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1. WO1997041170 - COMPOSITION DURCISSABLE PAR LES UV

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[ EN ]

UV CURABLE COMPOSITION

The invention relates to a UV curable composition comprising a monohydroxylated epoxidized polydiene polymer and a photomitiator . The invention further relates to a process for preparing the UV curable composition; to UV cured compositions and to articles containing the UV cured compositions.
The UV curable compositions are useful in
adhesives, sealants, coatings and other types of films, fibers or thin parts made from epoxidized
monohydroxylated polydiene polymers.
The use of epoxidized monohydroxylated polydienes in UV curable adhesive and sealants compositions is described in WO 96/11215. The polymers are combined with other ingredients such as a tackifying resm to make them suitable for adhesive and sealant products. A photomitiator is included in the combination to promote the UV curing (crosslmk g) of the
composition. As described in the examples of the aforesaid patent application, the components were dispersed a non-aqueous solvent, usually THF, and then adhesive films were cast from the solution. The non-aqueous solvent was necessary because difficulties were encountered in mixing the photomitiator
(triarylsulfomum hexafluoroantimonate) into the adhesive mixture because it was not readily compatible and would not dissolve or finely disperse. The THF was necessary to obtain effective UV curing - the curing was ineffective in the absence of the non-aqueous solvent.

For many applications, the use of non-aqueous solvents is undesirable because of environmental hazards and the cost of non-aqueous solvent removal and the non-aqueous solvent itself. One possible method for solving this problem is a non-aqueous solvent free method for mixing these components which requires the use of intensive mixing for dispersing the
photomitiator so that an effectively cured adhesive, sealant, or other composition is prepared. The present mvention achieves the same results for making thin films without the necessity for high shear equipment.
Now surprisingly, a UV curable composition and a non-aqueous solvent-free process for preparing the same, have now been found which solve one or more problems associated with the prior art.
Therefore, the present invention relates to a UV curable composition comprising a monohydroxylated epoxidized polydiene polymer and a photomitiator selected from the group consisting of diarylhalide salts of the general formula (I):


wherein X is a complex metal halide anion or a complex halid anion of a strong protonic acid;

3H
Y IS -CR2—C— —CRj-

wherein R is hydrogen, aryl, alkyl or a halide;

Z is iodine, bromine or chlorine; and
n is an integer of at least 1.
In formula (I), Z is preferably iodine.
Any one or both of R is preferably hydrogen or alkyl, typically containing up to 10 carbon atoms, preferably up to 6 carbon atoms, more preferably 1 to 4 carbon atoms .
Most preferably both of R is hydrogen.
Y is preferably
OH
I
-CH2-C- H
Again, in formula (I), n is preferably an integer in the range from 1 to 25, more preferably from 5 to

20, even more preferably from 10 to 15.
In one embodiment, X is preferably a complex metal halide anion wherein the metal is chosen from groups 3 to 15 (new IUPAC notation) of the Periodic Table of the

Elements, more preferably groups 13, 14 or 15
(including P) . The halide is preferably chosen from F,

Cl, Br, or I, more preferably F.
Examples of preferred complex metal halides include BF4-, PF6~, AsF6~ and SbF6~ . A particularly preferred complex metal halide is SbFg- .
According to another embodiment X is preferably a complex halide anion of a strong protonic acid.
Particularly preferred complex halide anions of strong protonic acids include CIO4", CF3SO3"", FSO3", CCI3SO3- and C4F9SO3-.
An especially preferred photomitiator is diaryl-lodonium hexafluoroantimonate, commercially available under the trade name CD-1012 from the Sartomer Company. Diaryliodoniumhexafluoroantimonate has the formula

(II) :

