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    • 专利摘要:
    UV-crosslinkable cationic acrylic polymers for pressure sensitive adhesives. an ultraviolet (UV) crosslinkable pressure sensitive acrylic adhesive comprises an acrylic copolymer and a cationic photoinitiator. the acrylic copolymer comprises reactive pending functional groups. the pressure sensitive adhesive formed from the acrylic copolymer with the reactive functional groups pending results in high green resistance and / or high retention resistance at high temperature of the adhesive.
    公开号:BR112012022560B1
    申请号:R112012022560
    申请日:2011-03-09
    公开日:2020-01-28
    发明作者:W Paul Charles；Foreman Paul；Palasz Peter；Liu Yuxia
    申请人:Henkel Corp；Henkel IP & Holding GmbH；Henkel US IP LLC；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for ADHESIVE SENSITIVE TO PRESSURE CURABLE BY ULTRAVIOLET AND MANUFACTURED ARTICLE.
    CROSS REFERENCE TO RELATED APPLICATIONS [001] This application claims the benefit of the Patent Application
    US Provisional No. 61 / 311,970 filed on March 9, 2010, whose contents are incorporated herein by reference.
    FIELD OF THE INVENTION [002] The invention relates to an ultraviolet-curable pressure sensitive adhesive comprising an acrylic polymer with pendent reactive functional groups.
    BACKGROUND OF THE INVENTION [003] Pressure sensitive adhesives (PSAs) are aggressive and permanently sticky at room temperature and adhere to surfaces by applying light finger pressure. PSA compositions are commonly applied to various substrates, such as paper, fabric, metal, and plastic films that are then converted into a large number of different products, especially pressure sensitive adhesive tapes and labels. These pressure-sensitive products have a wide field of application in the automotive industry, for example, for fixing or sealing, in the pharmaceutical industry, for example, for bandages or transdermal drug delivery systems, or in the packaging industry, for example, for sealing, mooring or labeling.
    [004] PSAs can be formulated by application as a solvent-borne adhesive or a melted adhesive. Hot-melt pressure sensitive adhesives (HMPSAs) are compositions that combine the properties of hot-melt adhesives with those of pressure-sensitive adhesives. Hot melt adhesives are solid at room temperature, melted at elevated temperatures to
    Petition 870190036793, of 17/04/2019, p. 8/57
    2/35 coat a substrate, and recover their solid form with cooling. The combination of these properties provides compositions that melt at elevated temperatures and cool to form a permanently sticky solid coating that adheres to contact. A good workability HMPSA should exhibit high cohesive resistance at room temperature, low shrinkage on substrates, conservation of pressure-sensitive properties during storage and use, and a relatively fluid viscosity at typical coating temperatures (for example, between 80 and 180 O Ç). Although very low molecular weight polymers produce hot melt adhesives with sufficient fluidity, the resulting adhesives lack cohesive resistance. Very high molecular weight polymers give much better cohesive strength, but are too viscous at the usual application temperatures to be easily applied to substrates. They must be mixed with a high proportion of low molecular weight oils or resins to reduce viscosity. The addition of low molecular weight oils or resins in turn decreases cohesive strength and heat resistance. To avoid these polymers, polymers of moderate molecular weight have been made with various functional groups that undergo cross-linking reactions by heat or actinic radiation. In this way, the cohesion of acrylic PSAs can be increased through sufficient crosslinking.
    [005] Acrylic polymers with epoxy functional groups are already known in the prior art. An example of such polymers is described in JP1186876, however, these polymers do not crosslink under UV radiation and / or heat.
    [006] JP2008-208149 refers to acrylic copolymers with oxymethane compounds not polymerized by free radicals as a polymerization medium and reactive diluent. Polymerization is completed with heat and / or x-ray irradiation to form an adhesive
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    3/35 for a flat panel display.
    [007] JP19940816 and 1996060127 describe UV-curable acrylic polymers, but require the addition of multifunctional polyol and other hydroxy-functional groups to crosslink the polymers.
    [008] JP2003147311 refers to the use of photopolymerizable diacrylate. Due to the difunctional acrylate that cross-links with radical polymerization, it is less desirable for use in an adhesive, and especially unsuitable for a solvent-borne adhesive or hot-melt adhesive, because it is necessary to polymerize the acrylate monomers subsequent to application to the substrate. final coated.
    [009] There is a growing demand and constant need in the art for UV crosslinkable acrylic polymers that can be formulated as solvent-borne adhesives and / or that are processable by hot fusion. The present invention satisfies this need by offering acrylic polymers that are functionalized with pendent reactive functional groups and cationic photoinitiators and, subsequent to the coating operation, are crosslinked under UV irradiation on the substrates. The invention provides the technique with both solvent-borne acrylic PSAs and hot-melt acrylic PSAs.
    SUMMARY OF THE INVENTION [0010] The invention offers a cationic ultraviolet-curable pressure sensitive adhesive comprising (a) crosslinkable acrylic polymers comprising pendent reactive functional groups and (b) a cationic photoinitiator.
    [0011] In one embodiment, the crosslinkable acrylic polymer (a) of the adhesive comprises (i) an acrylic monomer that is a derivative of acrylic or methacrylic acid of the formula CH2 = CH (R1) (COOR2), where R1
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    4/35 is H or CH3 and R2 is a C1-20 alkyl chain and (ii) a monomer with a pending reactive functional group selected from cycloaliphatic epoxide, oxyethane or mixtures thereof, and the amount of the monomer (ii) varies from about from 0.001 to about 0.015 equivalent per 100 g of acrylic polymer. The acrylic polymer is essentially free of multi- (meth) acrylate, polyol or OH-functional groups and the polymer remains substantially linear after polymerization.
    [0012] In another embodiment, the crosslinkable acrylic polymer (a) of the adhesive comprises (i) an acrylic monomer that is a derivative of acrylic or methacrylic acid of the formula CH2 = CH (Ri) (COOR2), where Ri is H or CH3 and R2 is a C1-20 alkyl chain and (ii) a monomer with a combination of outstanding reactive functional groups selected from (1) cycloaliphatic epoxide, oxyethane, benzophenone or mixtures thereof, and (2) monosubstituted oxirane; and the amount of monomer (ii) is the amount of about 0.001 to about 0.015 equivalent per 100 g of the acrylic polymer. The acrylic polymer is essentially free of multi- (meth) acrylate, polyol or OH-functional groups and the polymer remains substantially linear after polymerization.
    [0013] In another modality, the cationic photoinitiator (b) the adhesive has the structure of
    The Cl
    SbF6
    W [0014] where R is C3H7, C12H25, W is S, SO, SO2 or CO.
    [0015] In another modality, the pressure-sensitive adhesive curable by cationic ultraviolet also comprises an additive of the type
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    5/35 polyethylene copolymer, a plasticizer, fillers, inhibitors, antioxidants, accelerators, an adherent and / or a solvent.
    [0016] Another embodiment relates to a method for the preparation of a crosslinkable acrylic polymer that comprises pending reactive functional groups.
