HK1196391B - A one-component, dual-cure adhesive for use on electronics - Google Patents
A one-component, dual-cure adhesive for use on electronics Download PDFInfo
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- HK1196391B HK1196391B HK14109661.3A HK14109661A HK1196391B HK 1196391 B HK1196391 B HK 1196391B HK 14109661 A HK14109661 A HK 14109661A HK 1196391 B HK1196391 B HK 1196391B
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Description
This application claims benefit of U.S. provisional application No.61/510,806, filed on 7, 2012, month 22, incorporated herein.
Disclosure of Invention
In some aspects, the present invention relates to a method of making an electronic assembly comprising a first substrate, a second substrate, and at least one electronic component positioned between the two substrates. The method includes providing a one-part dual cure adhesive composition. The adhesive composition includes a moisture curable radiation curable prepolymer containing moisture curable and radiation curable functional groups. An adhesive is applied to at least a portion of the first substrate. At least a portion of the second substrate is then contacted with the adhesive on the first substrate. At least one of the first and second substrates includes at least one electronic component prior to application of the adhesive composition.
In some embodiments, the adhesive composition further comprises an additional moisture curable prepolymer and/or a radiation curable component.
In some aspects, the present invention relates to a method of making an electronic assembly comprising a first substrate, a second substrate, and at least one electronic component positioned between the two substrates. The method includes providing a one-part dual cure adhesive composition. The adhesive composition includes a moisture curable prepolymer and a radiation curable component. An adhesive is applied to at least a portion of the first substrate. At least a portion of the second substrate is then contacted with the adhesive on the first substrate. At least one of the first and second substrates includes at least one electronic component prior to application of the adhesive composition.
In some embodiments, any of the foregoing methods further comprises exposing the adhesive on the first substrate to radiation before or after contacting the adhesive on the first substrate with the second substrate.
In some aspects, the present invention relates to an electronic assembly prepared by any of the foregoing methods.
In one embodiment, the electronic assembly includes a first substrate, a second substrate, an electronic component positioned between the two substrates, and an adhesive composition comprising a dual cure reaction product of a moisture curable radiation curable prepolymer containing moisture curable and radiation curable functional groups. At least a portion of the first substrate is bonded to at least a portion of the second substrate by an adhesive. In some embodiments, the adhesive composition comprises a dual cure reaction product of a moisture curable radiation curable prepolymer containing moisture curable and radiation curable functional groups and an additional moisture curable prepolymer and/or an additional radiation curable component.
In one embodiment, the electronic assembly includes a first substrate, a second substrate, at least one electronic component positioned between the two substrates, and an adhesive composition comprising a dual cure reaction product of a moisture curable prepolymer and a radiation curable component. At least a portion of the first substrate is bonded to at least a portion of the second substrate by an adhesive.
In some embodiments, the aforementioned moisture-curable prepolymer is a moisture-curable aliphatic isocyanate-terminated prepolymer.
Drawings
Fig. 1 shows a cross-sectional view of an electronic component positioned between two substrates.
Fig. 2 shows a cross-sectional view of an electronic component positioned between two substrates with adhesive around the edges of the assembly.
Fig. 3 shows a cross-sectional view of an electronic component positioned between two substrates with adhesive throughout the assembly.
Glossary
In connection with the present invention, these terms have the following meanings:
"(meth) acrylate" means acrylate, methacrylate, and mixtures thereof.
"Dual cure" refers to compositions that cure by two different mechanisms, such as radiation to a radiation curable functional group and a chemical reaction between a moisture curable functional group (e.g., isocyanate functional group) and moisture (or water).
"aliphatic isocyanate-terminated prepolymer" refers to an isocyanate-terminated prepolymer that is the reaction product of an aliphatic isocyanate and a polyol.
Detailed Description
Adhesive composition
The adhesive composition is a one-part dual cure adhesive. In some embodiments, the adhesive composition comprises a mixture of a moisture curable prepolymer and a radiation curable component. In some embodiments, the adhesive composition comprises a moisture curable radiation curable prepolymer comprising moisture curable functional groups and radiation curable functional groups. In some embodiments, the adhesive composition comprises a mixture of moisture curable radiation curable prepolymers containing moisture curable functional groups and radiation curable functional groups, additional moisture curable prepolymers, and/or additional radiation curable components.
Because the adhesive cures by exposure to moisture and radiation, the adhesive is referred to as a "dual cure" adhesive. In practice, the applied adhesive composition produces an initial lap shear strength upon exposure to radiant energy, such as Ultraviolet (UV) light, by photopolymerization or crosslinking of the ethylenically unsaturated groups. Such compositions retain sufficient strength even at high temperatures compared to conventional hot melt adhesives. While not wanting to be bound by any theory, the initial lap shear strength is attributed to polymerization of the radiation curable functional groups (e.g., acrylate double bonds) upon exposure to radiation, thereby forming a network, albeit with slight crosslinking. The final properties of the adhesive composition result from the subsequent reaction of the moisture-curing functional groups with moisture.
The adhesive composition is a one-part, liquid composition that can be easily applied at ambient temperature. The composition preferably exhibits an initial lap shear strength of at least about 1 gram per square inch after exposure to radiant energy. The cured adhesive composition also preferably exhibits peel of at least 25 grams per lineal inchThe bond strength, or even the destructive bond exhibited to the substrate to which it is bonded. The composition preferably generates little or no volatile organic components, as well as provides a moisture barrier and exhibits no more than about 20 grams per square meter per day (g/m) in the form of a film having a thickness of about 60 mils2Day), or 15g/m2Day, or 10g/m2Moisture Vapor Transmission Rate (MVTR)/day. The composition preferably exhibits an elongation of at least about 10% or at least about 100% and preferably exhibits a glass transition temperature (Tg) of less than about 10 ℃ or-10 ℃.
When used with electronic assemblies, the adhesive preferably exhibits certain properties. For example, the adhesive is preferably capable of being processed at low temperatures on low cost substrates. It can preferably be used for automated roll-to-roll manufacturing processes. It preferably exhibits a quick attachment without the need for a B-stage. The composition preferably has a long open time or a long cure time. The composition preferably exhibits good initial strength and final bond strength compared to low energy materials such as plastics. It is also preferably flexible. It preferably exhibits good moisture and oxygen barrier properties. It is preferably optically transparent and does not yellow when exposed to ultraviolet radiation or higher temperatures. It preferably exhibits low air permeability and low voids. And it preferably acts as a desiccant or desiccant by consuming residual moisture inside the seal assembly.
The adhesive composition comprises at least one (moisture curable) first functional group capable of polymerizing upon exposure to moisture and at least one (radiation curable) second functional group capable of polymerizing upon exposure to radiation. Non-limiting examples of moisture curable functional groups include isocyanate functional groups, silane functional groups, and mixtures thereof. Non-limiting examples of radiation curable groups include ethylenically unsaturated groups such as acrylates, methacrylates, acryloyl groups such as acrylamide and acryloyloxy, methacryloyl groups such as methacrylamide and methacryloyloxy, and alkenyl groups such as vinyl, allyl, and hexenyl. These functional groups may be located at the side, end, or combinations thereof. Preferably, the functional group is terminal on the prepolymer, i.e., the prepolymer is end-capped with a functional group.
The number of reactive groups on the prepolymer is primarily controlled by the desired equivalent weight of the prepolymer. The higher the molecular weight of the prepolymer, the higher the elongation of the final product. However, this in turn reduces the reactive functionality present to achieve initial green strength. To achieve the desired properties, the functionality of the prepolymer must be balanced by adjusting the molar equivalents of the components in the resulting prepolymer.