The photomitiator present in the composition according to the invention is typically used m an amount of from 0.01 to 10% by weight of the total composition,
preferably 0.03 to 1.0°. by weight, more preferably 0.1 to 0.3 by weight. Typically, the photomit ator is compatible with the remainder of the composition, preferably soluble m the remainder of the composition. Useful photomitiators include those described in US Patent NO. 5, 079, 378.
An advantage of the UV curable composition
according to the present invention is that the
composition does not contain a non-aqueous solvent and does not require significant mixing with high shear equipment .
Thus the invention relates to UV curable adhesive, sealant, coating, or other compositions and a method for making such compositions from a epoxidized
monohydroxylated polydiene polymer comprised of at least two polymeπzable ethylemcally unsaturateα hydrocarbon monomers wherein at least one is a d^ene monomer which yields unsaturation suitable lor
epoxidation is used as the binder for the composition. The preferred epoxidized monohydroxylated polymers are block copolymers of at least two conjugated αienes, preferably isoprene and butadiene, and optionally, a vinyl aromatic hydrocarbon wherein a hydroxyl group is attached at one end of the polymer molecule. These polymers may be hydrogenated or unsaturated.
The photomitiator which is incorporated into this composition, is soluble or readiJy dispersible the mixture containing the other ingredients of the
composition (polymer blend) and very good curing with UV radiation is the result.
Polymers containing ethylenic unsaturation can be prepared by copolymeriz g one or more olefins, particularly diolef s, by themselves or with one or more alkenyl aromatic hydrocarbon monomers. The copolymers may, of course, be random, tapered, block or a combination of these, as well as linear, star or radial.
In general, when solution anionic techniques are used, copolymers of conjugated diolefms, optionally with vinyl aromatic hydrocarbons, are prepared by contacting the monomer or monomers to be polymerized simultaneously or sequentially with an anionic
polymerization initiator such as group IA metals, preferably lithium, their alkyls, amides, napthalides, biphenyls or anthracenyl derivatives. The
monohydroxylated polydienes are synthesized by anionic polymerization of conjugated diene hydrocarbons with these lithium initiators. This process is well known as described in U.S. Patents Nos. 4,039,593 and Re. 27,145. Polymerization commences with a monolithium initiator which builds a living polymer backbone at each lithium site. Typically, such polymerizations are capped by termination with ethylene oxide to provide a terminal hydroxyl group. Specific processes for making these polymers are described m detail m WO 96/11215. Conjugated diolefms which may be polymerized aniomcally include those conjugated diolefms
containing from 4 to 24 carbon atoms such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, 2-phenyl-1, 3-butadιene, 3, 4-dιmethyl-l, 3-hexadιene, and 4, 5-dιethyl-l, 3-octadιene. Preferred conjugated diolefms (dienes) are those containing from 4 to 12 carbon atoms, more preferably from 4 to 6 carbon atoms. Isoprene and butadiene are the most preferred
conjugated diene monomers for use in the present invention because of their low cost and ready
availability.
Alkenyl (vinyl) aromatic hydrocarbons which may be copolymeπzed include vinyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, vinyl napthalene, and alkyl-substituted vinyl napthalenes. Preferably, the alkenyl aromatic hydrocarbons are styrene and/or ciLkyl-substituted styrene, more preferably styrene. The alkyl or alkoxy substituents may typically comprise from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. The number of alkyl or alkoxy substituents per molecule, if present, may range from 1 to 3, and is preferably one.
The most preferred monohydroxylated polydiene polymer of the present invention has the structural formula
(HO)x-A-Sz-B- (OH)y (I)
wherein A and B are polymer blocks which may be
homopolymer blocks of conjugated diolefin monomers, copolymer blocks of conjugated diolefin monomers, or copolymer blocks of diolefin monomers and monoalkenyl aromatic hydrocarbon monomers. These polymers may contain up to 60% by weight of at least one vinyl aromatic hydrocarbon, preferably styrene. Generally, it is preferred that the A blocks should have a greater concentration of more highly substituted aliphatic double bonds than the B blocks have. Thus, the A blocks have a greater concentration of di-, tn-, or tetra-substituted unsaturation sites (aliphatic double bonds) per unit of block mass than do the B blocks. This produces a polymer wherein the most facile - 7 -epoxidation occurs in the A blocks. The A blocks have a number average molecular weight of from 100 to 6000 g/mol, preferably 500 to 4,000 g/mol, and most
preferably 1000 to 3000 g/mol, and the B blocks have a number average molecular weight of from 1000 to 15,000 g/mol, preferably 2000 to 10,000 g/mol, and most preferably 3000 to 6000 g/mol. S is a vinyl aromatic hydrocarbon block which may have a number average molecular weight of from 100 to 10,000. x or y is 1, the other bemg 0. z is 0 or 1. Preferably, y is 1. Either the A or the B block may be capped with a m iblock of polymer, 50 to 1000 number average
molecular weight, of a different composition, to compensate for any initiation, tapering due to
unfavorable copolymeπzation rates, or capping
difficulties. These monhydroxylated polydiene polymers may be epoxidized such that they contain from 0.1 to 7.0 milliequivalents (meq) of epoxide functionality per gram of polymer, preferably from 0.5 to 5 meq epoxide functionality per gram of polymer.
Diblocks falling within the above description are preferred. The overall number average molecular weight of sucn diblocks may range from 1500 to 15000 g/mol, preferably 300T -o 7000 g/mol. Either of the blocks m the diblock may contain some randomly polymerized vinyl aromatic hydrocarbon as described above. For example, where I represents isoprene, B represents butadiene, S represents styrene, and a slash (/) represents a random copolymer block, the diblocks may have the following structures:
I-B-OH I-B/S-OH I/S-B-OH I-I/B-OH or
B/I-B/S-OH B-B/S-OH I-EB-OH I-EB/S-OH or