    [0017] Yet another embodiment concerns an article manufactured using the inventive adhesives. The adhesive is in the form of a solvent-borne pressure-sensitive acrylic adhesive or in the form of a hot-melt pressure-sensitive acrylic adhesive. The adhesive article further comprises a liner which is a polyester, polypropylene, metal or glass. The adhesives are particularly advantageous as a tape, an adhesive transfer film, a decorative or protective film, a decal or a label.
    BRIEF DESCRIPTION OF THE FIGURES [0018] Figure 1 is a graph of viscosity against time at
    130 O C, measured by a Brookfield viscometer.
    DETAILED DESCRIPTION OF THE INVENTION [0019] The invention provides the technique with acrylic polymers comprising UV-reactive pendant functional groups attached to the polymer chain. Depending on the functional groups attached, the acrylic polymer undergoes a rapid UV crosslinking reaction and provides green resistance and / or undergoes a UV crosslinking in the presence of a cationic photoinitiator which results in adhesives with a high cohesive strength and high strength at high temperature.
    [0020] The choice and the relative quantity of the specific acrylic and vinyl monomers that make up the acrylic polymers used in the preparation of the adhesives of this invention depend on the desired end properties and the end uses contemplated for the adhesives. The choices of which acrylic and vinyl monomers and their quantities
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    6/35 relative to the final composition to achieve the desired properties are known to those skilled in the art.
    [0021] In one embodiment of the invention, acrylic polymers are those having the following composition or those that can be prepared by polymerizing (i) an acrylic monomer that is a derivative of acrylic or methacrylic acid (e.g., acid ester methacrylic) of the formula CH2 = CH (R 1 ) (COOR 2 ), where R 1 is H or CH3 and R 2 is a C1-20 chain, preferably C1-8, alkyl and (ii) a monomer with a functional group pending reactive, which is described in more detail below, and the amount of monomer (ii) ranges from about 0.001 to about 0.015 equivalent per 100 g of acrylic polymer. In a more preferred embodiment, the amount of the monomer ranges from about 0.002 to about 0.01 equivalent per 100 g of the acrylic polymer.
    [0022] For the polymerization process of the invention the monomers of components (i) and (ii), where appropriate, are converted into acrylic polymers by radical polymerization. In polymerization, monomers are chosen in such a way that the resulting polymers can be used to prepare adhesives, especially in such a way that the resulting polymers have pressure sensitive adhesive properties according to the Handbook of Pressure Sensitive Adhesive Technology by Donatas Satas (van Nostrand, NY 1989).
    [0023] Examples of acrylates and / or methacrylates useful as components of the monomer mixture (i) include methyl acrylate, ethyl acrylate, ethyl methacrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n- hexyl acrylate, n-heptyl acrylate, and n-octyl acrylate, n-nonyl acrylate, lauryl methacrylate, cyclohexyl acrylate, and branched (meth) acrylic isomers, such as i-butyl acrylate, i-butyl methacrylate, nbutyl methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, and isooctyl
    Petition 870190036793, of 17/04/2019, p. 13/57
    7/35 acrylate. Exemplary acrylates and / or methacrylates are monoacrylic monomers, and do not include diacrylate or multiacrylate monomers. [0024] The exemplary acrylic monomer mixture (i) has a Tg value of less than 0 ° C and an average molecular weight of about 10,000 to about 2,000,000 g / mol, more preferably between 50,000 and 1,000,000 g / mol and even more preferably between 100,000 and 700,000 g / mol. Mixture (i) can be a single monomer as long as the Tg of its homopolymer is less than 0 ° C.
    [0025] The appropriate polymer monomer (ii) is capable of undergoing a cationic UV-activated crosslinking reaction and provides green resistance to adhesive films, including cycloaliphatic epoxide monomers M100 and A400 (Daicel), OXE-10 oxyethane monomers ( Kowa Company), dicyclopentadienyl methacrylate (CD535, Sartomer Co., PA) epoxide, 4-vinyl-1-cyclohexene-1,2-epoxide (Dow). Other exemplary monomers (ii) include vinyl or acrylic compounds containing cationic UV-reactive functional groups with formula (1):
    R2 (1) [0026] where [0027] R 1 is O, S, C = O, or linear, branched, or cyclic alkylene, oxyalkylene, or arylene, [0028] R 2 is linear, branched, or cyclic alkyl, or alkoxy, aryl, H, halogen, C = O, or part of R 1 as a fused cycloaliphatic ring through a covalent bond connection, [0029] R 3 is (CH2) n, n = 0-3, [0030] X is acrylate, methacrylate or comprises a -WY group, where [0031] W is O, S, amide, carbonate, urethane, urea, siloxane or a combination thereof, and
    Petition 870190036793, of 17/04/2019, p. 14/57
    8/35 [0032] Y is -R 4 -C (R 5 ) = CH2, where R 4 is a linear or branched C2-10 alkylene or C2-10 oxyalkylene, arylene, or a derivative thereof, and R 5 is H or CH3.
    [0033] A preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1A):
    [0034] where R 2 = H or CH3, [0035] Another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1B):
    [0036] Another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1C):

    [0037] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1D):
    (1D) [0038] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1E):
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    9/35
    [0039] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1F):
    [0040] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1G):
    [0041]
    [0042] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (1H):
    [0043] where R = H or CH3.
    [0044] In another embodiment of the invention, acrylic polymers are capable of undergoing a post-reaction activated by cationic UV and, thus, providing high retention resistance at high temperature to adhesive films. Acrylic polymers are those that have the following composition or those that can be prepared by polymerizing (i) an acrylic monomer that is a derivative of
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    10/35 acrylic or methacrylic acid of the formula CH2 = CH (Ri) (COOR2), where Ri is H or CH3 and R2 is a C1-20 alkyl chain and (ii) a monomer with a combination of outstanding reactive functional groups selected from among (1) cycloaliphatic epoxide, oxyethane, benzophenone or mixtures thereof, and among (2) monosubstituted oxirane. The amount of monomer (ii) is the amount of about 0.001 to about 0.015 equivalent per 100 g of the acrylic polymer. The acrylic polymer is essentially free of multi- (meth) acrylate, polyol or OH functional groups and the polymer remains substantially linear after polymerization. In a more preferred embodiment, the amount of monomer (ii) ranges from about 0.002 to about 0.01 equivalent per 100 g of the acrylic polymer.
    [0045] Examples of the appropriate (i) mixture of acrylic monomers have already been given in this report.
    [0046] Examples of the monomer (ii) with pending reactive functional groups (1) of the cycloaliphatic epoxide and oxyethane type have also been given in this report.
