• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    STRUCTURAL ACRYLIC ADHESIVE. An adhesive composition is provided which comprises: a) at least one functional acrylic monomer; b) a first toughness agent; c) a second toughness agent; d) an adhesion promoter; and e) a high aspect ratio filler selected from at least one of a high aspect ratio fibrillated filler and a halosite clay filler.
    公开号:BR112014020560B1
    申请号:R112014020560-4
    申请日:2013-02-20
    公开日:2021-03-02
    发明作者:Michael A. Kropp；Zachary J. Thompson
    申请人:3M Innovative Properties Company；
    IPC主号:
    专利说明:

    Field
    [001] This description refers to two-part structural adhesive compositions. This description also refers to two-part structural acrylic adhesive compositions that have high aspect ratio fillers and, optionally, in combination with fillers of treated pyrolyzed silica to achieve higher adhesive performance. Background
    [002] Two-part structural acrylic adhesives are used to bond a variety of substrates, including plastics, composites and metals. They also connect minimally prepared surfaces.
    [003] There is a need for acrylic adhesive compositions that provide higher strength, particularly at higher temperatures, as well as improved service life and better fillet curing. summary
    [004] The adhesive composition presented here provides, among other things, higher strength, particularly at higher temperatures, as well as improved service life and better fillet curing.
    [005] In some respects, the present description features an adhesive composition comprising: a) at least one functional acrylic monomer; b) a first toughness agent; c) a second toughness agent; d) an adhesion promoter; and e) a high aspect ratio load selected from at least one of a high aspect ratio fibrillated filler and a haloite clay filler. In some embodiments, the high aspect ratio load is surface treated to improve miscibility with resins.
    [006] In some embodiments, the adhesive composition additionally comprises pyrolyzed silica. In some embodiments, the first toughness agent is selected from at least one of a block copolymer, a core-shell particle and combinations thereof. In some embodiments, the block copolymer is selected from a styrene-b-butadiene-b-poly (methyl methacrylate) block copolymer or a poly-block (methyl methacrylate) -b-poly (acrylate) block copolymer. n-butyl) -b-poly (methyl methacrylate). In some embodiments, the second toughening agent is a liquid rubber terminated with methacrylate.
    [007] In some embodiments, the adhesion promoter is an acid adhesion promoter. In some embodiments, the high aspect ratio fibrillated load is microfibrillated. In some embodiments, the composition has a peel value greater than 3.5 kN / m. In some embodiments, the composition has a detachment value greater than 4.4 kN / m. In some embodiments, the composition has a substantially cohesive flaw.
    [008] In some embodiments, the adhesive composition additionally comprises a curing initiator system. In some embodiments, the curing starter system comprises a derivative of barbituric acid and a metal salt. In some embodiments, the curing initiator system further comprises an organic peroxide, ammonium chloride salt or a mixture thereof.
    [009] The previous summary of this description is not intended to describe each of the embodiments of the present invention. Details of one or more embodiments of the invention are also presented in the description below. Other features, objectives and advantages of the invention will be evident from the description and the claims. Detailed Description
    [010] Before some embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in this application to the details of construction and arrangement of the components presented in the following description. The invention can comprise other modalities and be practiced or carried out in several ways. It should also be understood that the phraseology and terminology used in the present invention are for the purpose of description, and should not be considered as limiting. The use of "including", "comprising", or "having" and the variations thereof of the present invention are intended to cover the items mentioned after them and their equivalents as well as additional items. Any numerical range mentioned here includes all values from the lowest value to the highest value. For example, if a concentration range is declared as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly listed. There are only examples of what is specifically intended, and all possible combinations of numerical values between and including the lowest and highest listed values should be considered as expressly stated in this application. As used in this document:
    [011] “Fibrillated fiber” means fibers that have a relatively high surface area and / or a branched structure, which in the case of branched structures can lead to a high degree of mechanical interlacing of the fibers;
    [012] “High aspect ratio” means a ratio between the length and the diameter of an individual particle that is greater than 20, in some modalities it is between 20 and 60;
    [013] "Cohesive failure" means adhesive bond failure within the adhesive layer, with "substantially cohesive" meaning that 80% or more of the failure occurs within the adhesive layer.
