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Patent US5721289 - Stable, low cure-temperature semi-structural pressure sensitive adhesive - Google PatentS�k Bilder Kartor Play YouTube Nyheter Gmail Drive Mer » Avancerad patents�kning | Webbhistorik | Logga in Avancerad patents�kning PatentA curable pressure sensitive adhesive having long shelf stability comprising (a) at least one free radically polymerized polymer; (2) at least one cationically-polymerizable monomer; (3) a photo-activatable catalyst system for the cationically-polymerizable monomer comprising either at least one organometallic...http://www.google.se/patents/US5721289?utm_source=gb-gplus-sharePatent US5721289 - Stable, low cure-temperature semi-structural pressure sensitive adhesive PublikationsnummerUS5721289 ATyp av kung�relseBeviljande Ans�kningsnummer08/531,275 Publiceringsdatum24 feb 1998 Registreringsdatum5 okt 1995 Prioritetsdatum4 nov 1994�ven publicerat somEP0789720A1EP0789720B1WO1996014349A1 UppfinnareAlbert I. EveraertsLeo W. HalmNaimul KarimSteven J. KeipertKevin E. KinzerJerry W. Williams Ursprunglig innehavareMinnesota Mining And Manufacturing Company USA-klassificering522/31522/113522/28522/66522/129522/29522/25522/130 Internationell klassificeringC09J133/00C09J151/08C08F291/00C09J163/00C08G59/68C09J4/02C08F4/80C09J4/06C08F283/10C08F2/50 Kooperativ klassningC08F283/10C08F291/00C09J151/08C08G59/68C09J4/06 Europeisk klassificeringC09J 4/06C09J 151/08C08F 291/00C08G 59/68C08F 283/10H�nvisningarCitat fr�n patent (25)Citat fr�n andra k�llor (15) H�nvisningar finns i f�ljande patent (35)Externa l�nkarUSPTO �verl�telse av �gander�tt till patent som har registrerats av USPTO EspacenetStable, low cure-temperature semi-structural pressure sensitive adhesiveUS 5721289 A Sammanfattning A curable pressure sensitive adhesive having long shelf stability comprising (a) at least one free radically polymerized polymer; (2) at least one cationically-polymerizable monomer; (3) a photo-activatable catalyst system for the cationically-polymerizable monomer comprising either at least one organometallic complex salt or at least one onium salt; and (4) optionally, a monohydric or polyhydric alcohol, wherein there is essentially no conversion of the cationically-polymerizable monomer of the curable pressure sensitive adhesive when stored in a manner to exclude actinic radiation, and methods of making the same.
We claim: 1. A post curable pressure sensitive adhesive consisting essentially of: (1) at least one free radically polymerized polymer; (2) at least one cationically-polymerizable monomer; (3) a photo-activatable catalyst system for the cationically-polymerizable monomer comprising either at least one organometallic complex salt or at least one onium salt; and (4) optionally, a monohydric or polyhydric alcohol, wherein there is essentially no conversion of the cationically-polymerizable monomer component of the curable pressure sensitive adhesive for at least 10 days at 20 humidity, when the curable pressure sensitive adhesive is stored in a manner to exclude actinic radiation.
2. A method of preparing a post curable pressure sensitive adhesive (PSA) comprising the steps of: ( 1) preparing a polymerizable composition consisting essentially of (a) at least one free-radically polymerizable monomer, (b) at least one thermal free-radical initiator, (c) at least one cationically-polymerizable monomer, (d) a photoactivatable catalyst system for the cationically-polymerizable monomer comprising at least one organometallic complex salt or at least one onium salt, and (e) optionally, a monohydric or polyhydric alcohol; and (2) applying sufficient thermal energy to the mixture to effect essentially complete polymerization of the free-radically polymerizable monomer; and wherein there is essentially no conversion of the cationically-polymerizable monomer component of the curable pressure sensitive adhesive for at least 10 days at 20 humidity, when the curable pressure sensitive adhesive is stored in a manner to exclude actinic radiation.