As discussed above, the adhesive composition includes a combination of moisture curable functional groups and radiation curable functional groups.
In one embodiment, the adhesive composition comprises a mixture of a moisture curable prepolymer and a radiation curable component.
In one embodiment, the adhesive composition comprises a moisture curable radiation curable prepolymer comprising a moisture curable functional group and a radiation curable functional group.
In one embodiment, the adhesive composition comprises a mixture of a moisture curable radiation curable prepolymer comprising moisture curable functional groups and radiation curable functional groups and a further moisture curable prepolymer and/or a further radiation curable component.
The moisture-curable prepolymer, the radiation-curable component, and the moisture-curable radiation-curable prepolymer comprising a moisture-curable functional group and a radiation-curable functional group will now be discussed in more detail.
Moisture-curable prepolymer
The moisture curable prepolymer may be an isocyanate terminated polyurethane prepolymer or a silanized terminated prepolymer or a combination thereof. The silylated prepolymer includes silylated polyurethane prepolymer and other silylated prepolymer which are not polyurethane prepolymer. The number average molecular weight of the isocyanate-terminated or silanized-terminated polyurethane prepolymer is preferably from about 1500 to about 20,000 g/mol. Preferred isocyanate-terminated polyurethane prepolymers are described in U.S. patent No.6,355,317, which is incorporated herein by reference in its entirety. The preferably silanized terminated prepolymer as described above is terminated by at least one silane functional group and preferably contains no more than six silane functional groups. Most preferably, the moisture curable silane terminated prepolymer has less than about 25 mole equivalent percent, most preferably less than about 20 mole equivalent percent silane groups based on the mole equivalents of the prepolymer.
The moisture curable prepolymer is present in the adhesive composition in an amount of about 20 wt%, or about 30 wt%, to about 95 wt%, or to about 80 wt%, or to about 70 wt%, or to about 60 wt%, or to about 50 wt%, by weight of the composition.
The moisture curable prepolymer and radiation curable component are preferably present in a weight ratio of about 9:1 to about 1:9 or preferably about 4:1 to about 1: 4.
Isocyanate-terminated prepolymerThe isocyanate-terminated prepolymer is formed by reacting isocyanates with polyols. Isocyanates useful in preparing the prepolymer include any suitable isocyanate having at least two isocyanate groups including, for example, aliphatic, cycloaliphatic, araliphatic, aralkyl, alkaryl, and aromatic isocyanates, and mixtures thereof.
Preferred isocyanate-terminated prepolymers include those that are the reaction product of an aliphatic polyisocyanate and a polyol.
Such diisocyanates include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, pentamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate trimer, dodecamethylene diisocyanate, 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 4,4' -methylenebis (cyclohexyl isocyanate), methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate, 5-isocyanato-1- (isocyanatomethyl) -1,3, 3-trimethyl-cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 4 '-diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 4' -diphenylmethane diisocyanate, tolylene 2, 4-diisocyanate, tolylene 2, 6-diisocyanate, tolylene 4,4 '-toluidine diisocyanate, dimethoxyaniline diisocyanate (dianilidine diisocynate), 4' -diphenyl ether diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, omega '-diisocyanato-1, 4-diethylbenzene, methylene bis (4-cyclohexyl isocyanate), tetramethylene diisocyanate, toluene diisocyanate, 4' -methylenediphenyl diisocyanate, a blend of 2,4 '-methylenediphenyl diisocyanate and 4,4' -methylenediphenyl diisocyanate, 2',4' -diphenylmethane diisocyanate and naphthalene-1, 5-diisocyanate, and mixtures thereof. Other useful isocyanates are disclosed, for example, in U.S. Pat. Nos. 6,387,449, 6,355,317, 6,221,978, 4,820,368, 4,808,255, 4,775,719, and 4,352,858, which are incorporated herein.
Examples of other suitable diisocyanates include 1, 2-diisocyanatoethane, 1, 3-diisocyanatopropane, 1, 2-diisocyanatopropane, 1, 4-diisocyanatobutane, 1, 5-diisocyanatopentane, 1, 6-diisocyanatohexane, bis (3-isocyanatopropyl) ether, bis (3-isocyanatopropyl) sulfide, 1, 7-diisocyanatoheptane, 1, 5-diisocyanato-2, 2-dimethylpentane, 1, 6-diisocyanato-3-methoxyhexane, 1, 8-diisocyanatooctane, 1, 5-diisocyanato-2, 2, 4-trimethylpentane, 1, 9-diisocyanatononane, 1, 10-diisocyanatopropyl ether of 1, 4-butanediol, 1, 11-diisocyanatoundecane, 1, 12-diisocyanatododecane, bis (isocyanatohexyl) sulfide, 4-diisocyanatobenzene, 1, 3-diisocyanatooxyxylene, 1, 3-diisocyanato-xylene, 1, 3-diisocyanato-metaxylene, 2, 4-diisocyanato-1-chlorobenzene, 2, 4-diisocyanato-1-nitrobenzene, 2, 5-diisocyanato-1-nitrobenzene, m-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, a mixture of 2, 4-and 2, 6-toluene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 4-cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 1, 5-naphthalene diisocyanate, 1-methoxy-2, 4-phenylene diisocyanate, 4 '-diphenylmethane diisocyanate, 4' -biphenylene diisocyanate, 3 '-dimethyl-4, 4' -diphenylmethane diisocyanate and 3,3 '-dimethyldiphenylmethane-4, 4' -diisocyanate and 3,3 '-dimethyldiphenylmethane-4, 4' -diisocyanate.
Examples of suitable polyisocyanates include, for example, the triisocyanates such as 4,4',4 "-triphenylmethane triisocyanate and 2,4, 6-toluene triisocyanate; tetraisocyanates such as 4,4' -dimethyl-2, 2' -5,5' -diphenylmethane tetraisocyanate and polymethylene polyphenylene polyisocyanate.
Particularly preferred diisocyanates are aliphatic isocyanates or blends of aliphatic isocyanates because they provide excellent uv stability (no yellowing) and hydrolytic stability.
Useful aliphatic polyisocyanates include, for example, 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, hydrogenated MDI (i.e., dicyclohexylmethane diisocyanate, H12-MDI), methyl 2, 4-cyclohexane diisocyanate, methyl 2, 6-cyclohexane diisocyanate, 1, 4-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane.
Commercially available aliphatic isocyanates that may be used include, for example, DESMODUR W, DESMODUR I and DESMODUR N3600, all available from Bayer, Pittsburg, Pa., and VESTANAT IPDI and VESTANAT H12MDI available from Evonik Degussa, Parsippany, N.J.).
Suitable polyols that may be used to prepare the prepolymer include, for example, diols, triols, and mixtures thereof. Preferred polyols include polyester polyols, polyolefin glycols, polyether polyols, polydiene block polyols and combinations thereof. Preferred polyols have a functionality of at least about 1.5, more preferably at least about 1.8, most preferably at least about 2, preferably not more than about 4.0, more preferably not more than about 3.5, most preferably not more than about 3.0. Preferred polyols are amorphous, have a Tg of less than about 0 deg.C, preferably less than about-20 deg.C, and a molecular weight of greater than about 500g/mol, more preferably greater than about 500g/mol to about 15,000g/mol, most preferably about 1000g/mol to about 12,000 g/mol. Preferred polyols are hydrophobic, preferably predominantly hydrocarbon in structure.