    [014] "Adhesive failure" means failure of adhesive bonding at the interface between the adhesive and the substrate;
    [015] “Fine cohesive” means cohesive failure as described above, but where most of the adhesive is on a substrate
    [016] "Mixed fault" means that the fault is not entirely due to the type of fault reported and other fault modes are also present in the connection line.
    [017] The present description refers, in general, to an adhesive composition that provides high shear resistance by overlapping and adhesion in metals and plastics. Surprisingly, the adhesive composition presented here provides improvements in resistance to detachment and overlapping shear, as well as a desirable cohesive failure mode, when high aspect ratio fibrillated loads are used. It has also surprisingly been found that even better results in adhesion and overlapping shear performance, as well as desirable cohesive failure can be obtained when combining high-aspect ratio fibrillated fillers with pyrolysed silica in the adhesive compositions presented here.
    [018] The present description provides an adhesive composition comprising: a) at least one functional acrylic monomer; b) a first toughness agent; c) a second toughness agent; d) an adhesion promoter; and e) a high aspect ratio fibrillated charge.
    [019] The functional acrylic monomers useful in the present description include acrylate based ester monomers. In some embodiments, the functional acrylic monomers comprise an ester monomer based on methacrylate. Such a methacrylate ester monomer can be selected from at least one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and tetrahydrofurfuryl methacrylate. In some embodiments, the methacrylate-based ester monomer is selected from at least one of methyl methacrylate and ethyl methacrylate. In some embodiments, the methacrylate-based ester monomer is methyl methacrylate.
    [020] Toughening agents useful as the first toughening agent in the present description include elastomeric materials. In some embodiments, these elastomeric materials are polymer substances that have rubber elasticity at room temperature. For example, an elastomeric material that can be dissolved or dispersed in the adhesive composition is useful. Such an elastomeric material includes several synthetic rubbers such as a methyl-butadiene-styrene methacrylate (MBS) copolymer, an acrylonitrile-styrene-butadiene copolymer, a linear polyurethane, acrylonitrile-butadiene rubber, a styrene-butadiene rubber , a chloroprene rubber and a butadiene rubber, and natural rubbers. Among them, an acrylonitrile-butadiene rubber is particularly useful because of its solubility in the functional acrylic monomers presented here and their binding properties. Such electromeric materials can be used alone or in combination.
    [021] The toughness agents useful as the second toughness agent in the present description include elastomeric materials such as those disclosed above with respect to the first toughness agent.
    [022] Adhesion promoters useful in the present description include acid phosphate compounds of the following formula (I)
    where R is CH2CR4CO (OR5) M - (where R4 is hydrogen or a methyl group, R5 is --C2H4 -, --C3H6 -, --CHaCHfCHβ) -, --C4H8 -, - -C6H12 — or
    em is an integer from 1 to 10), and n is 1 or 2.
    [023] The acid phosphate compound of the formula (I) can be, for example, acid (phosphoxyethyl) (acrylate), acid (phosphoxypropyl) (meth) acrylate or bis (2- (meth) acryloyloxyethyl).
    [024] The high-aspect ratio fibrillated fillers useful in the present description include organic fibers. Organic fibers may include high density polyethylene fibers such as those commercially available under the trade names "SYLOTHIX 52 (R)", "SYLOTHIX 53 (R)" and "ARBOTHIX PE100" (from EP Minerals in Reno, Nev., USA), “SHORT STUFF (R) ESS2F”, “SHORT STUFF (R) ESS50F” and “SHORT STUFF (R) ESS5F” (with MiniFIBERS, INC. In Johnson City, Tenn., USA), and “INHANCE ( R) PEF ”(with Inhance / Fluoro-Seal, Limited in Houston, Tex., USA). Organic fibers may also include high density aramid fibers such as those commercially available under the trade name "INHANCE (R) KF" (from Inhance / Fluoro-Seal, Limited in Houston, Tex., USA).
