WO2005105857A1 - Oligomere d'acrylate d'urethane hybride polyester-polyether pour adhesifs autocollants durcisasnt par rayonnement uv - Google Patents

Oligomere d'acrylate d'urethane hybride polyester-polyether pour adhesifs autocollants durcisasnt par rayonnement uv Download PDF

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WO2005105857A1
WO2005105857A1 PCT/US2005/013371 US2005013371W WO2005105857A1 WO 2005105857 A1 WO2005105857 A1 WO 2005105857A1 US 2005013371 W US2005013371 W US 2005013371W WO 2005105857 A1 WO2005105857 A1 WO 2005105857A1
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Prior art keywords
acrylate
diisocyanate
psa
meth
polyester
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PCT/US2005/013371
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English (en)
Inventor
David E. Day
Vincent J. Pascarella
Thomas M. Moy
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Ashland Inc.
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Publication of WO2005105857A1 publication Critical patent/WO2005105857A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives

Definitions

  • the present invention generally relates to pressure sensitive adhesives (PSA's) and more particularly to PSA's that are ultraviolet radiation (UV) curable for use as, inter alia, screen-printable or flexo-printable labeling, tape, nameplate, or membrane switch adhesives.
  • PSA's ultraviolet radiation
  • UV-curing pressure-sensitive adhesives potentially offer a cost-effective, high productivity alternative to conventional solvent or waterborne adhesive technologies.
  • the UV-curing PSA's commonly are comprised of an acrylate-functionalized (aromatic or aliphatic) urethane or other oligomer, blended with acrylic monomers, photoinitiators, and various additives to aid processing. Rapid, complete conversion from unreacted liquid to crosslinked, solid adhesive is essential.
  • the basic construction of the urethane portion of the urethane acrylate oligomer is formed from the catalytic reaction of a difunctional or trifunctioinal polyol and a difunctional isocyanate. This reaction yields a molecular framework that gives a uniform soft, flexible constituent within the macromolecule from the polyol, which facilitates the UV PSA's ability to "wet-out" and adhere to bonding surfaces.
  • the isocyanate groups create a harder linkage segment, which joins the polyol to a capping acrylate, which reacts under UV light to incorporate the urethane acrylate oligomer into the acrylic network structure via free radical chain polymerization.
  • polyester polyol based urethane acrylate typically yields a UV curing PSA which possesses physical properties of higher peel and tack to high energy substrates, such as, for example, stainless steel, and at low energy surfaces, such as, for example, high density polyethylene, and of sufficient cross-link density to suspend 1 square inch 2-Kg shears at ambient temperature and 1 square inch 1-Kg shear at elevated temperatures (200°F) for > 2 weeks.
  • a deficiency of the polyester based system comes trom the internal hydrogen bonding of the polyester-based urethane's molecular backbone whereby the blending of this oligomer with acrylate monomers at 40 to 60 weight percent creates a UV curing PSA formulation with relatively high viscosity. This may hinder some application processes, such as screen-printing.
  • Another potential deficiency of the polyester-based system is in the area of thumb appeal, i.e., how "sticky" the adhesive feels to the touch.
  • the use of a polyester based urethane acrylate typically yields a UV curing PSA which possesses better UV environmental stability and resistance to yellowing as a result of weathering or oxidation, relative to polyether based oligomers.
  • Polyether polyols characteristically afford softer urethane oligomers with superior hydrolytic stability relative to the polyester-based materials.
  • the polyether based oligomer also typically possess physical properties of moderate peel and tack to high energy surfaces, such as, for example, stainless steel, and much lower peel and tack strengths to low energy surfaces. They also have sufficiently high cross-link density to suspend 1 square inch 2-Kg shears at ambient and marginally suspends 1-Kg shears at elevated temperatures (200°F) for > 2 weeks and intrinsically have much better thumb appeal and much lower viscosities as compared to the polyester based oligomer UV curing PSA of comparable molecular weights.
  • PSA pressure sensitive adhesive
  • UV ultraviolet radiation
  • the polyester-polyether-based urethane acrylate is the reaction product of between about 50 and 90 wt-% of a polyester diol having a molecular weight ranging from about 500 to 3200; between about 10 and 50 wt-% of a polyether polyol having a molecular weight ranging from about 1000 to 6000; between about 1 and 5 wt-% of a hydroxy-functional acrylate; and a polyisocyanate.
