Source: http://www.google.es/patents/US5612136?dq=flatulence
Timestamp: 2013-05-19 04:46:14
Document Index: 322216453

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Patente US5612136 - Pressure-sensitive adhesives having improved adhesion to acid-rain resistant ... - Google PatentesB�squeda Im�genes Maps Play YouTube Noticias Gmail Drive M�s » B�squeda avanzada de patentes | Historial web | Iniciar sesi�n B�squeda avanzada de patentesPatentesThe present invention provides a pressure-sensitive adhesive composition and tape prepared therefrom which has excellent ability to adhere to acidic surfaces such as acid-rain resistant automotive paints. The adhesive comprises a crosslinked copolymer comprising certain (meth)acrylate esters, certain...http://www.google.es/patents/US5612136?utm_source=gb-gplus-sharePatente US5612136 - Pressure-sensitive adhesives having improved adhesion to acid-rain resistant automotive paints N�mero de publicaci�nUS5612136 ATipo de publicaci�nConcesi�n N�mero de solicitud08/319,246 Fecha de publicaci�n18 Mar 1997 Fecha de presentaci�n6 Oct 1994 Fecha de prioridad16 Mar 1993Tambi�n publicado comoEP0615983A2EP0615983A3EP0615983B1 InventoresAlbert I. EveraertsPeter A. StarkSatoshi Takeda Cesionario originalMinnesota Mining And Manufacturing Company Clasificaci�n de EE.UU.428/355.0AK428/518428/520525/218 Clasificaci�n internacionalC09J133/26C09J7/02C09J133/14C09J133/10C08F220/18C09J133/06C09J133/04 Clasificaci�n cooperativaC09J7/0217C08F220/18C09J2201/606C09J2203/306C09J133/062 Clasificaci�n europeaC09J 133/06BC08F 220/18C09J 7/02F2DReferenciasCitas de patentes (34)Otras citas (4) Citada por (25)Enlaces externosUSPTO Cesi�n de USPTO EspacenetPressure-sensitive adhesives having improved adhesion to acid-rain resistant automotive paintsUS 5612136 A Resumen The present invention provides a pressure-sensitive adhesive composition and tape prepared therefrom which has excellent ability to adhere to acidic surfaces such as acid-rain resistant automotive paints. The adhesive comprises a crosslinked copolymer comprising certain (meth)acrylate esters, certain nitrogen containing basic monomers copolymerizable therewith, optional copolymerizable acidic monomer, and crosslinker.
The following is claimed: 1. A pressure-sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20 C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR7## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH.sub.3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR8## wherein R.sup.1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R.sup.2 is Selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R.sup.1 and R.sup.2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.
2. The pressure-sensitive adhesive of claim 1 wherein the (meth)acrylate esters are selected from the group consisting of n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, 2-methyl butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isooctyl methacrylate, isononyl acrylate, isodecyl acrylate, and mixtures thereof.
18. A pressure-sensitive adhesive consisting essentially of: a crosslinked copolymer comprising 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20 C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR9## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH.sub.3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR10## wherein R.sup.1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R.sup.2 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R.sup.l and R.sup.2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 1 to about 3 parts by weight of an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 1 to about 0.05 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.
19. A composite comprising a solid acidic surface which is a paint coating coated with a pressure sensitive adhesive, the pressure sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20 C.; (b) correspondingly, about 40 to about 10 parts by weight era basic copolymerizable monomer having the formula ##STR11## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH.sub.3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR12## wherein R.sup.1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R.sup.2 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R.sup.1 and R.sup.2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.
20. A composite comprising a solid acidic surface which is an automotive coating coated with a pressure sensitive adhesive, the pressure sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20 C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR13## wherein a represents an integer of 0 to 1; b represents an integer of 0 to 1; R is selected from the group consisting of H-- and CH.sub.3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR14## wherein R.sup.1 is selected from the group consisting of --H, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle; R.sup.2 is selected from the group consisting of --H, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle, wherein R.sup.1 and R.sup.2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight era crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.
FIELD OF THE INVENTION The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive tape prepared therefrom which shows excellent adhesion to solid acidic surfaces such as acidic non-melamine crosslinked, acid-rain resistant automotive paints.
BACKGROUND OF THE INVENTION Automobile body side molding and emblems are usually permanently mounted to exterior automobile surfaces either by mechanical fasteners or by pressure-sensitive adhesive tapes having a foamlike or foam core and relatively thin pressure-sensitive adhesive top layers or coatings. These exterior mounting tapes must not only strongly adhere to the protective and decorative automotive coatings and finishes, but must also withstand the environmental and mechanical stresses encountered by automobiles.
SUMMARY OF THE INVENTION Thus, a need exists for a pressure-sensitive adhesive and a pressure-sensitive adhesive tape prepared therefrom which adheres with sufficient peel strength and shear strength to acid-rain resistant automobile coatings having acidic character.