3. The method according to claim 2, further comprising the steps of: (a) applying sufficient irradiation to the curable PSA to activate the photoactivatable catalyst system, and (b) providing sufficient time and/or thermal energy to effect essentially complete polymerization of the cationically polymerizable monomer.
4. A method for preparing a curable pressure sensitive adhesive (PSA) comprising the steps: (1) preparing a first polymerizable composition consisting essentially of a mixture of (a) at least one free-radically polymerizable monomer, (b) at least one free-radical initiator, (c) at least one cationically-polymerizable monomer, and (d) optionally, a monohydric or polyhydric alcohol; (2) applying sufficient energy to the mixture to effect essentially complete polymerization of the free-radically polymerizable monomer; (3) mixing into the polymerized composition, (a) a photoinitiated catalyst system for the cationically-polymerizable monomer comprising at least one organometallic complex salt or at least one onium salt, and (b) optionally, a monohydric or polyhydric alcohol; and wherein there is essentially no conversion of the cationically-polymerizable monomer component of the curable pressure sensitive adhesive for at least 10 days at 20 sensitive adhesive is stored in a manner to exclude actinic radiation.
5. The method according to claim 4, further comprising the steps of: (a) applying sufficient irradiation to the curable PSA to activate the photoactivatable catalyst system, and (b) providing sufficient time and/or thermal energy to effect essentially complete polymerization of the cationically polymerizable monomer.
6. A method for preparing a curable pressure sensitive adhesive (PSA) comprising the steps: (1) preparing a first polymerizable composition consisting essentially of a mixture of (a) at least one free-radically polymerizable monomer, and (b) at least one free-radical initiator; and (2) applying sufficient energy to the mixture to effect essentially complete polymerization of the free-radically polymerizable monomer; (3) mixing into the polymerized composition, a second polymerizable composition comprising a mixture of: (a) at least one cationically-polymerizable monomer, (b) a photoinitiated catalyst system for the cationically-polymerizable monomer comprising at least one organometallic complex salt or at least one onium salt, and (c) optionally, a monohydric or polyhydric alcohol; and wherein there is essentially no conversion of the cationically-polymerizable monomer component of the curable pressure sensitive adhesive for at least 10 days at 20 sensitive adhesive is stored in a manner to exclude actinic radiation.
7. The method according to claim 6, further comprising the steps of: (a) applying sufficient irradiation to the curable PSA to activate the photoactivatable catalyst system, and (b) providing sufficient time and/or thermal energy to effect essentially complete polymerization of the cationically polymerizable monomer.
8. A pressure sensitive adhesive prepared according to the methods of claims 2, 4 or 6.
CROSS RELATED APPLICATIONS This is a continuation-in-part of U.S. Ser. No. 08/445,143, filed May 19, 1995, now abandoned, which is a continuation of U.S. Ser. No. 08/334,692, filed Nov. 4, 1994, now abandoned.
SUMMARY OF THE DISCLOSURE The present invention describes a curable pressure sensitive adhesive that upon curing provides a semi-structural or structural adhesive, wherein the pressure sensitive adhesive comprises:
wherein there is essentially no conversion of the cationically-polymerizable monomer of the curable pressure sensitive adhesive for at least 10 days, at 20 manner to exclude actinic radiation which is capable of activating the catalyst system.
Accordingly, the inventive process for the production of adhesives comprises allowing a carrier web coated with a free-radically polymerizable composition to remain in a thermal buffer for a time sufficient to effect conversion of the coating to an adhesive while controlling the reaction exotherm to maintain a reaction temperature within 20 buffer is characterized as a system for heat transfer wherein the heat transfer coefficient is at least 25 W/(m.sup.2 the particular polymerizable mixture, it may be advantageous to exclude oxygen from the polymerization zone.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S) Cationically-polymerizable monomers useful in the invention include but are not limited to epoxy-containing materials, alkyl vinyl ethers, cyclic ethers, styrene, divinyl benzene, vinyl toluene, N-vinyl compounds, cyanate esters, 1-alkenes (alpha olefins), lactams and cyclic acetals.