  • the invention in another aspect relates to urethane acrylate oligomers derived from a blend of a difunctional polyester polyol of great than about 85 parts per hundred and less than about 20 parts per hundred of a difunctional polyether polyol of the total polyol mixture dispersed in 10-20 weight percent ("wt-%") acrylic monomer reactive diluent.
  • the polyol mixture is co-reacted catalytically with a difunctional isocyanate in sufficient quantity so that, statistically, the diisocyanate is reacted with the polyol and a low molecular weight hydroxy functional acrylate to obtain a urethane oligomer "end capped” with acrylate groups available for further reaction.
  • Liquid compositions including between 20 to 70 wt-% of the urethane acrylate oligomers with one or more monofunctional acrylates, as reactive diluents, and one or more photoinitiators, exposed to an appropriate radiation source, e.g., ultraviolet light, will react to form solid, crosslinked thermoset materials.
  • the disclosed formulations have applicability in pressure sensitive adhesive applications.
  • the invention is a method for formulating an ultraviolet radiation (UV) curable pressure sensitive adhesive (PSA), which includes the steps of forming the novel polyester-polyether-based urethane acrylate and subjecting said reaction mixture to the influence of ultraviolet radiation to form a PSA.
  • UV ultraviolet radiation
  • PSA ultraviolet radiation curable pressure sensitive adhesive
  • Polyester and polyether polyols are not miscible; however, mixtures of polyester polyols with polyether polyols can be achieved in a common solvent or acrylate monomer at greater than about 15 weight percent.
  • Blending of a difunctional polyether polyol (minor component, say, less than about 50 weight percent) with a difunctional polyester polyol (major component) and carrier acrylate to solvate the mixture, followed by co-reaction of the resulting mixture with an aromatic or aliphatic di-functional isocyanate and hydroxyl-functional acrylate yields a "hybrid" polyester-polyether based urethane acrylate.
  • Formulation with an appropriate combination of acrylate monomers, photoinitator(s), and additives, followed by exposure to an appropriate UV source produces a PSA that exhibits a good balance of the physical properties possessed by an adhesive based solely on either the polyester or polyether based oligomer and is distinct from the physical blend of the urethane acrylate systems containing either polyester and polyether polyols in terms of compatibility and to some degree physical properties.
  • Urethane theoretical ⁇ M n >'s were in the range of ⁇ 8000 Daltons, however, considerably higher molecular weight urethanes could conceivably be used.
  • the basic construction of the urethane portion of a urethane acrylate oligomer is formed from the catalyzed reaction (e.g., tin catalyst) of a difunctional polyol and a difunctional isocyanate.
  • This reaction yields a molecular network that gives a uniform soft, flexible constituent within the macromolecule from the polyol segments, which facilitates the UV PSA's ability to "wet-out” and adheres to bonding surfaces.
  • the isocyanate groups create a harder linkage segment, which join the polyol to a capping acrylate, which reacts under UV light to tie the urethane acrylate oligomer into the polymerizing acrylate monomers free radically.
  • Polyesters can be synthesized, for example, by reacting C C 12 diacids (or their corresponding anhydrides) or other diacids with a diol or a mixture of diols. The mixture is heated in the presence of a catalyst to temperatures sufficient to remove the water formed in the condensation reaction.
  • These materials have molecular weights of, for example, about 500-3200 (Mn), and are typically room temperature fluids; if solid/semisolid at room temperature (25° C) it is preferred that they are noncrystalline.
  • Glass transition temperature (T g ) should be below room temperature (25° C) and preferably below 0° C.
  • Polyethers can be synthesized from ethylene oxide to have a molecular weight of, for example, about 1 ,000-6000 (Mn) by conventional techniques well known in the art.
  • Polyether polyols e.g., block polyethylene and polypropylene oxide homo- and co-polymers
  • optionally alkylated e.g., polytetramethylene ether glycols
  • ethylene oxide and propylene oxide can be co-reacted to form the polyether polyol, or the polyether polyol can be built on a di-functional compound that contains groups reactive with ethylene oxide and propylene oxide.
