EP0820486A1 - Auto-adhesif - Google Patents

Auto-adhesif

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Publication number
EP0820486A1
EP0820486A1 EP96909834A EP96909834A EP0820486A1 EP 0820486 A1 EP0820486 A1 EP 0820486A1 EP 96909834 A EP96909834 A EP 96909834A EP 96909834 A EP96909834 A EP 96909834A EP 0820486 A1 EP0820486 A1 EP 0820486A1
Authority
EP
European Patent Office
Prior art keywords
phr
layer
concentration
sensitive adhesive
pressure sensitive
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP96909834A
Other languages
German (de)
English (en)
Other versions
EP0820486A4 (fr
Inventor
Karl W. Kreckel
Horst Honig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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 Co filed Critical Minnesota Mining and Manufacturing Co
Priority to EP96909834A priority Critical patent/EP0820486A4/fr
Publication of EP0820486A1 publication Critical patent/EP0820486A1/fr
Publication of EP0820486A4 publication Critical patent/EP0820486A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09J151/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers

Definitions

  • the present invention relates to a removable and/or reactivatable transparent pressure sensitive adhesive obtainable by polymerizing an alkyl acrylate based precursor comprising a filler component.
  • the invention further relates to unsupported films and to supported films comprising said pressure sensitive adhesive arranged on a flexible or stiff backing or carrier film.
  • PSAs Removable pressure sensitive adhesives
  • smooth substrates such as glass, metal, wood, paper with matte or glossy finish surfaces or polymer substrates over a long period of time without damaging the substrate or leaving any adhesive residue or stain on the surface
  • PSAs Removable pressure sensitive adhesives
  • They are often provided as a sheet material which may be unsupported or supported by a flexible backing such as, for example, a biaxially-oriented polyethylene terephthalate film or by a stiff backing such as, for example, a polyurethane foam laminated with paper sheets.
  • the removable PSA must provide a quick initial adhesion (sufficient initial tack or quick stick) to quickly fix the adhesive to the desired substrate.
  • the PSA should exhibit only a low and at any rate acceptable adhesion build-up with time, even at elevated temperatures, to ensure clean peelability after a prolonged dwell.
  • the PSA should furthermore be characterized by an adequate peel strength to give a reliable, high performance adhesion to the substrate without damaging the substrate when removing the adhesive. Another requirement is a sufficient cohesive and tensile strength and hence form and dimensional stability of the PSA sheet to allow proper handling and, in particular, the reapplication of the PSA to substrate after having peeled it off once or several times.
  • the cohesive strength must be adjustable to the thickness of the adhesive layer and should typically be higher the thicker the adhesive layer. A sufficient cohesive strength is also required in order to limit the cold flow of the adhesive on a surface, a process which leads to an undesirable build-up of peel strength over time.
  • the static shear strength should be high enough to allow light-duty mounting applications without being too high to result in permanent adhesion.
  • the PSA should furthermore be relatively insensitive against contamination with, for example, dust, dirt or sweat, to ensure a sufficient number of cycles of removing and reapplication, and/or the PSA should be reactivatable or cleanable to increase the reusability and to ensure proper performance of the PSA during its lifetime.
  • the PSA should be transparent for visible light in order to allow, for example, an essentially invisible mounting of objects on transparent substrates such as glass or transparent polymers.
  • US 4,599,265 (Es ay) describes a removable PSA in which the monomer component is based on alkyl acrylates and can contain up to 3 mole% of strongly polar copolymerizable monomers and up to 15 mole% of moderately polar copolymerizable monomers.
  • the desired 180° peel properties from glass are adjusted by adding a crosslinker component to the precursor of the PSA.
  • the PSA material described by Es may exhibits rather low values of the shear strength and tensile strength which do not meet all practical requirements. It is furthermore often characterized by a rather high solubility for organic solvents.
  • the PSA material by Esmay furthermore exhibits some drawbacks with respect to its mechanical handleability and it is, for example, often difficult to diecut or to slit.
  • US 4,710,536 (Klingen et al.) describes a PSA, the precursor of which mainly relies on alkyl acrylates and additionally contains polar comonomers like, for example, acrylic acid in a concentration of typically 10%.
  • the precursor of the PSA further contains hydrophobic silica as a filler in an amount by weight of 2-15 phr. Tapes comprising the PSA by Klingen are, however, only initially removable, "but within a few days they normally cannot be removed" (see col.4, Ins. 43-50).
  • the PSA by Klingen is furthermore characterized by a relatively poor reactivatability.
  • WO 93/3,148 (Everaerts et al.) describes a removable, low melt viscosity acrylic PSA, the precursor of which comprises a lower alkyl and a higher alkyl acrylate component, a polar comonomer component and a crosslinker component.
  • the PSA by Everaerts is, however, characterized by a relatively poor reactivatability.
  • removable PSA materials described in the state of the art thus do not meet the profile of properties mentioned above to a sufficient and/or practically desirable degree. Therefore there currently exists a need for removable PSA materials which display a superior balance of tack, peel strength, cohesive strength, shear strength, resistance against water and organic solvents, reactivatability and optical transparency.
  • the present invention furthermore refers to unsupported or supported films which comprise the pressure sensitive adhesive according to the present invention.
  • Supported films comprise a backing bearing at least one exposed adhesive layer on one side of the backing or at least one exposed adhesive layer on each of the two opposite sides of the backing, thus forming a single-coated or a double-coated film, the adhesive layer in the single-coated film and at least one of the adhesive layers in the double-coated film being a pressure sensitive adhesive according to the present invention.
  • the invention furthermore refers to a double-coated film comprising a backing bearing at least one exposed adhesive layer on each of the opposite sides of a backing with at least one of the adhesive layers being a reactivatable and removable pressure sensitive adhesive which exhibits a value of 90° peel adhesion of the uncontaminated virgin pressure sensitive adhesive layer on stainless steel after a dwell time of 20 minutes at room temperature of between 3 N/1.27 cm and 20 N/1.27 cm.
