesive B was prepared as follows:
  • Adhesive B was then applied with a slot die onto 70 g/m wood-free paper at 0.6 g/sq ft dry weight. Drying was accomplished on 120°C hot cans. This coat weight resulted in an adhesion level of roughly 50 g/cm as measured by 90 degree peel adhesion to polyester film. Test results generated with this reference tape are referred to as ATB -Adhesive B.
  • Brookfield Viscosity A liquid sample was placed in a small container, and measured using Brookfield spindle #3 at 60 ⁇ m, except as noted specifically in the Examples. Brookfield viscometers can be obtained from Fisher Scientific.
  • Percent Solids A small aluminum pan was desiccated at 120°C overnight and a tare weight was obtained. A small amount (1-5 grams) of the liquid to be measured was placed into the pan and the gross weight was determined. This pan was placed in a 120°C oven for one hour, after which the pan was cooled to room temperature and reweighed. The Percent Solids is calculated based on the dry weight, after subtracting the tare weight of the aluminum pan.
  • ATB-810 A 2.54 cm wide stripe of 3M #810 tape was laminated to the release surface using a 2 kg rubber roller, with two rolldown passes executed at about 20 cm/second. Within one minute after lamination, the adhesive stripe was peeled off the surface at 30.5 cm/second using a 90 degree peel angle, and the force required to remove the strip at constant speed was measured.
  • Suitable devices for measuring ATB-810 tape include a tensile testing machine such as one manufactured by MTS Systems Co ⁇ . (Eden Prairie, MN) or Instron, Co ⁇ . (Canton, MA) Autopen Writability Test: This test is performed using an automatic writing device (such as one available from International Autopen, Sterling, VA), a variety of writing instruments, and an image analysis device.
  • AAT The reported result is the amount of ink coverage (area percentage covered) in a 1 cm x 1 cm area. Generally speaking, at least 4 pens are used and the results are averaged together to give a good indication of writability. Higher levels of ink coverage indicate better writability. Values are generally compared to a control surface such as office copy paper.
  • an autopen controls pen angle, pen position and pen speed according to an analog template.
  • An autopen delivers or "writes" ink in highly repeatable fashion much as a human hand deposits it during normal writing. A 60- degree pen angle is used.
  • the test pattern is not particularly important, but it should include straight lines, curved lines and changes in angle.
  • One suitable pattern for use is an autopen "adjustment template" available from International Autopen. It is desired that the inked pattern should have sufficient line density such that between 15% and 35% of the area is covered by ink after writing. After the ink is deposited, the sample is allowed to dry briefly. After drying, it is placed in an image analysis device that captures an image with a video microscope, then digitizes a 1 cm x 1 cm area. Using the uninked area as a "white standard” and the darkest inked area as a "black standard,” the number of dark pixels and light pixels are then counted, and the ratio is reported as an area percentage of dark pixels. The sample is lit circumferentially by a circular fluorescent tube. Suitable image analysis devices are available from Acuity Imaging Inc, of Nashua, New
  • ATB-Reference Adhesive A 2.54 cm wide of a suitable "reference" tape is laminated to the release surface using a 2 kg rubber roller, with two rolldown passes executed at about 20 cm/second. Samples may be variably handled and tested after that point. i. If an initial value is desired, within one minute after lamination, the adhesive strip is peeled off the surface at 30.5 cm/second using a 90 degree peel angle, and the force required to remove the strip at constant speed is measured on a tensile testing machine. This result would be referred to as "ATB-Adhesive A,” “ATB-Adhesive B" or
  • the laminated sample is clamped in a hydraulic press at a pressure of 250 psi (176,000 kg/sq meter) for 30 seconds. Within 20 minutes of clamping, the adhesive strip is peeled off the surface at 30.5 cm/second using a 90 degree peel angle, and the force required to remove the strip at constant speed is measured on a tensile testing machine. Test results generated this way would be referred to as "Clamped ATB.” i ⁇ .
  • the laminated sample (either after having been clamped or undamped) is prepared, then put into an temperature and humidity controlled aging chamber for a period of time. Typically the sample would be aged at either 24°C and 50% RH, or 49°C and 5% RH for 3-14 days. After aging, the adhesive strip is peeled off the surface at 30.5 cm/second using a 90 degree peel angle, and the force required to remove the strip at constant speed is measured on a tensile testing machine. Test results generated this way would be referred to as "Aged ATB" with a description of the aging conditions, and a description of whether the sample was clamped or not.
  • Example 1 ESCA data showing silicone functionality at the surface remains high despite reduced aggregate Si content.
  • ODA-containing polymers and silicone-containing polymers were blended according to Blend 1 preparation example above.
  • the polymers were prepared according to the Polymer 1-3 preparation examples above using the component percentages set forth in Table 1.
  • the coating compositions were coated onto paper at 0.86 g/m dry and dried on 20 cm diameter 121°C hot cans. The coated papers were then evaluated on a Hewlett Packard 5950 ESCA system. The results are reported in Table 1.
  • Example 2 Viscosity data for blends of polymers (1) and (2)