(a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20 C.;
R is selected from the group consisting of H-- and CH.sub.3 --;
R.sup.1 is selected from the group consisting of H--, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle;
R.sup.2 is selected from the group consisting of H--, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle,
wherein R.sup.1 and R.sup.2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle;
wherein when a=b, Z must not represent --NH.sub.2 ; and further wherein when b=0 and a=1, R.sup.1 may also represent ##STR3##
R.sup.2 may also represent ##STR4##
wherein R.sup.3 is an alkyl group comprising about 1 to about 6 carbon atoms provided that R.sup.1 and R.sup.2 cannot both simultaneously represent ##STR5## and further wherein when b=0 and a=1, Z may also comprise a monovalent aromatic radical comprising 1 to 3 aromatic ring structures, preferably 1, wherein at least 1 aromatic ring structure contains a basic nitrogen atom as a member of the ring structure itself;
DETAILED DESCRIPTION OF THE INVENTION The invention provides a pressure-sensitive adhesive composition and tape that has both a high cohesive strength and adheres permanently to acidic surfaces such as acid-rain resistant automotive paint systems.
The acrylic copolymers useful in the adhesive of the invention contain from about 60 to about 90 parts per hundred parts monomer contained in the copolymer of at least one monofunctional unsaturated monomer selected from the group consisting of acrylate esters of non-tertiary alkyl alcohols, the alkyl groups of which comprise from 4 to about 12 carbon atoms; methacrylate esters of non-tertiary alkyl alcohols, the alkyl groups of which comprise from about 4 to about 12 carbon atoms; and mixtures thereof. Such acrylate or methacrylate esters generally have, as homopolymers, glass transition temperatures below about -20
Preferred acrylates include those selected from the group consisting of isooctyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof. Acrylate or methacrylate or other vinyl monomers which, as homopolymers, have glass transition temperatures greater than about -20 vinyl acetate, and the like, may be utilized in conjunction with one or more of the acrylate or methacrylate ester monomers provided that the glass transition temperature of the resultant polymer is below about -20
The basic copolymerizable monomer is represented by Formula (I). Y is a divalent linking group comprising 1 to 5 carbon atoms and may optionally comprise 1 or more heteroatoms such as O, S, N, etc. Examples of specific Y groups include those selected from the group consisting of --(CH.sub.2).sub.n -- wherein n represents an integer of 1 to 5, and divalent alkyl groups having internal linkages selected from the group consisting of ether linking groups, thioether linking groups, keto linking groups, urea linking groups urethane linking groups, amido linking groups, combinations thereof, and the like. Examples of specific Z groups when a=1 and b=0 include but are not limited to those selected from the group consisting of --NH.sub.2, --N(CH.sub.3).sub.2, --N(C.sub.2 H.sub.5).sub.2, --NH(CH.sub.3), --NH(C.sub.2 H.sub.5), and --NH(CH.sub.2 OCH.sub.3). When a=0 or when a=b=1, Z can represent the previously listed groups except --NH.sub.2 [i.e., the basic copolymerizable monomer cannot be acrylamide, cannot be methacrylamide, nor can it have an unsubstituted amide terminated group]. Additionally, when a=1 and b=0, Z can also comprise a monovalent aromatic radical comprising 1 to 3 aromatic ring structures, preferably 1, wherein at least 1 aromatic ring structure contains a basic nitrogen atom as a member of the ring structure itself, such as pyridinyl, imidazyl, and the like.
The basicity of the nitrogen containing monomers utilized in the present invention is defined by their substitution. As mentioned previously, R.sup.1 and/or R.sup.2 may in certain situations represent an electron donating group. Substituents that increase the electron density on a nitrogen by field effects or resonance in the case of aromatic bases such as pyridine will increase the basicity of nitrogen. Examples of electron donating groups which R.sup.1 and/or R.sup.2 can comprise include but are not limited to those selected from the group consisting of --C(R.sup.4).sub.3, --CH(R.sup.4).sub.2, --CH.sub.2 (R.sup.4), and --CH.sub.3, wherein R.sup.4 represents an alkyl group, typically an alkyl group comprising about 1 to about 6 carbon atoms. The higher the degree of substitution on the nitrogen by such linear or branched alkyl groups, the higher the basicity of the monomer. Conversely, substituents which decrease the electron density on the nitrogen of a basic copolymerizable monomer, such as a phenyl group will reduce the basicity of the monomer.
Using these general principles, several common basic copolymerizable monomers possess the following ascending order of basicity: Acrylamide &lt;N-methyl acrylamide&lt;N,N-dimethyl acrylamide &lt;3-(3-pyridinyl)propyl acrylate&lt;N,N-(dimethylamino)ethyl acrylamide.