Additional cationically-polymerizable monomers are described in U.S. Pat. No. 5,252,694 at col. 4, line 30 thru col. 5, line 34, the description of which is incorporated herein by reference. Preferred monomers of this class include EPON�828, and EPON�1001F and the ERL series of cycloaliphatic epoxy monomers such as ERL-4221� or ERL-4206�; most preferred monomers are the ERL series because of their lower cure temperatures.
Two other criteria for the free-radical monomers are preferred, but not required: (a) these monomers should be miscible with the epoxy monomer(s) and (b) the free-radical monomers are preferably chosen such that their copolymers have composite Tgs in the range of 30 calculated by, e.g., the Fox equation, Bull. Am. Phys. Soc., 1, 123 (1956).
(L.sup.1)(L.sup.2)M.sup.p!.sup.+q Y.sub.n
M.sup.p represents a metal selected from the group consisting of: Cr, Mo, W, Mn, Re, Fe, and Co;
L.sup.2 represents none, or 1 to 3 ligands contributing an even number of sigma-electrons that can be the same or different ligand selected from the group of: carbon monoxide, nitrosonium, triphenyl phosphine, triphenyl stibine and derivatives of phosphorus, arsenic and antimony, with the proviso that the total electronic charge contributed to M.sup.p results in a net residual positive charge of q to the complex;
Preferred organometallic initiators are the cyclopentadienyl iron arenes (CpFeArenes), and preferably, SbF.sub.6.sup.- is the counterion. CpFe(arenes) are preferred because they are very thermally stable yet are excellent photoinitiation catalysts.
Cationic photoinitiators that are also useful include aromatic iodonium complex salts and aromatic sulfonium complex salts. The aromatic iodonium complex salts have the formula: ##STR1## wherein Ar.sup.1 and Ar.sup.2 are aromatic groups having 4 to 20 carbon atoms and are selected from the group consisting of phenyl, thienyl, furanyl and pyrasolyl groups;
Z is selected from the group consisting of oxygen, sulfur, ##STR2## where R is aryl (having 6 to 20 carbon atoms, such as phenyl) or acyl (having 2 to 20 carbon atoms, such acetyl, benzoyl, etc.), a carbon-to-carbon bond, or ##STR3## where R.sub.1 and R.sub.2 are independently selected from hydrogen, alkyl radicals of 1 to 4 carbon atoms, and alkenyl radicals of 2 to 4 carbon atoms;
X.sup.- is a halogen-containing complex anion selected from tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantinomate.
R.sub.3, R.sub.4 and R.sub.5 can be the same or different, provided that at least one of such groups is aromatic and such groups can be selected from the aromatic groups having 4 to 20 carbon atoms (for example, subsituted and unsubstituted phenyl, thienyl, furanyl) and alkyl radicals having 1 to 20 carbon atoms. The term "alkyl" as used here is meant to include substituted and unsubstituted alkyl radicals. Preferably, R.sub.3, R.sub.4, and R.sub.5 are each aromatic groups; and
Z, n and X.sup.- are as defined above.
Suitable azo initiators include, but are not limited to 2,2'-azobis(4-methoxy-2,4-dimethlvaleronitrile) (VAZO� 33), .2,2'-azobis(amidinopropane) dihydrochloride (VAZO� 50); 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO� 52); 2,2'-azobis(isobutrynitrile) (VAZ)� 64); 2,2'-azobis-2-methylbutyronitrile (VAZO� 67); 1,1'-azobis(1-cyclohexadecanecarbonitrile) (VAZO� 88), all of which are available from DuPont Chemicals and 2,2'-azobis(methyl isobutyrate) (V-601) available from Wako Chemicals.
Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (PERKADOX� 16S, available from AKZO Chemicals), di(2-ethylhexyl) peroxydicarbonate, t-butylperoxypivalate (Lupersol�11, available from Atochem), t-butylperoxy-2-ethylhexanoate (Trigonox� 21-C50, available from Akzo Chemicals, Inc.), and dicumyl peroxide.