  • the polymers were prepared according to the methods described earlier. Blends of polymers were prepared at different percentage ratios as set forth in Table 2. Final concentration of all samples was 10%. Viscosity was then measured using a Brookfield viscometer, spindle #3, 60 ⁇ m. These blends were all coated at 0.75 g/m 2 dry coat weight and dried on 120°C hot cans. The viscosity and ATB of the blends are reported in Table 2. Note that very large reductions in viscosity were seen, along with large improvements in ATB-810.
  • Example 3 A second set of samples were prepared using methods described earlier. In this example, three identical but separately compounded samples of one blend (20/80) and three separate obtained samples of a control (0/100) were prepared. These were coated on three separate occasions, and the samples were tested in double-blind fashion.
  • "0/100” refers to Polymer 2 by itself
  • "20/80” refers to a blend containing 20% Polymer 1 and 80% Polymer 2. Please note that in all three samples, better than a 50% improvement in ATB was noted. This indicates the improvement is repeatable. Table 3
  • Examples of a 20/80 blend of Polymer 1 and Polymer 2 were prepared at 10% solids. These were applied to 70 g/m 2 wood-free paper at 0.54 g/m 2 dry coat weight using a 3-roll coater at 274 m/min as described earlier. In this example, all variables were held constant except for drying method. Various drying methods were used as set forth in Table 4.
  • Drying method affected release. In this example, one can see that increased heat resulted in improved release as measured by ATB-810 as reported in Table 4. Radio frequency (rf) drying seemed to give particularly good results. In rf drying, water molecules are excited quickly and volatilize with a burst of steam. It is felt that this burst of steam is highly preferred in attaining the best release level possible.
  • a set of samples were coated of the same 20/80 blend as described in Example 3. As described in Example 4, a 3-roll coater was used to apply the LAB at about 0.65 dry grams/sq meter. Line speed was approximately 457 meters/minute. Drying was accomplished in a three-zone air flotation oven followed by a heat treatment step on 120°C steel cans. Residence time on the steel cans was approximately 0.8 second. Coated samples were prepared with and without the use of a steaming device. The steamer used was a "Coanda nozzle" full-web steamer of the type available from Thermo Electron, Inc. (Waltham, MA).
  • Polymers 1 and 2 were prepared as described earlier. Different blend ratios, recorded in Table 7, of Polymer 1 and Polymer 2 were prepared at 10% solids. These were applied at 0.75 g/sq meter dry weight to 70 g/sq meter wood-free paper at 15.2 meters/minute using a slot die. Drying was accomplished on 120°C stainless steel hot cans. All other variables were held constant except blend ratio. The various blends were tested for initial release with #810 tape (commercially available from 3M) and also with a Reference Tape. To show the significant change after aging, ATB was measured with Reference Tape B after accelerated aging at 24°C and 80% RH for 14 days. These three measures of release performance are reported in Table 7.
  • Example 7 This example shows the effects of blending together two different silicone containing polymers.
  • Polymer 2 is a silicone grafted (meth)acrylate copolymer with pendant silicone segments.
  • Polymer 3 is a (meth) acrylate grafted silicone copolymer with backbone silicone segments.
  • Table 8a and 8c The various ratios are recorded in Table 8a and 8c. Samples listed in Table 8a were applied to 70 g/m 2 wood-free paper at 0.75 g/m 2 dry weight, and were dried at low temperature using 27°C forced air drying. Samples listed in Table 8c were applied using a roll coated followed by air drying at 24°C with coat weights ranging between 0.4-0.6 g/m 2 .
  • Writability was measured by AWT as described earlier, wherein a higher % value indicates better writability. Writability was an average of four pens and is recorded in Table 8a. ATB-810 results and viscosity data are recorded in Table 8c. ATB results with the reference tapes before and after aging are reported in Table 8b.
  • the polymers were prepared and blended according to the procedures described above. Various ratios of three-way blends are reported in Table 10a.
  • the three way blends used two different silicone containing polymers, one being a silicone grafted (meth)acrylate polymer, and the second being a (meth)acrylate grafted silicone polymer.
  • the third component was an ODA-containing polymer.
  • Blend samples were applied to 70 g/sq meter wood-free paper at 0.07 g/sq ft dry weight, and were dried using 24°C forced air drying. No steaming or hot can treatment was used.
  • Sample U was the best LAB for Aged ATB with both Adhesive A and B.
  • Sample U was a 50/25/25 three-way blend of the three polymers. Note that the write-on of this blend was 18.3%, higher even than the baseline writability for Polymer 1 , an LAB with outstanding ink receptivity. The three-way blend was best for aging against these adhesives and still delivered outstanding writability.
  • three LAB's were coated onto 70 g/m 2 wood-free paper at 0.75 g/m dry coat weight. The coatings were dried on 120°C hot cans at a speed of 15.2 m min. The three materials coated were: (i) 100% Polymer 2, (ii) 100% Polymer 1 and (iii) a 20/80 blend of Polymer 1 and Polymer 2. All three LAB's were coated at a wide range of coat weights between 0.4 and 1.7 dry g/m 2 . This range spans "very light” to "extremely heavy.” ATB was measured to assess release and the results are set forth in Table 11, with lower ATBs indicating improved release levels.