1-S/EB-OH I/S-EB-OH HO-I-S/B HO-I-S/EB where EB is hydrogenated butadiene, -EB/S-OH means that the hydroxyl source is attached to a styrene repeating unit, and -S/EB-OH signifies that the hydroxyl source is attached to a hydrogenated butadiene repeating unit. This latter case, -S/EB-OH, requires capping of the S/EB "random copolymer" block with a mini EB block to compensate for the tapering tendency of the styrene prior to capping with ethylene oxide. These diblocks are advantageous in that they exhibit lower viscosity and are easier to manufacture than the corresponding triblock polymers. It is preferred that the hydroxyl be attached to the butadiene block because the
epoxiαation proceeds more favorably with isoprene and there will be a separation between the functionalities on the polymer. However, the hydroxyl may also be attached to the isoprene block if desired. This produces a more surfactant-like molecule with less load bearmg capacity. The isoprene blocks may also be hydrogenated .
Certain triblock copolymers are also preferred for use herein. Such triblocks usually include a styrene block or randomly copolymerized styrene to increase the polymers glass transition temperature, compatibility with polar materials, strength, and room temperature viscosity. These triblocks include the following specific structures:
I-EB/S-EB-OH 1-B/S-B-OH I-S-EB-OH I-S-B-OH or
I-I/S-1-0H I-S-I-OH B-S-B-OH B-B/S-B-OH or
I-B/S-I-OH I-EB/S-I-OH or
I-B-S-OH 1-EB-S-OH HO-I-EB-S
The latter group of polymers specified in the last line above wherein the styrene block is external are represented by the formula
(H0)χ-A-B-S-(0H)y (II)
where A, B, S, x, and y are as described above. These polymers and the other triblocks shown above are particularly advantageous for introducing blocks of epoxy functionality into the monohydroxylated polymers at multiple sites.
Epoxidation of the base polymer can be effected by reaction with organic peracids which can be preformed or formed in situ. Suitable preformed peracids include peracetic, performic, and perbenzoic acids. In situ formation may be accomplished by using hydrogen
peroxide and a low molecular weight fatty acid such as formic acid. These and other methods are described in more detail m U. S. Patents 5,229,464 and 5,247,02o. Alternately, tungsten catalyzed phase transfer
epoxidation can be carried out as described J.
Polymer Science, Pt A, 33 1881 (1995) by J. V. Crivello and B. Yang. The amount of epoxidation of these polydiene polymers ranges from about 0.1 to about 7 milliequivalents of epoxy groups (oxirane oxygen) per gram of polymer. Low levels are desirable to avoid overcure. Above 7 meq/g, the rigidity, crosslink density, cost, difficulty of manufacture, and polarity of the epoxidized are such that polymer does not provide any benefit. The preferred amount of
epoxidation is about 0.5 to about 5 meq/g and tne most preferred amount of epoxidation is about 1.0 to 3 meq/g. The most preferred amount provides the oest balance of rate of UV cure against undesired overcure and better maintains compatibility with a variety of formulating ingredients commonly used with polydiene based adhesives.
The molecular weights of the linear polymers or unassembled linear segments of polymers such as mono-, di-, triblock, etc., arms of star polymers before coupling are conveniently measured by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated. For anionically polymerized linear polymers, the polymer is essentially
monodisperse (weight average molecular weight/number average molecular weight ratio approaches unity) , and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. Usually, the peak value is between the number and the weight
average. The peak molecular weight is the molecular weight of the most abundant species shown on the chromatograph. For polydisperse polymers the number average and the weight average molecular weight should be calculated from the chromatograph and used. For materials to be used in the columns of the GPC,
styrene-divmylbenzene gels or silica gels are commonly used and give excellent molecular weight results.
Tetrahydrofuran is an excellent non-aqueous solvent for polymers of the type described herein. A refractive index detector may be used. For anionic polymers, it is also often convenient to determine the number average molecular weight by end group analysis using NMR.
If desired, these block copolymers can be partially hydrogenated. Hydrogenation may be effected
selectively as disclosed in U.S. Patent Reissue 27,145. The hydrogenation of these polymers and copolymers may be carried out by a variety of well established
processes including hydrogenation m the presence of such catalysts as Raney Nickel, noble metals such as platinum and the like, soluble transition metal
catalysts and titanium catalysts as m U.S. Patent 5,039,755. The polymers may have different diene blocks and these diene blocks may be selectively hydrogenated as described in U.S. Patent 5,229,464. Partially unsaturated hydroxylated polymers are useful for further functionalization to make the epoxidized polymers of this invention. The partial unsaturation preferably is such that 0.1 to 7 meq of aliphatic double bonds suitable for epoxidation remain on the polymer. It will be appreciated that m this
embodiment more preferably from 0.5 to 5, in particular from 1.0 to 3.0 of aliphatic double bonds suitable for epoxidation remain on the polymer. Further, it will be appreciated that if an epoxidation process is to be used which has an efficiency of less than 100?, the preffered total amount of aliphatic double bonds is typically higher than the preferred amount of
epoxidation .
If epoxidation is carried out before hydrogenation, then it is preferred that all remaining aliphatic double bonds be hydrogenated.
It is highly advantageous to include in the
composition a low molecular weight polydiene mono-ol order to improve the tack of the adhesive. Such mono-ols have a number average molecular weight of 2,000 to 30,000 g/mol and are preferably hydrogenated polydiene polymers with a termmal OH, such as monohydroxylated hydrogenated polybutadiene or polyisoprene . Preferred mono-ols include those with a number average molecular weight range of 2,000 to 10,000 g/mol. Tne polydiene is typically derived from one or more diene monomers having from 4 to 24 carbon atoms. Preferably from 4 to 12 carbon atoms, more preferably from 4 to 6 carbon atoms, in particular isoprene or butadiene.
For coating compositions it may highly advantageous to include in the composition a low molecular weight polydiene diol. Such diols typically have a number average molecular weight within the same ranges as given above for low molecular weight polydiene mono-ols .