Useful polyols include, for example, polyester polyols including, for example, lactone polyols and alkylene oxide adducts thereof, and dimer acid-based polyester polyols; specialty polyols, including, for example, polybutadiene polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, hydroxyalkyl derivatives of bisphenol a (e.g., bis (2-hydroxyethyl) bisphenol a), polythioether polyols, fluorinated polyether polyols, acrylic polyols, alkylene oxide adducts of polyphenols, polytetramethylene glycols, functionalized glycerides (e.g., castor oil), and polyhydroxy vulcanized polymers.
Useful polyester polyols are prepared from the reaction product of polycarboxylic acids, anhydrides thereof, esters thereof or halides thereof and a stoichiometric excess of a polyol. Suitable polycarboxylic acids include dicarboxylic acids and tricarboxylic acids, including, for example, aromatic dicarboxylic acids and anhydrides and esters thereof (e.g., phthalic acid, terephthalic acid, isophthalic acid, dimethyl terephthalate, diethyl terephthalate, phthalic acid, phthalic anhydride, methylhexahydrophthalic acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and tetrahydrophthalic acid), aliphatic dicarboxylic acids and anhydrides thereof (e.g., maleic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid, 1,2, 4-butane-tricarboxylic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid, and fumaric acid), and alicyclic dicarboxylic acids (e.g., 1, 3-cyclohexanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid).
Examples of suitable polyols from which the polyester polyols may be derived include ethylene glycols, propane glycols (e.g., 1, 2-and 1, 3-propanediol), butane glycols (e.g., 1, 3-butanediol), 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, polypropylene glycols (e.g., dipropylene glycol and tripropylene glycol), 1, 4-cyclohexanedimethanol, 1, 4-cyclohexanediol, dimer glycols, bisphenol A, bisphenol F, hydrogenated bisphenol A and hydrogenated bisphenol F, glycerol, and combinations thereof.
Examples of useful polyester polyols include polyglycol adipates, polyethylene terephthalate polyols, polycaprolactone polyols, and polycaprolactone triols.
Suitable commercially available polyols include, for example, dimer acid based polyester polyols available from procollagen (Croda) under the trade name PRIPLAST series (including, for example, PRIPLAST3187, 3190, 3196, and 3197); polyester polyols available under the trade names DESMOPHEN series (including, for example, DESMOPHEN XF-7395-. Exemplary polybutadiene polyols are available from Cray Valley, Pa., under the tradenames POLYBD R-20LM, R-45HT, and R-45M, and hydrogenated polybutadiene polyols are available from Mitsubishi chemical Corp., Japan, under the tradename POLYTAIL.
Useful polyether polyols are prepared from polyoxyalkylenes. Non-limiting examples of suitable polyether polyols include polyethylene oxide, polypropylene oxide, polytetramethylene ether glycol. Useful polyether polyols also include reaction products of polyols and polyalkylene oxides. Polyols useful in the preparation of the polyether polyols include ethylene glycol, propylene glycol, butylene glycols, hexylene glycols, glycerol alcohols, trimethylolethane, trimethylolpropane and pentaerythritol and mixtures thereof. The alkylene oxides useful in the preparation of the polyether polyols include ethylene oxide, propylene oxide and butylene oxide, and mixtures thereof. Suitable polyether polyols include products resulting from the polymerization of cyclic oxides such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, or the addition of one or more such oxides with polyfunctional initiators having at least two active hydrogens such as water, polyols (e.g., ethylene glycol, propylene glycol, diethylene glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, pentaerythritol and bisphenol a), ethylenediamine, propylenediamine, triethanolamine and 1, 2-propanedithiol. Particularly useful polyether polyols include, for example, polyoxypropylene glycols and triols, poly (oxyethylene-oxypropylene) glycols and triols obtained by the simultaneous or sequential addition of ethylene oxide and propylene oxide to a suitable initiator, and polytetramethylene ether glycols obtained by the polymerisation of tetrahydrofuran.
Silanized end-capped prepolymersThe silylated terminated prepolymer is formed by reacting a silane functional compound having a reactive functional group capable of reacting with isocyanate or hydroxyl functional groups (e.g., polyol). An organofunctional silane useful for preparing a prepolymer comprises at least one functional group that reacts with an isocyanate group of a polyurethane prepolymer (For example hydrogen) and has at least one silyl group. Another organofunctional silane useful for preparing the prepolymer contains at least one functional group reactive with a polyol or an-OH terminated polyurethane and has at least one silyl group. Examples of useful silyl groups include alkoxysilyl groups, aryloxysilylsilyl groups, alkoxyiminosilyl groups, oximinosilyl groups, and aminosilyl groups.
Preferred hydrogen-reactive organofunctional silanes include, for example, amino silanes (e.g., secondary aminoalkoxysilanes and mercaptoalkoxysilanes). Examples of suitable aminosilanes include phenylaminopropyltrimethoxysilane, methylaminopropyltrimethoxysilane, n-butylaminopropyltrimethoxysilane, t-butylaminopropyltrimethoxysilane, cyclohexylaminopropyltrimethoxysilane, dibutylaminopropenyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, dibutylamate-substituted 4-amino 3, 3-dimethylbutyltrimethoxysilane, aminopropyltriethoxysilane, and mixtures thereof. Specific examples of the aminosilanes include N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxysilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropylmethyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3- (N-methyl-3-amino-1-methyl-1-ethoxy) propyltrimethoxysilane, N-methyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-1-methyl-1-ethoxy) propyltrimethoxysilane, N-ethyl-4-amino-3, 3-dimethylbutyldimethoxymethylsilane, N-ethyl-4-amino-3, 3-dimethylbutyltrimethoxysilane, bis (3-trimethoxysilyl-2-methylpropyl) amine, N- (3' -trimethoxysilylpropyl) -3-amino-2-methylpropyltrimethoxysilane, N-bis [ (3-triethoxysilyl) propyl ] amine, N-bis [ (3-tripropoxy-silyl) propyl ] amine, N- (3-trimethoxysilyl) propyl-3- [ N- (3-trimethoxysilyl) -propylamino ] propionamide, N-ethyl-4-amino-3, 3-dimethylbutyltrimethoxysilane, N- (3-trimethoxysilyl) -2-methylpropyl-trimethoxysilane, N-bis [ (3-triethoxysilyl) propyl ] amine, N-bis [ (, N- (3-triethoxysilyl) propyl-3- [ N-3-triethoxysilyl) -propyl-amino ] propanamide, N- (3-trimethoxysilyl) propyl-3- [ N-3-triethoxysilyl) -propylamino ] propanamide, 3-trimethoxysilylpropyl 3- [ N- (3-trimethoxysilyl) -propylamino ] -2-methylpropionate, 3-triethoxysilylpropyl 3- [ N- (3-triethoxysilyl) -propylamino ] -2-methylpropionate, 3-trimethoxysilylpropyl 3- [ N- (3-triethoxysilyl) -propylamino ] -2-methylpropionate Esters, gamma-mercaptopropyl-trimethoxysilane and N, N' -bis ((3-trimethoxysilyl) propyl) amine.
Commercially available aminosilanes that may be used include, for example, those available under the trade names SILQUEST series (including, for example, SILQUEST A-1170, SILQUEST A-1110, SILQUEST Y-9669, and SILQUEST A-15) from Connecticut Glynergen Meigy Milligy (Momentive, Greenwich, Conn.), those available under the trade names DYNASYLAN series (including, for example, DYNASYLAN1189N- (n-butyl) aminopropyltrimethoxysilane and DYNASYLAN MTMO 3-mercaptopropyltrimethoxysilane) from Degussa Corporation of Nervell, Ill., and those available under the trade names SILQUEST A-189 gamma-mercaptopropyltrimethoxysilane from Megine (Momentive).