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  • 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

La présente invention concerne une composition pour couches de colle à faible adhérence faite de deux composants. Le premier composant est un polymère d'acrylate siliconé. Le second composant est (a) un polymère siliconé différent du premier composant, (b) un polymère contenant un octadécyle acrylate, ou (c) un mélange de ces deux produits. En outre, lorsque le second composant est un polymère siliconé, ce polymère siliconé contient des segments silicone pendants se rattachant au squelette du polymère.
PCT/US1998/017558 1997-09-04 1998-08-25 Compositions pour couches de colle a faible adherence WO1999011683A1 (fr)

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AU93729/98A AU9372998A (en) 1997-09-04 1998-08-25 Low adhesion backsize coating compositions

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US92323497A 1997-09-04 1997-09-04
US08/923,234 1997-09-04

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2001027212A1 (fr) * 1999-10-08 2001-04-19 3M Innovative Properties Company Formulations de revetement detachable fournissant des surfaces detachables a faible adherence a des adhesifs autocollants
US6406787B1 (en) 1999-03-30 2002-06-18 3M Innovative Properties Company Digital printable and releasable form construction and composition useful thereto
WO2007063165A1 (fr) * 2005-12-01 2007-06-07 Upm-Kymmene Oyj Materiaux fibreux impermeable nanostructure
US7964264B1 (en) 1999-03-30 2011-06-21 3M Innovative Properties Company Adhesion-enhancing surfaces for marking materials
EP2338452A1 (fr) 2009-12-23 2011-06-29 3M Innovative Properties Company Article d'hygiène
WO2011087828A1 (fr) * 2009-12-22 2011-07-21 3M Innovative Properties Company Feuille adhésive possédant un revêtement de décollage d'épaisseur variée
US8937133B2 (en) 2012-09-25 2015-01-20 National Chiao Tung University Dissoluble PDMS-modified p(HEMA-MAA) amphiphilic copolymer and method for fabricating the same
US9266144B2 (en) 2009-12-22 2016-02-23 3M Innovative Properties Company Method and apparatus for producing a non-uniform coating on a substrate
US9545344B2 (en) 2013-10-23 2017-01-17 Sca Hygiene Products Ab Packaging unit having improved sealing and a method of forming a packaging unit having improved sealing