  • the PSA materials and the films according to the present invention exhibit advantageous properties and they are highly suitable for a great variety of applications such as, for example, as reactivatable mounting devices, as skid- resistant pads or skid-resistant feet, cushions or spacers to provide protection, as cleaning devices, as temporary labels, signs or decorative sheetings or strips, protective coatings, free layer vibration dampers or constrained layer vibration dampers.
  • the PSA materials and the films according to the present invention can be tailor-made and optimized in order to meet the requirements of a specific application to an especially high degree.
  • the present invention relates to removable PSA materials which preferably are also reactivatable.
  • PSA materials which predictably adhere but are repeatedly peelable from a variety of smooth substrates over a long period of time without damaging the substrate or leaving any adhesive residue or stain on the surface, are usually described as removable.
  • PSA materials which exhibit an initial value of 90° peel adhesion after 20 minutes dwell time at room temperature on stainless steel of the fresh, i.e., uncontaminated adhesive layer of less than 20 N/1.27 cm which value does not change by more than 50% after 3 days dwell time at room temperature, are termed as removable. Above the limit of 20 N/ 1. 27 cm, removing of the PSA materials from stainless steel is often found to be difficult, and splitting is frequently a, observed, in particular, for PSA materials exhibiting a low crosslinking density.
  • the removable PSA materials according to the present invention can be classified as follows:
  • PSA materials as used in the present specification thus refers to materials which exhibit low or very low values of adhesion (peel adhesion > 0, in particular >O.l N/1.27 cm and ⁇ 3 N/1.27 cm) to medium or high values of adhesion (peel adhesion ⁇ 20N/1.27 cm) and which can be designed for a wide variety of applications ranging from mounting devices to skid-resistant pads. It should be noted that the present use of the term PSA thus extends beyond what in conventional use is covered by this term.
  • reactivatable as used above and below, relates to PSA materials exhibiting after 10 cycles of contamination and reactivation according to methods I or II as described below, values of 90° peel adhesion after 20 minutes dwell time at room temperature on stainless steel of 50% or more with respect to the corresporidiniz values of 90° peel adhesion measured for the fresh, uncontaminated adhesive layer.
  • PSA materials exhibiting after 10 cycles ofcontamination and reactivation a value of 90°desiree peel adhesion of 50% or more with respect to the value of 90° peel measured for the fresh, uncontaminated adhesive layer for one of the two methods I and ⁇ , and a value of 60% or more for the other of both methods.
  • the precursor of the removable PSA material according to the present invention comprises one or more alkyl acrylates the alkyl groups of which have an average of 4-14 C atoms.
  • the term average of 4-14 C atoms means that the average number of C atoms of the alkyl acrylate compounds, weighed by their respective percentage by weight with respect to the mass of the alkyl acrylate component, is between 4-14 and, in particular, between 4-12 C atoms.
  • lower alkyl acrylates used in the invention include but are not limited to, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2- ethylhexyl acrylate, isooctyl acrylate, n-octyl acrylate, n-octyl methacrylate, 2- methylbutyl acrylate, isononyl acrylate, n-nonyl acrylate, isoamylacrylate, n-decyl acrylate, isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, 4-methyl-2- pentyl acrylate and dodecyl acrylate.
  • Preferred lower acrylate and methacrylate esters include isooctyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate and dodecyl acrylate.
  • the precursor of the PSA can contain alkyl esters of unsaturated aliphatic carboxylic acids other than acrylic acid such as, for example, alkyl maleates and alkyl fumarates (based, respectively, on maleic and fumaric acid).
  • alkyl maleates and alkyl fumarates based, respectively, on maleic and fumaric acid.
  • dibutyl maleate, dioctyl maleate, dibutyl fumarate and dioctyl fiimarate are preferred.
  • the amount of ester compounds of unsaturated aliphatic carboxylic acids are preferred.
  • polar monomers includes both moderately polar and strongly polar monomers.
  • Polarity i.e., hydrogen-bonding ability
  • references describing these and other solubility terms include 'Solvents Paint Testing Manual, 3rd ed., G.G. Seward, Ed., American Society for Testing and Materials, Philadelphia, Pennsylvania, and 'A Three-Dimensional Approach to Solubility ', Journal of Paint Technology, Vol. 38, No. 496, pp. 269-280.
  • strongly polar monomers are acrylic acid, methacryhc acid and acrylamides while N-vinyl lactams such as, for example, N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile and dimethyl amino-propyl methacrylate are typical examples of moderately polar monomers.
  • Hydrophobic silica is commercially available, for example, from Degussa, Hanau as “Aerosil” R972, R974 or R976. According to a Degussa bulletin entitled "Product
  • hydrophobic silicas “Aerosil” R972, R974 and R976 are prepared from hydrophilic silicas denoted as "Aerosil” 130, 200 and 300, respectively, which exhibit a surface area of 130, 200 and 300 m 2 /g, respectively.
  • Hydrophobic silica is furthermore commercially available, for example, as TS-720 from Cabot Cab-O-Sil Division, Tuscola, Illinois, U.S.A.
  • TS-720 from Cabot Cab-O-Sil Division, Tuscola, Illinois, U.S.A.
  • US 2,859, 198 Sears et al.
  • it is proposed that the surface of finely-divided inorganic solid silicon-containing materials, such as silica can be rendered hydrophobic by treating the material with an organo-siloxane material.
  • silica can be treated with organosilicon materials such as chlorosilanes, silazanes, alkoxysilanes and cyclic siloxanes to produce hydrophobic surfaces" (col.6, Ins. 47-52).
  • hydrophobic silica in combination with the other components of the precursor of the PSA materials according to the present invention as specified, results in an outstanding and especially advantageous balance of properties.