Useful isocyanatoalkoxysilanes include, for example, gamma-isocyanatopropyltriethoxysilane and gamma-isocyanatopropyltrimethoxysilane, which are commercially available under the trade names SILQUEST A-35 and SILQUEST A-25 from Momentive.
Other useful silane terminated polyurethanes are PERMAPOL urethanes described in U.S. Pat. No.4,960,844 and silylated polyurethane compositions described in U.S. Pat. No.6,498,210, which are incorporated herein by reference. Other useful silane-functionalized moisture-curable prepolymers that are not polyurethanes include silyl-terminated polyethers available under the tradenames kanekas POLYMERs and KANEKA SILYL; and silyl terminated polyisobutylenes available under the trade name KANEKA epicon, all available from U.S. donuina, New York (KANEKA America Corporation, New York, NY).
Radiation curable component
The radiation curable component is present in the adhesive composition in an amount of about 5 wt%, or about 15 wt%, or about 20 wt% to about 80 wt%, or to about 60 wt%, by weight of the composition. The radiation curable component may be a monomer, oligomer or polymer. Oligomers are compounds which generally contain on average 2 to 10 base structures or monomer units. In contrast, polymers are compounds that generally contain on average at least more than 10 base structures or monomer units. The radiation curable component is preferably derived from monomers, oligomers and polymers of acrylates, such as (meth) acrylates, or combinations thereof.
Suitable acrylates include (meth) acrylates including, for example, acrylic and methacrylic esters prepared from acrylic and/or methacrylic acid and aliphatic alcohols, aromatic polyols, aliphatic polyols, cycloaliphatic polyols, and combinations thereof, (meth) acrylates of polyether alcohols, urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and combinations thereof. The number average molecular weight of the unmodified acrylate will generally be from about 500 to 50,000g/mol, preferably from 1000 to 5000 g/mol.
Exemplary acrylate monomers include acrylates of aliphatic diols containing 2 to about 40 carbon atoms, such as neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and (meth) acrylates of sorbitol and other sugar alcohols. The (meth) acrylates of these aliphatic or cycloaliphatic diols may be modified with aliphatic esters or alkylene oxides. Exemplary acrylates modified by aliphatic esters include neopentyl glycol hydroxypivalate di (meth) acrylate, caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylate, and the like. The alkylene oxide-modified acrylate compound includes, for example, ethylene oxide-modified neopentyl glycol di (meth) acrylates, propylene oxide-modified neopentyl glycol di (meth) acrylates, ethylene oxide-modified 1, 6-hexanediol di (meth) acrylates or propylene oxide-modified 1, 6-hexanediol di (meth) acrylates, or a mixture of two or more thereof.
Acrylate monomers based on polyether polyols include, for example, neopentyl glycol modified trimethylolpropane di (meth) acrylates, polyethylene glycol di (meth) acrylates, propylene glycol di (meth) acrylates, and the like. Trifunctional or higher acrylate monomers include, for example, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [ (meth) acryloyloxyethyl ] isocyanurate, caprolactone-modified tris [ (meth) acryloyloxyethyl ] isocyanurate or trimethylolpropane tetra (meth) acrylate, or mixtures of these.
Preferred acrylates include tripropylene glycol diacrylate, neopentyl glycol polyoxypropylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol triacrylate.
Exemplary acrylates of aliphatic alcohols include, for example, isobornyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, and combinations thereof. Useful acrylates of aliphatic diols include, for example, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and (meth) acrylates of sorbitol and other sugar alcohols. The (meth) acrylates of these aliphatic and cycloaliphatic diols may be modified with aliphatic esters or with alkylene oxides. Acrylates modified by aliphatic esters include, for example, neopentyl glycol hydroxypivalate di (meth) acrylate, caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylate, and combinations thereof. The alkylene oxide-modified acrylate compound includes, for example, ethylene oxide-modified neopentyl glycol di (meth) acrylates, propylene oxide-modified neopentyl glycol di (meth) acrylates, ethylene oxide-modified 1, 6-hexanediol di (meth) acrylates, or propylene oxide-modified 1, 6-hexanediol di (meth) acrylates, and combinations thereof.
Suitable multifunctional (meth) acrylate monomers include, for example, tripropylene glycol diacrylate, neopentyl glycol polyoxypropylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol triacrylate, and combinations thereof.
Exemplary acrylate oligomers include acrylated polyesters, acrylated aromatic urethanes, aliphatic urethanes, vinyl acrylates, acrylated oils, and acrylated acrylics. Examples of acrylated aliphatic urethanes include those available under the trade designation PHOTOMER6010(MW =1500) from Hopkincoko, N.J., Henkel Corp., Hoboken, N.J.), EBECRYL8401(MW =1000), and EBECRYL8402 (MW =1000, urethane diacrylate) from UCB Radcure, Inc., UCB Radcure, Smyrna, Ga., of Mermania, and CN9635, CN9645, and CN9655 from Sarton Saddoma, Sartomer, Exton, Pa., of Georgia.
Exemplary acrylate polymers include polybutadiene diacrylate, polybutadiene urethane diacrylate, mono-and multifunctional acrylates (i.e., acrylates and methacrylates), acrylated polyesters, acrylated aromatic urethanes, acrylated aliphatic urethanes, acrylated acrylics, and combinations or blends thereof.
Preferred acrylates are hydrophobic, have a predominantly hydrocarbon structure, have a low Tg (preferably below about 0 ℃, more preferably below about-10 ℃) and have sufficient compatibility with moisture-curable prepolymers. Such acrylates are commercially available as BAC-45 from San ester company (SanEsters corporation, a distributor of Osaka organic chemical Industry Ltd., Osaka, Japan) and CN302 from Sartomer, Exton, Pa., Osaka, Inc.
Moisture-curable radiation-curable prepolymer
The moisture curable radiation curable prepolymer includes moisture curable and radiation curable functional groups. Exemplary moisture curable functional groups include isocyanate and/or silane functional groups as discussed above for the moisture curable prepolymer. These functional groups may be located at the side, end, or combinations thereof on the prepolymer. Preferably, the functional group is terminal on the prepolymer, i.e., the prepolymer is end-capped with a functional group. Examples of radiation curable functional groups on the moisture curable radiation curable prepolymer include monomers, oligomers, and polymers of (meth) acrylates and combinations thereof as described above for the radiation curable component.
The moisture curable radiation curable prepolymer preferably contains about 5 wt%, or about 10 wt% to no more than 50 wt% isocyanate and/or silane functional groups, and an amount of radiation curable functional groups sufficient to provide a composition that exhibits lap shear strength suitable for subsequent processing when exposed to radiation.
The equivalent ratio of radiation curable functional groups to moisture curable functional groups is preferably from about 0.1:1 to about 5:1, or from about 0.5:1 to about 4:1, or from about 0.6:1 to about 3:1, or about 1: 1. The average functionality of the moisture curable radiation curable prepolymer is preferably at least about 1.8, or about 2 and not more than about 8, or not more than about 4. The number average molecular weight of the moisture curable radiation curable prepolymer is preferably from about 200 to about 100,000g/mol, or from about 400 to about 50,000g/mol, or from about 600 to about 10,000 g/mol.