    [025] The adhesive composition shown here may also include pyrolyzed silica.
    [026] The curing systems useful in the present description include redox initiator systems having (i) a derivative of barbituric acid and / or a malonylsulfamide and (ii) an organic peroxide, selected from the group among peroxide esters of mono- or multifunctional carboxylic acid. They can be used as derivatives of barbituric acid, for example, 1,3,5-trimethylbarbituric acid, 1,3,5-triethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,5-dimethylbarbituric acid, 1 -methyl-5-ethylbarbituric, 1-methyl-5-propylbarbituric acid, 5-ethylbarbituric acid, 5-propylbarbituric acid, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid and thiobarbituric acids mentioned in German patent application DE-A-42.19.700.
    [027] The barbituric acids and barbituric acid derivatives described in the German patent specification DE-C-14.95.520 as well as the malonylsulfamides named in the European patent specification EP-B-0.059.451 are isobutylmalonylsulfamide.
    [028] The redox initiator system presented here contains peroxyesters of mono- or multifunctional carboxylic acid as organic peroxides. Carbonic peroxyesters are also included among the multifunctional carboxylic acid peroxyesters within the meaning of the present application. Suitable examples include carbonic diisopropyl peroxidiester, neodecanoic acid tertiary butyl peroxyester, neodecanoic acid tertiary amyl peroxyester, maleic acid tertiary butyl monoperoxyester, benzoic acid tertiary butyl peroxyester, tertiary butyl acid peroxyester 2-ethyl-hexane-peroxyester-ethyl ether-hexane-peroxide - tertiary liquefied 2-ethylhexanoic acid, tertiary monobutyl peroxyester - carbon monoisopropyl ester, carbonic dicyclohexyl peroxyester, carbonic dimiristyl peroxyester, carbonic dicetyl peroxyester, carbonic (butyl-tertiary) carbonic di-2-ethyl peroxyester, carbonic-tertiary tertiary peroxy- (2-ethylhexyl) 3,5,5-trimethylhexanoic acid tertiary butyl ester or peroxyester, benzoic acid tertiary amyl peroxyester, acetic acid tertiary butyl peroxyester, di (4- tertiary-butyl-cyclohexyl peroxyester ) carbonic, cumene-peroxyester of neodecanoic acid, tertiary amyl peroxyester of pivalic acid and pero tertiary butyl xiester of pivalic acid.
    [029] In particular, carbonic tertiary-butyl-peroxy- (2-ethylhexyl) ester or tertiary-butyl-peroxyester 3,5,5-trimethylhexanoic acid can be used as organic peroxides in accordance with this description.
    [030] It was found that the addition of both high aspect ratio fillers and pyrolysed silica improved the detachment and shear strengths by overlapping more than the use of any of the same alone, and provided improved properties compared to the loads clay with modified surface.
    [031] For the adhesives of the present invention, it is desirable to obtain overlapping shear strengths greater than 20 MPa and peel strengths of> 2.5 kN / m, preferably> 3.5 kN / m. In addition, the failure must occur within the adhesive (cohesive failure).
