Patent Application
20150004405
This disclosure relates to viscoelastic damping materials and constructions which may demonstrate low temperature performance and adhesion and which may be used in making vibration damping composites.
Briefly, the present disclosure provides a viscoelastic damping material comprising: a) a copolymer of: i) at least one monomer according to formula I:
CH2═CHR1—COOR2 [I]
wherein R1 is H, CH3 or CH2CH3 and R2 is a branched alkyl group containing 12 to 32 carbon atoms, and ii) at least one second mononomer; and b) at least one adhesion-enhancing material. In some embodiments, the adhesion-enhancing material is one of: inorganic nanoparticles, core-shell rubber particles, polybutene materials, or polyisobutene materials. Typically R2 is a branched alkyl group containing 15 to 22 carbon atoms. Typically R1 is H or CH3. Typically second mononomers are acrylic acid, methacrylic acid, ethacrylic acid, acrylic esters, methacrylic esters or ethacrylic esters esters. The viscoelastic damping material may additionally comprise a plasticizer.
In another aspect, the present disclosure provides a viscoelastic damping material comprising a copolymer of: i) at least one monomer according to formula I:
CH2═CHR1—COOR2 [I]
wherein R1 is H, CH3 or CH2CH3 and R2 is a branched alkyl group containing 12 to 32 carbon atoms, and ii) a monofunctional silicone (meth)acrylate oligomer. Typically R2 is a branched alkyl group containing 15 to 22 carbon atoms. Typically R1 is H or CH3. The viscoelastic damping material may additionally comprise a plasticizer.
In another aspect, the present disclosure provides a viscoelastic construction comprising: a) at least one viscoelestic layer comprising a polymer or copolymer of at least one monomer according to formula I:
CH2═CHR1—COOR2 [I]
wherein R1 is H, CH3 or CH2CH3 and R2 is a branched alkyl group containing 12 to 32 carbon atoms; bound to b) at least one PSA layer comprising a pressure sensitive adhesive. In some embodiments, the viscoelestic layer is bound to at least two layers comprising a pressure sensitive adhesive. Typically R2 is a branched alkyl group containing 15 to 22 carbon atoms. Typically R1 is H or CH3. In some embodiments, the viscoelestic layer comprises copolymer which is a copolymer of at least one second mononomer selected from acrylic acid, methacrylic acid, ethacrylic acid, acrylic esters, methacrylic esters, or ethacrylic esters. In some embodiments, the PSA layer comprises an acrylic pressure sensitive adhesive. In some embodiments, the PSA layer comprises an acrylic pressure sensitive adhesive which is a copolymer of acrylic acid.
In another aspect, the present disclosure provides a viscoelastic construction comprising: a) discrete particles of a polymer or copolymer of at least one monomer according to formula I:
CH2═CHR1—COOR2 [I]
wherein R1 is H, CH3 or CH2CH3 and R2 is a branched alkyl group containing 12 to 32 carbon atoms; dispersed in b) a PSA layer comprising a pressure sensitive adhesive. In some embodiments, the PSA layer comprises an acrylic pressure sensitive adhesive. In some embodiments, the PSA layer comprises an acrylic pressure sensitive adhesive which is a copolymer of acrylic acid.
In another aspect, the present disclosure provides a vibration damping composite comprising a viscoelastic damping material or a vibration damping composite of the present disclosure adhered to at least one substrate. In some embodiments, the material or construction is adhered to at least two substrates. In some embodiments, at least one substrate is a metal substrate.
The present disclosure provides material sets and constructions that demonstrate a pressure sensitive adhesive (PSA) that offers both vibration damping performance at very low temperatures and high frequencies as well as substantial adhesive performance and durability when used with a variety of substrates over a wide range of temperatures. The combination of both low temperature damping and adhesive performance attained using a single material set or construction represents a significant technical challenge in the field of visco-elastic damping materials. In some embodiments of the present disclosure, this is achieved through the use of specialty acrylic materials, specific additives, multi-layer construction, or combinations of the above.