Preferred thermal free-radical initiators are selected from the group consisting of peroxides and azo compounds that do not contain nitriles or basic groups. Most preferred initiators are V-601, Lupersol� 11 and Perkadox� 16S, and mixtures thereof, because of their preferred decomposition temperature is in the range of about 45 95 polymerization initiators.
Method 1 A first step in the preparation of a syrup is to mix free radically polymerizable monomers with a catalytically effective amount of a free radical initiator, preferably a free radical photoinitiator. Preferably, the free radical photoinitiator is not a crosslinking agent and is generally present in an amount within the range of 0.001 to 5.0% by weight of the polymerizable composition, preferably in the range of 0.01 to 1.0% by weight of the polymerizable composition.
A second step, that is simultaneous and concurrent with step (3) is to purge the system (the polymerizable composition, as well as the reaction environment), for example by bubbling an inert gas, such as N.sub.2, Ar, or He through the polymerizable composition to remove any residual oxygen.
Method 2 A first step in this alternative preparation for a syrup is to mix the polymerizable monomers (cationically and free radically polymerizable monomers) with a catalytically effective amount of at least one free radical initiator. Preferably, the free radical initiator is not a crosslinking agent and is generally present in an amount within the range of 0.001 to 5.0% by weight of the polymerizable composition, preferably in the range of 0.01 to 1.0% by weight of the polymerizable composition.
A second step, that is simultaneous and concurrent with step (3) is to purge the system (the polymerizable composition, as well as the reaction environment), for example by bubbling an inert gas, such as N.sub.2, Ar, or He, through the polymerizable composition to remove any residual oxygen.
Once coated, the curable adhesive composition is processed through at least one polymerization zone wherein the curable adhesive composition is thermally polymerized by heating the same within a thermal buffer having a heat transfer process characterized by a heat transfer coefficient of at least 25 W/(m.sup.2 thermal polymerization for a period a time sufficient to effect about 5-100% conversion of the free-radically polymerizable monomeric mixture or prepolymerized syrup to polymer. When the process is carried out in one heating zone, it is preferred that the time and temperature be such that at least 90% of the free radically polymerizable monomeric mixture or prepolymerized syrup is converted to polymer. Furthermore, it is advantageous that the heat transfer coefficient for the heat transfer process within the thermal buffer be relatively high, preferably 100 W/(m.sup.2 Thermal control of the polymerization process of the current invention can be stated as follows. As the polymerization occurs throughout the cross-section of the polymerization mixture, the energy balance on a small unit volume of polymerizable mixture contains components relating to the internal heat generation created by the polymerization reaction and on the heat transfer by conduction into and out of the small unit volume from the surrounding units volumes. The rate of heat flow out of a unit volume must be fast enough to prevent an excessive temperature rise within the unit volume caused by the reaction exotherm.
The heat transfer process within the thermal buffer can include but is not limited to forced or impinged air, helium, or hydrogen; heat transfer via conduction, such as a metal platen, or heated metal rolls; or via convective transfer to liquids, such as water, perfluorinated liquids, glycerin, or propylene glycol. Heat transfer processes that are characterized by having heat transfer coefficients of at least 25 W/(m.sup.2 present invention. Additionally, it is also within the scope of the present invention to add salts or low molecular weight organic compounds to a fluid heat transfer medium to alter the characteristics of the thermal buffer, such as providing for reduced oxygen content, solubility of monomers and the like. It should be noted that it is not necessary within the thermal buffer to surround the coated construction with the heat transfer medium; contact on one side of the carrier web or polymerization mixture may be sufficient. Furthermore, physical properties, such as boiling point of the heat transfer fluid should be taken into consideration when designing a thermal buffer, along with initiator type and concentration, processing temperature and the like.
In practice, a monomer mixture or prepolymer as described in Method One or Method Two, above, is prepared in a premix tank or holding tank where it is degassed and covered with a blanket of inert gas such as nitrogen. From the holding tank, it may optionally be pumped to a static mixer, where it may optionally be preheated to a temperature in the range of 35 to 55 reactor at a pressure sufficient to maintain process stability. After an appropriate residence time, the resulting polymeric material is withdrawn from the reactor and directed to a coater or otherwise packaged.