In addition to these substituent effects on the basicity and usefulness of these monomers in the pressure-sensitive adhesive of the present invention, it is also important to prevent or minimize sterical hinderance of the nitrogen in basic copolymerizable monomer. As such, examples of non-sterically hindering electron donating groups present in the non-sterically hindered group Z defined above are --CH(R.sup.4).sub.2 ; --CH.sub.2 (R.sup.4); and --CH.sub.3 [i.e., not --C(R.sup.4).sub.3 ] wherein R.sup.4 is defined as above and cannot be a tertiary alkyl group, a cycloaliphatic group, nor can two R.sup.4 groups combine to form a cyclic group (i.e., R.sup.4 can be n-alkyl and sec-alkyl). Other non-sterically hindering electron donating groups R.sup.1 and R.sup.2 including but not limited to those selected from the group consisting of --CH.sub.2 CH.sub.2 OCH.sub.3, --CH.sub.2 OCH.sub.2 CH.sub.3, --CH.sub.2 OCH.sub.3, can also be useful.
When Z represents a monovalent aromatic radical as described above, substituents on the basic nitrogen-containing ring structure which increase the electron density on the basic nitrogen (i.e., electron donating substituents such as alkyl or alkoxy groups) enhance the basicity of these types of basic copolymerizable monomers. Electron withdrawing substituents on the basic nitrogen-containing ring structure, such as halogens, --COOH, --NO.sub.2, and the like, decrease the electron density on these aromatic nitrogens and, correspondingly, their basicity. Additionally, similar to the case when Z represents ##STR6## sterical hinderance of such aromatic basic nitrogens by constraint of and/or the presence of bulky substituents such as a tert-butyl group on the basic nitrogen-containing ring structure must be minimized or prevented.
In one solution polymerization method, the acrylate ester component, basic copolymerizable component and, if used, acidic polar component along with a suitable inert organic solvent and free radically copolymerizable crosslinker are charged into a four-neck reaction vessel which is equipped with a stirrer, a thermometer, a condenser, addition funnel and a thermowatch. After this monomer mixture is charged into the reaction vessel, a concentrated thermal free radical initiator solution is added to the addition funnel. The whole reaction vessel and addition funnel and their contents are then purged with nitrogen to create an inert atmosphere. Once purged, the solution within the vessel is heated to about 55 the course of the reaction. A 98 to 99 percent conversion should be obtained in about 20 hours.
Another polymerization method is the ultraviolet (UV) radiation initiated photopolymerization of the monomer mixture. This composition, along with suitable photoinitiator and crosslinker, is coated onto a flexible carrier web and polymerized in an inert, i.e., oxygen free, atmosphere, e.g., a nitrogen atmosphere. A sufficiently inert atmosphere can be achieved by covering a layer of the photoactive coating with a plastic film which is substantially transparent to ultraviolet radiation, and irradiating through that film in air using fluorescent-type ultraviolet lamps which generally give a total radiation dose of about 500 milliJoules/cm.sup.2. The coating of the tapes may be accomplished using any conventional means such as roller coating, dip coating or extrusion coating.
This test is conducted in accordance with ASTM D3330-87. A strip of tape 12.7 mm wide and about 20 cm long is adhered (with the functional adhesive layer down) at one end of a test panel. The other end is held such that the strip does not touch the test panel. The strip is then rolled down with a 2 kg hard rubber covered steel roller and allowed to dwell for the time periods specified in the following tables. The free end of the tape is then double-backed and the 180 min.sup.-1 peel back rate. The peel force, measured in Newtons/decimeter (N/dm), and the peel failure mode (as defined below) is then recorded:
A strip of tape 12.7 mm wide and about 12.7 cm long is adhered (with the functional adhesive layer down) at one end of a test panel, leaving about 2.5 cm of the tape free so that it can be clamped in the upper jaw of the Instron� tensile testing device. The strip is then rolled down with a 4.54 kg steel roller and allowed to dwell for the time periods specified in the Tables. The test panel is then clamped in a special fixture for the lower jaw of the Instron� that maintains a 90 tape is peeled from the test panel. The free end of the tape is then clamped in the upper jaw of the Instron� and the tape sample is peeled at a rate of 300 mm min.sup.-1. The peel force, measured in Newtons/decimeter (N/dm), and the peel failure mode (as defined below) is then recorded.
This test is conducted in accordance with ASTM D3654M-88. A 12.7 mm wide the adhesive of the present invention is adhered to a test panel. The liner is then removed from the sample and the newly exposed surface (non-functional side) is then applied to a stainless steel panel. The test sample is then placed in a horizontal position and a 1 kg weight is applied for a period of 15 minutes to ensure intimate contact between the PSA and the test panels. The assembly is then mounted in a test stand at an angle of 0 specified in the Tables is applied. The time to failure is reported in minutes. After 5,000 minutes (or 10,000 minutes), the test is discontinued.