The present disclosure provides material sets and constructions that demonstrate a pressure sensitive adhesive that offers both vibration damping performance at very low temperatures and high frequencies as well as substantial adhesive performance and durability when used with a variety of substrates over a wide range of temperatures. In some embodiments, materials or constructions according to the present disclosure exhibit high tan delta, as measured by Dynamic Mechanical Analysis (DMA) at −55° C. and 10 Hz as described in the examples below. In some embodiments, materials or constructions according to the present disclosure exhibit tan delta (as measured by Dynamic Mechanical Analysis (DMA) at −55° C. and 10 Hz as described in the examples below) of greater than 0.5, in some embodiments greater than 0.8, in some embodiments greater than 1.0, in some embodiments greater than 1.2, and in some embodiments greater than 1.4. In some embodiments, materials or constructions according to the present disclosure exhibit high peel adhesion, as measured as described in the examples below. In some embodiments, materials or constructions according to the present disclosure exhibit peel adhesion (as measured as described in the examples below) of greater than 10 N/dm, in some embodiments greater than 20 N/dm, in some embodiments greater than 30 N/dm, in some embodiments greater than 40 N/dm, in some embodiments greater than 50 N/dm, and in some embodiments greater than 60 N/dm. In some embodiments, materials or constructions according to the present simultaneously achieve high tan delta, at one or more of the levels described above, and high peel strength, at one or more of the levels described above.
In some embodiments, viscoelastic damping materials according to the present disclosure include long alkyl chain acrylate copolymers which are copolymers of monomers including one or more long alkyl chain acrylate monomers. The long alkyl chain acrylate monomers are typically acrylic acid, methacrylic acid or ethacrylic acid esters but typically acrylic acid esters. In some embodiments, the side chain of the long alkyl chain contains 12 to 32 carbon atoms (C12-C32), in some embodiments at least 15 carbon atoms, in some embodiments at least 16 carbon atoms, in some embodiments 22 or fewer carbon atoms, in some embodiments 20 or fewer carbon atoms, in some embodiments 18 or fewer carbon atoms, and in some embodiments 16-18 carbon atoms. Typically, the long alkyl chain has at least one branch point to limit crystallinity in the formed polymer that may inhibit damping performance. Long chain alkyl acrylates with no branch points may be used in concentrations low enough to limit crystallinity of the formed polymer at application temperatures. In some embodiments, additional comonomers are selected from acrylic acid, methacrylic acid or ethacrylic acid, but typically acrylic acid. In some embodiments, additional comonomers are selected from acrylic, methacrylic or ethacrylic esters, but typically acrylic esters.
In some embodiments, the long alkyl chain acrylate copolymers comprise additional comonomers or additives that join in the polymerization reaction, which imparting adhesive properties. Such comonomers may include polyethylene glycol diacrylates.
In some embodiments, the long alkyl chain acrylate copolymers comprise additional comonomers or additives that join in the polymerization reaction, which can help to impart greater adhesive properties through modulation of the rheological properties of the viscoelastic damping copolymer, or through the addition of functional groups. Such comonomers may include but are not limited to (meth)acrylic acid, hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, monofunctional silicone (meth)acrylates, and isobornyl (meth)acrylate.
In some embodiments, the viscoelastic damping copolymer may be crosslinked to improve the durability and adhesion properties of the material. Such crosslinking agents can include but are not limited to photoactivated crosslinkers such as benzophenones, or 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-triazine. Crosslinking agents can also include copolymerizable multifunctional acrylates such as polyethylene glycol diacrylate or hexanediol diacrylate as examples.
In some embodiments the viscoelastic damping copolymer may be polymerized through all known polymerization methods including thermally activated or photoinitiated polymerization. Such photopolymerization processes can include for example common photoinitiators such as diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide.
In some embodiments, viscoelastic damping materials according to the present disclosure include long alkyl chain acrylate copolymers and additional adhesion-enhancing materials which impart adhesive properties. Such additional adhesion-enhancing materials may include polybutenes, silicones, or polyisobutenes. Such additional adhesion-enhancing materials may also be particulate materials. Such particulate adhesion-enhancing materials may include fumed silica, core-shell rubber particles, or isostearyl acrylate microspheres.
In some embodiments, long alkyl chain acrylate copolymers according to the present disclosure form a part of a multilayer viscoelastic construction. In some embodiments, the long alkyl chain acrylate copolymers according to the present disclosure form a viscoelastic damping layer of a two-layer viscoelastic construction, the second, attached layer being a layer of more highly adhesive material over a broader temperature range. In some embodiments, the long alkyl chain acrylate copolymers according to the present disclosure form a viscoelastic damping core layer of a multilayer viscoelastic construction, sandwiched between two layers of more highly adhesive material. In some embodiments, the long alkyl chain acrylate copolymers according to the present disclosure form a layer of a multilayer viscoelastic construction which additionally comprises at least one layer of more highly adhesive material. In some embodiments, the long alkyl chain acrylate copolymers according to the present disclosure form an interior layer of a multilayer viscoelastic construction which additionally comprises at least two layers of more highly adhesive material. In some embodiments, the more highly adhesive material is an acrylic PSA material.