  • hydrophilic silica When mixing hydrophilic silica with the other components of the precursor of the PSA according to the present invention, uniform and useful dispersions are obtained only up to loadings of about 4 phr while hydrophobic silica allows concentrations of up to 25 phr or even more.
  • the limited range of concentration accessible with hydrophilic silica results in a lower mechanical strength of the PSA materials and restricts the possibilities of the formulator to finetune the properties of the PSA material.
  • polysaccharide fillers such as cellulose fibres, starch fibres or cotton fibres, yield PSA materials with limited reactivatability, especially after contamination with finely divided or powdered particles such as dust.
  • Mixing polysaccharide fillers with the other components of the precursor of the present invention results in PSA materials which exhibit on smooth surfaces such as, for example, stainless steel or glass a decrease of shear strength with increasing crosslinker concentration while the PSA materials according to the present invention show the opposite behavior.
  • PSA materials containing cellulose fillers are furthermore white-opaque and therefore both less attractive from an aesthetic point of view and of restricted applicability.
  • the filler component of the PSA materials according-, to the present invention mainly consists of one or more hydrophobic silicas which may differ with respect to their surface area and/or the method of preparation used.
  • the filler component preferably contains at least 75 wt.%, especially not less than 85 wt.% and very particularly 100 wt.% of one or more hydrophobic silicas With respect to the mass of the filler component.
  • the precursor according to the present invention contains a crosslinker component to increase the cohesive strength and the tensile strength of the resulting PSA material
  • a crosslinker component to increase the cohesive strength and the tensile strength of the resulting PSA material
  • Useful crosslinkers include benzaldehyde, acetaldehyde, anthraquinone, various benzophenone-type and vinyl-halomethyl-s-triazine type compounds such as, for example, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine.
  • polyacrylic-functional monomers such as, for example, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 1,2-ethylene glycol diacrylate, tripropyleneglycoldiacrylate, 1,6-hexanediol diacrylate or 1, 12-dodecanediol diacrylate.
  • the compounds listed above, which can be substituted or unsubstituted, are intended to be illustrative and by no means limitative.
  • the crosslinking component to be used in the present invention preferably contains 1-5, especially between 1-3 and very particular 1-2 crosslinker compounds.
  • Especially preferred crosslinker compounds are 1,6-hexanedioldiacrylate and tripropyleneglycoldiacrylate.
  • crosslink density The degree of crosslinking (crosslink density) which can be expressed as the number of cross-links per gram or per unit volume of the polymer, can be estimated theoretically and determined experimentally, for example, by swelling measurements or via stress strain curves (see Encyclopedia of Polymer Science and Engineering, 2nd. ed., New York 1988, vol. 4, p. 355-357). A detailed description of swelling measurements which are preferred, is given in P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaca and London, 1953, p. 579.
  • crosslink density obtained depends on the chemical nature of the crosslinkers used, their functionality and their respective concentratin.
  • the crosslink density is reported with respect to the crosslink density which is obtainable by using variable amounts of tripropyleneglycol diacrylate (TPGDA) as a reference crosslinker component under standardized reaction conditions (bulk photopolymerization, photoinitiator: Irgacure 651, supplied by Ciba Geigy, in a concentration of 0.24 phr; UV irradiation with an exposure of 90°- 1500 mJ/cm 2 from an UV lamp, 90% of the emissions of which are between 300 and 400 nm, with a maximum at 351 nm-, room temperature-, normal pressure-, exclusion of oxygen).
  • TPGDA tripropyleneglycol diacrylate
  • the precursor according to the present invention contains one or more crosslinker compounds in a concentration to give a crosslink density obtainable by using
  • the precursor according to the present invention preferably contains one or more crosslinker compounds in a concentration to cave a crosslink density obtainable by using TPGDA in a concentration between 0.3 - 4.5 phr.
  • concentration of TPGDA preferably is between 0.4 to 4.0 phr, and especially preferably between 1.0 and 4.5 phr.
  • the PSA materials according to the present invention can be obtained by applying generally known polymerization methods such as bulk, solution, emulsion or suspension polymerization. Due to environmental reasons bulk polymerization is often preferred in order to avoid using organic solvents.
  • the polymerization reaction is preferably started by means of a polymerization initiator and preferably proceeds via a radical polymerization mechanism
  • polymerization initiators include photoactivatable initiators such as, for example, benzoin ethers (e.g., benzoin methyl ether, benzoin isopropyl ether,
  • Substituted benzoin ethers such as anisoin-methyl ether), acetophenones (e.g., 2- diethoxyacetophenone) or alpha-ketols (e.g., 2-methyl-2-hydroxy-propiophenone), and/or thermally activatable initiators such as, for example, organic peroxides (e.g., benzoyl peroxide and lauryl peroxide) and 2,2'-azobis(isobutyronitrile). Photopolymerization and the addition of photoactivatable initiators are preferred.
  • organic peroxides e.g., benzoyl peroxide and lauryl peroxide
  • 2,2'-azobis(isobutyronitrile 2,2'-azobis(isobutyronitrile
  • the initiator component preferably comprises between 1-3 and, in particular, between 1-2 initiator compounds, especially preferred are initiator components containing only one photoinitiator.
  • the initiator component is preferably present in an amount of 0.01 -2.00 phr, in particular, between 0.05-1.00 phr and very specifically between 0.1 -0.5 phr.
  • a part of the initiator component is added to the alkyl acrylate component which is partly polymerized to a degree of typically 2- 30% to form a syrup of coatable viscosity of, for example, 300-20,000 cps (Brookfield) at ordinary room temperatures.
  • the viscosity of the syrup is preferably adjusted to the amount of hydrophobic silica to be added.
  • the viscosity of the syrup preferably is not more than 1,000 cps and, in particular, between 250 and 1,000 cps.
  • the polymerization is carried out with UV black lights having over 60 percent, and preferably over 75 percent of their emission spectra between 280 to 400 nm, with an intensity between about 0.1 to about 25 mW/Cm 2 .