    [032] Some exemplary non-limiting modalities and combinations of modalities are presented below: 1. An adhesive composition, comprising: a) at least one functional acrylic monomer; b) a first toughness agent; c) a second toughness agent; d) an adhesion promoter; and e) a high aspect ratio charge selected from at least one of a high aspect ratio fibrillated charge and a haloisite clay charge. 2. The adhesive composition of modality 1 in which the high aspect ratio load is surface treated to improve miscibility with resins. 3. The adhesive composition of any of the foregoing embodiments which further comprises pyrolyzed silica. 4. The adhesive composition of any of the foregoing modalities in which the first toughness agent is selected from at least one of a block copolymer, a core-shell particle and combinations thereof. 5. The adhesive composition of modality 4 in which the block copolymer is selected from a block copolymer of styrene-b-butadiene-b-poly (methyl methacrylate) or a block copolymer of poly (methyl methacrylate) -b-poly (n-butyl acrylate) -b-poly (methyl methacrylate). 6. a. The adhesive composition of modality 4 in which the block copolymer is selected from a block copolymer of polystyrene-b-butadiene-b- (methyl methacrylate) or a block copolymer of poly (methyl methacrylate) - b-poly ( n-butyl acrylate) -b-poly (methyl methacrylate). 7. The adhesive composition of any of the previous embodiments in which the second toughening agent is a liquid rubber terminated with methacrylate. 8. The adhesive composition of any of the above embodiments in which the adhesion promoter is an acid adhesion promoter. 9. The adhesive composition of any of the above embodiments in which the high aspect ratio fibrillated filler is microfibrillated. 10. The adhesive composition of modality 3 in which the composition has a peel value greater than 3.5 kN / m. 11. The adhesive composition of modality 3 in which the composition has a peel value greater than 4.4 kN / m. 12. The adhesive composition of any of the previous modalities that has a substantially cohesive failure. 13. The adhesive composition of any of the foregoing embodiments which further comprises a curing initiator system. 14. The adhesive composition of modality 12 in which the curing initiator system comprises a derivative of barbituric acid and a metal salt. 15. The adhesive composition of modality 13 in which the curing initiator system further comprises an organic peroxide, ammonium chloride salt or a mixture thereof.
    [033] Various modifications and alterations of this invention will become evident to those versed in these techniques without deviating from the scope and spirit of the invention. Test Methods
    [034] Each adhesive composition was loaded on the 10 part side of a 10: 1 dual syringe cartridge applicator, using the accelerator described above on the 1 part side of the applicator in each case. All connections were prepared by dispensing the adhesive composition and accelerator through a static mixing tip.
    [035] The adhesives were used to prepare the samples for the detachment and overlap shear tests on 2024 T3 AlClad aluminum substrates. For the detachment test samples, the aluminum was chemically cleaned and attacked according to ASTM D 2651. Overlapping shear was measured according to ASTM D 1002. Bell detachment was measured according to ASTM D 3167. Thick metal panels , measuring 10.16 cm x 17.78 cm x 0.16 cm thick, and thin metal measuring 10.16 cm x 25.4 cm x 0.051 cm thick, were each coated with the test adhesive and 0.069 mm spacer capsules were spread over the connecting line. Weights were left on the panels for 24 hours at 25 ° C, then the panels were cut to 2.54 cm wide, after the adhesive was cured, giving three 2.54 cm wide specimens per panel. These were tested for floating roller peel. Results are reported in pounds per inch wide (piw) and are the average of 3 samples.
    [036] The samples for overlapping shear were aluminum coupons of 2.54 cm x 10.16 cm x 0.16 cm with the use of 0.076 mm - 0.0127 mm spacer capsules with an overlap of 1.27. The connecting line was fixed with fixing clips during curing and the clips were removed after 24 hours at 25 ° C. The test was carried out under a load cell of 2,268 kg (5,000 lb) for overlapping shear and under a load cell of 90,7 kg (200 lb) for the pull-out test for both at 2, 54 mm / min. Materials
    [037] These examples are for illustrative purposes only and are not intended to be limited in the scope of the appended claims. All parts, percentages, ratios and the like in the examples are by weight, unless otherwise stated. The materials used were obtained from Sigma-Aldrich Chemical Company; Milwaukee, Wisconsin, USA unless otherwise specified.