In some embodiments, a two-layer viscoelastic construction comprises a viscoelastic layer attached to a second layer which is a layer of more highly adhesive material. In some embodiments, the two-layer viscoelastic construction is made by lamination of a viscoelastic layer to an adhesive layer. In some embodiments, the two-layer viscoelastic construction is made by application of an adhesive tape to a viscoelastic layer. In some embodiments, the two-layer viscoelastic construction is made by application of an adhesive in liquid or aerosolized form to a viscoelastic damping layer to provide greater adhesion to the damping layer. In some embodiments, the two-layer viscoelastic construction is made by application of an adhesive in paste form to a viscoelastic layer. In some embodiments, a two-layer viscoelastic construction is provided in the form of a roll, sheet, or pre-cut article. In some embodiments, a two-layer viscoelastic construction is made shortly prior to use by application of an adhesive to a viscoelastic layer. In some embodiments, a two-layer viscoelastic construction is made in situ by application of an adhesive to a substrate followed by application of a viscoelastic layer to the adhesive.
In some embodiments, the multilayer viscoelastic construction comprises a viscoelastic layer sandwiched between two layers of more highly adhesive material. In some embodiments, the multilayer viscoelastic construction is made by lamination of a viscoelastic layer to at least one adhesive layer. In some embodiments, the multilayer viscoelastic construction is made by application of an adhesive tape to at least one side of a viscoelastic layer. In some embodiments, the multilayer viscoelastic construction is made by application of an adhesive in liquid form to at least one side of a viscoelastic layer. In some embodiments, the multilayer viscoelastic construction is made by application of an adhesive in paste form to at least one side of a viscoelastic layer. In some embodiments, a multilayer viscoelastic construction is provided in the form of a roll, sheet, or pre-cut article. In some embodiments, a multilayer viscoelastic construction is made shortly prior to use by application of an adhesive to a viscoelastic layer. In some embodiments, a multilayer viscoelastic construction is made in situ by application of an adhesive to a substrate followed by application of a viscoelastic layer to the adhesive, followed by application to the viscoelastic layer of additional adhesive or an additional adhesive-bearing substrate. In some embodiments, the multilayer construction is made in-situ by application of the viscoelastic damping composition in liquid form between two adhesive layers followed by a subsequent cure of the damping layer to form the viscoelastic damping copolymer.
The materials or constructions according to this disclosure may be useful for aerospace applications in which maximum damping performance of high frequency vibration energy is required at very low temperatures, in combination with good adhesion properties.
Objects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.
Unless otherwise noted, all reagents were obtained or are available from Sigma-Aldrich Company, St. Louis, Mo., or may be synthesized by known methods. Unless otherwise reported, all ratios are by weight percent.
The following abbreviations are used to describe the examples:
mm: millimeters
The force required to peel the test material from a substrate at an angle of 180 degrees was measured according to ASTM D 3330/D 3330M-04. Using a rubber roller, the adhesive sample was manually laminated onto a primed 2 mil (50.8 μm) polyester film, obtained under the trade designation “HOSTAPHAN 3SAB” from Mitsubishi Plastics, Inc., Greer, S.C., and allowed to dwell for 24 hours at 23° C./50% relative humidity. A 0.5×6 inches (1.27×12.7 cm) section was cut from the laminated film and taped to either a 0.10 inch (2.54 mm) or 0.20 inch (5.08 mm) thick, Shore A 70, 320 Kg/m3 polyether-polyurethane foam, or a grade 2024 aluminum test coupon, obtained from Aerotech Alloys, Inc., Temecula, Calif. The tape was then manually adhered onto the test coupon using a 2 Kg rubber roller and conditioned for 24 hours at 23° C./50% relative humidity. The peel adhesive force was then determined using a tensile force tester, model “SP-2000”, obtained Imass Inc., Accord, Massachusetts, at a platen speed of 12 in./min (0.305 m/min.). Three tape samples were tested per example or comparative, and the average value reported in N/dm. Also reported are the failure modes, abbreviated as follows:
Dynamic Mechanical Analysis (DMA) was determined using a parallel plate rheometer, model “AR2000” obtained from TA Instruments, New Castle, Del. Approximately 0.5 grams of visco-elastic sample was centered between the two 8 mm diameter, aluminum parallel plates of the rheometer and compressed until the edges of the sample were uniform with the edges of the plates. The temperature of the parallel plates and rheometer shafts was then raised to 40° C. and held for 5 minutes. The parallel plates were then oscillated at a frequency of 10 Hz and a constant strain of 0.4% whilst the temperature was ramped down to −80° C. at a rate of 5° C./min. Storage modulus (G′), and tan delta were then determined.