  • the exposure is typically between 90° -1,500 mJ/cm 2 .
  • the polymerization may be stopped either by removal of the radiation or heat source and/or introduction of, for example, radical scavenging oxygen.
  • the filler component essentially comprising hydrophobic silica, s subsequently added to the prepolymerized syrup.
  • hydrophobic silica exceeds about 8 phr, it has been found necessary to employ a high-shear mixer such as a paint mill to obtain uniform dispersions. By doing so and by properly adjusting the viscosity of the prepolymerized syrup, useful and essentially uniform dispersion can be obtained for loadings as high as about 25 phr.
  • the dispersion obtained is mixed with the remaining part of the initiator component and, optionally, with other adjuvants such as, for example, chain transfer agents, polymer additives like, for example, those described in EP 0,349,216 or EP
  • solvents fire retardants, pigments, colorants, odor masking agents and or other adjuvents known in the tape art.
  • solvents, fire retardants, pigments, colorants, odor masking agents and or other adjuvents known in the tape art are especially preferred.
  • pigments, colorants and/or paints which impart color to the resulting PSA materials without adversely affecting their transparency and clarity.
  • An example of a suitable paint is Yellow Permalink CTL-Druckate (printing paint) which is obtainable from
  • the above dispersion or mixture obtained is coated onto a backing, a carrier web or a release liner and polymerized in an inert, i.e. oxygen free atmosphere, for example a nitrogen atmosphere.
  • an inert i.e. oxygen free atmosphere
  • film is used to describe a structure whose thickness is substantially, less than either its length or width and which has two, essentially parallel opposed surfaces.
  • film includes, for example, sheets, ribbons, tapes and discs.
  • the films obtained can be supported or unsupported, and they exhibit a thickness between 30 to 20,000 ⁇ m, preferably between 100 10,000 ⁇ m, especially between 200-10,000 ⁇ m and very specifically of more than 250 ⁇ m.
  • Supported films comprising two exposed adhesive layers on opposite sides of the backing, will be termed above and below as double-coated films while supported films comprising one exposed adhesive layer on one side of the backing only, will be termed above and below as single-coated films.
  • the present invention allows the preparation of relatively thick to thick adhesive films which is due to the excellent mechanical properties of the PSA material according to the present invention.
  • unsupported films with a thickness of at least 200 ⁇ m comprising a
  • Supported films exhibiting at least one adhesive layer according to the present invention with a thickness of at least 200 ⁇ m are also especially preferred.
  • the properties of the PSA material and films according to the present invention can be optimized in view of the intended use or application within wide limits.
  • the amount of hydrophobic silica (or hydrophobic silicas) must be at least about 2 phr because below this limit, the internal mechanical strength and the handleability in terms of diecuttability, for example, was found to be insufficient in many cases.
  • the mechanical properties of the PSA materials according to the present invention mainly depend both on the loading with hydrophobic silica and on the crosslink density. It was found that for low crosslink densities obtainable by using TPGDA in a concentration of 0.30 phr or less, the loading with hydrophobic silica preferably is at least 5 phr, in particular, not less than 10 phr and very specifically 12.5 phr or more.
  • the amount of hydrophobic silica is at least 2 phr, preferably at least 4 phr, in particular, not less than 5 phr and very specifically not lower than 8 phr.
  • the upper limit of the amount of hydrophobic silica of about 25 phr is due to practical reasons because it was found difficult to obtain uniform dispersions above this limit.
  • the PSA materials according to the present invention preferably contain 4-20 phr and especially between 5-15 phr of hydrophobic silica.
  • the PSA materials according to the present invention preferably contain no polar comonomer component in order to obtain a high resistivity against water and organic solvents and hence a high reactivatability.
  • a small amount of polar comonomers might be added in order to improve the abrasion resistance of the PSA material. The addition of a small amount of polar monomers was found to be particularly useful in case of skid resistant materials.
  • the cohesive strength, the tensile strength, the elongation, the shear strength and the peel adhesion are interrelated and they are mainly influenced by the crosslink density, the loading with filler and the thickness of the adhesive layer.
  • the PSA material typically is a rather soft mass, especially in case the loading with hydrophobic silica is less than 10 phr, and exhibits a high peel adhesion.
  • this PSA material is preferably stabilized by a backing or carrier layer in order to render it diecuttable; the backing can be omitted in case the PSA material is used in form of a roll.
  • the low crosslink density PSA material exhibits a rather high to high peel adhesion and sticks also to rather rough surfaces.
  • the loading with hydrophobic silica preferably is at least 5 phr, especially at least 7.5 phr and very specifically not less than 10 phr.
  • the thickness of the adhesive layer must not be too high and is preferably not more than 1,000 ⁇ m, especially less than 500 ⁇ m and very particularly less than 250 ⁇ m.
  • the crosslink density is not lower than the crosslink density obtainable by using about 0, 15 phr, preferably not lower than about 0.3 phr and very especially not lower than about 0.35 phr of
  • the PSA material exhibits a limited internal mechanical strength which adversely affects the requirement of clean removability, dimensional stability and proper handleability, and it was found that the mechanical properties typically cannot be sufficiently improved when increasing the loading with hydrophobic silica to high levels of more than 15 phr.
  • the peel strength of the PSA materials from stainless steel was often found to be too high to ensure reliable removability which is, in particular, true for medium to low fillings with hydrophobic silica of 12.5 phr and especially of 10 phr or less.
  • the PSA materials furthermore often exhibit a pronounced cold flow on a surface which results in an undesirable build-up of peel strength over time, and they furthermore show an increased sensitivity against contamination, especially against contamination with organic compounds.
  • the cohesive strength of the PSA materials according to the present invention increases while peel adhesion decreases.
  • the PSA material typically sticks to itself but can be easily separated.
  • the PSA material only slightly sticks to itself but still adheres well, especially to smooth surfaces such as lass, metal or plastic surfaces or to glossy paper.