  • Such suitable groups include, for example, hydroxyl groups, thiol groups, acid groups, and amine groups. Accordingly, diols, triols, dithiols, diacids, diamines, and the like, are suitable di-functional compounds which can be reacted with ethylene oxide and/or propylene oxide for synthesizing the polyether of the present invention. Suitable such compounds include, for example, alkylene glycols, typically ranging from about 2 to 8 carbon atoms (including cycloalkylene glycols).
  • diols Illustrative of such diols are ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,2-propanediol, 1 ,3-butanediol, 2,3-butanediol, 1 ,3- pentanediol, 1 ,2-hexanediol, 3-methyl pentane,1 ,5-diol, 1 ,4-cyclohexanedimethanol, and the like, and mixtures thereof.
  • hydroxy (meth)acrylate monomer is included to functionalize the polyester- polyether urethane for later UV curing.
  • Suitable hydroxy (meth)acrylates include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone acrylate and the like.
  • other hydroxy functional monomers may be employed, for example, hydroxybutyl vinyl ether or allyl alcohol.
  • the parenthetical group is optional.
  • (alkyl)acrylate” means "acrylate and alkylacrylate”.
  • Isocyanate-functional reactants are made from polyisocyanates reacted with a compound containing active hydrogen functionality with hydroxyl groups being typical, although mercaptan groups, amine groups, and carboxyl groups also can be used.
  • Polyisocyanates are conventional in nature and include, for example, hexamethylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), m- and p-phenylene diisocyanates, bitolylene diisocyanate, cyclohexane diisocyanate (CHDI), bis-(isocyanatomethyl) cyclohexane (H 6 XDI), dicyclohexylmethane diisocyanate (H 12 MDI), dimer acid diisocyanate (DDI), trimethyl hexamethylene diisocyanate, lysine diisocyanate and its methyl ester, isophorone diiso
  • Triisocyanates and high- functional isocyanates also are well known and can be used to advantage.
  • Aromatic and aliphatic diisocyanates for example, (including biuret and isocyanurate derivatives) often are available as pre-formed commercial packages and can be used to advantage in the present invention.
  • Isocyanate equivalents should predominate over active hydrogen equivalents in the polyisocyanate/polyol reaction mixture in order for the resulting prepolymer to contain residual isocyanate groups. Reaction conditions for this reaction are well known in the art, such as described by Heiss, et al., "Influence of Acids and Bases on Preparation of Urethane Polymers", Industrial and Engineering Chemistry, Vol. 51 ,. No. 8, August 1959, pp.
  • the reaction may lead to the formation of ureas, allophanates, biurets, or isocyanates.
  • the difunctional polyester polyol and difunctional or trifunctional polyether polyol, hydroxy-functional acrylate, and isocyanate are reacted under conventional condensation conditions to form a urethane acrylate.
  • the thus-formed urethane acrylate then is blended with additional acrylate monomers, UV sensitizers, and other optional ingredients to form the inventive PSA.
  • Representative useful additional acrylate monomers include, for example, one or more of acrylic acid, beta-CEA (beta-carboxyethyl acrylate), 2(2-ethoxyethoxy) ethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, alkoxylated lauryl acrylate, alkoxylated phenol acrylate, alkoxylated terahydrofurfuryl acrylate, caprolactone acrylate, cyclic trimethylolpropane formal acrylate, ethoxylated (10) hydroxyethyl methacrylate, ethoxylated (2) hydroxyethyl methacrylate, ethoxylated (4) nonyl phenol acrylate, ethoxylated (4) nonyl phenol methacrylate, ethoxylated (5) hydroxyethyl methacrylate, ethoxylate nonyl phenol acrylate, isoborn
  • Useful UV sensitizers or photosensitizers include halogenated polynuclear ketones such as disclosed in U.S. Pat. No. 3,827,957; and organic carbonyl compounds selected from alkyl phenones, benzophenones, and tricyclic fused ring compounds as disclosed in U.S. Pat. No. 3,759,807. Further useful UV sensitizers include carbonylated phenol nuclear sulfonyl chlorides, such as set forth in U.S. Pat. No. 3,927,959.