Tan delta, the ratio of G″/G′, was plotted against temperature. Tg is taken as the temperature at maximum tan delta curve.
A composite material was prepared for Damping Loss Factor as follows. A nominally 6 by 48 inch by 7 mil (15.24 by 121.92 cm by 0.178 mm) strip of aluminum was cleaned with a 50% aqueous solution of isopropyl alcohol and wiped dry. A primer, type “LORD 7701”, obtained from Lord Corporation, Cary, N.C., was applied to a nominally 6 by 48 by 0.1 inch (15.24 by 121.92 cm by 2.54 mm) strip of 20 pcf (0.32 g/cm3) white foraminous micro cellular high density polyurethane foam. The adhesive tape was applied to the aluminum strip, nipped together to ensure wet out, then applied to the primed surface of the high density urethane. A 5 mil (127 μm) adhesive transfer tape, obtained under the trade designation “VHB 9469PC” obtained from 3M Company, St. Paul, Minn., was then applied on the opposite side of the urethane strip. The resulting composite material cut into 2 by 24 inch (5.08 by 60.96 cm) samples and applied to a 3×40 inch×0.062 mil (7.62×101.4 cm×1.58 mm) aluminum beam.
The beam was suspended by its first nodal points, and the center of the beam mechanically coupled to an electromagnetic shaker model “V203” from Brüel & Kjaer North America, Inc., Norcross, Ga., via an inline force transducer, model “208M63” from PCB Piezotronics, Inc., Depew, New York, in a thermally controlled chamber at temperatures of −10° C., −20° C. and −30° C. On the opposite side of the beam to the inline force transducer was mounted an accelerometer, model “353B16 ICP”, also from Piezotronics, Inc. A broad band signal was sent to the electromagnetic shaker and the force the shaker excerpted on the beam was measured, as was the resulting acceleration of the beam. The frequency response function (FRF) was calculated from the cross spectrum of the measured acceleration and force, and from the magnitude of the FRF, peak amplitudes were used to identify the modal frequencies. The half power bandwidth around each modal frequency was also identified as the span of frequencies between the −3 dB amplitude points above and below the modal frequency. The ratio of the half power bandwidth to modal frequency was calculated and reported as the Damping Loss Factor.
Abbreviations for the reagents used in the examples are as follows:
A 25 dram (92.4 mls) glass jar was charged with 19.6 grams HEDA, 0.4 grams AA and 0.008 grams I-651. The monomer mixture was stirred for 30 minutes at 21° C., purged with nitrogen for 5 minutes, and then exposed to low intensity ultraviolet light, type “BLACK RAY XX-15BLB” obtained from Fisher Scientific, Inc., Pittsburgh, Pa., until a coatable pre-adhesive polymeric syrup was formed. An additional 0.032 grams I-651 and 0.03 grams PEGDA were blended into the polymeric syrup using a high speed mixer, model “DAC 150 FV” obtained from FlackTek, Inc., Landrum, S.C. The polymeric syrup was then coated between silicone release liners T-10 and T-50 at an approximate thickness of 8 mils (203.2 μm) and cured by means of UV-A light at 2,000 mJ/cm2.
The procedure generally described in Sample 1 was repeated, according to the quantities of acrylate monomers listed in Table 1. Physical characteristics of the resultant cured adhesive coatings are listed in Table 2.
A 25 dram (92.4 mls) glass jar was charged with 19.6 grams HEDA, 0.4 grams AA and 0.008 grams I-651. The monomer mixture was stirred for 30 minutes at 21° C., purged with nitrogen for 5 minutes, and exposed to the low intensity ultraviolet light until a coatable pre-adhesive polymeric syrup was formed. An additional 0.032 grams I-651, 0.046 grams PEGDA and 2.0 grams R-972 were subsequently blended into the polymeric syrup using the high speed mixer. The polymeric syrup was then coated between silicone release liners at an approximate thickness of 8 mils (203.2 μm) and cured by means of UV-A light at 2000 mJ/cm2.