The average number of hydroxyl groups per molecule typically ranges from 1.6 to 2.4, preferably from 1.8 to 2.2, more preferably 1.9 to 2.0.
The composition of this invention is typically cured by means of ultraviolet or electron beam
radiation. Radiation curing utilizing a wide variety of electromagnetic wavelength is feasible. Either ionizing radiation such as alpha, beta, gamma, X-rays and high energy electrons or non-ionizmg radiation such as ultraviolet, visible, infrared, microwave and radio frequency may be used. A complete description of how this irradiation may be accomplished is found in U.S. Patent 5,229,464.
As described in the examples of WO 96/11215, a photomitiator can be dispersed m a non-aqueous solvent along with the polymer and the tackifymg resm m order to provide a composition which is effectively radiation curable. The present process accomplishes this without the use of a non-aqueous solvent. No solvent is necessary because the photomitiator is very compatible with and unusually soluble or spontaneously dispersible in the polymer blend. Excellent cured films can be made according to the present invention without the trouble and expense oi special processing techniques.
Radiation induced cationic curing may also be carried out in combination with free radical curing. Free radical curing can be further enhanced by the addition of additional free radical photoini tiators and photosensitizers .
The materials of the process of the present
invention are useful m pressure sensitive adhesives, sealants, (including packaging adhesives, contact adhesives, laminating adhesives, weatherable tapes transfer and mounting tapes structural adhesives, - 13 -automotive adhesives, and assembly adhesives),
coatings, inks, labels, and printing plate and film applications. It may be necessary for a formulator to combine a variety of ingredients together with the polymers of the present invention in order to obtain products having the proper combination of properties (such as adhesion, cohesion, durability, low cost, etc.) for particular applications. In most of these applications, suitable formulations would also contain various combinations of resins, plasticizers, fillers, pigments, reactive diluents, oligomers, and polymers, non-aqueous solvents, stabilizers and other ingredients such as asphalt.
It is common practice to add an adhesion promoting or tackifymg resin that is compatible with the
polymer, generally from 20 to 400 parts per hundred parts of polymer. A common tackifymg resm is a diene-olefm copolymer of piperylene and 2-methyl-2-butene having a softening point of about 95°C. This resm is available commercially under the tradename Wmgtack 95 and is prepared by the cationic polymerization of a mixture containing appoximately 60% piperylene, 10% isoprene, 5% cyclo-pentadiene, 15% 2-methyl-2-butene and about 10% dimer, as taught in U.S. Patent No.
3,577,398. Other tackifymg resins may be employed wherein the resinous copolymer comprises 20-80 weight percent of piperylene and 80-20 weight percent of 2-methyl-2-butene . The tackifymg resins normally have ring and ball softening points as determined by ASTM method E28 between about 20°C and 150°C. Hydrogenated hydrocarbon resins are especially useful. These hydrogenated resins include such resins as Regalrez 1018, 1085, 1094, 1126, and 1139, and Regalite 91, 101, 125, and T140 supplied by Hercules, Arkon P70, P90, P115, P125 supplied by Arakawa, and similar other resins such as the Escorez 5300 resm series supplied by Exxon. mgtack, Regalrez, Regalite, Arkon and Escorez are trade marks.
Aromatic resins may also be employed as tackifymg agents, provided that they are compatible with the particular polymer used in the formulation. Useful resins include coumarone-mdene resins, polystyrene resins, vinyl toluene-alpha methylstyrene copolymers and polymdene resins.
Optional components of the present invention are stabilizers which inhibit or retard heat degradation, oxidation, skm formation and color formation.
Stabilizers are typically added to the commercially available compounds in order to protect the polymers against heat degradation and oxidation durmg the preparation, use and high temperature storage of the composition.
Adhesives are frequently thin layers of tacky compositions which are used in protected environments (adhering two substrates together) . Therefore,
unsaturated epoxidized polymers will often have
adequate stability so resm type and concentration will be selected for maximum tackiness without great concern for oxidation or photostability, and pigments will usually not be used. However, for high performance adhesives, hydrogenated epoxidized polymers will be used, often conjunction with hydrogenated tackifymg resins .
Sealants are gap fillers. Therefore, they are used in fairly thick layers to fill the space between two substrates. Since the two substrates frequently move relative to each other, sealants are usually low modulus compositions capable of withstanding this movement. Because sealants are frequently exposed to the weather, the hydrogenated epoxidized polymers are usually used to provide adequate stabiltiy to the environment. Resins and plasticizers will be selected to maintain low modulus and minimize dirt pick-up.
Fillers and pigments will be selected to give
appropriate durability and color. Since sealants are applied m fairly thick layers, their nonaqueous solvent content should be as low as possible to
minimize shrinkage.
EXAMPLES
In the following examples several adhesive tests are used to demonstrate the properties of test
formulations using the improved process and composition of this mvention. The degree of covalent cure
obtained for each of the adhesive samples was measured by use of a polymer gel content test developed by J. R. Erickson for radiation curing adhesives, and first described m the article "Experimental Thermoplastic Rubbers for Enhanced Radiation Crosslmkmg of Hot Melt PSA's", TAPPI 1985 Hot Melt Symposium Proceedings, June 1985. The method as practiced for the present
examples is essentially identical to the method as published, but for a few minor improvements and
corrections to the method as first published. 180° Peel from polished stainless steel was determined using Pressure Sensitive Tape Council Method No . 1. A 30 or 60 minute dwell time was used to assure good wetting before the peel was executed. Large values indicate high strength when peeling a test tape from the
substrate. Loop Tack (LT) was determmed using a TLMI Loop Tack Tester. Polyken Probe Tack (PPT) was
determmed by ASTM D2979. High values for LT and PPT indicate aggressive tack. Holding Power (HP) is the time required to pull a standard area (2.54 cm x
2.54 cm(l in x 1 in)) of tape from a standard test surface under a standard load 2° antipeel (Pressure - 1 6 - Sensitive Tape Council Method No. 7), at a certain temperature. Long times indicate high adhesive and cohesive strength. Shear Adhesion Failure Test (SAFT) is similar to HP, except that the temperature at which failure occurs is recorded. SAFT is carried out in a oven that ramps up at a rate of 22.2°C (40°F) per hour. High temperature values indicate high cohesive and adhesive strength.
The Polymer 1 used the first example is an epoxidized linear monohydroxy diene polymer with a number average molecular weight of 5500. Ihe polymer is a diblock polymer where the first block consists of hydrogenated epoxidized polyisoprene and the second block is hydrogenated polybutadiene. The second block has a termmal primary hydroxyl group. The number average molecular weight ratio between the second block and the first block was 2/1. The polymer has 1.4 meq of epoxide functionality per gram, and 0.17 meq of hydroxyl groups per gram. Polymer 2 is a linear monohydroxy diene polymer with a number average
molecular weight of 3950 and 0.25 meq/g of hydroxyl functionality. The mono-ol has a terminal primary hydroxyl group. The compatible photomitiator
discussed above was used. It s a diaryliodomum hexafluoroantimonate having a C]?H25 alkyl group attached. The tackifier is Regalrez 1085, a
hydrogenated tackifymg resm made by Hercules. A conventional amount of the antioxidant Irganox 1010 is included.
Comparative Example A
Previous adhesives comprised of epoxidized
polydiene mono-ol polymer, polydiene mono-ol polymer, Regalrez 1085 tackifymg resm, and the photomitiator UVI-6974 (triarylsulphonium hexafluoroantimonate) would not UV cure unless mixed together with tetrahydrofuran (THF) . Without the THF , the relatively dense
photomitiator would phase separate in the adhesive and fall to the bottom of the container where it could be easily seen by the unaided eye as an insoluble bead or beads of material. The lack of effective UV cure was evident by lack of cohesion of the adhesive.
Essentially the adhesive remained a viscous liquid (goo) and when one tried a finger tack test, adhesive would simply transfer to the finger. This performance after UV exposure is totally unacceptable. The perceived role of the THF was to dissolve the
photomitiator and evaporate after the adhesive film was applied, thereby leaving the photomitiator finely dispersed in the dry adhesive film. The film could then be successfully UV cured. Alternatively, the photomitiator could be directly dispersed into the adhesive, in the absence of a non-aqueous solvent, by using very high shear mixing or sonication, and then be successfully UV cured.
Example 1
A UV curable composition according to the
invention, in particular the pressure sensitive adhesive (PSA) formulation shown m Table IA was prepared using only simple low shear mixing equipment without a non-aqueous solvent. The PSA was evaluated at 5 and 20 mm thickness, at two film temperatures durmg irradiation, and the 96 hour melt stability at 93°C (200°F) was determmed. These evaluation
treatments are summarized in Table IB. Treatment A is the control treatment against which the other three treatments are compared.