In another aspect of this invention a mixture of free-radically polymerized polymer, cationically-polymerizable monomer and catalyst system may be melt blended. A melt blend is formed by heating the mixture to at least the softening point of the free-radically polymerized polymer, typically between about 100 to produce a homogeneous mixture. During the process of melt-blending, the free-radically polymerized polymer, cationically-polymerizable monomer and catalyst system are mixed, such as in the mixing barrel of a single screw or twin-screw extruding apparatus wherein the mixture is heated during mixing in the absence of actinic radiation that would activate the catalyst. See, for example, "Polymer Extrusion" by Chris Rauwendaal, ed. Hanser Publishers, 1986, pages 322-330, for a detailed description of mixing in screw extruders.
__________________________________________________________________________Glossary__________________________________________________________________________350BL bulbs    fluorescent bulbs available from Sylvania Corp. under the trade    designation F15T8/350BLCpFeXyl SbF.sub.6    (eta.sup.6 -xylenes(mixed isomers))(eta.sup.5 -cyclopentadienyl)i    ron(1+)    hexafluoroantimonateEPON 1001F    diglycidyl ether of bisphenol A (epoxy equivalent weight =    525-550    g/eq) (available from Shell Chemical Co.)EPON 828 diglycidyl ether of bisphenol A (epoxy equivalent weight    =185-192    g/eq) (available from Shell Chemical Co.)ERL-4206 vinyl cyclohexene dioxide (available as BAKELITE ERL-4206    from Union Carbide Corp.)ERL-4221 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate    (available as BAKELITE ERL-4221 from Union Carbide Corp.)ESACURE KB-1    2,2-dimethoxy-2-phenyl acetophenone (available from Sartomer    Chemicals)IBA      isobutyl acrylatenBA      n-butyl acrylatePERKADOX 16    di(4-t-butylcyclohexyl)peroxydicarbonate(available from Akzo    Chemicals, Inc.)POEA     phenoxy ethyl acrylateSuper Actinic bulbs    fluorescent bulbs available from Philips Lighting under the    trade    designation TLD 15W/03tBOX     di-t-butyl oxalate (available from Aldrich Chemical Company)THFA     tetra hydrofurfuryl acrylateUVI-6974 50% mixed triarylsulfonium hexafluoroantimonate salts in    propylene carbonate (available as CYRACURE UVI-6974 from    Union Carbide Corp.)V-601    dimethyl 2,2'-azobisisobutyrate (available from Wako Chemical    Co.)__________________________________________________________________________
Differential Scanning Calorimetry was used to measure the exothermic heat of reaction (Joule/gram (J/g)) associated with the cure of the cationically polymerizable monomer. The exotherm profile, that is, peak temperature, onset temperature, etc., of the exotherm provided information on conditions that were needed to cure the material. DSC samples were typically 6 to 12 milligrams and were run in sealed pans on a Seiko Instruments DSC 220C at a heating rate of 10 temperature (T.sub.onset) is the point of intersection between the tangents drawn to the curve along the baseline, and after the onset of the exotherm at the point of maximum change in slope. The integrated energy under the exothermic peak is related to the extent of cure. For a stable composition, more of that exotherm should remain with time indicating the composition is not curing prematurely. For an unstable composition, the exotherm energy will decrease more rapidly with time indicating that the composition has undergone some degree of cure prematurely.
Photo Differential Scanning Calorimetry was used to measure the exothermic heat of reaction (Joule/gram (J/g)) associated with the cure of the cationically polymerizable monomer upon exposure to light. PDSC samples were typically 6-12 milligrams and were run in open pans on a Seiko Instruments PDC121 at a heating rate of 10 photolysis step using a 200 watt mercury-xenon lamp. The analysis of the exotherm profile was conducted in the same manner as described under the DSC description.