  • PSA materials with a crosslink density obtainable by using about 4.0 - 5.0 phr or more of TPGDA are characterized by a very high shear strength and an excellent skid resistance but by a low to very low peel adhesion even on smooth surfaces. It was found that the PSA materials according to the present invention exhibit a continuous increase in shear strength with increasing, crosslink density especially on smooth or relatively smooth substrates which allows, for example, the realization of skid-resistant supports which simultaneously exhibit a high shear strength and a low peel adhesion, This behavior is surprising and is not observed, for example, for PSA materials containing cellulose fillers. These state of the art materials exhibit decreasing values of shear strength with increasing a crosslink densities at a constant filler loading and therefore provide low peel adhesiorTlow shear strength materials.
  • the cohesive strength, the shear strength and the peel adhesion can also be influenced by varying the loading with filler and the thickness of the adhesive layer.
  • the peel adhesion is being decreased by increasing the filler load with hydrophobic silica so that using high filler loads of at least 10 phr is preferred in case of PSA materials exhibiting a low crosslink density obtainable with TPGDA concentrations of 0.50 wt.% or less. It was further found that for a given crosslink density and filler load, the peel adhesion can be increased with increasing thickness of the adhesive layer.
  • Crosslink density, filler load and layer thickness can be adjusted and optimized with respect to the respective application. Some especially preferred combinations of these parameters will be discussed below. It should be noted that this discussion refers to the properties of unsupported PSA materials according to the present invention, i.e., to the PSA material as such. The person skilled in the art can use below compilation of parameter combinations as a guidline when designing specific film or tape constructions such as, for example, single-coated or double-coated films.
  • crosslink density obtainable by using a concentration of TPGDA between 0.15 and 0.5 phr, especially between 0.20 and 0.50 phr and very particularly between 0,20 and 0.40 phr • hydrophobic silica between 10 - 25 phr, especially between 10-20 phr
  • These materials are characterized by an especially advantageous combination of peel adhesion and shear strength, and they are especially suited for use on smooth surfaces such as glass, metal or plastic surfaces which optionally may be painted or otherwise coated with a smooth coating material. Due to their high shear and adhesion strength especially on smooth surfaces, they can be used, for example, for light weight mounting applications but also for a great variety of other applications. They exhibit a high internal mechanical strength and can be cleanly and reliably removed from a surface both when used as a supported or phr or more, can cleanly be removed from the matte-finish offset paper substrate mentioned above.
  • crosslink density obtainable by using a concentration of TPGDA between 2.0 and 5.0 phr • hydrophobic silica between 2.5 - 12.5 phr, especially between 10 phr
  • PSA materials exhibit a low to very low peel adhesion even on smooth surfaces and are characterized by a very high shear strength on smooth surfaces, an excellent internal mechanical strength and a high to very high skid resistance.
  • PSA materials according to the present invention exhibiting a medium crosslink level obtainable by using TPGDA in a concentration between 0.40 and 3.0 phr.
  • the PSA materials according to the present invention are preferably reactivatable and/or exhibit a low sensitivity towards contamination. Even after heavy contamination with dust, dirt or organic compounds etc., the surface of the PSA materials according to the present invention typically can be cleaned by applying, for example, an aqueous soap solution, lower alcohols like methanol or ethanol or acetone. The PSA layer is then typically rinsed with water and dried.
  • the process of reactivation described is intended to be only illustrative and by no means limitative; the expert can easily give other methods without any inventive input. It was found that the adhesion recovers even after several cycles of contamination and reactivation to a substantive to high or very high percentage with respect to the adhesion of the fresh and uncontaminated PSA layer.
  • the PSA materials according to the present invention are characterized by an outstanding balance of tack, peel strength, cohesive strength, shear strength, resistance against water and organic solvents, optical transparency, removability and/or reactivability and they can advantageously be used for a number of applications.
  • the PSA material according to the present invention is used as unsupported film which when used in the form of single sheets or stripes is typically protected by two release liners while one release liner is usually sufficient when used in form of a roll.
  • Suitable release liners are, for example, siliconized papers, siliconized polyesters, polyethylenes or polymer films treated with fluorochemicals; when using the unsupported film in form of a roll, the release liner preferably exhibits release properties on both sides with the backside typically exhibiting a lower adhesion than the front side.
  • Especially preferred unsupported films exhibit a thickness between 50 and 2,000 ⁇ m, in particular, between 100 and 1,500 ⁇ m and especially of at least 250 ⁇ m.
  • the loading with hydrophobic silica preferably varies between 5 and 17.5 phr and, in particular, between 5 and 15 phr.
  • Crosslinking densities obtainable by using a TPGDA concentration between 0.4 and 2.0 phr, in particular, between 0.4 and 1.8 phr and very specifically between 0.4 and 1.5 phr are preferred.
  • These especially preferred unsupported films are characterized by a high cohesive strength and a medium peel adhesion.
  • the unsupported films can be diecut, for example, 'on edge', i.e., in such a way that the diecut parts are directly adjacent to each other with no supporting spacings being left between them. This results in a considerable reduction or even complete avoidance of waste.
  • the supported films can be used in light-duty mounting applications on rough surfaces such as, for example, mounting a piece of paper on the wall, or in higher load mounting applications on smooth surfaces such as, for example, mounting advertising emblems on walls. Since the PSA material is transparent, transparent or translucent signs such as those made of polycarbonate or polymethylmethacrylate can be attached, for example, to glass surfaces with no glue lines or adhesive strips being visible from the front which is especially attractive from an aesthetic point of view.
  • Another especially preferred embodiment of unsupported films according, to the invention exhibits the following properties:
  • crosslink density obtainable by using a concentration of TPGDA between 0.17 and 0.4 phr
  • hydrophobic silica between 10 - 20 phr • film thickness between 50 and 2,000 ⁇ m, in particular between 100 and
  • These unsupported films exhibit an advantageous shear strength especially on rough, embossed surfaces and can be used for mounting applications on these surfaces which can be found, for example, in display boards used in exhibitions.