The moisture curable radiation curable prepolymer comprises the reaction product of any of the foregoing moisture curable prepolymers and any of the foregoing radiation curable components.
In one embodiment, the moisture-curable radiation-curable prepolymer is preferably prepared by reacting a compound comprising an active hydrogen and a radiation-curable functional group (e.g., the aforementioned radiation-curable component) with a polyisocyanate prepolymer (e.g., the aforementioned moisture-curable isocyanate-terminated polyurethane prepolymer), preferably in the presence of an excess of isocyanate. Preferably, the compound comprising active hydrogen and radiation curable functional groups is reacted with the isocyanate functional prepolymer in an amount such that from about 10% to about 80%, or from about 20% to about 70%, or from about 30% to about 60% of the isocyanate groups on the isocyanate functional prepolymer are replaced by the compound comprising active hydrogen and radiation curable functional groups.
The term "active hydrogen" refers to an active hydrogen on a hydroxyl, amine, or sulfhydryl functional group.
Examples of radiation curable functional groups include acrylate, methacrylate, alkenyl groups (e.g., vinyl, allyl, and hexenyl), vinyl ether, vinyl ester, vinyl amide, maleate, fumarate, and styrene functional groups, and combinations thereof.
In another embodiment, the moisture curable radiation curable prepolymer is preferably prepared by reacting a compound comprising an active hydrogen and a radiation curable functional group with a polyisocyanate prepolymer, preferably in the presence of an excess of isocyanate (which may be silane terminated). Suitable isocyanates and polyols and suitable organofunctional silanes are described above. Suitable compounds containing active hydrogen and radiation curable functional groups include, for example, hydroxyalkyl esters of acrylic and methacrylic acid (e.g., 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate (HPA) and 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 1, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl acrylate and methacrylic acid, 2-hydroxyethyl acrylamide and methacrylamide, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and mixtures thereof, 1, 4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphates, 4-hydroxycyclohexyl (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, N-alkyl-N-hydroxyethyl acrylamides and methacrylamides, β -carboxyethyl hydroxyethyl acrylate, hydroxyhexyl acrylate and hydroxyoctyl methacrylate, and mixtures thereof.
Useful hydroxyethyl acrylates and hydroxypropyl acrylates are commercially available from Dow Chemical company, Midland michi, Midland, michigan and Osaka Organic Chemical Industry co. Useful hydroxybutyrates are commercially available from Osaka Organic chemical industry Ltd. Useful hydroxy polyester acrylates are commercially available from the Dow Chemical Company under the trade name TONMONOMER M-100 and VISCOAT2308 from Osaka Organic Chemical industry Ltd. Useful hydroxy polyether acrylates are commercially available from Bayer Chemicals, Pittsburgh, Pa., under the trade designation ARCOL R-2731.
Other additives
The adhesive may optionally include other additives including, for example, antioxidants, photoinitiators, plasticizers, tackifiers, adhesion promoters, non-reactive resins, uv stabilizers, catalysts, rheology modifiers, defoamers, biocides, corrosion inhibitors, dehydrating agents, organic solvents, colorants (e.g., pigments and fuels), fillers, surfactants, flame retardants, waxes, reactive plasticizers, thermoplastic polymers, tackifiers, organofunctional silane adhesion promoters, and mixtures thereof.
The adhesive may optionally include a photoinitiator. Suitable photoinitiators are capable of promoting free radical polymerization, or crosslinking, or both, of the ethylenically unsaturated moieties upon exposure to radiation of a suitable wavelength and intensity. The photoinitiators can be used alone or in combination with suitable donor compounds or suitable coinitiators. The photoinitiator and its amount are preferably selected to achieve consistent reaction conversion, depending on the thickness of the cured composition, and a sufficiently high degree of overall conversion to achieve the desired green handling strength (i.e., green strength).
Useful photoinitiators include, for example, "alpha cleavage-type" photoinitiators including, for example, benzyl dimethyl ketal, benzoin ethers, hydroxyalkyl phenyl ketones, benzoyl cyclohexanol, dialkoxy acetophenone ketones, 1-hydroxycyclohexyl phenyl ketone, trimethylbenzoylphosphine oxide, methylthiophenyl morpholinones, and morpholinophenyl aminoketones; hydrogen abstraction photoinitiators comprising photoinitiators and coinitiators based on benzophenones, thioxanthones, benzyl, camphorquinones and coumarones; and combinations thereof. Preferred photoinitiators include acylphosphine oxides including, for example, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) phosphine oxide, and 2,4, 4-trimethylbenzoyldiphenylphosphine oxide.
Useful commercially available photoinitiators are available under the following trade names: IRGACURE369 morpholinophenylamino ketones, IRGACURE819 bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and its preferred forms CGI819XF, IRGACURE CGI403 bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) phosphine oxide, IRGACURE651 benzyl dimethyl ketal, IRGACURE184 benzoylcyclohexanol, DAROCUR1173 hydroxyalkylphenylketones, DAROCUR 42652-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide 50:50 blends and 1700 25:75 blends of bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine and 2-hydroxy-2-methyl-1-phenylpropan-1-one, all of which are available from BASF corporation (BASF).
The photoinitiator is preferably present in an amount sufficient to provide the desired rate of photopolymerization. The amount will depend in part on the light source, the thickness of the layer to be exposed to the radiant energy, and the extinction coefficient of the photoinitiator at the respective wavelength. Typically, the photoinitiator component will be present in an amount of up to about 5% by weight, or from about 0.01% to about 5% by weight, more preferably from about 0.01% to about 1% by weight, based on the weight of the composition. The adhesive may optionally comprise a plasticizer. Suitable plasticizers include, for example, phthalates, benzoates, sulfonamides, and mixtures thereof, and epoxidized soybean oil. Useful sources of dioctyl phthalate and diisodecyl phthalate include those available from Exxon Chemical under the tradenames JAYFLEXDOP and JAYFLEX DIDP. Useful dibenzoates are available from Istman Chemical company (Eastman Chemical Co.) under the tradenames BENZOFLEX9-88, BENZOFLEX50, and BENZOFLEX 400. Soybean oil is commercially available, for example from Dow Chemical under the trade name FLEXOL EPO.
The plasticizer, when present, is preferably present in an amount of about 0.25 to about 10 weight percent, no more than about 5 weight percent, no more than about 3 weight percent, or even about 0.5 to 2 weight percent.
The adhesive may also optionally comprise a reactive plasticizer, i.e., a plasticizer comprising at least one functional group capable of reacting with the moisture-reactive component of the moisture-curable, radiation-curable polyurethane prepolymer, or the moisture-curable polyurethane prepolymer, or a combination thereof. The term "reactive plasticizer" encompasses plasticizers which become capable of reacting with the moisture reactive groups of the polyurethane prepolymer or with themselves upon exposure to moisture. Such reactive plasticizers include plasticizers that have active hydrogen groups when exposed to moisture. The reactive plasticizer is preferably selected to have functional groups similar to those of the polyurethane prepolymer, functional groups that will become capable of reacting with the polyurethane prepolymer or the plasticizer itself after application of the composition to a substrate or during its intended use (e.g., upon exposure to ambient atmosphere, such as air, moisture, or combinations thereof), or combinations of such functional groups. The reactive plasticizer is preferably selected to polymerize or crosslink the polyurethane prepolymer upon exposure to ambient conditions (e.g., moisture, air, or a combination thereof). The reactive plasticizer may comprise any suitable reactive group, such as alkoxy groups, isocyanates, aldimines, ketimines, bisoxazolidinones, and combinations thereof.