The procedure generally described in Sample 7 was repeated, wherein various amounts of fumed silica, plasticizer, polybutenes, polyisobutenes, silicones, core-shell rubber particles and isostearyl acrylate microspheres, were blended into the pre-adhesive polymeric syrup according to the quantities listed in Table 3. Physical characteristics of the resultant cured adhesive coatings are listed in Table 4.
A 25 dram (92.4 mls) glass jar was charged with 19.8 grams HEDA, 0.2 grams DMAEMA and 0.008 grams I-651. The monomer mixture was stirred for 30 minutes at 21° C., purged with nitrogen for 5 minutes, and exposed to the low intensity ultraviolet light until a coatable pre-adhesive polymeric syrup was formed. An additional 0.032 grams I-651 and 0.03 grams TMT were subsequently blended into the polymeric syrup using the high speed mixer. The polymeric syrup was then coated between silicone release liners T-10 and T-50 at an approximate thickness of 8 mils (203.2 μm) and cured by means of UV-A light at 2,000 mJ/cm2.
The procedure generally described in VEC-1 was repeated, according to the compositions listed in Table 5. With respect to VEC-6, the nominal thickness was 16 mils (406.4 μm). Physical characteristics of the visco-elastic cores are listed in Table 6.
A one quart (946 mls.) glass jar was charged with 372 grams IOA, 28 grams AA and 0.16 grams I-651. The monomer mixture was stirred for 30 minutes at 21° C., purged with nitrogen for 5 minutes, and exposed to the low intensity (0.3 mW/cm2) ultraviolet light until a coatable pre-adhesive polymeric syrup was formed. An additional 0.64 grams I-651 and 0.6 grams TMT were subsequently blended into the polymeric syrup using the high speed mixer. The polymeric syrup was then coated between silicone release liners T-10 and T-50 at an approximate thickness of 1 to 2 mils (25.4-50.8 μm) and cured by means of UV-A light at 1,500 mJ/cm2.
The procedure generally described in SKN-1 was repeated, according to the monomer and tackifier compositions listed in Table 7.
Adhesive skin SKN-1 was laid on a clean 12 by 48 by 0.5-inch (30.5 by 121.9 by 1.27 cm) glass plate and the upper silicone release liner removed. One of the silicone release liners was removed from a sample of visco-elastic core VEC-3, and the exposed surface of the core laid over the exposed adhesive skin of SKN-1. The core and skin were then laminated together by manually applying a hand roller over the release liner of the visco-elastic core. The release liner covering the visco-elastic core removed, as was a release liner of another sample of adhesive skin SKN-1. The skin was then laminated onto the exposed core by means of the hand roller, resulting in a SKN-1:VEC-3:SKN-1 laminate. The laminate was then allowed to dwell for 24 hours at 50% RH and 70° F. (21.1° C.) before testing.
The procedure generally described in Sample 34 was repeated, according to the adhesive skin and visco-elastic core constructions listed in Table 8. With respect to Sample 42, the adhesive skin is represented by adhesive transfer tape 467-MP/467-MPF. Physical characteristics of the resultant multi-layer constructions are also presented in Table 8.
A one quart jar glass jar was charged with 405 grams ISA, 45 grams IOA and 0.18 grams I-651, corresponding to the composition “VEC-7” of Table 5. The monomer mixture was stirred for 30 minutes at 21° C., purged with nitrogen for 5 minutes, and exposed to the low intensity ultraviolet light until a coatable pre-adhesive polymeric syrup was formed. An additional 0.72 grams I-651 and 0.675 grams TMT were subsequently blended into the polymeric syrup using the high speed mixer. The polymeric syrup was then coated between layers of adhesive transfer tapes 467-MP and 467-MPF, at an approximate thickness of 8 mils (203.2 μm), and cured by means of UV-A light exposure through the 467-MPF side at 2,000 mJ/cm2.
The procedure generally described in Sample 43 was repeated, according to the compositions for VEC-8, VEC-9 and VEC-10, respectively, listed in Table 5. Physical characteristics of the visco-elastic cores and of the resultant multi-layer constructions are listed in Table 7 and Table 8, respectively.
DLF values were determined for selected adhesive samples according to the test method described above. Results are listed in Table 9.
Various modifications and alterations of this disclosure will become apparent to those skilled in the art without departing from the scope and principles of this disclosure, and it should be understood that this disclosure is not to be unduly limited to the illustrative embodiments set forth hereinabove.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2012/071650 | 12/26/2012 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61581374 | Dec 2011 | US | |
| 61675536 | Jul 2012 | US |