  • Display boards are available, for example, through Form &technik, Neckartailfingen, Germany as Hardboard MDF (medium density fibre) MEWA Standard White (3.2 mm thick, PVC coated).
  • MDF medium density fibre
  • MEWA Standard White 3.2 mm thick, PVC coated.
  • one exposed adhesive layer is applied to each of the opposite sides of a carrier layer or backing thus forming a double-coated film with at least one of these adhesive layers comprising a PSA material according to the present invention.
  • the other adhesive layer may also comprise a PSA material according to the present invention or another PSA material known . In the art which may be removable or permanent.
  • the double-coated film can comprise more than two adhesive layers which is the case, for example, when a laminated backing comprising one or more adhesive layers, is used.
  • the term double-coated film means that the film comprises two exposed adhesive layers.
  • the carrier layer or backing may be selected from a group of materials comprising polymeric films of various stiffness such as, for example, polyolefins, polyesters, polycarbonates or polymethacrylates, papers, non-wovens, laminates (such as, for example, polyethylene or polyurethane foams laminated on both sides with permanent acrylic adhesives, or papers laminated or jig- welded with polyethylene terephthalates), one part mechanical fasteners (which are described, for example, in US 5,077,870) or metals.
  • the thickness of the carrier layer typically varies between 25 ⁇ m and 3,000 ⁇ m, preferably between 25 and 1,000 ⁇ m.
  • the carrier material should be selected such that both layers of the adhesive bond very strongly to it. Such a choice can be made easily and does not require any inventive input from the expert.
  • the carrier material may be treated with chemical primers or may be corona treated.
  • the respective adhesive masses can be laminated onto the carrier sheet by means of transfer tapes in the form of cured adhesive films but it is also possible to coat the precursors of the respective adhesive layers onto the carrier layer with subsequent, for example, photochemical curing.
  • the adhesive layers which are applied to the opposite sides of the carrier layer may be different from each other or equal to each other.
  • the double-coated films When storing the double-coated films, for example, in form of a roll or in form of sheets or stripes, these must be protected on both sides of the film with release liners.
  • the release liners discussed above for unsupported films, can also be used for double-coated films.
  • double-coated films comprising two exposed adhesive layers according to the invention on opposite sides of the carrier layer.
  • at least one of the adhesive layers exhibits a crosslinker density obtainable by using TPGDA in a concentration of at least O.3 phr.
  • differential adhesion double-coated films which is to be termed as differential adhesion double-coated films
  • the two adhesion layers are different from each other and or exhibit different values of peel adhesion.
  • the values of 90° peel adhesion on stainless steel differ by at least 10%, especially by at least 30% and very particularly by at least 50% or more.
  • Differential adhesion double-coated films are especially important from a practical point of view because the adhesion properties of the film can be adjusted and optimized with respect to the intended application.
  • a permanent, non-removable high adhesion PSA such as, for example, the acrylate based adhesives described in US Re 24,406, US 4,181,752, US 4,303,485, US
  • rubber resin adhesives or block copolymer adhesives may be coated on one side of the carrier sheet while the other side is coated with a removable PSA material according to the present invention which may -depending on the application- exhibit a low, medium or high crosslinking density.
  • both sides of the double-coated film are coated with an adhesive layer containing a PSA material according to the present invention with the two PSA layers exhibiting a different crosslinker density- the higher adhesion side of the carrier sheet is coated with a PSA material having a lower crosslink density in comparison to the PSA material used on the lower adhesion side.
  • differential adhesion double-coated films according to the invention are differential adhesion double-coated transfer films comprising at least one adhesive layer containing a PSA material according to the present invention.
  • This specific film is useful for various mounting applications where a medium to high value of initial adhesion of the uncontaminated sample is required in order to maintain a sufficient peel adhesion after having performed one or more contamination/reactivation cycles.
  • at least one of the exposed adhesive layers comprises a reactivatable pressure sensitive adhesive according to the present invention.
  • double-coated films the two exposed adhesive layers of which comprise pressure sensitive adhesive materials according to the present invention.
  • the two exposed adhesion layers are different from each other and or exhibit different values of peel adhesion.
  • PSA material according to the present invention preferably exhibits a crosslink density obtainable by using], TPGDA in a concentration between 0.15 and 0.40 phr.
  • Exposed layer 2 preferably exhibits a thickness between 30 and 300 ⁇ m and a silica loading between 20 phr and, in particular, between 4-15 phr.
  • the carrier can be selected from the materials listed above but preferably is selected from the group comprising polyesters, polyethylenes, polystyrenes, polycoated papers, polymethylmethacrylates and laminates; the thickness of the carrier layer preferably varies between 20 ⁇ m and 3 mm.
  • This preferred double-coated film A can be used to immobilize lightweight objects such as, for example, keyboards or tape dispensers on horizontal surfaces.
  • the high adhesion side 2 of the double-coated film is applied to the respective lightweight object while the low adhesion side I serves to removably and slightly adhere the object upon the surface upon which it rests, providing an improved skid resistance.
  • the skid resistance of the low-adhesion side I on a typical table surface can be adjusted and optimized with respect to the respective use by varying the crosslinker level-, the tape and hence the object to which it adheres, is non-slideable and practically immovable on the table when using a crosslink density obtainable by using TPGDA in a concentration between about 1.0-3.5 while it was found to be movable for higher TPGDA concentrations.
  • the skid-resistant film can be re-adhered to the underlying surface and reactivated in case of contamination because of the excellent reactivatability of the PSA material according to the present invention.
  • Preferred double-coated film A can be further used, for example, for transportation and shipping of sensitive electronic components and other fragile goods.
  • large styrofoam corners are used to immobilize objects in a shipping box. the remaining space Is typically filled with free-flowing styrofoam pieces.