Tabl e IA - PSA Formulat ion

Ingredients wt .
Polymer 1 24.4
Polymer 2 25.4
Regalrez 1085 (Hercules) 49.8
CD-1012 (Sartomer) 0.25
Irganox 1010 (Ciba) 0.15

Table 1] Treatment Summary

Treatment A B C D

Film Thickness, mm 5 20 5 5

Film temperature durmg 121 121 93 121 irradiation, °C
96 hour melt aging 23 23 23 93 temperature, °C

The adhesive (400 g batch) was prepared according to the formula in Table IA using the following
procedure. All of the ingredients, except for the photomitiator, CD-1012, were added to a stainless steel beaker, and heated in a 135°C oven for one hour. The beaKer was removed and placed onto a cold hot plate and the ingredients were mixed at medium speed with a four-fin paddle stirrer until the temperature dropped to 93°C. The photomitiator was added and mixing was continued for 30 minutes using the hot plate to
maintain the temperature at 93°C. The PSA appeared clear upon microscopic examination in bright field at 500 magnification.
The hot PSA was divided into two aliquots. The first aliquot consisted of 100 grams poured into a 200 ml tall form Pyrex beaker. The beaker was covered with aluminum fo l and placed into an air oven at 93°C, for 96 hours. The remaining aliquot in the steel beaker was covered with foil and held at room temperature for

96 hours. The viscosity profile of each aliquot after the 96 hour aging was obtained using a Bolin Rheo eter. Using a 93°C application temperature and a hand applicator, portions of the room temperature and the 93°

C aged PSA aliquots were cast onto one mm polyester film to give either approx. 5 or 20 mm of adhesive.
Two castings were made for each of the four treatments (A - D) . The test films were placed m a 93 or 121°C oven for 2 minutes, removed, and immediately irradiated using a Fussion Lab Coater operating with one "H" bulb.

Irradiation was carried out with the adhesive facing the incident light. The conveyor speed (43 meters per
2 minute) was selected to yield a dose of 125 mJ/cm , as measured on a Lightbug radiometer.
All of the samples except those of treatment B cured instantly to the touch. All testing, except for gel on B, was started after the irradiated test films had aged at room temperature for approximately 24 hours in the dark. Gel content testing on B was started about 48 hours after irradiation. Test specimens were taken from both castings for replicate testing. The actual cured film thickness was determmed on each casting using a micrometer. All of the films apϋeared clear to the eye both before and after curing.
Table IC shows the mean values obtained for each of the tests, and the 95έ confidence limits on the means. The 95't confidence limits associated with the mean values were calculated using the experimental error associated with the available test observations.

Table IC - PSA Test Results, Mean Values
Treatment A B c D No. of 95%
repliConfidence
cates limits on
means

Measured adhesive film thickness, mm 4.50 17.7 4.40 4.45 2 ± 0.21*

Examination for through cure through surface through through 2 "~
cure cure cure cure
Polymer gel content, % 88.0 60.5** 90.0 86.0 2 ± 1.6

Rolling ball Tack, cm 3.16 - 3.36 2.30 5 ± 0.20

Polyken Probe Tack, kg 1.16 - 0.95 1.34 5 ± 0.23

TLMI loop Tack, N/m (oz/in) 780 *"* 905 905 3 (+ 12.1)
(71.3) (82.7) (82.7)
180° Peel from steel, Nm (pli) 683 779 753 2 (± 0.83)
(3.90) (4.45) (4.30)
23°C Holding power to steel, >648 >648# >648# 2 ± 0 6.45 cm2 (1 in2) * 2 kg, hour '
Shear adhesion failure temperature >143 >130 >157# 3 ± 46

(SAFT) to Mylar,
6.45 cm2 (1 in2) * 500g, °C
95°C Holding power to Mylar, >71 >71 >71 2 ± 0 6.45 cm2 (1 in2) * 500g, hour

* This confidence interval does not apply to treatment B. The upper cured layer cf the film was floating on an uncured liquid layer, making the micrometer measurements less reliable.
**The gel value shown for B represents the average obtained from including both the cured surface layer and the uncured bottom layer. Treatment B films could not be tested using standard PSA performance tests because of the uncured liquid adhesive at the polyester interface.
# One of the replicates was an statistical outlier, and was dropped. The confidence limits for the mean value of SAFT for treatment D is ± 56.