Examples of useful reactive plasticizers capable of reacting with the silane-functionalized polyurethane prepolymer include plasticizers having alkoxysilyl reactive groups (including, for example, methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl groups) and acyloxysilyl reactive groups, such as silyl esters of various acids (including, for example, acetic acid, 2-ethylhexanoic acid, palmitic acid, stearic acid, and oleic acid, and combinations thereof). Suitable reactive plasticizers also include polymers terminated with the above-described alkoxysilyl groups. Such polymers include, for example, polyalkyleneoxides (e.g., polypropylene oxides), polyether-sulfide-urethanes (e.g., low molecular weight PERMAPOL urethanes derived from PRC and as disclosed, for example, in U.S. Pat. No.4,960,844), polyisoalkylene oxides (e.g., polyisobutylene oxide), polyglycols, polyisobutylene, and combinations thereof.
Useful reactive plasticizers capable of reacting with the isocyanate functional polyurethane prepolymer include, for example, aldimines, ketimines, oxazolidines (e.g., bisoxazolidines, 1- (hydroxyethyl) -2-isopropyl-1, 3-oxazolidine, and 2-isopropyl-1, 3-oxazolidine), dioxolanes (e.g., 2-dimethyl-1, 3-dioxolane, 2-dimethyl-4-hydroxymethyl-1, 3-dioxolane), and combinations thereof.
The molecular weight of the reactive plasticizer is preferably from about 300g/mol to about 10,000g/mol, more preferably from about 500g/mol to about 6000 g/mol.
The reactive plasticizer is present in the composition in an amount of no more than about 20% by weight, preferably from about 2% to about 15% by weight, more preferably from about 3% to about 10% by weight.
Suitable reactive plasticizers can be cured by actinic radiation or heat. If used, the reactive plasticizer is preferably cured by actinic radiation, most preferably ultraviolet radiation. Exemplary reactive plasticizers are positionally isomeric diethyloctyl glycols or hydroxyl-containing hyperbranched compounds or dendrimers, or polycarbonate glycols, polyester polyols, poly (meth) acrylate glycols or hydroxyl-containing polyadducts.
Examples of suitable reactive solvents that may be used as reactive plasticizers include, but are not limited to, butanediol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, trimethylolpropane, ethyl 2-hydroxypropionate or 3-methyl-3-methoxybutanol, and propylene glycol-based derivatives such as ethoxyethyl propionate, isopropoxypropanol or methoxypropyl acetate.
Preferred reactive plasticizers include (meth) acrylic acids and esters thereof, maleic acid and esters thereof (including monoesters), vinyl acetate, vinyl ethers, vinyl ureas, and the like. Additional examples include alkylene glycol di (meth) acrylates, polyethylene glycol di (meth) acrylates, 1, 3-butylene glycol di (meth) acrylates, vinyl (meth) acrylates, allyl (meth) acrylates, glycerol tri (meth) acrylates, trimethylolpropane di (meth) acrylates, styrene, vinyl toluene, divinylbenzene, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, propylene glycol di (meth) acrylates, hexanediol di (meth) acrylates, carbitol acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl (meth) acrylate, butoxyethyl acrylate, and mixtures thereof, Isobornyl (meth) acrylate, dimethylacrylamide, dicyclopentyl acrylate, long-chain linear diacrylates of molecular weight 400 to 4000, preferably 600 to 2500, described in EP0250631a 1. For example, two acrylate groups may be separated by a polyoxybutylene structure. It is also possible to use 1, 12-dodecylpropylene glycol and the reaction product of 2 moles of acrylic acid with one mole of a dimer fatty alcohol, usually having 36 carbon atoms. Mixtures of the foregoing monomers are also suitable.
The binder may optionally comprise a catalyst. Suitable catalysts facilitate the reaction between the polyol and polyisocyanate, hydrolysis, and/or subsequent crosslinking of the silane groups, isocyanate groups, or combinations thereof. Useful catalysts include, for example, tertiary amines including, for example, N-dimethylaminoethanol, N-dimethyl-cyclohexylamine-bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N', N "-pentamethyl-diethylene-triamine, and 1-2 (hydroxypropyl) imidazole; and metal catalysts including, for example, tin (e.g., dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin diacetate; stannous salts of carboxylic acids such as stannous octoate and stannous acetate; tetrabutyl dioleoyl distannoxane), titanium compounds, bismuth carboxylates, organosilicone titanates, alkyl titanates, and combinations thereof.
For moisture curable, radiation curable compositions, the catalyst is preferably present in an amount of about 0.01 wt% to about 2 wt%.
The adhesive may optionally include a filler. Suitable fillers include, for example, fumed silica, precipitated silica, talc, calcium carbonate, carbon black, aluminum silicate, clay, zeolite, ceramic, mica, titanium dioxide, and combinations thereof. When present, the adhesive preferably comprises filler in an amount of at least 0.5 wt%, from about 1 wt% to about 50 wt%, or even from about 5 wt% to about 10 wt%. For most applications, no filler will be used to maintain transparency.
The adhesive may optionally comprise a thermoplastic polymer. Commercially available thermoplastic polymers include, for example, random polypropylene copolymers available under the trade name REXTAC series (including, for example, REXTAC RT2535 and RT 2585) from Rexene Products, daras Products co., Dallas, Tex, and from EASTOFLEX Chemical company, Eastman, tennessee, including, for example, EASTOFLEX E1060; ethylene-vinyl acetate copolymers available under the trade name ELVAX series from DuPont de Nemours, Wilmington, Del, and available under the trade name ultrethene series from mlindns and medley petrochemicals, millennium petrochemicals, Rolling Meadows, ll; ethylene-methyl acrylate copolymers available under the trade name OPTEMA series from Exxon chemical co., Houston, Tex; ethylene n-butyl acrylate copolymers available as the LOTRYL series from Sartomer, philiadelphia, Pa, Philadelphia, Pa, under the trade name ESCORENE series from Exxon Chemical Co, and from american petroleum chemicals under the trade name ENATHENE series; ethylene-n-butyl acrylate-carbon monoxide terpolymers available from DuPont under the trade name ELVALOY series; thermoplastic polyurethane polymers available under the trade name PEARLSTICK series from Aries Technologies, Derry, N.H, a distributor of the company Barcelona mercuria, Spain; butene/poly (alkylene ether) phthalate polymers available from DuPont under the trade name HYTREL series; ethylene-acrylate copolymers available under the trade name ELVALOY series also from DuPont; and acrylic polymers available from st louis ICI Acrylics, st.
The thermoplastic polymer is present in the composition in an amount of about 0 wt.% to about 15 wt.%, preferably about 0 wt.% to about 10 wt.%.
The adhesive may optionally comprise a tackifier. Preferred tackifiers have a ball and ring softening point of from about 70 ℃ to about 120 ℃, more preferably from about 80 ℃ to about 100 ℃. Examples of suitable tackifiers include aliphatic, cycloaliphatic, aromatic, aliphatic aromatic, aromatic modified cycloaliphatic and cycloaliphatic hydrocarbon resins and modified forms and hydrogenated derivatives thereof; terpenes (e.g., polyterpenes), modified terpenes (e.g., phenolic modified terpene resins), hydrogenated derivatives thereof, and mixtures thereof; natural and modified rosins such as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; rosin esters including, for example, glycerol and pentaerythritol esters of natural and modified rosins (e.g., glycerol esters of pale rosin, glycerol esters of hydrogenated rosin, glycerol esters of polymerized rosin, pentaerythritol esters of hydrogenated rosin, and phenolic-modified pentaerythritol esters of rosin); alpha methyl styrene resins and hydrogenated derivatives thereof; low molecular weight polylactic acid; and combinations thereof. Other useful tackifiers are disclosed, for example, in U.S. patent No.6,355,317, incorporated herein.