    [0047] Monomers (ii) suitable with pending reactive functional groups (1) of the benzophenone type include the following compounds of formula (2), (3), and (4):
    R 8 OR 1 R 8 OR 1 0 R 1 (2) (3) (4) [0048] where [0049] Z is S, O, CH2, or NH, [0050] R 1-8 is independently H, Cl , Br, I, F, C 1-24 alkoxy, C1-24 alkyl, or aryl; and where at least one of R 1-8 must comprise a WXY-group, where [0051] W is a C1-12 alkylene or C1-12 oxyalkylene,
    Petition 870190036793, of 17/04/2019, p. 17/57
    11/35 [0052] X is carbonate, urethane, urea, tetramethyldisiloxane or a combination thereof, and [0053] Y is -R9-C (R 10 ) = CH2, where R9 is a C2-10 alkylene or C2-10 linear or branched oxyalkylene, arylene, or a derivative thereof, and R 10 is H or CH3.
    [0054] A preferred vinyl or acrylic compound for use as

    monomer (ii) is represented by the structural formula (3A):
    O
    Vo o
    n (3A).
    [0055] where n = 1-12, preferably n = 1.
    [0056] Another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (3B):
    O
    (3B) [0057] where n = 1-12, preferably n = 1.
    [0058] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (3C):
    O
    (3C) [0059] Yet another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (3D):
    Petition 870190036793, of 17/04/2019, p. 18/57
    12/35
    O
    (3D) [0060] Another preferred vinyl or acrylic compound for use as a monomer (ii) is represented by the structural formula (4A):
    O
    (4A) [0061] where n = 1-12, preferably n = 1.
    [0062] Monosubstituted oxirans (2) exemplifying the monomer (ii) include glycidyl methacrylate (GMA), 1,2-epoxy-5-hexene, 4-hydroxybutylacrylate glycidyl ether (4-HBAGE), cycloaliphatic epoxy monomer M100 and A400, OXE- 10, CD535 epoxide, 4-vinyl-1-cyclohexene-1,2-epoxide. Another example of a suitable reactive functional group has the following formula (5A):
    (5A) [0063]
    The invention also provides the technique with UV crosslinkable adhesives comprising the acrylic polymers presented in this report and a cationic photoinitiator.
    [0064] The main function of a photoinitiator is to initiate the crosslinking reaction when the photoinitiator is irradiated with UV radiation. There are two main types of photoinitiators that can be used in this invention to initiate crosslinking by irradiation: radical photoinitiators and cationic photoinitiators.
    [0065] The most frequently used cationic photoinitiators
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    13/35 are organic salts of iodonium or sulfonium. The mechanism of a cationic photoinitiator, when irradiated, is that it forms an excited state that then breaks off to release a radical cation. This radical cation reacts with the solvent, or with other hydrogen atom donors, and generates a protonic acid, which is the active species that initiates the crosslinking reaction.
    [0066] Any of the many compounds known to initiate polymerization by a cationic mechanism can be used for the crosslinking reaction in this invention. These include, for example, diaryliodonium salts, triaryl sulfonium salts, dialkylphenyl sulfonium salts, dialkyl (hydroxydialkylphenyl) sulfonium salts and ferrocene salts. Anions in these salts generally have a low nucleophilic character and include SbFe - , PFe _ AsFe _ BF4 - , B (CeF5) 4 _ or Ga (CeF5) 4 _ . Specific examples include Cyracure UVI-6976 (Dow Chemical). Particularly useful cationic initiators are red-shifted soluble sulfonium salt type photoinitiators, which have increased solubility in UV crosslinkable compositions, promote efficient UV curing of thick films, and exhibit increased thermal stability in UV crosslinkable compositions before of cure, exhibit increased cure rates, and have a reduced cure time in the dark, having the structural formulas (6A) and (7A):
    The Cl qhF®
    SbF6
    W (6A) [0067] where R is C3H7, C12H25, W is S, SO, SO2 or CO.
    Petition 870190036793, of 17/04/2019, p. 20/57
    14/35
    O
    Cl
    SbF 6
    R
    R 1 (7A) [0068] where R 1 and R 2 are independently H, CH3, C2H5, C3H7,
    C12H25, OCH3, OC2H5, OC3H7, OR OC12H25.
    [0069] Adhesives can also comprise several other additives, such as plasticizers, adhesives, and fillers, all of which are conventionally used in the preparation of PSAs. As adherent or adherent resins to be added, it is possible to use any of the adherent resins described in the literature. Non-limiting examples include pinene resins, indene resins, and their disproportionate, hydrogenated, polymerized, and esterified derivatives and their salts, aliphatic and aromatic hydrocarbon resins, terpene resins, terpene-phenolic resins, C5 resins, C9 resins, and other hydrocarbon resins. Any desired combination of these or other resins can be used to adjust the properties of the resulting adhesive according to the desired final properties.
    [0070] In general, it is possible to use any resin that is compatible with the corresponding acrylic polymers; in particular, all aliphatic, aromatic, alkylaromatic hydrocarbon resins, hydrocarbon resins based on hydrocarbon resins, hydrogenated hydrocarbon resins, functional hydrocarbon resins and natural resins can be mentioned. We can explicitly mention the description of the state of the art in Handbook of Pressure Sensitive Adhesive
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    15/35
    Technology by Donatas Satas (van Nostrand, 1989).
    [0071] In another advantageous improvement, one or more plasticizers, such as low molecular weight acrylic polymers, phthalates, benzoates, adipates, or plasticizer resins, are added to acrylic HMPSAs.
    [0072] Acrylic PSAs can also be mixed with one or more additives such as aging inhibitors, antioxidants, light stabilizers, compounding agents, and / or accelerators.
    [0073] The adhesive can also be mixed with one or more fillers such as fibers, carbon black, zinc oxide, titanium dioxide, solid or hollow glass microspheres, microspheres of other materials, silica, silicates, and chalk.
    [0074] For the inventive process, it may also be advantageous to add to the acrylic PSAs compounds that facilitate the subsequent cross-linking. For this, the copolymers can be optionally blended with crosslinkers. Examples of suitable lattices are functional acrylates. Preferred substances according to the inventive process in which the crosslinking takes place under radiation are, for example, difunctional or trifunctional acrylates, difunctional or polyfunctional urethane acrylates, difunctional, trifunctional or multifunctional acrylic epoxy resins such as Lumicryl 1000 and 1100 (Estron Chemical). However, it is also possible in this context to use any other difunctional or polyfunctional compounds which are known to the person skilled in the art and which are capable of crosslinking acrylic polymers. For optional thermal or moisture crosslinking, it is possible to use blocked difunctional or polyfunctional isocyanates, (meth) acrylates or other functional groups.
    [0075] Another improvement that makes the process of the invention particularly advantageous for the production of hot-melted PSAs
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    16/35 is that all additives are either mixed with the solvent-free acrylic polymers fused, or, what is more efficient, are added to the copolymer solutions at the end of the polymerization reactions. Upon removal of the solvent, the mixtures are concentrated to give hot melted PSAs.
    [0076] As those skilled in the art know, the preparation of acrylic polymers can be carried out by solution, emulsion, or bulk polymerization procedures using well-known polymerization techniques, such as free radical techniques. The copolymers can then be made into hot melt adhesives by removing the solvent, coagulating the latex, or processing by melting the simple polymers.