Treatment B obviously differs significantly from the other three treatments. The concentration of the CD-1012 photomitiator was too great or the UV light intensity was too low to adequately cure a 17.7 mm film. The top layer of the film cured while the bottom layer remained as an uncured liquid. Because the cured layer was "floating" on the liquid layer, it was impossible to run any quantitative test except for polymer gel content. The 60.5?, gel content observed indicates that the cured surface layer was roughly 12 mm thick 48 hours after irradiation.
The PSA formulation tested under the control conditions (treatment A) gave excellent performance results. It had excellent gel formation, aggressive tack, peel, holding power, and SAFT values. Treatment C, carried out at a 93°C film temperature during irradiation, gave the same excellent results.
Treatment D, simulating 96 hours in a holding tank at 93°C, also gave the excellent results like A, except that D had a slightly better rolling ball tack. The viscosity profiles show that holding the uncured adhesive for 96 hours at 93°C caused very little thermally induced reaction since the viscosity only rose about 50° compared to the adhesive held at room temperature.
The data presented in thi example shows that excellent PSA properties can be obtained using the CD-1012 photomitiator UV cured epoxidized
monohydroxylated diene polymer/diene mono-ol based adhesives. The CD-1012 photomitiator easily mixes into the formulation. Five mm films were easily cured, but curing much thicker films is more difficult. Using a 93°C film temperature durmg irradiation produces cures which perform as well as those made using a higher temperature. Lower film temperatures are expected to work as well. Melt stability at 93°C is good, indicating there is no problem with the pot life of the adhesive in a holding tank of a production unit operating at this temperature. Curing and film
properties are unaffected by this treatment. 93°C is believed to be a higher temperature than needed for commercial application.
If the adhesive is applied with a commercial coater at temperatures in the range of 40 to 80°C, the film temperature could be raised to 93°C, if desired, by passing it over a hot roll immediately before
irradiation. Alternatively, heating could be achieved by other means, such as through the use of infrared heaters .
Example 2
PSA's E, F, G, H, and I (Table 2A) are examples of the present invention. They were also prepared using a simple stirrer. PSA's J, K, and L are not examples of the invention and were prepared using a Branson 450 Somfier. Polymer 3 (in Table 2A) is identical to Polymer 1 except that its number average molecular weight is 6070 and it has 1.6 meq of epoxide
functionality per gram. Polymer 4 (in Table 2A) is identical to Polymer 2 except that its number average molecular weight is 3900.



Table 2A - Pressure Sensitive Adhesives

PSA E F G H I J K L
Polymer 3 (epoxidized 99.4 g 99.4 99.4 99.4 99.4 99.4 99.4 99.4
mono-ol)
Polymer 4 (mono-ol) 99.4 99.4 99.4 99.4 99.4 99.4 99.4 99.4
Regalite R91 198.7 - - - - 198.7 - - Arkon P90 - 198.7 - - - - 198.7 - Regalrez 1085 - - 198.7 - - - - - Escorez 5380 - - - 198.7 - - - - ingtack 95 198.7 - - 198.7
SarCat CD-1012 1.0 1.0 1.0 1.0 1.0 - - - Cyracure UVI-6974 * - - - - - 2.0 2.0 2.0
Irganox 1010 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6

* UVI-6974 is 50% active. It consists of 50% mixed triarylsulfonium hexafluoroantimonate
salts and 50% propylene carbonate.

All of the ingredients for adhesives E, F, G, H, and I except for the CD-1012 photomitiator, were weighed into quart cans and each can was heated in a 1 9°C oven for about one hour. Each can was removed, hand stirred, and returned to the oven for another 1/2 hour. Immediately upon final removal from the oven, each partial formulation was mixed with a lab stirrer equipped with an impeller blade until the temperature cooled to about 93°C. This mixing step converts the crude pol ymers/tacki fying resm mixture into a fluid, homogeneous mixture. Half of the required CD-1012 was added and each of the partial formulations was slowly stirred for about 15 minutes until the CD-1012 appeared dissolved. The remainder of the required CD-1012 was added and complete formulations were stirred for an additional 30 minutes while holding the temperature between 88°C and 99°C. The 400 g batches were cooled to room temperature, covered with a lid, and used within one week.
To prepare 400 g batches of adhesives J, K, and L, the following procedure was followed. A 50 gram 5%wt UVI-6974 photomitiator master batch in Polymer • was prepared by weighing 2.5 g of UVI-6974 and 47.5 σ of Polymer 4 into a bottle, heating for 30 minutes m a ]21°C oven, hand mixing, and finally sonicating with a Branson 450 Sonifier for two one minute periods with a cooling time of about 2 minutes between each period. The ingredients for adhesives J, K, and L, less
photo tiator and some of Polymer 4, were weighec into quart cans and each can was heated a 149°C oven for about one hour. Each can was then removed, hand stirred, and returned to the oven for another 1/2 hour. After the final removal from the oven, each partial formulation was mixed with a lab stirrer equipped with an impeller blade until the temperature cooled tc about 93°C. Then 40 grams of the photomitiator master batch was added and stirring was continued for an additional 30 minutes while holding the batch temperature between 88°C and 104°C. Upon completion of mixing, each batch was placed m a 121°C oven to keep the material very fluid. One by one, 50 gram aliquots were poured into bottles and sonicated for 1 to 1.5 minutes, and then transferred to a clean can where all of the aliquots for the particular batch were collected. Sonication was carried out using the Branson 450 Sonifier
operating m continuous mode, such that power density was approximately 2.8 watts per ml of adhesive. The collected material was remixed with the lab stirrer for 5 minutes. The batches were cooled to room
temperature, covered with a lid, and used within one week.
Adhesives E - L were coated using a Chemlnstruments HLCL-1000 hot melt coater and lammator onto Akrosil SBL80SC Silox FIU/O thermal cure release liner to a thickness of 5 mm. The application temperature
required was 49°C. Samples of each film were warmed for 2 minutes m a pre-heated oven, removed, and then immediately UV cured while still hot using an Eye
Ultraviolet PL-1 portable benchtop UV curing unit. The UV dose was 180 mJ/c ^, except for PSA I, which
required a 400 mJ/cm2 dose. The dose was determmed by calibration with an EIT UVIMAP hand-held dosimeter supplied by Eye Ultraviolet. After curing, the
adhesives were laminated to Pitcher Hamilton 2 mm untreated polyester film and allowed to age at room temperature for 5 to 15 days before testing.
Adhesives E, F, G, H, and I of the present invention were tested against Adhesives J, K, and L (those requiring sonication to disperse the photomitiator) , two solvent based acrylic adhesives, and two commercial transfer tapes. The commercial transfer tapes consisted of 5 mm thick adhesive self-wound on release liner. These tapes are believed to be acrylic tapes manufactured by solvent coating the acrylic compositions, drying, and curing. To test the
commercial tapes, they were laminated to the 2 mm untreated polyester film. The test results, shown in Table 2B, indicate that overall, adhesives E, F, G, H, and I give properties as good as the adhesives made by the sonication method or as the acrylic adhesives or the commercial transfer tape adhesives.