Suitable commercially available tackifiers include, for example, partially hydrogenated cycloaliphatic petroleum hydrocarbon resins available under the trade names easotac series (including easotac H-100, H-115, H-130, and H-142, providing grades E, R, L and W with varying degrees of hydrogenation from lowest hydrogenation (E) to highest hydrogenation (W)) from Eastman Chemical co, Kingsport, Tenn, available under the trade names ESCOREZ series (including ESCOREZ5300 and ESCOREZ 5400) from Houston Exxon, Houston, Tex, and hercol 2100; a partially hydrogenated, aromatic modified petroleum hydrocarbon resin available under the trade name ESCOREZ5600 from Exxon chemical co; an aliphatic aromatic petroleum hydrocarbon resin available under the tradename WINGTACK EXTRA; styrenated terpene resins made from d-limonene, available from Arizona Chemical Co., Panamacity, Fla., under the tradename ZONATAC105 LITE; aromatic hydrogenated hydrocarbon resins available from Hercules under the trade name REGALREZ1094 (Hercules); and alpha methyl styrene resins available from Hercules under the trade names KRISTALEX3070, 3085 and 3100 (which have softening points of 70 ℃,85 ℃ and 100 ℃ respectively).
For those adhesive compositions comprising ethylene vinyl acetate, the tackifier is preferably selected based on the vinyl acetate content of the ethylene vinyl acetate copolymer. For ethylene-vinyl acetate copolymers having a vinyl acetate content of at least 28 weight percent, the tackifier is preferably an aromatic or aliphatic aromatic resin having a ball and ring softening point of from 70 ℃ to about 120 ℃. For vinyl acetate copolymers having a vinyl acetate content of less than 28 wt.%, the tackifier is preferably an aliphatic or aliphatic aromatic resin having a ball and ring softening point of from 70 ℃ to about 120 ℃.
The tackifier is present in the composition in an amount of about 0 wt% to about 10 wt%, preferably about 0 wt% to about 5 wt%.
Methods of making and using
The disclosed adhesives may be used throughout an electronic manufacturing process. In some embodiments, an adhesive is used to bond the layers of the assembly together. An exemplary multi-layer assembly is shown in fig. 1. Fig. 1 shows a generic assembly 10. The assembly 10 includes a first substrate 12 and a second substrate 14. Assembly 10 includes at least one electronic component 20 positioned between substrate 12 and substrate 14. It should be understood that the assembly 10 may include more than one electronic component 20 as shown in fig. 1.
Assembly 10 may optionally include conductive layers 16 and 18 positioned between electronic component 20 and substrates 12 and 14. The conductive layer may be a conductive coating, a conductive ink, or a conductive adhesive. The conductive layer may be continuous or discontinuous along the substrate. An exemplary conductive layer is Indium Tin Oxide (ITO). Electronic component 20 may be disposed between first substrate 12 and second substrate 14 in a manner that allows direct or indirect electrical communication with conductive layers 16 and 18. Direct conduction may be intimate contact, while indirect conduction may be via conductive materials or media. It may be desirable for one side of the electronic component to correspond to the anode side and the other side to correspond to the cathode side.
The adhesive may be used to bond or seal the layers of the assembly 10 together by applying an adhesive 24 to the edges of the assembly as shown in fig. 2 or by flooding the assembly with the adhesive 24 as shown in fig. 3.
The disclosed adhesive compositions are useful in the manufacture of electronic components. The adhesive composition may also function as a conductive adhesive, a semiconductive adhesive, an insulative adhesive, or an encapsulant when used with an electronic device. The assembly may include a plurality of electronic components. Exemplary electronic components include Light Emitting Diodes (LEDs), organic LEDs, high brightness LEDs, Radio Frequency Identification (RFID) tags, electrochromic displays, electrophoretic displays, batteries, sensors, solar cells, and photovoltaic cells.
The use of adhesives to adhere substrates together or to seal an electronic device between two substrates can provide benefits such as protecting the components from effects such as moisture, ultraviolet radiation, oxygen, and the like. It also avoids the escape of gas from the material in the assembly. It also allows electrons to move between the two substrates.
In some embodiments, the disclosed adhesives can be used to laminate a plurality of electronic components between two flexible substrates. In particular, the adhesive may be used to bond at least two substrates together, at least one of the substrates having at least one electronic component thereon prior to application of the adhesive. An exemplary lamination process includes a roll-to-roll manufacturing process. The adhesive may be applied to the substrate in a variety of ways. For example, the adhesive may be applied in a liquid state. The adhesive may be applied using any suitable coating process including, for example, air knife, spray, drag knife, spray, brush, dip, doctor blade, roll coating, gravure coating, rotogravure coating, linear extruder, hand spray gun, extruder bead, and combinations thereof. The adhesive may also be printed in a predetermined pattern. The adhesive may also be applied to a release liner wherein the adhesive/liner composite is adhered to a substrate.
The adhesive composition is preferably liquid at room temperature. Useful coating temperatures are in the range of 65 ° f to 170 ° f. The thickness of the coating of the adhesive can vary widely depending on the desired properties of the laminate. After the adhesive is applied to at least a portion of the first substrate, the first substrate is contacted with a second substrate. At least one of the substrates has at least one electronic component thereon prior to application of the adhesive. The second substrate may be of the same or different material relative to the material of the first substrate, but sufficiently transparent to ultraviolet radiation. The bonding/lamination process may be repeated multiple times, making it possible to produce a laminated article consisting of more than two bonded layers.
In one embodiment, a method of making an electronic assembly includes coating a first substrate with a one-part dual cure adhesive composition, exposing the coated adhesive composition to radiation, and then contacting the coated adhesive composition on the first substrate with a second substrate. At least one of the substrates has at least one electronic component thereon prior to application of the adhesive. In another embodiment, a method of making an electronic assembly includes coating a first substrate with a one-part dual cure adhesive composition, contacting a second substrate with the coated adhesive on the first substrate, and then exposing the laminated two substrates to radiation. At least one of the substrates has at least one electronic component thereon prior to application of the adhesive.
The exposure of the adhesive composition to radiation can be performed before and/or after contacting the coated adhesive on the first substrate with the second substrate. The adhesive composition may be exposed to radiation directly or through at least one of a substrate, wherein the substrate is sufficiently transparent to ultraviolet radiation. Exposure of the adhesive composition to radiation initiates free radical polymerization of the radiation curable functional groups present in the composition, which will impart initial adhesive properties, such as lap shear strength, to the laminate. The relatively slow chemical reactions involving the isocyanate and/or silane groups and moisture present in the composition also occur over time and provide the final performance characteristics of the cured adhesive composition and the laminated assembly constructed therefrom.
The adhesive composition may be radiation cured using, for example, electron beam, ultraviolet light (i.e., radiation in the range of about 200nm to about 400 nm), visible light (radiation having a wavelength in the range of about 400nm to about 800 nm), and combinations thereof. Useful radiation sources include, for example, ultra-high pressure mercury lamps, medium pressure mercury lamps, metal halide lamps, microwave powered lamps, xenon lamps, laser beam sources (including, for example, excimer lasers and argon ion lasers), and combinations thereof.