Example 1 A mixture of 70 parts isooctyl acrylate (IOA), 30 parts of the moderately basic copolymerizable monomer N,N-dimethyl acrylamide (NNDMA), 0.04 part 2,2-dimethoxy-2-phenyl acetophenone (obtained as Irgacure�-651 from Ciba-Geigy Corporation) was inerted and partially photopolymerized under ultraviolet (UV) irradiation (40 watt fluorescent black lamp having 90% of the emissions between 300 and 400 nm and a maximum at 351 nm and which provides radiation intensity of about 1-2 mW/cm.sup.2) to yield a coatable syrup of about 3,000 cPs. After adding 0.1 part of Irgacure�-651 and 0.08 part 1,6-hexanediol diacrylate (HDDA) to the syrup with thorough mixing, the sample was coated at 100 micrometer thickness between two siliconized polyester liners and polymerized under a bank of the same fluorescent UV lamps. The total UV dose was about 400 mJ cm.sup.-2.
One of the liners was then removed and the pressure-sensitive adhesive layer was heat laminated to an acrylic foam core. The foam core was made in accordance with U.S. Pat. No. 4,415,615 (Esmay et al.), incorporated herein by reference. Removal of the second release liner yielded a pressure-sensitive foam tape ready for 180 static shear testing as described above against an acidic acid-rain resistant paint test panel. The results of these tests can be found in Table 1.
Example 2 A foam tape sample was made and tested as in Example 1, except at a ratio of 68 parts IOA and 32 parts NNDMA. The results of these tests can be found in Table 1.
Example 3 A foam tape sample was made and tested as in Example 1, except at a ratio of 65 parts IOA and 35 parts NNDMA. The results of these tests can be found in Table 1.
Example 4 A foam tape sample was made and tested as in Example 1, except at a ratio of 32.5 parts IOA, 32.5 parts n-butyl acrylate (BA), and 35 parts NNDMA. The results of these tests can be found in Table 1.
Example 5 A foam tape sample was made as in Example 1, except at a ratio of 67.3 parts IOA, 31 parts NNDMA, and 1.7 parts acrylic acid (AA). The results of these tests can be found in Table 1.
Comparative Example C-1 For this comparative example, a foam tape sample was made as in Example 1, except at a ratio of 90 parts IOA and 10 parts AA. The results of these tests can be found in Table 1.
Comparative Example C-2 For this comparative example, a foam tape sample was made as in Example 1, except at ratio of 42 parts IOA, 46 parts BA and 12 parts AA. The results of these tests can be found in Table 1.
Comparative Example C-3 For this comparative example, a foam tape sample was made and tested as in Example 1, except at ratio of 47 parts IOA, 47 parts BA and 6 parts AA. The results of these tests can be found in Table 1.
TABLE 1__________________________________________________________________________               180                           Static Shear*,               20 min.                   24 hr.                       24 hr.                           70Ex.   Comp.     Amounts               R.T.                   R.T.                       80                           1000 g                               500 g__________________________________________________________________________1  IOA/NNDMA/        70/30/0.08               231.2                   215.7                       106.2                           114 5000+   HDDA             (FS)                   (FS)                       (FS)                           (POP)2  IOA/NNDMA/        68/32/0.08               213.3                   214.9                       108.7                           311 5000+   HDDA             (FS)                   (FS)                       (FS)                           (POP)3  IOA/NNDMA/        65/35/0.08               204.3                   224.7                       114.4                           423 5000+   HDDA             (FS)                   (FS)                       (FS)                           (POP)4  IOA/BA/   32.5/32.5/               158.5                   194.5                       107.1                           5000+   NNDMA/    35/.08         (FS)   HDDA5  IOA/NNDMA/        67.3/31/               138.9                   147.1                       94.8                           5000+   AA/HDDA   1.7/0.08C-1   IOA/AA/   90/10/0.08               113.6                   118.5                       35.1   HDDAC-2   IOA/BA/AA/        42/46/12/  112 4.1   HDDA      0.08C-3   IOA/BA/AA/        47/47/6/               62.9                   63.7                       19.6   HDDA      0.08__________________________________________________________________________ *Measured in minutes
Example 6 A 250 ml round bottom flask was equipped with a stirrer, a condenser and an addition funnel. 40 ml of the monomer mix consisting of 70 parts of isooctyl acrylate (IOA), 30 parts of N,N-dimethyl acrylamide (NNDMA), and 0.2 parts acryloxy-benzophenone (ABP) and 50 ml of ethylacetate was charged in this flask and a solution of 0.08 g. of VAZO� 64 [2,2'-azobis(isobutyronitrile), an initiator commercially available from duPont] in 10 ml ethyl acetate was added to the addition funnel. This reaction apparatus was then inerted with nitrogen and the flask contents were heated to 55 and the temperature was maintained at 55 The sample was allowed to cool to room temperature. The cooled solution was then coated on a siliconized release liner and oven dried to give a dried coating thickness of about 1.5 mils. Exposure of the sample to about 80 mJ cm.sup.-2 of high intensity UV (medium pressure mercury lamps, no inerting) yielded a tape having a UV cured pressure-sensitive adhesive coating. This UV cured adhesive was then heat laminated at about 60 without the use of any primer and subjected to 90 testing against an acidic acid-rain resistant paint test panel which was identical to that used in Example 1 and static shear testing using a stainless steel test panel. The results of these tests can be found in Table 2.