    [0077] Polymerization can be carried out in the presence of one or more organic solvents and / or in the presence of water. Suitable organic solvents or solvent mixtures are alkanes, such as hexane, heptane, octane, isooctane, and cyclohexane; aromatic hydrocarbons, such as benzene, toluene, and xylene; esters, such as ethyl, propyl, butyl and hepty acetate; halogenated hydrocarbons, such as chlorobenzene; alkanols, such as methanol, ethanol, iso-propanol, ethylene glycol, and ethylene glycol monomethyl ether; ethers, such as diethyl ether and dibutyl ether; or mixtures thereof.
    [0078] In an advantageous mode of the process, the polymerization reactions proceed in a solvent of the ethyl acetate type, thermally initiated, for example, by azobisisobutyronitrile (AIBN).
    [0079] The acrylic polymers prepared will generally have a weight average molecular weight (Mw) of 10,000 to 2,000,000 g / mol, more preferably between 50,000 and 1,000,000 g / mol and even more preferably between 100,000 and 700,000 g / mol . Mw is determined by gel permeation chromatography (GPC) or matrix-assisted laser desorption / ionization mass spectrometry (MALDIPetition 870190036793, of 4/17/2019, page 23/57
    17/35
    MS).
    [0080] Acrylic polymers can be prepared by polymerizing the mixtures of monomers of (i) and (ii). Alternatively, the preparation of UV-crosslinkable acrylic polymers can comprise a two-step reaction: (1) preparation of acrylic polymers that have pending isocyanate functionality using mTMI® (3-isopropenyl -α, α-dimethylbenzyl isocyanate, Cytec) or MOI ( 2 methacryloyloxyethyl isocyanate, Showa Denko) as a comonomer in polymerization reactions; and then (2) reaction of the pending isocyanate groups with epoxide functionalized with hydroxyl, oxyethane, or benzophenone.
    [0081] The acrylic polymer does not contain any multifunctional acrylate and is substantially linear in structure before the UV crosslinking reaction. Therefore, the acrylic polymer, before crosslinking, is completely soluble in many organic solvents, and can also be easily applied to substrates in the solvent-free form as a hot melt adhesive.
    [0082] The adhesives can be formulated as a solvent-borne adhesive and used by coating films or paper with polymer solutions or suspensions and subsequently removing the solvent by drying.
    [0083] To be used as hot-melt PSAs, acrylic polymers must be solvent-free. For this purpose, the copolymers prepared in the manner described above are concentrated to a solvent content of less than 2% by weight, preferably less than 0.2% by weight. This process preferably takes place in a reaction tank, or a vacuum mixer, concentration extruder, such as vent extruder, ring extruder, single screw extruder, or double screw extruder, which are known to the person skilled in the art.
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    18/35 [0084] The application of hot-melted PSAs can be carried out by any conventional means, such as roller coating, oval orifice, spray, or extrusion. Non-limiting examples of substrate are films, tapes, sheets, panels, foam, among others; and can be made of materials such as paper, fabric, plastic (polyesters, PE, PP, BOPP, and PVC), non-woven fiber, metal, foil, glass, natural rubber, synthetic rubber, wood, or plywood. If the coated substrate is used in the form of an automatically rolled roll, the back of the substrate is usually coated with a release coating to prevent the adhesive from sticking to the reverse side of the substrate. If the substrate is coated with the adhesive on both sides and rolled up, a peel-off paper or other protective medium is deposited on the adhesive on one side to prevent the adhesive from adhering to the adhesives on the other side. In some uses, a second substrate can be applied directly to the adhesive.
    [0085] In most uses of pressure sensitive adhesives, a hot melt adhesive is applied to a liner or substrate before crosslinking. The adhesive is preferably formulated to result in a composition that can be heated to produce a coatable fluid on the substrate. The commonly used industrial coating temperatures vary in the range of 80-180 o C. Typically, the hot-melted PSAs of this invention have a melt viscosity between 1000500,000 mPa.s, preferably between 5000-100,000 mPa.s at these application temperatures.
    [0086] A pressure sensitive adhesive film can be formed by applying the hot flux to a release liner, such as paper coated with silicone or plastic film, and then, after irradiation, the adhesive can be detached from the release liner and used as a film. Alternatively, the adhesive can be applied to a release liner, laminated and transferred to a substrate.
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    19/35 [0087] The hot-melted PSAs of the invention can be cross-linked in the air by irradiation with UV light in the range of 200 to 500 nm, preferably 280 to 400 nm. The irradiation can be immediately while the adhesive compositions are still in the molten form, or after they have cooled to room temperature. [0088] The adhesive composition is irradiated for a period of time sufficient to transform the low cohesion composition into a higher modulus viscoelastic adhesive. The exact time of exposure depends on the nature and intensity of radiation, the amount of cationic photoinitiator, the composition of the polymer, the formulation of the adhesive, the thickness of the adhesive film, environmental factors, and the distance between the radiation source and the adhesive film. Dosage or exposure time is conveniently controlled by the speed of the belt. It may be appropriate to adapt the power of the lamp to the speed of the belt or to protect the belt partially from light to reduce its thermal load.
    [0089] Actinic light from any source can be used on the adhesive, as long as the source provides an effective amount of UV radiation. Suitable sources of radiation are charcoal arcs, mercury vapor arcs, fluorescent lamps with special ultraviolet light emitting phosphor, electronic discharge lamps, among others, specific wavelength lasers, UV LED, or combinations thereof. Preferred lamps are Fusion Systems microwave-free electrode lamps, or commercially available high and medium pressure mercury lamps with a wattage, for example, of 80 to 240 W / cm. The adhesive compositions of the invention generally exhibit their maximum sensitivity to wavelengths in the ultraviolet range.
    [0090] In addition, the hot-melt acrylic PSAs described according to the invention can be cross-linked with bundles of
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    20/35 electrons. This type of crosslinking can also occur in addition to UV crosslinking.
    [0091] The adhesives of the present invention can be used to bond one substrate to a second substrate. Substrates include, but are not limited to, plastic, glass or glass coated with plastic, wood, metal, etc. The adhesive can be applied by several methods that include coating or spraying in an amount sufficient to make the substrates to be bonded stick. The adhesive coated substrate can be irradiated before or after bonding. As the cure begins immediately with the irradiation, but it can take several days to complete, there is time immediately after the irradiation, but before the gelation, for the connection to occur. [0092] The pressure sensitive adhesives of the invention can be advantageously used in the manufacture of adhesive articles which include, but are not limited to, industrial tapes and transfer films. Single-sided and double-sided tapes, as well as supported and unsupported free films are covered by the invention. In one embodiment, the adhesive article comprises an adhesive applied to at least one main surface of a liner having a first and a second main surface. Useful support substrates include, but are not limited to, foam, metal, paper, fabric, and various polymers such as polypropylene, polyamide, polyester, polyethylene terephthalate, and mixtures thereof. The adhesive may be present on one or both surfaces of the ceiling. When the adhesive is applied to both surfaces of the ceiling, the adhesive coatings can be the same or different.