    EXAMPLES
    [038] The following examples are for illustrative purposes only and are not intended to limit the scope of the appended claims in any way. All parts, percentages, ratios and the like in the examples are, by weight, unless otherwise indicated. Throttle side:
    [039] All adhesive compositions used an accelerator having 37.5 kg / h (82.7 pph) of BENZOFLEX 9-88, 6.12 kg / h (13.5 pph) of benzylphenylbarbituric acid, 0.86 kg / h (1.9 pph) of peroxybenzoate, 0.86 kg / h (1.9 pph) of CAB-O-SIL TS 720. The components were weighed into a plastic container, then placed in a mixer of the planetary type such as that available under the trade name “SPEED MIXER”, Model DA 400 FV, from Synergy Devices Limited, Buckinghamshire, United Kingdom) set at a speed of 2,500 rpm for 2 minutes, followed by a propellant mixer until they are not most observed clusters of barbituric acid. Base side of adhesives for Examples 1-2 and CE 1-2:
    [040] A solution of 70 parts of MMA with 30 parts of NANOSTRENGTH E21 was prepared by dispersing NANOSTRENGTH E21 in MMA in a vial, then the vial was kept under rotation agitation on rotating cylinders to obtain a clear solution. Stock solution for EX 1, EX 2, CE1 and CE2:
    [041] A solution of 5.5% N + Cl- in HEMA was prepared by adding 5.5 g of N + Cl- in 94.5 g of HEMA and was manually stirred until the N + Cl- was completely dissolved. Weight percentages are based on the total weight of the solution. A stock solution of adhesive was then prepared by mixing 200 g of the MMA / E21 solution prepared previously, 3.8 g of PAM 200, 0.3 g of CUNAP, and 6.9 g of N + Cl- / HEMA.
    [042] The adhesive compositions shown in the following Table 1 were prepared by weighing the specified components into DAC Speedmixer cups and then mixed using a DAC Speedmixer at approximately 2,500 rpm for 2 minutes.

    [043] For Comparative Example 1 (CE1) and Comparative Example 2 (CE 2), the amount of POLYFIL WC was increased to almost 2.5 times the amount of ESS50F or INHANCE PEF used in Examples 1 and 2, respectively, for the purpose of providing approximately the same percentage by volume of loading material for all samples. This was done because the density of POLYFIL WC is 2.6 g / cm3, which is almost 2.5 times the density of ESS50F or INHANCE PEF. CAB-O-SIL TS 720 was added in CE1 and CE2 to reduce the sedimentation of POLYFIL WC.
    [044] These adhesive compositions have been evaluated for peel and shear strengths by overlapping, and failure mode according to the test methods described above. The results of these tests are reported in Table 2.

    Table 2 shows the total performance improved with the use of ESS50F or INHANCE PEF versus the use of POLYFIL WC. Base side of adhesives for EX3, EX4, EX5 and CE3:
    [045] Using the MMA / Nanostrength E21 and N + Cl- / HEMA solutions described above a stock solution was prepared containing 220 g MMA / E21, 11.0 g SR 540, 11.0 g VTBN 33, 2.3 g of PAM 200, 0.32 g of CUNAP (in ligroin), and 7.6 g of N + Cl- / HEMA stock solution. The adhesive compositions shown in the following Table 3 were prepared as described in EX1:

    [046] The adhesive compositions shown in Table 3 were evaluated for shear strengths by overlapping and detachment and failure mode according to the test method described above. The results for these tests are reported in Table 4.

    Base side of adhesives for EX6-10 and CE4-14.
    [047] A solution of 70 parts of MMA with 30 parts of NANOSTRENGTH E21 or NANOSTRENGTH M53 was prepared by dispersing NANOSTRENGTH E21 or NANOSTRENGTH M53 in MMA in a flask, then the flask was subjected to rotation agitation on rotating cylinders for one day to the other with the use of a rotating cylinder table to obtain a transparent solution. Stock solution for EX6-10 and CE4-14:
    [048] A stock solution of 5.5% N + Cl- in HEMA was prepared as described above and used to prepare the following solutions. Master batches EX6-10 and CE4-14:
    [049] The MMA / Nanostrength M53 (EX 6-7 and CE4-6) or E21 (EX8-9 and CE7-9) solution and all other components, totaling 275 g, were weighed into the MAX 300 DAC Speedmixer in the amount indicated in Table 5 below and then mixed for 2 minutes at 2,500 rpm. Separate MAX 100 cups were each loaded with 46.0 g of the mixtures obtained and the various charges were added and mixed for 1 minute at 2,500 rpm. The charges used are summarized in Table 6. The resulting adhesive compositions are shown in Table 7 and Table 8. These adhesive compositions were loaded into the 10: 1 10-part cartridge compartment, with the accelerator described above loaded in. of the 1 part compartment.