Example 7 A foam tape sample was made and tested as in Example 6, except at a ratio of 80 parts IOA, 20 parts NNDMA, and 0.2 parts ABP. The results of these tests can be found in Table 2.
Example 8 A foam tape sample was made and tested as in Example 6, except at a ratio of 70 parts n-butyl acrylate (BA), 30 parts NNDMA, and 0.2 parts ABP. The results of these tests can be found in Table 2.
Example 9 A foam tape sample was made and tested as in Example 6, except at a ratio of 80 parts BA, 20 parts NNDMA, and 0.2 parts ABP. The results of these tests can be found in Table 2.
Comparative Example C-4 For this comparative example, a foam tape sample was made and tested as in Example 6, except the formulation of IOA/NNDMA/ABP was equal to 90/10/0.2. The results of these tests can be found in Table 2.
Comparative Example C-5 For this comparative example, a foam tape sample was made and tested as in Example 6, except at ratio of 90 parts BA, 10 parts NNDMA, and 0.2 parts ABP. The results of these tests can be found in Table 2.
Comparative Example C-6 For this comparative example, a foam tape sample was made according to the following method. To a 1 liter mixing vessel was charged 98.8 parts IOA, 45.6 parts methyl acrylate (MA), 7.6 AA, 248 parts ethyl acetate and 0.456 parts VAZO� 64. This mixture (IOA/MA/AA=65/30/5) was then purged with nitrogen for two minutes (1 liter/min. flow), sealed, and placed in a rotary water bath at 55 the product was 1.8 dL/g in ethyl acetate. The solution was diluted with toluene to 20.7% solids and 0.5 part of a proprietary multifunctional aziridine amide crosslinker (AZA) at 5 % solids in toluene was added to 100 parts of the solution. This mixture was reverse-roll coated and cured in a forced air oven to form a transfer tape. This transfer tape was then heat laminated at about 60 previously been primed and dried at 80 forced air oven. This foam tape sample was tested as in Example 6 and the results of these tests can be found in Table 2.
TABLE 2__________________________________________________________________________                           Static               90                           Shear*, R.T.Ex.   Comp.     Amounts               20 min.                   24 hr.                       90 hr.                           1000 g                                500 g__________________________________________________________________________6  IOA/NNDMA/        70/30/0.2               206.6                   374.8   3071 10000+   ABP                  (FS)    (POP)7  IOA/NNDMA/        80/20/0.2               154.1                   241.7                       248.7                           201  10000+   ABP                      (SH)                           (POP)8  BA/NNDMA/ 70/30/0.2               224.2                   378.3   5202 10000+   ABP                  (FS)    (POP)9  BA/NNDMA/ 80/20/0.2               150.6                   241.7                       318.7                           282  9724   ABP                      (SH)                           (POP)                                (POP)C-4   IOA/NNDMA/        90/10/0.2               84.1                   94.6    134  8124   ABP                          (POP)                                (POP)C-5   BA/NNDMA/ 90/10/0.2               84.1                   119.1   270  5198   ABP                          (POP)                                (POP)C-6   IOA/MA/AA/        65/30/5/               175.1                   224.2                       252.2                           10000+                                10000+   AZA       0.12__________________________________________________________________________ *Measured in minutes
Example 10 A foam tape sample was made and tested as in Example 6, except at a ratio of 70 parts IOA, 30 parts N-hexyl acrylamide (HAcm), and 0.2 parts ABP. The results of these tests can be found in Table 3.
Comparative Example C-7 A foam tape sample was made and tested as in Example 6, except at a ratio of 80 parts IOA, 20 parts HAcm, and 0.2 parts ABP. The results of these tests can be found in Table 3.
Example 11 A foam tape sample was made and tested as in Example 6, except at a ratio of 70 parts BA, 30 parts HAcm, and 0.2 parts ABP. The results of these tests can be found in Table 3.
Comparative Example C-8 A foam tape sample was made and tested as in Example 6, except at a ratio of 80 parts BA, 20 parts HAcm, and 0.2 parts ABP. The results of these tests can be found in Table 3.
Example 12 A foam tape sample was made and tested as in Example 6, except that 50 ml of a monomer mix of 80 parts BA, 20 parts N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and 0.2 parts ABP in 40 ml of ethyl acetate was charged in the reaction flask. The results of these tests can be found in Table 3.
Example 13 A foam tape sample was made and tested as in Example 14, except at a ratio of 90 parts BA, 10 parts DMAEMA, and 0.2 parts ABP. The results of these tests can be found in Table 3.