    [0093] The following examples are provided for illustrative purposes only.
    EXAMPLES [0094] Adhesive samples were tested according to the following test methods for pressure sensitive tapes, some of them
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    21/35 having been developed by the Pressure Sensitive Tape Council (PSTC) or FINAT (Féderation INternationale des fabricants et transformateurs d’Adhésifs et Thermocollants sur papier et autres supports).
    GEL FRACTION [0095] The percentage of gel fraction was used as an indication of the level of crosslinking and the efficiency of the photoinitiator.
    [0096] A sample of UV-irradiated acrylic polymer (or formulated adhesive) was separated from the silicone release liner and weighed to the nearest 0.1 mg. The sample was then placed in a glass jar and immersed in toluene for 24 to 48 hours. The ratio of the sample mass after extraction of toluene to the initial mass gave the gel fraction expressed as a percentage. If the sample was a formulated adhesive, the mass of any toluene-soluble component such as an adherent resin was subtracted from the initial weight.
    PREPARATION OF ADHESIVE COATINGS [0097] A laboratory coating device with two heatable rollers was used to apply the adhesive. The adhesive was heated to 150 O C and applied to a 2 mil (51 pm) thick PET release liner and coated with silicone. The adhesive on the ceiling was irradiated at a line speed of 15 meters per minute under a H series bulb (Fusion Systems) with a dosage of UV C 257 mJ / cm 2 . The film was then laminated and transferred to a polyethylene terephthalate substrate (Mylar®, DuPont) and conditioned at 23 ° C and 50% relative humidity. Unless otherwise indicated, the thickness of the adhesive film was 3.5 mil (89 pm).
    UV CURE [0098] Adhesive films were cured using medium pressure mercury arc lamps (using a laboratory IST UV curing unit). The dose of UV C was measured and recorded using a
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    EIT Power Puck. UV C is the region between 200 and 280 nm.
    TIE ADHESION [0099] The loop adhesion was measured according to test method B, PSTC-16, adapted as follows. A loop adhesion tester was used for the measurement. All test samples of the acrylic polymers were irradiated with UV according to the procedure described above. The adhesive was applied to a 50 qm PET film liner and the specimen strip size was 125 mm x 24 mm.
    DISCHARGE ADHESION [00100] The adhesives were deposited in a range of coating weights (from 20-100 g / m 2 ) of film on a silicone liner using a Chemsultants ® hot melt laminator and then , cured (as indicated above). The cured free film was transferred to a 50 pm PET liner film.
    [00101] The peel adhesion was measured as the force required to remove a pressure - sensitive tape from a standard stainless steel panel at an angle and a specific rate according to the FINAT test method No. 1 adapted as follows. The equipment used to measure this value included a 2 kg roll coated with standard FINAT rubber, and a standard Instron® tensile testing machine.
    [00102] A stainless steel panel (steel (Rocholl AFERA
    GmbH) was washed by the standard FINAT method. Before the stainless steel panel was used, it was sanded along the length of the test panel with a 400 grit wet and dry sandpaper under the spout, until the water flowed evenly through the steel plate. After that, it was rinsed with water and dried, washed with ethyl acetate, and conditioned in a climate controlled room maintained at 23oC and 50% relative humidity (RH) for at least 1 hour.
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    23/35 [00103] The coating to be tested was conditioned for 24 hours at 23 ° C + 2 ° C and 50% + 5% relative humidity. The test strips were cut to a size of 25 mm x 175 mm.
    [00104] The liner paper was removed from each strip and placed, with the adhesive facing downwards, on a clean test plate with light pressure of the finger, and then turned twice in each direction with the standard 2 kg FINAT test at a speed of approximately 10 mm per second. After applying the strips to the test plate at a rate of one per 2 minutes, the strips were reserved until the first test piece had 20 minutes or 24 hours of elapsed time (rest).
    [00105] The traction tester was set at a crosshead speed of 300 mm / minute. The free end of the tape was folded at an angle of 180 ° C and attached to the upper jaw of the machine. The end of the panel was attached to the lower jaw. The test strip was then pulled out of the panel and the detachment force was recorded in Newtons / 25 mm tape width.
    [00106] The results obtained for the failure in the adhesive mode were classified as failure of adhesion (the test piece separated from the test plate without leaving residues) or cohesive failure (the adhesive film separated cohesively and left residues in the test piece and on the test plate).
    SAFT ADHESION FAILURE TEMPERATURE (SAFT) [00107] Three samples, with dimensions of 25 mm x 100 mm, were cut from each cured sample in the coating direction of the machine. SAFT panels (mirrored steel) were washed with ethyl acetate. The samples were adhered to the steel panel until they coincided with an engraved line so that a 25 x 25mm square of adhesive was in contact with the test panel. The test area was
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    24/35 worn with a straight-edge wooden applicator to ensure good contact between the panel and the test sample. The samples were placed in the test oven at room temperature. The heating program was started and a 1kg shear load was applied when the temperature reached 40 C. The furnace temperature was raised at 0.5 ° C / minute until reaching 200 ° C and failure temperature (SAFT) was recorded .
    SHEAR STRENGTH [00108] The shear strength of a stainless steel surface was measured according to the FINAT test method No. 8, adapted as follows. Three samples, with dimensions of 25 mm x 100 mm, were cut from each cured coating towards the machine. Shear panels (pre-sanded steel) were washed with ethyl acetate. The samples were adhered to the steel panel until they coincided with the engraved line so that a 25 x 25mm square of adhesive was in contact with the test panel. The test area was worn out with a wooden straight wire applicator to ensure good contact between the panel and the test sample. The test samples were conditioned for 15 minutes at 23 ° C + 2 ° C and 50% + 5% relative humidity. They were then mounted on the tester and a weight of 1 or 2 kg was applied. The time to failure has been recorded.
    HOT SHARP RESISTANCE [00109] The above procedure for shear strength was followed with the difference that the test specimens were placed in a preheated oven at 70 ° C, and allowed to acclimatize for 10 minutes. A weight of 1 kg was applied and the time to failure occurred.
    VISCOSITY [00110] Viscosity was measured by a Brookfield viscometer
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    DV-I at 135 O C, as shown in figure 1. A 10 g sample was used with a No 27 axis at a speed of 4 rpm.