    [050] The adhesive compositions shown in tables 7 and 8 have been evaluated for shear strength by overlap, peel strength, and failure mode according to the test methods described above. The results for these tests are reported in Table 9.

    Example 10 and comparative examples 10-14
    [051] The adhesive components, totaling 300 g, were weighed in MAX 300 DAC Speedmixer in the relative amounts shown in Table 10 below and then mixed for 2 minutes at 2,500 rpm. The N + Cl- stock solutions described above were used. The Separate MAX 100 cups were then each loaded with 50.0 g of the mixture obtained and 5.0 g of the various loads and mixed for 1 minute at 2,500 rpm, giving the final formulations described in Table 11 the various loads identified in Table 12.


    [052] This set of adhesives represents a weaker-odor acrylic adhesive compared to the MMA adhesives described above. These adhesives were used to bond overlapping peel and shear samples as described above. The results of these tests are reported in Table 13.
    权利要求:
    Claims (12)
    [0001]
    1. Adhesive composition CHARACTERIZED by the fact that it comprises: a) at least one functional acrylic monomer; b) a first toughness agent selected from at least one block copolymer, a core-shell particle and combinations thereof; c) a second toughening agent, wherein the second toughening agent is a liquid rubber terminated with methacrylate; d) an adhesion promoter; and e) a high aspect ratio load selected from at least one of a high aspect ratio fibrillated load and a clayite load.
    [0002]
    2. Adhesive composition, according to claim 1, CHARACTERIZED by the fact that the high aspect ratio load is surface treated to improve miscibility with resins.
    [0003]
    3. Adhesive composition, according to claim 1, CHARACTERIZED by the fact that it additionally comprises pyrogenic silica.
    [0004]
    4. Adhesive composition according to claim 1, CHARACTERIZED by the fact that the block copolymer is selected from a block copolymer of polystyrene-b-butadiene-b- (methyl methacrylate) or a block copolymer from poly (methyl methacrylate) -b-poly (n-butyl acrylate) -b-poly (methyl methacrylate).
    [0005]
    5. Adhesive composition, according to claim 1, CHARACTERIZED by the fact that the adhesion promoter is an acid adhesion promoter.
    [0006]
    6. Adhesive composition, according to claim 1, CHARACTERIZED by the fact that the high aspect ratio fibrillated load is microfibrillated.
    [0007]
    7. Adhesive composition, according to claim 3, CHARACTERIZED by the fact that the composition has a detachment value greater than 3.5 kN / m.
    [0008]
    8. Adhesive composition, according to claim 3, CHARACTERIZED by the fact that the composition has a detachment value greater than 4.4 kN / m.
    [0009]
    9. Adhesive composition, according to claim 1, CHARACTERIZED by the fact that it has a substantially cohesive failure.
    [0010]
    10. Adhesive composition, according to claim 1, CHARACTERIZED by the fact that it also comprises a curing initiator system.
    [0011]
    11. Adhesive composition according to claim 10, CHARACTERIZED by the fact that the curing initiator system comprises a derivative of barbituric acid and a metal salt.
    [0012]
    Adhesive composition according to claim 11, CHARACTERIZED by the fact that the curing initiator system further comprises an organic peroxide, an ammonium chloride salt or a mixture thereof.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261602353P| true| 2012-02-23|2012-02-23|
    US61/602,353|2012-02-23|
    PCT/US2013/026814|WO2013126377A1|2012-02-23|2013-02-20|Structural acrylic adhesive|
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