TABLE 3__________________________________________________________________________                           Static               90                           Shear*, R.T.Ex.   Comp.     Amounts               20 min.                   24 hr.                       90 hr.                           1000 g                               500 g__________________________________________________________________________10 IOA/HAcm/ 70/30/0.2               178.6                   252.2                       297.7                           316 10000+   ABP                          (POP)C-7   IOA/HAcm/ 80/20/0.2               105.1                   147.1                       168.1                           263 10000+   ABP                          (POP)11 BA/HAcm/  70/30/0.2               150.6                   224.2                       283.7                           69  7124   ABP                          (POP)                               (POP)C-8   BA/HAcm/  80/20/0.2               105.1                   119.1                       133.1                           55  4321   ABP                          (POP)                               (POP)12 BA/DMAEMA/        80/20/0.2               143.6                   364.3   211 7121   ABP                  (FS)    (POP)                               (POP)13 BA/DMAEMA/        90/10/0.2               94.6                   350.3   130 5334   ABP                  (FS)    (POP)                               (POP)__________________________________________________________________________ *Measured in minutes
Example 14 A foam tape sample was made and tested as in Example 6, except at a ratio of 68 parts IOA, 30 parts NNDMA, 2 parts acrylic acid (AA), and 0.2 parts ABP. The results of these tests can be found in Table 4.
Example 15 A foam tape sample was made and tested as in Example 6, except at a ratio of 68 parts BA, 30 parts NNDMA, 2 parts AA, and 0.2 parts ABP. The results of these tests can be found in Table 4.
Example 16 A foam tape sample was made and tested as in Example 6, except at a ratio of 78 parts IOA, 20 parts DMAEMA, 2 parts AA, and 0.2 parts ABP. The results of these tests can be found in Table 4.
Example 17 A foam tape sample was made and tested as in Example 6, except at a ratio of 78 parts BA, 20 parts DMAEMA, 2 parts AA, and 0.2 parts ABP. The results of these tests can be found in Table 4.
Comparative Example C-9 For this comparative example, a foam tape sample was made and tested as in Example 14, except the formulation of IOA/NNDMA/AA/ABP was equal to 65/30/5/0.2. The results of these tests can be found in Table 4.
Comparative Example C-10 For this comparative example, a foam tape sample was made and tested as in Example 15, except at ratio of 65 parts BA, 30 parts NNDMA, 5 parts AA, and 0.2 parts ABP. The results of these tests can be found in Table 4.
TABLE 4__________________________________________________________________________                90                        Static                (N/dm)  Shear*, R.T.Ex. Comp.     Amounts                24 hr.  1000 g                             500 g__________________________________________________________________________14  IOA/NNDMA/         68/30/2/0.2                353.8   10000+                             10000+    AA/ABP           (FS)15  BA/NNDMA/ 68/30/2/0.2                273.2   10000+                             10000+    AA/ABP           (FS)16  IOA/DMAEMA/         78/20/2/0.2                371.3    AA/ABP           (FS)17  BA/DMAEMA/         78/20/2/0.2                364.3.    AA/ABP           (FS)C-9 IOA/NNDMA/         65/30/5/0.2                TACK-FREE    AA/ABPC-10    BA/NNDMA/ 65/30/5/0.2                TACK-FREE    AA/ABP__________________________________________________________________________ *Measured in minutes
Example 18 The foam tape samples made in accordance with Examples 6, 8, 12-15, and C-6 were tested for their peel adhesions against an epoxy-acid crosslinked acid-rain resistant coating available from PPG Industries. The results of these 90
TABLE 5______________________________________                  90                  RT (N/dm)Ex.  Comp.            Amounts    20 min.                                  72 hr.______________________________________6    IOA/NNDMA/ABP    70/30/0.2  350.3                            (FS)8    BA/NNDMA/ABP     70/30/0.2  322.2                            (SH)12   BA/DMAEMA/ABP    80/20/0.2  157.6 182.1                                  (SH)13   BA/DMAEMA/ABP    90/10/0.2  301.2                            (FS)14   IOA/NNDMA/AA/ABP 68/30/2/0.2                            147.1                            (SH)15   BA/NNDMA/AA/ABP  68/30/2/0.2                            406.3                            (FS)C-6  IOA/MA/AA/AZA    65/30/5/0.12                            262.7 385.3                                  (FS)______________________________________
Example 19 Foam tape samples prepared similarly to those of Examples 6, 8, 13-15, and C-6 were tested for their adherence against an epoxy-acid crosslinked acid-rain resistant automotive coating (DCT-5001, available from PPG Industries). The results of these tests are recorded in Table 6.
TABLE 6______________________________________                  90                  RT (N/dm)Ex.  Comp.            Amounts    20 min.                                  72 hr.______________________________________6    IOA/NNDMA/ABP    70/30/0.2  273.2                            (FS)8    BA/NNDMA/ABP     70/30/0.2  329.2                            (FS)13   BA/DMAEMA/ABP    90/10/0.2  385.3                            (FS)14   IOA/NNDMA/AA/ABP 68/30/2/0.2                            378.3                            (FS)15   BA/NNDMA/AA/ABP  68/30/2/0.2                            374.8                            (FS)C-6  IOA/MA/AA/AZA    65/30/5/0.12                            308.2 357.3                                  (FS)______________________________________
Comparative Example C-11 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, strongly basic copolymerizable monomer [N-morpholinoethyl acrylate (MOA)] in a formulation of BA/MOA/ABP equal to 80/20/0.2. The results of these tests can be found in Table 7.