  • Additional useful photosensitizer combinations particularly suited for pigmented formulations are a combination of sensitizers comprising aromatic carbonyl compounds, aromatic aldehydes or aromatic ketones, and a synergistic sensitizer of about 0.05% to about 3% of 2,2'-dithiobis(benzothiazole), as set forth in U.S. Pat. No. 3,847,771.
  • a synergistic sensitizer of about 0.05% to about 3% of 2,2'-dithiobis(benzothiazole), as set forth in U.S. Pat. No. 3,847,771.
  • at least about 0.5% by weight of the UV sensitizer, and preferably about 1%-5% sensitizer is added to the ingredients and thoroughly mixed or otherwise dispersed in the liquid carrier ingredients.
  • Additional conventional additives may be incorporated into the adhesive composition, including, for example, wetting agents, pigments, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, fillers, opacifying agents, anti-foam agents, rheology agents, and the like and mixtures thereof.
  • the adhesives may be in a conventional manner, for example, by spraying, knife coating, roller coating, casting, drum coating, dipping, and the like. Indirect application using a transfer process with silicon release paper also can be used. After the adhesive has been applied, the coated stock is dried conventionally. While the invention has been described with reference to a preferred embodiment, those skilled in the art will understand that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention.
  • Loop Tack Test ASTM D6195-03, ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959 USA. Results are reported in pounds/inch for a 1 in strip (pli).
  • Shear Adhesion Test ASTM WK211 , ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959 USA. Results are reported in hours (hrs) for a sample of 1" x 1" x 4 lbs (no dwell).
  • Thumb Appeal A subjective test using the thumb or forefinger, a qualitative description of how "sticky” the adhesive feels to the touch. 6.
  • Photoinitiators (a) 2,2-dimethoxy-2-phenyl acetophenone (BDK) (b) 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPP) (c) bis(2,4,6-trimethyl benzoyl) phenyl phosphineoxide benzophenone (d) benzophenone
  • Reagents (a) Acclaim 3205: poly(oxyalkylene) polymer (polyethylene-polypropylene glycol), hydroxyl value 35, average molecular weight (M n ) 3,000, average functionality 2, viscosity 637 mPas @ 25°C. Bayer (b) Acclaim 6320N poly(oxyalkylene) polymer (polyethylene-polypropylene glycol), hydroxyl value 28, average molecular weight (M n ) 6,000, average functionality 3, viscosity 1 ,725 mPas @ 25°C. Bayer.
  • Lexorez 1640-35 polyester polyol of adipic acid, 1 ,4-butanediol and neopentyl glycol; hydroxyl value 35, average molecular weight (M n ) 3200, average functionality 2.0, melting range 20-30°C, viscosity 3100 cps at 60°C. Inolex Chemical.
  • Mondur ML diphenyl methane diisocyanate, mixture of 4,4' ( ⁇ 60%) and 2,4' and 2,2' isomers ( ⁇ 50%) isomers.
  • DC-11 silicone flow agent, Dow Corning.
  • UV Curing Source 600 W/in "H" bulb, Fusion UV Systems.
  • acrylate terminated urethane oligomers were synthesized from either a linear polyether or linear and branched polyether polyols whereby the linear polyether polyol is in the 3200 MW range and the branched polyether polyol is in the 6000 MW range and a diisocyanate comprised of Mondur ML aromatic diisocyanate and an acrylic monomer or either phenoxyethyl acrylate or isobornyl acrylate at 0-20 weight percent as a reactive diluent.
  • Urethane theorethical ⁇ M n >'s were in the range of 8,000 - 1 ,000 for the linear polyether based oligomer and 18,000 - 21,000 for the linear and branched polyether based oligomers.
  • Example 3 representing a 100% polyester based UV curing adhesive system, an acrylate terminated urethane oligomer was synthesized from a linear polyester polyol in the 3200 MW range and a diisocyanate comprised of Mondur ML aromatic diisocyanate and an acrylic monomer or either phenoxyethyl acrylate or isobornyl acrylate at 0-20 weight percent as a reactive diluent resulting in a theoretical ⁇ M n >'s in the range of 8,000 - 11 ,000.