  • preferred double-coated adhesive film A can be used to immobilize the roods in the box in combination with free-flowing styrofoam pieces, for example, being still required to provide the shock-absorption function.
  • the double-coated films according to the present invention require distinctly less space than the styrofoam corners and allow use of smaller boxes.
  • the high adhesion side 2 of the double-coated film is preferably adhered to the transportation box so that the double-coated film remains with the packaging and releases from the roods when they are unpacked,
  • these are especially designed, for example, for low-weight mounting applications such as, for example, as penholders, and they can also be used as a frequently reusable closure system of, for example, tobacco bags or bags of paper handkerchiefs.
  • exposed low adhesion layer 1 comprises a PSA material according to the present invention exhibiting a crosslinker density obtainable by using TPGDA in a concentration between 0.5 and 1.5 phr and very specifically between 0.8 and 1.3 phr.
  • the layer thickness preferably amounts to 100-1,500 ⁇ m, and the silica loading preferably is between 5 and 15 phr.
  • This PSA material is characterized both by a high shear strength and a medium to low peel adhesion, and is thus well suited for preparing light-weight mounting devices.
  • Exposed adhesive layer 2 comprises a high adhesion PSA material which may be removable or permanent. Suitable permanent PSA materials include but are not limited to acrylate type adhesives which are described, for example, in US Re 24,406, US
  • Layer 2 preferably comprises a high adhesion PSA material according to the present invention which exhibits a crosslink density obtainable by using TPGDA in a concentration between 0.20 and 0.60 phr, a layer thickness between 30 and 700 ⁇ m and a loading with hydrophobic silica between 2-
  • the carrier layer can be selected from the materials given above.
  • layer 2 Is a PSA material according to the present invention and exhibits a crosslink density obtainable by using TPGDA in a concentration between 0.20 and 0.40 phr, a layer thickness between 30 and 200 ⁇ m and a silica loading between 2-14 phr.
  • Adhesive layer 2 may be laminated onto a rather stiff carrier like, for example, a thick PS foam (typically 300-2,000 ⁇ m) laminated with printable paper sheets; such a carrier material is provided, for example, by Fa. Kapa, Bielefeld. This construction is especially useful for the preparation of light-weight mounting, devices such as, for example, a penholder with the pens being attached to layer 1 while layers 2 fixes the construction onto the respective substrate.
  • layer 2 is a PSA material according to the present invention which exhibits a crosslink density obtainable by using TPGDA in a concentration of between 0.3 - 0.6 phr, a layer thickness of between 50 - 600 ⁇ m and a loading with silica of typically 5-15 phr.
  • Layer 1 is chosen as described above.
  • the carrier layer is, for example, a PET film with a thickness of typically 30-200 ⁇ m. This construction can be used, for example, for attaching printed films of, for example, polypropylene, PET or paper, onto a billboard.
  • the high adhesion layer 1 is replaced with a mechanical, interlocking fastener such as, for example, the Dual LockTM fastener available through 3M, or the hook or loop part of a hook and loop fastener.
  • Low adhesion layer 2 is coated or laminated onto the backside of the fastener.
  • the resulting hybrid construction comprising a mechanical and a chemical fastener, is fixed by means of the mechanical fastener on the respective substrate, which carries, for example, the counterpart of the hook and loop system or another Dual LockTM fastener, while low adhesion layer 2 is exposed.
  • suitable materials include metals such as iron, steel, nickel, aluminum, chromium, cobalt, and copper, and alloys thereof and stiff polymeric materials such as polystyrene; polyester; polyvinylchloride; polyurethane; polycarbonate; polyamide; and polyepoxide; fiber-reinforced plastics such as glass fiber, ceramic fiber, and metal fiber-reinforced polyester, glasses, and ceramics.
  • stainless steel (SS), glass, polypropylene (smooth and glossy surface finish), matte finish paper and glossy paper were used as substrates.
  • the values of 90 and 180 degree peel adhesion were measured after 20 minutes and 3 days dwell time, respectively, at room temperature by moving the free end of the aluminum strip away from the respective substrate by 90 or 180 degree, respectively, and at rate of 305 mm per minute using a tensile tester.
  • adhesive samples were obtained according to the method used in Example 1 except that the amount of hydrophobic silica was kept constant at a value of 10 phr while the concentration of tripropyleneglycoldiacrylate was varied between 0.2 and 5.0 phr.
  • an adhesive sample was prepared according to the method of Example 1 except that acrylic acid was added as a polar comonomer with the mass ratio of acrylic acid to isooctylacrylate amounting to 10/90.
  • the amount of tripropyleneglycoldiacrylate was adjusted to 1.0 phr, and the concentration of hydrophobic silica was 10 phr.
  • adhesive samples were obtained according to the method used in Example 1 except that the amount of hydrophobic silica and tripropyleneglycoldiacrylate, respectively, were kept constant at values of 10 phr and 0.27 phr, respective y, the radiation energy was varied between 500-1,300 mJ/cm 2 .
  • Comparative examples 7-8 In this series of experiments, adhesive samples were obtained according to the method used in examples 39 and 40 except that no hydrophobic silica was added. For these adhesive samples, the same properties as for the adhesive samples of examples 39-40 were determined; they are listed in table 5.
  • PE foam tape 0.8 mm and 1.6 mm thick, available through 3M as PE foam tapes 9528 and 9529, respectively
  • polyester film 40 ⁇ m thick
  • polymethylmethacrylate film PMMA, 2.0 mm thick
  • PET polyethylene terephthalate film
  • LLDPE linear low-density polyethylene
  • adhesive samples were obtained according to the method used in Example 1 except that the prepolymerization was stopped at a lower conversion to give a viscosity of about 400 cps.
  • the amount of hydrophobic silica was chosen to be 13.5 and 20 pph, and the concentration of tripropyleneglycoldiacrylate was 0.3 and 0.4 pph, respectively.