Comparative Example C-12 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, strongly basic copolymerizable monomer [N-morpholinoethyl methacrylate (MOMA)] in a formulation of IOA/MOMA/ABP equal to 80/20/0.2. The results of these tests can be found in Table 7.
Comparative Example C-13 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, strongly basic copolymerizable monomer (MOA) in a formulation of BA/MOA/ABP equal to 85/15/0.2. The results of these tests can be found in Table 7.
Comparative Example C-14 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, strongly basic copolymerizable monomer (MOMA) in a formulation of IOA/MOMA/ABP equal to 85/15/0.2. The results of these tests can be found in Table 7.
Comparative Example C-15 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, strongly basic copolymerizable monomer (MOA) in a formulation of BA/MOA/ABP equal to 90/10/0.2. The results of these tests can be found in Table 7.
Comparative Example C-16 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, strongly basic copolymerizable monomer (MOMA) in a formulation of IOA/MOMA/ABP equal to 90/10/0.2. The results of these tests can be found in Table 7.
Comparative Example C-17 For this comparative example, a foam tape sample was made and tested as in Example 16 using a sterically hindered, strongly basic copolymerizable monomer (MOA) and small amounts of an acidic copolymerizable monomer (AA) in a formulation of IOA/MOA/AA/ABP equal to 78/20/2/0.2. The results of these tests can be found in Table 7.
Comparative Example C-18 For this comparative example, a foam tape sample was made and tested as in Example 14 using a sterically hindered, strongly basic copolymerizable monomer (MOA) and small amounts of an acidic copolymerizable monomer (AA) in a formulation of IOA/MOA/AA/ABP equal to 75/20/5/0.2. The results of these tests can be found in Table 7.
TABLE 7______________________________________                  90                  RT (N/dm)Ex.  Comp.            Amounts    20 min.                                  24 hr.______________________________________C-11 BA/MOA/ABP       80/20/0.2  98.1  108.6C-12 IOA/MOMA/ABP     80/20/0.2  77.1  66.5C-13 BA/MOA/ABP       85/15/0.2  77.1  101.6C-14 IOA/MOMA/ABP     85/15/0.2  63.0  66.5C-15 BA/MOA/ABP       90/10/0.2  66.5  84.1C-16 IOA/MOMA/ABP     90/10/0.2  73.6  66.5C-17 IOA/MOA/AA/ABP   78/20/2/0.2                            98.1  87.6C-18 IOA/MOA/AA/ABP   75/20/5/0.2                            196.1 220.7C-6  IOA/MA/AA/AZA    65/30/5/0.12                            199.6 245.2______________________________________
Comparative Example C-19 For this comparative example, a foam tape sample was made and tested as in Example 6 using a sterically hindered, weakly basic copolymerizable monomer [N-octyl acrylamide (OAcm)] in a formulation of IOA/OAcm/ABP equal to 70/30/0.2. The results of these tests can be found in Table 8.
Comparative Example C-20 For this comparative example, a foam tape sample was made and tested as in Example 8 using a sterically hindered, weakly basic copolymerizable monomer (OAcm) in a formulation of BA/OAcm/ABP equal to 70/30/0.2. The results of these tests can be found in Table 8.
TABLE 8__________________________________________________________________________                         Static             90                         Shear*, R.T.Ex.   Comp.   Amounts             20 min.                 24 hr.                     90 hr.                         1000 g                              500 g__________________________________________________________________________C-19   IOA/OAcm/      70/30/0.2             150.6                 171.6                     203.1                         867  2879   ABP                        (POP)                              (POP)C-20   BA/OAcm/      70/30/0.2             161.1                 189.1                     224.2                         45   7103   ABP                        (POP)                              (POP)C-6   IOA/MA/AA/      65/30/5/0.12             175.1                 224.2                     252.2                         10000+                              10000+   AZA__________________________________________________________________________ *Measured in minutes
Example 20 A mixture of 70 parts isooctyl acrylate (IOA), 30 parts of the moderately basic copolymerizable monomer N,N-dimethyl acrylamide (NNDMA), 0.04 part 2,2-dimethoxy-2-phenyl acetophenone (obtained as Irgacure�-651 2,2-dimethoxy-2-phenyl acetophenone from Ciba-Geigy Corporation) was inerted and partially photopolymerized under ultraviolet (UV) irradiation (40 watt fluorescent black lamp) to yield a coatable syrup of about 3,000 cPs. After adding 0.1 part of Irgacure�-651 and 0.08 part 1,6-hexanediol diacrylate (HDDA) to the syrup with thorough mixing, the sample was coated at 100 micrometer thickness between two siliconized polyester liners and polymerized under a bank of the same fluorescent UV lamps. The total UV dose was about 400 mJ cm.sup.-2.