  • acrylate terminated urethane oligomers were synthesized from either a linear polyether or linear and branched polyether polyols and a linear polyester polyol whereby the linear polyether polyol is in the 3200 MW range, the branched polyether polyol is m the- 6000 MW range and the linear polyester polyol is in the 3200 MW range and a diisocyanate comprised of Mondur ML aromatic diisocyanate and an acrylic monomer or either phenoxyethyl acrylate or isobornyl acrylate at 0-20 weight percent as a reactive diluent.
  • the linear polyether polyol or linear and branched polyether were co-reacted with the linear polyester polyol at a 1 to 20 weight percent combination.
  • Examples 8 and 9 representing physical mixtures of 100% polyether and 100% polyester based UV curing adhesive systems, identically synthesized acrylate terminated oligomers from example I and III were combined as analogues to examples IV and VI at a comparable ratio to the coreacted versions
  • the acrylate terminated urethane oligomers were blended at 50 weight percent with 3 to 5 acrylic monofunctional monomers (isobornyl, phenoxyethyl, ethoxyethoxy ethyl acrylate, beta-carboxyethyl acrylate, tetrahydrofurfuryl acrylate), a silicone containing flowing agent containing toluene at 0.5 to 1.0 pph and a photoinitiator as the "crosslinker" of either 2,2-dimethoxy-2-phenyl acetophenone (BDK) in
  • Adhesive compositions were cast on PET film and cured in air using a single 500 mJ/cm 2 (40 ft/min) exposure to a 600 W/in Fusion "H" bulb.
  • Reported adhesive properties are for polyester to stainless steel; peel and tack values indicate the pressure-sensitive character of the cured resin compositions, and the good cohesive strengths (300+ hr shears) are indicative of the crosslinked nature of the adhesives.
  • EXAMPLE 1 Comparative (100% Linear Polyether-Based Acrylate-Terminated Urethane UV-Curable PSA) A comparative linear polyether-based acrylate-terminated urethane was synthesized in this example, with theoretical number average molecular weight ( ⁇ M n >) 10,832.
  • Acclaim 3205 diol (571.23 g) and Mondur ML isocyanate (59.25 g) were charged into a reactor vessel fitted with a mixer, N 2 purge, air sparge, and thermocouple. Mixing was initiated at 500 rpm.
  • Dibutyl tin dilaurate catalyst (10% solution of Metacure T-12 brand dibutyl tin dilaurate catalyst, Air Products Company, 0.64g) was charged into the reactor and the temperature rise monitored, while stirring at 500 rpm was continued. After about forty minutes reaction time, 2-hydroxyethyl acrylate (13.52 g) was metered into the reaction vessel over a 5-minute period. Thereafter, the reaction was permitted to proceed over a 5-6 hour time period while monitoring the reaction temperature. Upon completion of the reaction, the resulting linear polyether based, aeryfate-terminated urethane was withdrawn from the reactor. Titration indicated NCO% ⁇ 0.1 %; a mixture of acrylic monomers.
  • the comparative linear polyether-based acrylate-terminated urethane (46.95 g) was blended 50/50 (wt wt) with a mixture of monofunctional monomers, isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate, weight ratio of 4:1 :1 (46.94 g), a silicone flow agent (0.47 pph), and BDK photoinitiator (5.63 pph) (1754 cps viscosity @ 25 ° C for the formulated mixture), cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • HDPE high density polyethylene
  • the comparative mixed linear and branched polyether-based acrylate- terminated urethane (46.95 g) was blended 50/50 (wt/wt) with a mixture of monofunctional monomers, isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate, weight ratio of 4:1 :1 (46.94 g), a silicone flow agent (0.47 pph), and BDK photoinitiator (5.63 pph) (4837 cps viscosity @ 25 ° C for the formulated mixture), cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • HDPE high density polyethylene
  • the comparative linear polyester-based acrylate-terminated urethane (46.95 g) was blended 50/50 (wt/wt) with a mixture of monofunctional monomers, isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate, weight ratio of 4:1 :1 (46.94 g), a silicone flow agent (0.47 pph), and BDK photoinitiator (5.63 pph) (8990 cps viscosity @ 25 ° C for the formulated mixture), cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • HDPE high density polyethylene
  • EXAMPLE 4 Hybrid Polyester-Polyether Acrylate-Terminated Urethane UV-Curable PSA
  • An inventive polyester-polyether acrylate-terminated urethane (theoretical MW of 10,832) was synthesized by the same general reaction procedure set forth in Example 1 from the following ingredients, except that isobornyl acrylate was added as a non-reactive (for the purposes of urethane synthesis) diluent.