Example 3
A simple coating formulation is prepared by warming a mixture of 100 grams of Polymer 3 and 0.25 grams of CD-1012 photomitiator and mixing for 30 minutes at about 93°C with a laboratory stirrer at medium speed. A portion of the coating was poured into a Petri dish to give a 20 mm film. The film was warmed to back to 93°C
2
and then immediately irradiated with 250 mJ/cm of dose delivered by single "H" bulb of a Fusion Lab Processor. Within 5 minutes the film was probed with a wood splint and was found to be cured completely through to give a solid coating film. Another portion of the coating was poured into another Petri dish to give 50 mm of liquid coating, and it was heated and irradiateα with
2
500 mJ/cm of dose. It too immediately cured
completely through to give a solid coating or thin part.
Example 4
A simple coating, printing plate, or fiber
formulation was prepared by warming a mixture of 60.2 grams of Polymer 3, 39.8 grams of Polymer 5, and 0.25 grams of CD-1012 photomitiator and mixing for 30 minutes at about 93°C with a laboratory stirrer at medium speed. Polymer 5 is a hydrogenated
polybutadiene diol polymer having a number average molecular eight of 3530 and having 0.53 meq of hydroxyl functionality per gram. The hydroxyl groups are primary and are terminally located, one on each end of the polymer. A portion of the coating was poured into a Petri dish to give a 20 mm film. The film was warmed to back to 93°C and then immediately irradiated with 250 mJ/cm2 of dose delivered by single "H" bulb of a Fusion Lab Processor. Within 5 minutes the film was probed with a wood splint and found to be cured completely through to give a solid coating film. Another portion of the coating was poured into another Petri dish to give 50 mm of liquid coating, and it was heated and irradiated with 500 mJ/cm2 of dose. It too immediately cured completely through to give a solid material.
Example 5
The pressure sensitive adhesives shown m Table 5A were prepared by simple mixing according to the method of example 2. These adhesives use different relative ratios of epoxidized Polymer 3 to mono-ol Polymer 4, and use several levels of tackifier resin Regalite 91.

Table 5A - Pressure Sensitive Ahesives

RR1 wt. RR2 RR3 RR4 RR5 RR6 RR7 RR8

Polymer 3 22.71 18.92 15.14 29.88 19.92 37.05 30.88 24.70

Polymer 4 37.05 30.88 24.70 29.88 19.92 22.71 18.92 15.14

Regalite 91 39.84 49.80 59.76 39.84 59.76 39.84 49.8 59.76

SarCat CD-1012 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25

Irganox 1010 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15

Adhesives RR-1 to RR-8 were coated using a
Chemlnstruments HLCL-1000 hot melt coater and lammator onto Akrosil SBL80SC Silox FIU/O thermal cure release liner to a thickness of 5 mm. The application
temperature required was 49°C. Samples of each film were warmed for 2 minutes in an oven at 50°C and then immediately UV cured using an Eye Ultraviolet PL-1 portable benchtop UV curing unit. The UV dose was 180 mJ/cm2. The dose was determmed by calibration with an EIT UVIMAP nand-held dosimeter supplied by Eye
Ultraviolet. After curing, the adhesives were
laminated to Pilcher Hamilton 2 mm untreated polyester film and allowed to age at room temperature for 5 to 15 days before testing.
All of the adhesives exhibited excellent cure and PSA properties as shown in Tables 5B and 5C .



Table 5B - PSA Properties at 5 mm of Adhesive

RR1 RR2 RR3 RR4 RR5 RR6 RR7 RR8
Polymer gel content, % 85 90 82 92 95 95 96 98
Loop tack, N/m (pli) 823 1208 1663 735 1330 683 1103 595
(4.7) (6.9) (9.5) (4.2) (7.6) (3.9) (6.3) (3.4) c
Probe tack, kg 0.86 1.31 1.61 0.74 1.62 0.62 1.33 1.58
180° peel from stainless steel 3.5 4.9 9.6 2.6 9.6 2.5 4.7 8.6
180° peel from glass 2.9 4.6 7.7 2.3 7.8 2.6 4.5 6.2
180° peel from polymethyl- 3.6 4.8 6.9 2.6 9.3 2.6 4.6 7.4
methacrylate
180° peel from polycarbonate 3.3 4.8 6.6 2.6 8.0 2.8 4.5 6.7
180° peel from high density 1.2 2.2 5.2 0.6 5.2 0.4 1.8 1.4
polyethylene
23 °C holding power to stainless > 114 47.7 96.6 > 114 > 114 > 160 > 160 > 160
steel, 6.45 cm2 (1 in2) * 2 kg,
hour
95 °C holding power to stainless > 160 > 160 > 160 > 160 > 160 > 160 > 160 > 160
steel, 6.45 cm2 (1 in2) * 500 g,
hour
Shear Adhesion Failure 204 192 159 > 204 153 > 204 > 204 > 204
Temperature to stainless steel,
6.45 cm2 (1 in2) * 500 g, hour

c is cohesive splitting of the film.


Table 5C - PSA Properties at 1.5 mm of Adhesive

RR1 RR2 RR3 RR4 RR5 RR6 RR7 RR8
Polymer gel content, * 83 87 71 84 87 95 87 94
Loop tack, N/m (pli) 525 875 1138 438 245 508 893 123
(3.0) (5.0) (6.5) (2.5) (1.4) (2.9) (5.1) (0.7)
Probe tack, kg 0.77 0.79 1.13 0.51 0.76 0.47 0.58 0.57
180° peel from stairless steel 2.2 4.4 7.1 c 2.3 6.1 2.1 3.5 2.4
180° peel from glass 2.2 3.1 6.4 c 1.8 2.1 c 1.6 3.6 1.8
180° peel from polymethyl- 3.0 3.7 6.5 c 2.2 6.8 c 2.3 3.6 1.9
ethacrylate
180° peel from polycarbonate 1.4 4.2 6.3 c 2.3 3.5 2.2 3.7 1.5
180° peel from high density 0.5 1.3 3.1 0.2 1.0 0.1 1.0 0.8
polyethylene
23 °C holding power to > 118 > 118 > 118 > 118 > 114 > 114 > 114 > 114
stainless steel,
6.45 cm2 (1 in2) * 2 kg, hour
95 °C holding power to > 112 > 112 > 112 > 160 > 160 > 160 > 160 > 160
stainless steel,
6.45 cm2 (1 in2) * 500 g, hour
Shear Adhesion Failure -> 204 > 204 200 > 204 > 204 > 204 > 204 > 204
Temperature to stainless steel,
6.45 cm2 (1 m2) * 500 g, hour
c is cohesive splitting of the film.