  • Polyethylene terephthalate 50 ⁇ m is used as a backing layer.
  • the double-coated tape obtained was applied to a StikitTM Disc Pad PN05575 (diameter 125 mm, obtainable through 3M) and mounted to a random orbital abrasive machine (Dynabrade 57018).
  • the following flexible abrasives were applied to the double-coated tape subsequently to evaluate adhesion of typical abrasives to the double-coated tape of the invention:
  • ILF 3 mil polyester film coated with a layer of abrasive minerals, Imperial Lapping FilmTM, commercially available through 3M
  • IDLF 1-3 mm polyester film coated with a layer of diamond minerals, Imperial Diamond Lapping FilmTM, commercially available through 3M
  • IMFF 3-5 mil polyester film coated with a layer of abrasive minerals, Imperial Microfinishing FilmTM, commercially available through 3M
  • Polyester/cotton cloth J wt in which the cloth had a phenolic/latex presize and a glue/starch backsize
  • polyester/cotton cloth, X wt in which the cloth had a phenolic/latex presize and a glue/starch backsize
  • the first 5 flexible abrasive classes enumerated showed a good to excellent adhesion on the double-coated tape while the adhesion of the last three flexible abrasive classes was inferior to the first 5 materials but still acceptable.
  • All abrasive discs enumerated were used to abrade wood, steel and stainless steel up to the abrasive endpoint.
  • the temperature resistance of the double-coated tape was excellent even under severe load (offhand sanding with portable tool).
  • Differential adhesion, removable, double-coated adhesive films are prepared according to the method of example 39.
  • the IOA, Irgacure and A/R972 concentration are chosen in each case as follows
  • Polyethylene terephthalate 50 ⁇ m is used as a backing layer.
  • Layer 1 of the double-coated film obtained was applied to a Stikit Disc Pad PN05575 (diameter 125 mm, obtainable through 3M) and mounted to a random orbital abrasive machine (Dynabrade 57018).
  • the following flexible abrasive discs A-D were subsequently applied to layer II of the double-coated film:
  • B:3M 210A Resin Bond Jwt Abrasive Cloth with fuzzy surface (commercially available from 3M)
  • the adhesion was assessed in the following states or after the following treatments, respectively:
  • composition (b) of adhesive layer II For composition (b) of adhesive layer II, additional 15 cycles of contamination and recycling according to (iii) were performed. The result of the subsequent assessment of adhesion was identical to that obtained after 10 cycles in (iv).
  • Example 62 For composition (b) of adhesive layer II, additional 15 cycles of contamination and recycling according to (iii) were performed. The result of the subsequent assessment of adhesion was identical to that obtained after 10 cycles in (iv).
  • UK6006 reflective sheeting (containing a PET backing, commercially available through 3M, UK) which was printed with a thermal transfer system, was coated with an adhesive layer following the method of example 1.
  • the precursor of the adhesive layer had the following composition:

Abstract

La présente invention concerne un auto-adhésif transparent, pouvant être enlevé et/ou réactivé. Cet auto-adhésif peut être obtenu par polymérisation d'un précurseur comprenant un composant monomère qui contient un ou plusieurs acrylates d'alkyle, dont les groupes alkyle comprennent, en moyenne, 4-14 atomes de C, et qui est sensiblement dépourvu de comonomères polaires. En outre, le précurseur comprend au moins 2,0 phr de dioxyde de silicium hydrophobe et un ou plusieurs initiateurs de polymérisation. Ce précurseur comprend également un ou plusieurs composés de réticulation dans une concentration permettant d'obtenir une densité de réticulation, à l'aide d'un tripropylèneglycoldiacrylate utilisé comme composé de réticulation étalon, à raison d'une concentration de 0,15 phr ou plus.
EP96909834A 1995-04-03 1996-03-20 Auto-adhesif Withdrawn EP0820486A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96909834A EP0820486A4 (fr) 1995-04-03 1996-03-20 Auto-adhesif

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP95104953A EP0736585B1 (fr) 1995-04-03 1995-04-03 Adhésif sensible à la pression
EP95104953 1995-04-03
EP96909834A EP0820486A4 (fr) 1995-04-03 1996-03-20 Auto-adhesif
PCT/US1996/003932 WO1996031564A1 (fr) 1995-04-03 1996-03-20 Auto-adhesif

Publications (2)

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EP0820486A1 true EP0820486A1 (fr) 1998-01-28
EP0820486A4 EP0820486A4 (fr) 1998-08-26

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EP96909834A Withdrawn EP0820486A4 (fr) 1995-04-03 1996-03-20 Auto-adhesif

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JP (1) JP4139914B2 (fr)
KR (1) KR100434678B1 (fr)
CN (1) CN1105747C (fr)
AU (1) AU5320896A (fr)
BR (1) BR9604804A (fr)
CA (1) CA2214630A1 (fr)
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KR20150143610A (ko) 2013-04-15 2015-12-23 쓰리엠 이노베이티브 프로퍼티즈 컴파니 (메트)아크릴레이트 기 및 올레핀 기를 갖는 가교결합제를 포함하는 접착제 및 방법
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DE69511843T2 (de) 2000-06-29
CN1105747C (zh) 2003-04-16
EP0736585A1 (fr) 1996-10-09
AU5320896A (en) 1996-10-23
EP0736585B1 (fr) 1999-09-01
CA2214630A1 (fr) 1996-10-10
CN1179788A (zh) 1998-04-22
BR9604804A (pt) 1998-06-09
EP0820486A4 (fr) 1998-08-26
KR19980703512A (ko) 1998-11-05
MX9707436A (es) 1997-12-31
DE69511843D1 (de) 1999-10-07
KR100434678B1 (ko) 2004-10-22
JP4139914B2 (ja) 2008-08-27
JPH11503191A (ja) 1999-03-23
WO1996031564A1 (fr) 1996-10-10

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