  • the inventive polyester-polyether based acrylate-terminated urethane was blended with a mixture of monofunctional monomers (isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate) such that urethane oligomer and acrylate monomers were present in equal amounts (wt wt), and the relative weight ratio of isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate was 4:1 :1.
  • the silicone flow agent (0.47 pph) and BDK photoinitiator (5.63 pph) were added (3926 cps viscosity @ 25° C for the formulated mixture), the mixture was cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • UV-A 750 mJ/cm 2
  • EXAMPLE 5 Hybrid Polyester-Polyether Acrylate-Terminated Urethane UV-Curable PSA
  • An inventive polyester-polyether acrylate-terminated urethane (theoretical MW 12,302) was synthesized by the same general reaction procedure set forth in Example 1 from the following ingredients.
  • the inventive polyester-polyether based acrylate-terminated urethane was blended with a mixture of monofunctional monomers (isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate) such that urethane oligomer and acrylate monomers were present in equal amounts (wt/wt), and the relative weight ratio of isobornyl acrylate, ethoxyethoxy ethylacrylate, tetrahydrofurfuryl acrylate was 4:1 :1.
  • the silicone flow agent (0.47 pph) and BDK photoinitiator (5.63 pph) were added (3750 cps viscosity @ 25° C for the formulated mixture), the mixture was cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • UV-A 750 mJ/cm 2
  • EXAMPLE 6 Hybrid Polyester-Polyether Acrylate-Terminated Urethane UV-Curable PSA
  • the monomer mixture included isobornyl acrylate, 2-phenoxyethyl acrylate, beta-CEA, ethoxy ethoxy ethylacrylate and tetrahydrofurfuryl acrylate (weight ratio 15.6 : 4.7 : 4.7 : 1.3 : 1 ).
  • the silicone flow agent (0.47 pph) and BDK photoinitiator (5.63 pph) were added (4443 cps viscosity @ 25 ° C for the formulated mixture), the mixture was cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • UV-A 750 mJ/cm 2
  • EXAMPLE 7 Hybrid Polyester-Polyether Acrylate-Terminated Urethane UV-Curable PSA
  • the silicone flow agent (0.47 pph) and BDK photoinitiator (5.63 pph) were added (4353 cps viscosity @ 25° C for the formulated mixture), the mixture was cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • UV-A 750 mJ/cm 2
  • EXAMPLE 8 Comparative (Physical Mixture of 100% Polyether and 100% Polyester UV-Curable PSA) A comparative sample was formulated from the acrylate-terminated oligomers of Examples 1 and 3, which were combined as analogues to the co-reacted versions of Examples 4 and 6.
  • the comparative physical mixture of a polyether and a polyester was combined with a silicone flow agent (0.47 pph), and BDK photoinitiator (5.63 pph) (5623 cps viscosity @ 25 ° C for the formulated mixture; cloudy within one day), cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • UV-A 750 mJ/cm 2
  • EXAMPLE 9 (Physical Mixture of 100% Polyether and 100% Polyester UV-Curable PSA) A comparative sample was formulated from the acrylate-terminated oligomers of Examples 1 and 3, which were combined as analogues to the co-reacted versions of Examples 4 and 6. TABLE 14
  • the comparative physical mixture of a polyether and a polyester was combined with a silicone flow agent (0.47 pph), and BDK photoinitiator (5.63 pph) (6365 cps viscosity @ 25° C for the formulated mixture; cloudy within one day), cast onto a polyethylene terephthalate (PET) film at a 2 mil film thickness, and air cured by exposure to UV-A (750 mJ/cm 2 ) to produce a PSA.