    EXAMPLE 1 [00111] A 500 mL three-necked round-bottom flask was equipped with a reflux condenser, an addition funnel and a magnetic stirrer, and placed in a gentle nitrogen stream. The flask was loaded with 1,1,3,3-tetramethyldisiloxane (TMDS, 364 ml, 2.06 mol). The addition funnel was loaded with allyl alcohol (20.0 g, 0.34 mol). Approximately 2 mL of allyl alcohol was added to the reaction flask. The temperature of the heating bath was increased to 50 ° C, when then chlorotris (triphenylphosphine) rhodium (40 ppm or 18.7 mg) was added to the reaction flask. The internal reaction temperature was then increased to 70 ° C. Allyl alcohol was added in drops to the reactor over a period of 30 minutes, while the reaction mixture was maintained at an internal temperature below 75 ° C. A stationary reaction exotherm was observed during the addition. The reaction was stirred at 70 ° C for 10 minutes after the addition was finished. FT-IR analysis indicated complete consumption of allyl double bonds by the disappearance of C = C stretch bands between 1645 cm-1 and 1606 cm-1. The reaction was allowed to cool to less than 40 ° C, when the excess TMDS was then removed by vacuum distillation. TMDS was pure, as determined by GC analysis, 1 H NMR and 29 Si, and could be recycled. A light yellow solid was obtained as an intermediate.
    [00112] A 500 mL round-bottomed flask with a neck was equipped with a reflux condenser and a magnetic stirrer, and placed in a smooth nitrogen stream. A solution of the above intermediate, and 4-vinyl cyclohexene 1,2-epoxide (42 g, 0.34 mol) in toluene (anhydrous, 200 mL) was loaded and stirred at 75-85 ° C. The platinum-cyclovinylmethylsiloxane complex in cyclic methylvinylsiloxanes
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    26/35 (15 mg) was added and the reaction mixture was continuously stirred for about 24 hours. The reaction process was monitored by FTIR until the SiH peak disappeared (~ 2119 cm -1 ).
    [00113] The reaction mixture was cooled to 60 O C and 3-isopropenylα, α-dimethylbenzyl isocyanate (m-TMI, 69 g, 0.34 mol) and dibutyltin dilaurate (0.06 g, 0.1 mmol) subsequently added. The reaction process was monitored by FTIR and stopped when the isocyanate peak (~ 2260 cm -1 ) disappeared. The solvent was then removed in vacuo at room temperature and the product was collected as a light yellow liquid in quantitative yield. The identity of this compound was confirmed by 1 H NMR as having the following structure (1F):
    (1F)
    EXAMPLE 2 [00114] A solution of 3-cyclohexene-1-carboxaldehyde (30 g,
    0.27 mol), 2-aminoethyl methacrylate hydrochloride (67 g, 0.4 mol), 2-hydroperoxy-2-methylpropane (40 ml, 0.3 mol), CuI (0.5 g, 2.7 mmol), AgO (0.76 g, 2.7 mmol) and CaCOs (60 g, 0.6 mol) in acetonitrile (100 mL) was stirred at 40 ° C for 24 hours. The reaction mixture was cooled to room temperature. Oxon (330 g, 0.53 mol) and deionized water (100 ml) were added and the mixture was stirred for 3 hours at room temperature. The reaction mixture was extracted with toluene and washed with deionized water. The solvent was then removed in vacuo at room temperature and the product was collected as a liquid with a quantitative yield. The identity of this compound was confirmed by 1 H NMR as having the following structure (1H, where R = Me):
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    EXAMPLE 3 [00115] A solution of 1-methanol-3,4-cyclohexene (9.6 g, 86 mmol), methyl methacrylate (7.5 g, 87 mmol), and methanesulfonic acid (0.5 g, 5 , 2 mmol) in toluene (150 mL) was stirred at 120 ° C for 2 hours. The reaction mixture was cooled to room temperature. Sodium bicarbonate (60 g, 0.71 mol), oxonium (120g, 195 mmol), acetone (100 ml), and deionized water (100 ml) were added and the mixture was stirred for 3 hours at room temperature. The reaction mixture was left to stand for 1 hour to separate the phases. The aqueous layer was removed. The organic layer was dried over anhydrous magnesium sulfate and the toluene was then removed in vacuo at room temperature. The final product was collected as a light yellow liquid with a quantitative yield. The identity of this compound was confirmed by 1 H NMR and GC-MS as having the following structure, 1-methacrylomethyl-3,4-cyclohexene epoxide (1J).
    O (1J) [00116] The acrylate version of this monomer can be prepared by the same procedure.
    EXAMPLE 4 [00117] The polymer compositions in Table 1 were prepared following the same procedure as that described in detail in this report for polymer I.
    TABLE 1. Copolymer compositions (constituent monomers in% by weight)
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    PolymerI II III IV V SAW VII VIII IX X XI 2-EHA 49.9 50.2 49.6 49.9 49.9 49.9 49.9 52.1 51.9 51.2 52.0 BAD 48.1 48.3 47.8 48.0 48.0 48.0 48.0 46.5 46.4 45.7 46.2 GMA 1.5 0 2.0 1.5 1.5 1.5 1.5 - 1.5 - - M100 0.5 0.5 - - - - - - - - - OXE-10 - - - 0.6 - - - - - - - 5A - 1.0 - - - - - - - - - 1A - - 0.6 - - - - - - - - 1F - - - - 0.6 - - - - - - 1H - - - - - 0.6 - - - - - 3A - - - - - - 0.6 - - -1J - - - - - - - 1.4 0.2 1.2 0.5 HPMA - - - - - - - - - 2.0 0 HBAGE - - - - - - - - - - 1.3
    [00118] A 1 L round bottom polymerization flask, with four necks, was equipped with a thermometer connected to a temperature control device, a condenser, a suspended mechanical stirrer, two addition funnels, and an inlet / outlet nitrogen. The system was purged with nitrogen gas for 15 minutes. A mixture of the following monomers was prepared: 2-ethylhexylacrylate (2-EHA, 99.8 g), methyl acrylate (MA, 96.2 g), glycidyl methacrylate (GMA, 3.0 g), epoxide 1 -acrylomethyl-3,4-cyclohexene (M100, 1.0 g). 160 g of the monomer mixture were introduced into one of the funnels. In the other funnel, the initiator 2,2'-azobis- (2-methyl propionitrile) (AIBN, 0.5 g) and ethyl acetate (60 ml) were introduced. The polymerization flask was loaded with the rest of the monomer mixture (40 g), the AIBN initiator (0.27 g), and ethyl acetate (100 ml). The mixture was heated to vigorous reflux (7680 ° C) and maintained for 15 minutes. Then, the monomer mixture in the funnel was added continuously for 2 hours at a constant rate. Simultaneously, the initiator solution in the funnel was added continuously for 3 hours at a constant rate. After the addition of the initiator solution, the mixture was stirred for another 2 hours at reflux. A short half-life initiator (0.75 g) and ethyl acetate (25 mL) were introduced into the initiator funnel and then added to the polymerization flask for 1 hour to reduce
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    29/35 residual monomers. The polymerization solution was cooled to 60 o C and the Cyracure UVI-6976 cationic photoinitiator (1.0 g, 50% propylene carbonate) was added and mixed vigorously for 15 minutes. After the ethyl acetate was removed in vacuo at 5560oC, the acrylic polymer (I) was obtained with an Mw of approximately 97,000 determined by GPC. The viscosity (Brookfield) of the polymer was about 40,000 mPa.s at 135 ° C. The properties of the adhesive film were as follows: shear strength (weight 2 kg, area 25 mm x 25 mm)> 168 hours at 21 oC on a stainless steel panel, peel resistance 19 N / 25 mm on a panel stainless steel, 23 N / 25mm loop grip on a stainless steel panel, SAFT 171 oC on a PET film and 160 ° C on an aluminum foil lining.