One of the release liners was then removed and the pressure-sensitive adhesive layer was heat-laminated to one major surface of a neoprene foam core coated with an acrylate based adhesive. Removal of the second release liner from the 70/30/0.08 IOA/NNDMA/HDDA layer yielded a pressure-sensitive foam tape ready for 180 static shear testing as described above against an alternative surface of acidic character (i.e., polyvinyl chloride). The results of these tests can be found in Table 9.
Example 21 A foam tape sample was made and tested as in Example 20, except at a ratio of 65 parts IOA and 35 parts NNDMA. The results of these tests can be found in Table 9.
Example 22 A foam tape sample was made and tested as in Example 20, except at a ratio of 32.5 parts IOA, 32.5 parts BA, and 35 parts NNDMA. The results of these tests can be found in Table 9.
Example 23 A foam tape sample was made as in Example 20, except at a ratio of 68 parts IOA, 31 parts NNDMA, and 1.0 parts AA. The results of these tests can be found in Table 9.
Example 24 A foam tape sample was made as in Example 20, except at a ratio of 64 parts IOA, 33 parts NNDMA, and 3 parts AA. The results of these tests can be found in Table 9.
Comparative Example C-21 For this comparative example, a foam tape sample was made as in Example 20, except at a ratio of 90 parts IOA and 10 parts AA. The results of these tests can be found in Table 9.
Comparative Example C-22 For this comparative example, a foam tape sample was made as in Example 20, except at ratio of 75 parts IOA and 25 parts n-vinyl pyrrolidone (NVP). The results of these tests can be found in Table 9.
Comparative Example C-23 For this comparative example, a foam tape sample was made and tested as in Example 20, except at ratio of 44 parts IOA, 44 parts BA, and 12 parts AA. The results of these tests can be found in Table 9.
Comparative Example C-24 For this comparative example, the adhesive of Comparative Example C-6 was heat laminated to the neoprene core of Example 20. This foam tape sample was tested as in Example 20 and the results of these tests can be found in Table 9.
TABLE 9__________________________________________________________________________                     180Ex.   Comp.         Amounts  20 min. R.T.                            24 hr. R.T.__________________________________________________________________________20 IOA/NNDMA/HDDA            70/30/0.08                     223.1  256.6                            (FP)21 IOA/NNDMA/HDDA            65/35/0.08                     241.9  264.0                            (FP)22 IOA/BA/NNDMA/HDDA            32.5/32.5/35/0.08                     266.4  276.2                            (FP)23 IOA/NNDMA/AA/HDDA            68/31/1/0.08                     272.1  280.3                            (FP)24 IOA/NNDMA/AA/HDDA            64/33/3/0.08                     278.7  268.9                            (FP)C-21   IOA/AA/HDDA   90/10/0.08                     134.0  158.5C-22   IOA/NVP/HDDA  75/25/0.08                     221.5  277.0C-23   IOA/BA/AA/HDDA            44/44/12/0.08                     167.5  197.0C-24   IOA/MA/AA/AZA 65/30/5/0.12                     167.5  226.4                            (FP)__________________________________________________________________________
Example 25 A foam tape sample was made as in Example 6 and was tested for adherence against an epoxy-acid crosslinked acid-rain resistant coating from PPG Industries, identical to that used in Example 18, at a ratio of 88 parts BA, 10 parts 3-(3-pyridinyl)propyl acrylate (PPA) and 2 parts AA. The results of this test can be found in Table 10.
Example 26 A foam tape sample was made and tested as in Example 25, except at a ratio of 78 parts BA, 20 parts PPA and 2 parts AA. The results of this test can be found in Table 10.
TABLE 10______________________________________                 90                 RT (N/dm)Ex.   Comp.         Amounts     24 hrs.                                 72 hrs.______________________________________25    BA/PPA/AA/ABP 88/10/2/0.08                           173.4 305.1                                 (SH)26    BA/PPA/AA/ABP 78/20/2/0.08                           262.7 412.9                                 (FS)______________________________________
Example 27 A foam tape sample was made as in Example 6 and was tested for adherence against an epoxy-acid crosslinked acid-rain resistant coating (DCT-5001, available from PPG Industries) at a ratio of 88 parts BA, 10 parts 3-(3-pyridinyl)propyl acrylate (PPA) and 2 parts AA. The results of this test can be found in Table 11.
Example 28 A foam tape sample was made and tested as in Example 27, except at a ratio of 78 parts BA, 20 parts PPA and 2 parts AA. The results of this test can be found in Table 10.
TABLE 11______________________________________                         90Ex.  Comp.         Amounts    24 hrs.______________________________________27   BA/PPA/AA/ABP 88/10/2/0.08                         364.3 (FS)28   BA/PPA/AA/ABP 78/20/2/0.08                         371.3 (FS)______________________________________
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