Samples were prepared by cutting 12.7 mm adhesive film. The silicone release liner was removed from one side of the specimen and the exposed adhesive was applied to one end of an aluminum test coupon measuring 1.7 mm release liner was removed from the other side of the specimen and another identical aluminum coupon was placed over the adhesive such that there was a 12.7 mm overlap of the coupons and with the uncoated ends of the coupons aligned in opposite directions from each other. The coupons were clamped together and thermally cured. The prepared samples were cooled for at least 1 hour at about 22 determined using an Instron Model 1122 tensile tester according to ASTM Test Method D1002-72 with a crosshead speed of 5 cm/min. The lap shear strength is reported in Megapascals (MPa).
Peel adhesion samples were prepared by applying a 12.7 mm wide strip of the PSA tape to a desired panel (either 1.7 mm thick 50 mm aluminum or standard 25 mm average peel adhesion value was determined by doubling one end of the adhesive strip back over itself at 180 required to peel the tape from the substrate at a rate of 30.5 cm/minute using an Instron Model 1122 tensile tester. The 180 values were reported in Newton/centimeters (N/cm). Further details of this test are shown in "Test Methods for Pressure Sensitive Tapes", available from the Specifications and Technical Committee of the Pressure Sensitive Tape Council, 5700 Old Orchard Road, First Floor, Skokie, Ill. 60077, under the test designation PSTC-1.
A mixture of 60 parts 75:25 ratio of phenoxyethyl acrylate:isobornyl acrylate, 40 parts 75:25 ratio of EPON� 828:EPON� 1001F, 3.8 parts 1:1 ratio of cyclohexane dimethanol:1,6-hexanediol, 1.2 parts WAKO V-601� (25 weight percent in propylene carbonate) and 1.6 parts CpFeXyl SbF.sub.6 (25 weight percent in propylene carbonate) was metered into the throat of an 18 mm counter-rotating twin screw extruder by means of a peristaltic pump. The mixture was conveyed down the length of the extruder, operated at a screw speed of 50 rpm, through 8 heated zones (72 115 120 analysis of the material, cooled to room temperature, indicated a peak exotherm temperature of 229.9.degree. C. and a cure exotherm of 74.6 J/g. PhotoDSC analysis showed a peak exotherm temperature shift to 105.2.degree. C. and an increase in cure exotherm to 173 J/g after a two-minute photolysis step. After 429 days of storage in the dark at room temperature, photoDSC of the sample gave a peak exotherm temperature of 110.3.degree. C. and a cure exotherm of 171 J/g. This example shows that the PSA prepared by reactive extrusion has a very long shelf life, with essentially no advancement of the epoxy resin over a 14-month period.
Adhesive tapes were prepared by pressing this polymeric material to a thickness of 0.200 mm between a 0.036 mm poly(ethylene terephthalate) film and 0.100 mm silicone-coated poly(ethylene terephthalate) film using a heated platen press at a temperature of 170 room temperature these tapes were tested for 180 glass and aluminum substrates with and without curing. Curing was carried out by exposing the previously prepared panels to irradiation under Super Actinic� bulbs for 5 minutes and then heating in an oven at 100 C. for 10 minutes. The resulting peel values are summarized below.
A mixture of 30 parts phenoxyethyl acrylate, 30 parts isobornyl acrylate, 40 parts ERL-4221� epoxy monomer and 0.01 parts KB-1 photoinitiator was prepared and purged with nitrogen and irradiated with 350BL fluorescent bulbs with stirring until the viscosity of the mixture was suitable for coating (about 1055 kPa).
A mixture of 100 parts of the above syrup, 0.4 parts ground CpFeXyl SbF.sub.6, 0.8 parts methyl ethyl ketone, 0.1 parts hexanediol diacrylate, 0.1 parts V601 initiator, 0.075 parts PERKADOX� 16 initiator and 4.0 parts 1:1 mixture of 1,4-cyclohexane dimethanol:1,6-hexane diol was degassed and knife-coated at 0.125 mm thickness between two 0.050 mm silicone-coated white poly(ethyleneterephthalate) films under subdued lighting. The sandwich construction was placed on an aluminum plate heated to 90 analysis of the acrylate-cured film, in the absence of a photopolymerization step, showed an exotherm onset temperature of 210.4.degree. C., a peak exotherm temperature of 226.8.degree. C. and a cure exotherm of 45.2 J/g. PhotoDSC of the sample showed an exotherm onset temperature of 77.9.degree. C., a peak exotherm at 94.6.degree. C. and a cure exotherm of 204.7 J/g after a five-minute photolysis step.