    EXAMPLE 5 [00119] The viscosities at 135oC of the polymers prepared in the
    Example 4 and its properties of cured adhesive film (2 mil, 50pm) on stainless steel were measured. Shear strength was measured using a weight of 1 kg or 2 kg, as indicated, with a connection area of 25 x 25 mm. SAFT was measured using PET and aluminum foil films.
    TABLE 2. Adhesive properties
    Polymer Viscosity mPa.s Detachment N / 25mm Loop grip N / 25mm Shear hours SAFTOCPET Al I 40,000 19 23 > 168 (1 kg) 171 160 II 52,000 24 28 6 (2 kg) 110 125 III 46,000 19 24 > 168 (1 kg) > 190 > 190
    EXAMPLE 6: Comparative polymer compositions [00120] Polymers XII and XIII were prepared in the same manner as in Example 4. In addition to the cationic photoinitiators, Cyacure UVI-6976, polymers XII and XIII were synthesized using a monosubstituted oxirane monomer , and their compositions are shown in Table 3.
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    TABLE 3. Comparative copolymer compositions (constituent monomers in% by weight)
    PolymerXII XIII 2-EHA 49.9 49.9 BAD 48.1 48.1 GMA 2 0 4-HBAGE 0 2
    [00121] The viscosity at 135 O C of polymer XII was 46,500 mPa.s initially, and increased very quickly and gelled in less than 2 hours. [00122] The viscosity at 135OC of polymer XIII was 38,750 mPa.s initially, and increased 10% at 135OC in 7 hours. The adhesive film was not fully cured with the application of UV radiation and did not show green resistance. However, he continued to heal in the dark for 24 hours. The shear strength of the adhesive film, one week after curing in the dark, was> 168 hours (2 kg, 25 mm x 25 mm) at 21 oC on a stainless steel panel.
    EXAMPLE 7 [00123] An adhesive formulation was made using the acrylic polymer (VIII) of Example 4 (75% by weight), Kristalex ® F85, Eastman, Netherlands (15% by weight), and EVA 28-150 ( 10% by weight). The release adhesion values, measured in 20 minutes and 24 hours with 50 pm PET stainless steel, are listed in Table 4.
    TABLE 4. Peel off stainless steel 50 pm PET
    Detachment adhesion ( Nl / 25mm) in 20 minutes Dose (mJ / cm 2 ) UVC 20 g / m 2 40 g / m 2 60 g / m 2 100 g / m 2 5 15.2 16.8 21.0 21.3 10 12.8 16.2 18.8 22.5 20 3.6 15.9 16.1 22.2 40 12.5 17.0 18.5 19.1 60 12.5 15.7 17.4 20.0 Detachment adhesion ( Nl / 25mm) in 24 hours Dose (mJ / cm 2 ) UVC 20 g / m 2 40 g / m 2 60 g / m 2 100 g / m 2 5 23.1 23.1 32.5 29.9 10 18.0 25.1 28.3 38.9 20 12.2 23.5 23.5 37.4 40 15.3 17.1 25.4 30.9 60 16.2 21.3 24.2 30.5
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    31/35 [00124] All peeling adhesions resulted in the failure mode of the adhesive.
    [00125] The release adhesion values indicate that the cationic formulation can be cured at a variety of dose levels and coating weights typically used in the tape and label industry.
    [00126] SAFT experiments were conducted at a temperature of 40 to 200 O C at a load of 1 kg, a connection area of 25 by 25 mm, on mirrored stainless steel, and the failure temperatures are shown in Table 5. The Hot shear strength results are also shown in Table 5.
    TABLE 5. Results of the SAFT test and the shear test
    SAFT (° C) Dose (mJ / cm 2 ) UVC 20 g / m 2 40 g / m 2 60 g / m 2 100 g / m 2 5 > 200 * > 200 * > 200 * 127 ° C 10 > 200 * > 200 > 200 * 170 ° C 20 > 200 * > 200 * > 200 * > 200 * 40 178 ° C 178 ° C > 200 * > 200 * 60 177 ° C > 200 * > 200 * > 200 * Hot shear strength (hrs) Dose (mJ / cm 2 ) UVC 20 g / m 2 40 g / m 2 60 g / m 2 100 g / m 2 5 > 120 * > 120 * > 120 * > 120 * 10 > 120 * > 120 * > 120 * > 120 * 20 > 120 * > 120 * > 120 * > 120 * 40 > 120 * > 120 * > 120 * > 120 * 60 > 120 * > 120 * > 120 * > 120 *
    * The test was stopped before the failure occurred.
    [00127] The results of the SAFT experiment in Table 5 indicate that the adhesive can maintain retention at high temperature. The results of the hot shear strength experiment in Table 5 demonstrate that the adhesive has a robust curing window because it is completely cured over a wide range of UVC doses and coating weights.
    EXAMPLE 8 [00128] A first set of adhesive films having the compositions according to the examples listed in Table 6 were
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    32/35 applied at 25 ° C, 50% relative humidity, a release liner, dried, and cured by UV rolled and then transferred to a PET film liner in the usual way to prepare for the peel adhesion test .
    [00129] A second set of adhesive films, after coating and drying, was placed in a regulated chamber to have a controlled environment of 25 ° C, 50% relative humidity, for 72 hours, with an adhesive surface exposed to air. After conditioning for 72 hours, the films were then UV cured and laminated. The adhesive properties for the two sets of adhesive films are compared in Table 6.
    TABLE 6. Properties of the cured adhesive following exposure to moisture
    Coating weight (g / m 2 ) Dose (mJ / cm 2 ) UVC Coated at 25% relative humidity and 25 ° C and UV cured immediately after coating Exposed to 50% relative humidity and 25 ° C for 72 hours before UV curing Detachment N / 25mm N / 25mm Ex 11 67 60 27.1 25.0 Ex 9 60 80 28.1 20.0 Polymer X 60 80 16.9 12.7 SAFT ° C ° C Ex 11 67 60 167-200 > 200 * Ex 9 60 80 > 200 * > 200 * Polymer X 60 80 > 200 * > 200 * Hot shear Hrs Hrs Ex 11 67 60 127-168 > 168 * EX 9 60 80 > 168 * > 168 * Polymer X 60 80 > 168 * > 168 *
    * The test was stopped before the failure occurred.
    [00130] The presence of water in cationic epoxies during UV curing usually abruptly cools the propagating superacid species, leading to reduced crosslinking, and thus decreases the cohesive properties in the adhesive. Surprisingly, the above results indicate that the presence of water resulting from exposure to a humid environment did not negatively affect the cured adhesives of this invention.
    EXAMPLE 9
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    33/35 [00131] A formulation was made of polymer VIII (90% by weight) and
    Foral 85E (10% by weight), and the adhesive properties are summarized in Table 7.