  • PET polyethylene terephthalate
  • UV-A 750 mJ/cm 2

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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition adhésive autocollante (PSA), produit de réaction durci par rayonnement ultraviolet (UV) d'un acrylate d'uréthane à base de polyester-polyéther, d'un ou de plusieurs monomères d'acrylate, et d'un photosensibilisant UV. L'acrylate d'uréthane à base de polyester-polyéther est le produit de réaction d'environ 50 à 90% en poids d'un polyester diol ayant un poids moléculaire d'environ 500 à 3200; d'environ 10 à 50% en poids d'un polyéther polyol ayant un poids moléculaire d'environ 1000 à 6000; d'environ 1 à 5% en poids d'un acrylate d'hydroxy fonctionnel; et d'un polyisocyanate.
PCT/US2005/013371 2004-04-27 2005-04-20 Oligomere d'acrylate d'urethane hybride polyester-polyether pour adhesifs autocollants durcisasnt par rayonnement uv WO2005105857A1 (fr)

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DE102007015801A1 (de) 2007-03-30 2008-10-02 Henkel Ag & Co. Kgaa Strahlenvernetzender Schmelzklebstoff
DE102010002622A1 (de) 2010-03-05 2011-09-08 Henkel Ag & Co. Kgaa Ionische Gruppen aufweisender Schmelzklebstoff
WO2011141245A1 (fr) 2010-05-11 2011-11-17 Henkel Ag & Co. Kgaa Adhésif filmogène réticulable par radiation
EP2527383A1 (fr) * 2011-05-27 2012-11-28 Henkel AG & Co. KGaA Procédé de fabrication de couches épaisses d'adhésifs durcis par radiation
WO2015135800A1 (fr) * 2014-03-11 2015-09-17 Henkel Ag & Co. Kgaa Adhésif thermofusible durcissable aux uv pour stratifier des films transparents
CN107090265A (zh) * 2016-02-18 2017-08-25 东洋油墨Sc控股株式会社 再剥离型粘合剂和表面保护膜
CN107501514A (zh) * 2017-08-15 2017-12-22 百恩实业（深圳）有限公司 一种生产丝网印刷胶刮用的浇注型聚氨酯弹性体半预聚体
CN109266281A (zh) * 2018-08-15 2019-01-25 瑞声科技(新加坡)有限公司 Uv胶
WO2019122042A1 (fr) * 2017-12-19 2019-06-27 Henkel IP & Holding GmbH Agent d'étanchéité d'imprégnation pour composants électroniques
CN110452360A (zh) * 2019-09-02 2019-11-15 淄博华天橡塑科技有限公司 硬度75a丝网刮刀用强极性支化聚氨酯弹性体及其制备方法
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CN111154067A (zh) * 2020-01-21 2020-05-15 江苏景宏新材料科技有限公司 一种低粘度高剥离强度uv固化复合胶及其制备方法
CN111334225A (zh) * 2020-04-27 2020-06-26 广东硕成科技有限公司 一种抗静电半导体uv减粘胶层及保护膜
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CN111433306A (zh) * 2018-06-04 2020-07-17 株式会社Lg化学 背面研磨带
CN111944433A (zh) * 2019-05-14 2020-11-17 汉能移动能源控股集团有限公司 胶黏剂组合物以及由该组合物制备得到的胶黏剂
WO2021009565A1 (fr) * 2019-07-17 2021-01-21 Arkema France Oligomères fonctionnalisés par méthacrylate et procédés de préparation et d'utilisation de tels oligomères
CN113801623A (zh) * 2014-01-21 2021-12-17 积水化学工业株式会社 电子部件用粘接剂和显示元件用粘接剂
CN113956432A (zh) * 2021-11-16 2022-01-21 广东十辰十新材料有限公司 一种可降解uv树脂及基于其的可降解uv压敏胶
CN115287014A (zh) * 2022-07-07 2022-11-04 江苏景宏新材料科技有限公司 一种保护膜用水性丙烯酸酯压敏胶及其制备方法
CN115537174A (zh) * 2022-08-26 2022-12-30 佳信新材料(惠州)有限公司 一种亲肤、低致敏uv湿气双固化胶水及其制备方法

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DE102007015801A1 (de) 2007-03-30 2008-10-02 Henkel Ag & Co. Kgaa Strahlenvernetzender Schmelzklebstoff