TABLE 2__________________________________________________________________________Component C1 C2  C3 C4  3   4   5  6__________________________________________________________________________Epoxy/Acrylate     100        100 100               100 100 100 100                              100MixtureCyclohexane     -- 4.0 -- 4.0 --  4.0 -- 4.0dimethanolt-BOX     -- --  0.4               0.4 --  --  0.4                              0.4KB-1      0.6        0.6 0.6               0.6 --  --  -- --CpFeXylSbF.sub.6     0.4        0.4 0.4               0.4 0.4 0.4 0.4                              0.4V-601     -- --  -- --  0.1 0.1 0.1                              0.1PERKADOX P-16     -- --  -- --   0.15                        0.15                            0.15                               0.15__________________________________________________________________________
Prior to coating, each of the formulations was de-aerated in a vacuum chamber, then knife coated at 0.75 mm thickness between two 0.100 mm transparent polyethylene terephthalate release liners. Samples C1 through C4 were irradiated for 13 minutes with 350BL fluorescent bulbs at a light dosage of 1960 mJ/cm.sup.2. These films were transparent, tacky, self-supporting pressure sensitive adhesives. Samples 3 through 5 were immersed in 83 100 self-supporting pressure sensitive adhesives.
Samples of these adhesives were used to bond 50.8 mm mm clean with isopropanol. Samples 3 through 5 were irradiated for 5 minutes under Super Actinic� bulbs prior to preparing the bond. An overlap joint of approximately 1.2 cm in length was formed and the bonded strips were placed in an air circulating oven at 100 The overlap shear bond strength was measured using an Instron Tensile Tester, model #1122. The jaw separation rate was 5 cm/min. The results are summarized in Table 3.
Samples 3 and 4 were found not to be fully cured. Additional overlap shear panels were prepared in the same manner as described above with the exception that the bonded strips were placed in an air circulating oven at 120 samples was measured as described above and the results are tabulated below.
The room temperature shelf-stability of these samples was monitored by determining the epoxy cure exotherm energy using a Seiko DSC as a function of time at room temperature. Samples 3 through 6 were irradiated for 5 minutes under Super Actinic� bulbs prior to analyzing in the DSC. Samples C1 through C4 were analyzed without the photolysis step.
A mixture of 100 parts of the above syrup, 0.4 parts ground CpFeXyl SbF.sub.6, 0.8 parts methyl ethyl ketone, 0.4 parts hexanediol diacrylate, 0.1 parts V-601 initiator, and 0.15 parts Perkadox 16 initiator was degassed and knife-coated at 0.125 mm thickness between two 0.100 mm silicone-coated PET films under subdued lighting. The sandwich construction was placed in 85 98 film was a transparent, tacky, self supporting pressure sensitive adhesive. DSC analysis of the film after 5 minutes of irradiation with Super Actinic� bulbs showed a peak exotherm at 72.2.degree. C. and a cure exotherm of 297.1 J/g. The rate of cure of this film at an isothermal temperature of 60 minutes with Super Actinic� bulbs with the top liner removed, after which the liner was replaced and the sample immersed in a silicone oil bath heated to 60 5). DSC analysis was performed on the sample after removing it from the silicone oil to determine the extent of cure.
TABLE 5______________________________________Minutes at60       Cure Energy (J/g)                   Residual Cure (%)______________________________________0           297.1       100.02           91.6        30.85           28.7        9.710          16.5        5.640          0.0         0.0______________________________________
The rate of cure of this film at room temperature was determined by irradiating the film for 2 minutes with Super Actinic� bulbs with the top liner removed, after which the liner was replaced and the sample stored in the dark at room temperature (�22 analysis was performed on the sample after various lengths of time to determine the extent of cure.