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EP0379146A2 (fr) * 1989-01-17 1990-07-25 Menicon Co., Ltd. Matériel pour lentille oculaire souple
EP0421588A2 (fr) * 1989-08-14 1991-04-10 Minnesota Mining And Manufacturing Company Methode de préparation de copolymères vinylsiliconiques utilisant un agent de transfert de chaîne de silicone à fonction mercapto et revêtements antiadhésifs ainsi fabriqués
US5262087A (en) * 1991-05-01 1993-11-16 Kose Corporation Water-in-oil type emulsified composition
WO1996005962A1 (fr) * 1994-08-24 1996-02-29 Avery Dennison Corporation Compositions d'organopolysiloxane pour couche antiadhesive durcissant sous l'effet de radiations
EP0781811A2 (fr) * 1995-12-28 1997-07-02 Dow Corning Toray Silicone Co., Ltd. Compositions réticulables de silicone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0379146A2 (fr) * 1989-01-17 1990-07-25 Menicon Co., Ltd. Matériel pour lentille oculaire souple
EP0421588A2 (fr) * 1989-08-14 1991-04-10 Minnesota Mining And Manufacturing Company Methode de préparation de copolymères vinylsiliconiques utilisant un agent de transfert de chaîne de silicone à fonction mercapto et revêtements antiadhésifs ainsi fabriqués
US5262087A (en) * 1991-05-01 1993-11-16 Kose Corporation Water-in-oil type emulsified composition
WO1996005962A1 (fr) * 1994-08-24 1996-02-29 Avery Dennison Corporation Compositions d'organopolysiloxane pour couche antiadhesive durcissant sous l'effet de radiations
EP0781811A2 (fr) * 1995-12-28 1997-07-02 Dow Corning Toray Silicone Co., Ltd. Compositions réticulables de silicone

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6406787B1 (en) 1999-03-30 2002-06-18 3M Innovative Properties Company Digital printable and releasable form construction and composition useful thereto
US6482510B1 (en) 1999-03-30 2002-11-19 3M Innovative Properties Company Digital printable and releasable form construction and composition useful thereto
US7964264B1 (en) 1999-03-30 2011-06-21 3M Innovative Properties Company Adhesion-enhancing surfaces for marking materials
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
AU752554B2 (en) * 1999-08-24 2002-09-19 3M Innovative Properties Company Digitally printable releasable coating and form construction using this coating
WO2001027212A1 (fr) * 1999-10-08 2001-04-19 3M Innovative Properties Company Formulations de revetement detachable fournissant des surfaces detachables a faible adherence a des adhesifs autocollants
US6541109B1 (en) 1999-10-08 2003-04-01 3M Innovative Properties Company Release coating formulation providing low adhesion release surfaces for pressure sensitive adhesives
GB2446999B (en) * 2005-12-01 2011-06-15 Upm Kymmene Oyj Nanostructured release paper
GB2446999A (en) * 2005-12-01 2008-08-27 Upm Kymmene Oyj Nanostructured repellent fibrous material
WO2007063165A1 (fr) * 2005-12-01 2007-06-07 Upm-Kymmene Oyj Materiaux fibreux impermeable nanostructure
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
WO2011087828A1 (fr) * 2009-12-22 2011-07-21 3M Innovative Properties Company Feuille adhésive possédant un revêtement de décollage d'épaisseur variée
US9266144B2 (en) 2009-12-22 2016-02-23 3M Innovative Properties Company Method and apparatus for producing a non-uniform coating on a substrate
US9950339B2 (en) 2009-12-22 2018-04-24 3M Innovative Properties Company Method for producing a non-uniform coating on a substrate
EP2338452A1 (fr) 2009-12-23 2011-06-29 3M Innovative Properties Company Article d'hygiène
WO2011079046A1 (fr) 2009-12-23 2011-06-30 3M Innovative Properties Company Article d'hygiène
US8937133B2 (en) 2012-09-25 2015-01-20 National Chiao Tung University Dissoluble PDMS-modified p(HEMA-MAA) amphiphilic copolymer and method for fabricating the same
US9545344B2 (en) 2013-10-23 2017-01-17 Sca Hygiene Products Ab Packaging unit having improved sealing and a method of forming a packaging unit having improved sealing
US9821940B2 (en) 2013-10-23 2017-11-21 Sca Hygiene Products Ab Packaging unit having improved sealing and a method of forming a packaging unit having improved sealing

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