Example 6
The pressure sensitive adhesives shown m Table 6A were prepared by simple mixing according to the method of example 2. These adhesives use different relative ratios of epoxidized Polymer 3 to mono-ol Polymer 4, and use several levels of tackifier resm Arkon P90.
Table 6A - Pressure Senisitive Ahesives

API AP2 AP3 AP4 AP5 AP6 AP7 AP8 wt. %
Polymer 3 22.71 18.92 15.14 29.88 19.92 37.05 30.88 24.70

Polymer 4 37.05 33.88 24.70 29.88 19.92 22.71 18.92 lb.14

Arkon P90 39.84 49.80 59.76 39.84 59.76 39.84 49.8 59.76

SarCat 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 CD-1012
Irganox 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 1010

Adhesives API to AP8 were coated using a
Chemlnstruments HLCL-1000 hot melt coater and lammator onto Akrosil SBL80SC Silox FIU/O thermal cure release liner to a thickness of 5 mm. The application
temperature required was 49°C. Samples of each film were warmed for 2 minutes in an oven at 50°C and then im ediately UV cured using an Eye Ultraviolet PL-1 portable benchtop UV curing unit. The UV dose was 180 mJ/cm . After curing, the adhesives were laminated to Pilcher Hamilton 2 mm untreated polyester film and allowed to age at room temperature for 5 to 15 days before testing.
All of the adhesives exhibited excellent cure and PSA properties as shown m Table 6B.


Table 6B - PSA Properties at 5 mm of Adhesive

API AP2 AP3 AP4 APS AP6 AP7 A8
Polymer gel content, % 88 86 85 94 95 96 97 93
Loop tack, N/m (pli) 840 1348 945 665 263 718 735 70
(4.8) (7.7) (5.4) c (3.8) (1.5) c (4.1) (4.2) (0.4)
Probe tack, kg 0.82 1.30 > 1.64 0.75 1.44 0.66 1.06 0.32
180° peel from stainless steel 3.3 5.3 9.4 2.8 7.0 2.6 4.4 5.3
180° peel from glass 3.0 5.4 7.7 2.7 2.5 2.2 4.6 1.7
180° peel from polymethyl- 3.4 5.7 7.0 3.2 7.8 2.6 4.3 6.3
methacrylate
180° peel from polycarbonate 3.2 6.0 6.8 3.0 7.2 2.9 4.2 5.7
180° peel from high density 1.2 2.7 5.7 0.7 1.0 0.4 2.1 0.4
polyethylene
23 CC holding power tc 82 93 > 118 > 118 > 118 > 118 > 118 > 118
stainless steel,
6.45 cm2 (1 in2) * 2 kg, hour
95 °C holding power to > 117 > 117 > 112 > 112 > 112 > 112 > 112 > 112
stainless steel,
6.45 cm2 (1 in2) * 500 g, hour
Shear Adhesion Failure > 204 172 136 > 204 153 > 204 > 204 193
Temperature to stainless steel,
6.45 cm2 (1 in2) * 500 g, hour

c is cohesive splitting of the film.

Example 7
PSA formulation PLl was made using the stirrer method.
Table 7A - Pressure Sensitive Adhesive

Ingredient % by weight
Polymer 3 (epoxidized polymer) 19.72
Polymer 5 (mono-ol polymer) 25.10
Regalite 91 54.78
SarCat CD-1012 0.25
Irganonox 1010 0.15

The PLl adhesive was continually coated and UV cured on a pilot coater line using a slot die and an Eye Ultraviolet portable unit for cure. The adhesive was slot coated at 80°C to Akrosil SBL80SSC release liner at a line speed of 9.144 m/πun (30 feet per minute) and irradiated with a dose of 250 mJ/cm^. 2 mm corona treated polyester film was then continually laminated to the UV cured adhesive, the laminate was rewourd, and stored at room temperature. A portion of the adhesive laminate was coated with 5.0 mm of PLl and a second portion was coated with 1.5 mm.
One week after coating, the adhesive was tested for properties .

Table 7B - Adhesive Properties

Test : 5 mm 1.5 mm

Polymer gel content, % 78 79

Loop tack, N/m (pli) 1383 1050
(7.9) (6.0)

Probe tack, kg 2.1 0.8

180° peel from stainless steel 5.6 5.3

23 °C holding power to stainless steel, > 720 > 720 6.45 cm2 (1 m2) * 2 kg, hour
95 °C holding power to stainless steel, > 120 > 120 6.45 cm2 (1 m2) * 500 g, hour
Shear Adhesion Failure Temperature to 168 > 168 stainless steel, 6.45 cm2 (1 in2) *
500 g, hour

4 months after coating, the 5 mm adhesive was tested for 180° peel to various substrates, including the difficult to bond thermoplastic polyolefin.
Excellent results were obtained from the adhesive as shown in Table 7C.
Table 7C - 180° Peel Results

Substrate Peel, N/m (pli)

Polymethymethacrylate 945 (5.4)

Polypropylene 963 (5.5)

High density polyethylene 490 (2.8)

Polycarbonate 963 (5.5)

Glass 893 (5.1)

Stainless steel 910 (5.2)

DEFLEX 880 thermoplastic polyolefin 805 (4.6)

HIMONT RTA 3263 thermoplastic polyolefin 945 (5.4)