DE102010002622A1 (de) 2010-03-05 2011-09-08 Henkel Ag & Co. Kgaa Ionische Gruppen aufweisender Schmelzklebstoff
WO2011107546A1 (fr) 2010-03-05 2011-09-09 Henkel Ag & Co. Kgaa Adhésif fusible contenant des groupes ioniques
WO2011141245A1 (fr) 2010-05-11 2011-11-17 Henkel Ag & Co. Kgaa Adhésif filmogène réticulable par radiation
DE102010028870A1 (de) 2010-05-11 2011-11-17 Henkel Ag & Co. Kgaa Filmbildender strahlenvernetzender Klebstoff
WO2012163593A1 (fr) * 2011-05-27 2012-12-06 Henkel Ag & Co. Kgaa Procédé de formation d'épaisses couches d'adhésifs durcis par rayonnement
CN103582661A (zh) * 2011-05-27 2014-02-12 汉高股份有限及两合公司 辐射固化粘合剂厚层的制造方法
EP2527383A1 (fr) * 2011-05-27 2012-11-28 Henkel AG & Co. KGaA Procédé de fabrication de couches épaisses d'adhésifs durcis par radiation
CN113801623A (zh) * 2014-01-21 2021-12-17 积水化学工业株式会社 电子部件用粘接剂和显示元件用粘接剂
US10703942B2 (en) 2014-03-05 2020-07-07 Lumina Adhesives Ab Low cytotoxicity switchable adhesive compositions, medical dressings and skin coverings, and methods of treatment using same
US10407596B2 (en) 2014-03-11 2019-09-10 Henkel Ag & Co. Kgaa UV-reactive hot-melt adhesive for laminating transparent films
WO2015135800A1 (fr) * 2014-03-11 2015-09-17 Henkel Ag & Co. Kgaa Adhésif thermofusible durcissable aux uv pour stratifier des films transparents
CN106103524A (zh) * 2014-03-11 2016-11-09 汉高股份有限及两合公司 用于层压透明膜的uv反应性热熔粘合剂
RU2687096C2 (ru) * 2014-03-11 2019-05-07 Хенкель Аг Унд Ко. Кгаа Уф-реактивный термоплавкий клей для ламинирования прозрачных пленок
CN107090265A (zh) * 2016-02-18 2017-08-25 东洋油墨Sc控股株式会社 再剥离型粘合剂和表面保护膜
US10526511B2 (en) 2016-12-22 2020-01-07 Avery Dennison Corporation Convertible pressure sensitive adhesives comprising urethane (meth)acrylate oligomers
US10525406B2 (en) 2017-05-30 2020-01-07 Saudi Arabian Oil Company Polymer blended membranes for sour gas separation
US11311837B2 (en) 2017-05-30 2022-04-26 Saudi Arabian Oil Company Polymer blended membranes for sour gas separation
CN107501514B (zh) * 2017-08-15 2020-07-14 百恩实业（深圳）有限公司 一种生产丝网印刷胶刮用的浇注型聚氨酯弹性体半预聚体
CN107501514A (zh) * 2017-08-15 2017-12-22 百恩实业（深圳）有限公司 一种生产丝网印刷胶刮用的浇注型聚氨酯弹性体半预聚体
WO2019122042A1 (fr) * 2017-12-19 2019-06-27 Henkel IP & Holding GmbH Agent d'étanchéité d'imprégnation pour composants électroniques
US11725128B2 (en) 2017-12-19 2023-08-15 Henkel Ag & Co. Kgaa Impregnation sealant for electronic components
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US11424153B2 (en) 2018-06-04 2022-08-23 Lg Chem, Ltd. Back grinding tape
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EP3696242A4 (fr) * 2018-06-04 2021-02-17 Lg Chem, Ltd. Bande d'abrasion arrière
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WO2021009565A1 (fr) * 2019-07-17 2021-01-21 Arkema France Oligomères fonctionnalisés par méthacrylate et procédés de préparation et d'utilisation de tels oligomères
CN110452360B (zh) * 2019-09-02 2021-06-04 淄博华天橡塑科技有限公司 硬度75a丝网刮刀用强极性支化聚氨酯弹性体及其制备方法
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CN111334225A (zh) * 2020-04-27 2020-06-26 广东硕成科技有限公司 一种抗静电半导体uv减粘胶层及保护膜
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