    TABLE 7. Adhesive properties with the addition of an adhesive
    UVC Dose (mJ / cm 2 ) Coating weight (g / m 2 ) Detachment 20 min (N / 25mm) 24 hrs (N / 25mm)60 60 11.9 12.4125 60 10.7 13.1 SAFT Failure temperature (° C) 60 60 > 200 * 125 60 > 200 *Hot shear Hrs 60 60 Not tested 125 60 > 168 *
    * The test was stopped before the failure occurred.
    [00132] Surprisingly, the above results indicate that the addition of adherent did not negatively affect the adhesive properties.
    EXAMPLE 10 [00133] A formulation was made of polymer VIII (80% by weight),
    Foral 85E (10% by weight) and Licocene® PP 1302, Clariant (10% by weight) and the adhesive properties are summarized in Table 8.
    TABLE 8. Adhesive properties with the addition of an adherent and an ethylene copolymer
    Dose (mJ / cm 2 ) UVC Coating weight (g / m 2 ) Detachment 20 min (N / 25mm) 24 hrs (N / 25mm)60 80 18.9 20.4 SAFT Failure temperature ( o C) 60 80 > 200 *Hot shear Hr 60 80 Not tested 60 20 > 168 *
    * The test was stopped before the failure occurred.
    [00134] Surprisingly, the data above indicates that the addition of the polyethylene copolymer improves the release
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    34/35 adhesive without loss of cohesion compared to Example 9 under similar coating weight and UV dose conditions. EXAMPLE 11 [00135] A formulation was made using acrylic polymer VIII (80% by weight), Kristalex F85 (20% by weight), and the adhesive properties are summarized in Table 9.
    TABLE 9. Adhesive properties with the addition of an aromatic adherent
    Dose (mJ / cm 2 ) UVC Coating weight (g / m 2 ) Detachment 20 min 24 hrs60 63 17.0 25.0115 115 20.0 26.9 SAFT Failure temperature ( o C) 60 63 > 200 * 115 115 > 200 *Hot shear Hours 60 63 > 168 * 115 115 > 168 *
    * The test was stopped before the failure occurred.
    [00136] Typically, the addition of an adhesive to the adhesive results in lower cohesive properties. An aromatic adherent is expected to result in an even greater loss of cohesion due to strong UV absorption by the aromatic rings. Surprisingly, the data above indicates that even a 20% addition of aromatic adherent to the formulation resulted in good adhesive properties.
    [00137] Figure 1 shows the viscosity over time for polymer VIII and polymer IX. The viscosity of each sample was measured by a Brookfield viscometer at 130 o C. The polymer VIII, according to this figure 1, showed a stable viscosity around 45,000 mPa.s for about 300 minutes. The formulated adhesive, Examples 9, also exhibited stable viscosity, even at a temperature of up to 140 ° C, which indicates a long service life.
    [00138] Many modifications and variations of this invention can be
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    35/35 made without departing from its spirit and scope, as will be evident to those skilled in the art. The specific modalities described in this report are offered by way of example only, and the invention should only be restricted by the terms of the attached claims, together with the full scope of equivalents to which such claims are entitled.
    权利要求:
    Claims (10)
    [1]
    1 Ultraviolet-curable pressure sensitive adhesive, characterized by the fact that it comprises an acrylic polymer and a cationic photoinitiator, the said acrylic polymer being prepared from the group consisting of:
    (i) an acrylic monomer consisting of a derivative of acrylic or methacrylic acid with the formula CH2 = CH (Ri) (COOR2), where Ri is H or CH3 and R2 is a C1-20 alkyl chain;
    (ii) a monomer, said monomer comprising a pending reactive functional group selected from cycloaliphatic epoxide, oxetane or mixtures thereof, and containing from 0.001 to 0.015 equivalent per 100 g of said acrylic polymer;
    the acrylic polymer being:
    (a) it is essentially free of multi- (meth) acrylate, (b) it has a Tg value below 0 ° C, and (c) it has an average molecular weight of 50,000 to 1,000,000 g / mol; and the ultraviolet-curable pressure sensitive adhesive having a viscosity range of 1,000 to 500,000 mPa.s at 80 to 180 o C.
    [2]
    2. Sensitive adhesive according to claim 1, characterized by the fact that (ii) monomer contains from 0.002 to 0.010 equivalent per 100 g of acrylic polymer.
    [3]
    3. Sensitive adhesive according to claim 1, characterized by the fact that (ii) monomer is a cycloaliphatic epoxide with the formula:

    [4]
    4. Sensitive adhesive according to claim 1, characterized by the fact that the cycloaliphatic epoxide has the formula:

    [5]
    5. Sensitive adhesive according to claim 4, characterized by the fact that the cycloaliphatic epoxide is:

    [6]
    6. Sensitive adhesive according to claim 1, characterized by the fact that the cationic photoinitiator has the structure of:
    SbF
    The Cl

    [7]
    7. Sensitive adhesive according to claim 6, characterized by the fact that the cationic photoinitiator is:
    O
    Cl
    SbF6

    [8]
    Sensitive adhesive according to claim 1, characterized by the fact that it also comprises a polyethylene copolymer additive.
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    5/5
    [9]
    Sensitive adhesive according to claim 8, characterized in that the adhesive has a solvent content of less than 2% by weight of the total adhesive.
    [10]
    10. Manufactured article, characterized by the fact that it comprises the adhesive as defined in claim 9.
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    同族专利:
    公开号 | 公开日
    CN102782072A|2012-11-14|
    WO2011112643A2|2011-09-15|
    EP2545132A4|2013-11-06|
    US8796350B2|2014-08-05|
    JP5711767B2|2015-05-07|
    US9469794B2|2016-10-18|
    CN104893626B|2017-08-08|
    EP2545132B1|2015-11-04|
    BR112012022560A2|2016-08-30|
    EP2985330B1|2017-05-03|
    US20140303274A1|2014-10-09|
    WO2011112643A3|2012-03-01|
    KR20130053397A|2013-05-23|
    EP2545132A2|2013-01-16|
    EP2985330A1|2016-02-17|
    US20120329900A1|2012-12-27|
    CN104893626A|2015-09-09|
    JP2013522394A|2013-06-13|
    CN102782072B|2015-06-03|
    KR101650693B1|2016-08-25|
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    法律状态:
    2018-02-14| B25A| Requested transfer of rights approved|Owner name: HENKEL US IP LLC (US) |
    2018-03-06| B25A| Requested transfer of rights approved|Owner name: HENKEL IP AND HOLDING GMBH (DE) |
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09J 137/00 (2006.01), C08F 220/28 (2006.01), C09J |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-19| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-08-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-12-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-01-28| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    2022-01-04| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    US31197010P| true| 2010-03-09|2010-03-09|
    PCT/US2011/027632|WO2011112643A2|2010-03-09|2011-03-09|Cationic uv-crosslinkable acrylic polymers for pressure sensitive adhesives|
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