TABLE 6______________________________________Minutes at Room Cure Energy                     Residual CureTemperature (22           (J/g)     (%)______________________________________0               297.1     100.030              237.8     80.060              111.9     37.7180             80.9      27.2540             50.1      16.94680            36.9      12.4______________________________________
A mixture of 100 parts of the above syrup, 3.8 parts 1:1 mixture of 1,4-cyclohexane dimethanol:1,6 hexane diol, 0.3 parts V-601 initiator, 0.1 parts PERKADOX 16 initiator, and the cationic photocatalyst listed in Table 7 was degassed and knife-coated at 0.200 mm thickness between a 0.036 mm poly(ethylene terephthalate) film and 0.100 mm silicone-coated poly(ethylene terephthalate) film under subdued lighting. The sandwich construction was placed in 85 98
These tapes were tested for 180 substrates with and without curing. Curing of the Example 8 material was carried out by exposing the panels to irradiation under Super Actinic� bulbs for 5 minutes and then heating in an oven at 100 minutes. Curing of the Example 9 material was carried out by exposing the panels to irradiation under 350BL bulbs for 5 minutes with no heating step. The resulting peel values are summarized in Table 7.
TABLE 7______________________________________               Average Peel Adhesion               (N/cm width)Example Catalyst          Glass    Aluminum______________________________________8       0.4 parts  Before cure                         0.06   4.4   CpFeXylSbF.sub.6              After cure 86.4   6.69       3.0 parts  Before cure                         0.09   3.0   UVI-6974   After cure 2.1    6.6______________________________________
Mixture 2: A mixture of 100 parts of the above syrup, 3.8 parts 1:1 mixture of 1,4-cyclohexane dimethanol:1,6 hexane diol, 0.2 parts KB-1 photoinitiator was degassed and coated at 0.75 mm thickness between two 0.100 mm silicone-coated poly(ethylene terephthalate) films. This dual-liner construction was irradiated for 15 minutes using 350BL fluorescent bulbs at a light dosage of 2260 mJ/cm.sup.2. The polymerized mixture was used in Examples 10 and 11. The liners, used to polymerize the mixture were removed prior to further processing with the photo-activatable catalyst of the pressure sensitive adhesive.
In Example 10, a molten mixture of the polyacrylate-epoxy material with cationic photocatalyst was prepared by combining 100 parts of the polymerized Mixture 2 (the liners having been previously removed before combination) with 3.0 parts UVI-6974 cationic photo-initiator with stirring in an aluminum container heated to 150
Pressure sensitive adhesive tapes were prepared by pressing this polymeric material to a thickness of 0.250 mm between a 0.036 mm poly(ethylene terephthalate) film and 0.100 mm silicone-coated poly(ethylene terephthalate) film using a heated platen press at a temperature of 120 for 180 the epoxy component of the pressure sensitive adhesive. Curing was carried out by exposing the previously prepared panels to irradiation under 350BL bulbs for 5 minutes without a heating step. The resulting peel values are summarized in Table 8 below.
In Example 11, a molten mixture of the polyacrylate-epoxy material with cationic photocatalyst was prepared by combining 100 parts of the polymerized Mixture 2 with 1.0 parts CpFeXylSbF.sub.6 cationic photo-initiator, predissolved at 25 wt-% in propylene carbonate, with stirring in an aluminum container heated to 150
Pressure sensitive adhesive tapes were prepared by pressing this polymeric material to a thickness of 0.250 mm between a 0.036 mm poly(ethylene terephthalate) film and 0.100 mm silicone-coated poly(ethylene terephthalate) film using a heated platen press at a temperature of 120 for 180 the epoxy component of the pressure sensitive adhesive. Curing was carried out by exposing the panels to irradiation under Super Actinic bulbs for 5 minutes followed by heating in a 100 resulting peel values are summarized in Table 8 below.
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