In some embodiments, the disclosed adhesives may be used to seal electronic components to provide further protection. In such applications, the adhesive may be applied only to the edges of the substrate, or may be applied to the entire surface of the substrate, thereby encapsulating the electronic component. The adhesive may be applied using any of the processes described above.
In some embodiments, the disclosed adhesives may be used to bond electronic components together as part of a manufacturing process. This application is similar to the lamination process in that two substrates are being bonded together. However, this process can be used with rigid and flexible substrates.
Substrate
The disclosed adhesive compositions may be used with a variety of rigid or flexible substrates. Exemplary substrates include flexible films such as metal foils (aluminum foil), polymeric films made from polymers including, for example, polyolefins (e.g., polypropylene, polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, and oriented polypropylene; copolymers of polyolefins and other comonomers), metallized polyolefins (e.g., metallized polypropylene), metallized polyether terephthalate, ethylene vinyl acetate, ethylene methacrylic acid ionomers, ethylene vinyl alcohol, polyesters (e.g., polyethylene terephthalate), polycarbonates, polyamides (e.g., nylon-6 and nylon-6, 6), polyvinyl chloride, polyvinylidene chloride, polylactic acid, cellulose, polystyrene, cellophane, and paper. The thickness of the film can vary, but the thickness of the flexible film is typically less than about 0.50 millimeters, such as from about 10 microns to about 150 microns, more typically from about 8 microns to about 100 microns. The surface of the substrate may be surface treated to improve adhesion using any suitable method including, for example, corona treatment, chemical treatment, and flame treatment.
Other suitable substrates include, for example, woven webs, nonwoven webs, paper, cardboard, and porous flexible sheets (e.g., polyethylene foam, polyurethane foam, sponge, and foam rubber). Woven and nonwoven webs may comprise fibers including, for example, cotton, polyester, polyolefin, polyamide, and polyimide fibers.
Other substrates may include glass, transparent plastics (such as polyolefins, polyethersulfones, polycarbonates, polyesters, polyacrylates), and polymer films.
In order that the invention may be more fully understood, the following examples are given to illustrate certain embodiments. These examples and experiments are to be understood as illustrative and not restrictive. All parts, ratios, percentages, and amounts described in the examples are by weight unless otherwise indicated.
Examples of the invention
Test method
Lap shear strength
Lap shear strength was determined according to ASTM D3163, where test pieces were configured with a 5 mil adhesive coating on a 10 mil thick polyethylene terephthalate (PET) first substrate laminated to a 10 mil thick polyethylene terephthalate (PET) second substrate with a1 inch by 1 inch substrate overlap.
The maximum load was determined and the results are given in g/in2The lap shear strength is reported in units. The average of three samples was recorded.
Moisture Vapor Transmission Rate (MVTR)
Moisture Vapor Transmission Rate (MVTR) was determined according to ASTM F1249-90 entitled "Standard Test Method for Water vapor Transmission Rate Through Plastic Film and Sheeting using a modulated dInFrared Sensor" (Standard Test Method for modulating the transmission of Water vapor Through Plastic films and sheets using an infrared Sensor). The test was performed on adhesive samples in the form of films having the specified thickness at about 37 ℃ (100 ° f) and 90% relative humidity.
Elongation percentage
Elongation is measured according to ASTM D638 entitled "Standard Test Method for Tensile Properties of plastics".
Method for testing peel adhesion strength
T-Peel strength was determined according to ASTM D1876-01 entitled "Standard Test Method for Peel Resistance of adhesives", wherein Test pieces were configured with a 5 mil adhesive coating on a 10 mil thick polyethylene terephthalate (PET) first substrate laminated to a 10 mil thick polyethylene terephthalate (PET) second substrate with a1 inch x 1 inch substrate overlap.
The peel rate was 12 inches per minute. Results are reported in grams per linear inch. The average of three samples was recorded.
Glass transition temperature (Tg)
The glass Transition temperature (Tg) of the uncured adhesive composition was determined according to ASTM D-3418-83 entitled "Standard Test Method for Transition temperature of Polymer Scanning measurement (DSC)" (Standard Test Method for determining Polymer Transition temperature by Differential Scanning Calorimetry (DSC)) by conditioning the sample at 60 ℃ for two minutes, quenching the sample to-60 ℃ and then heating the sample to 60 ℃ at a rate of 20 ℃ per minute. The recorded Tg is the temperature at which the phase transition starts to occur. For the cured compositions, Tg is measured as the peak temperature of the TanD curve obtained by DSC.
%NCO
The percentage of isocyanate (% NCO) present in the adhesive composition is determined by first dissolving the prepolymer in toluene and reacting a predetermined volume of the prepolymer/toluene solution with a predetermined volume of dibutylamine solution. The amine reacts with the isocyanate group. The excess amine is then titrated with a predetermined hydrogen chloride solution. The volume of the hydrogen chloride solution was then used to calculate the% NCO present in the composition.
Examples of the invention
Prepolymers and Components
The adhesive to be tested in the examples was prepared using the following prepolymers and components:
moisture-curable isocyanate terminated prepolymer A
To prepare prepolymer a, 377 grams of DESMOPHEN S-107-55 (polyester polyol,% moisture < 0.05%) was added to a clean dry reactor and then heated to 180 ° f while stirring under full vacuum (>28 "Hg) until bubbling ceased. Then, while stirring under a nitrogen blanket, 174 grams DESMODUR W (dicyclohexylmethane diisocyanate), 0.06 grams DABCO T-12 (catalyst), and 0.06 grams MODAFLOW (flow aid) were added, the reaction was resealed, heating was maintained at 180 ° f, and the mixture was allowed to mix under full vacuum for 3 hours. The final% NCO of the prepolymer was checked and found to be 7.17%. The prepolymer obtained was discharged and stored under a blanket of dry nitrogen.
Moisture-curable radiation-curable prepolymer B
To prepare prepolymer B, 935.23 grams of ACCLAIM12200 (PPG polyol) was added to a clean dry reactor and heated to 180 ℉ while stirring under full vacuum. Then 124.3 grams of DESMODURE W (dicyclohexylmethane diisocyanate), 0.12 grams of dabco t-12 (catalyst), 0.12 grams of MODAFLOW (flow aid) and 0.12 grams of 85% phosphoric acid were added while slowly stirring under a nitrogen blanket. The mixture was sealed again, the heat was maintained at 180 ° f, and then the mixture was mixed under full vacuum for 3 hours. The final% NCO of the prepolymer was checked and found to be 3.14%. The mixture was cooled to 160 ° f and then 40.2 grams of 2-hydroxyethyl acrylate (2HEA) was added with slow stirring. The reactor was again sealed and the mixture was stirred under partial (20 "Hg) vacuum for 1.5 hours and again checked for final% NCO, which was found to be 1.80%. The prepolymer was discharged and stored.
Moisture-curable radiation-curable prepolymer B2
To prepare prepolymer B2, 491.81 grams of ACCLAIM12200 (PPG polyol) was added to a clean dry reactor and heated to 180 ℉ while stirring under full vacuum. Then, 92.54 g DESMODUR N3600 (homopolymer of hexamethylene diisocyanate), 0.06 g DABCO T-12 (catalyst), 0.06 g MODAFLOW (flow aid) and 0.06 g 85% phosphoric acid were added while slowly stirring under a nitrogen blanket. The mixture was sealed again, the heat was maintained at 180 ° f, and then the mixture was mixed under full vacuum for 3 hours. The final% NCO of the prepolymer was checked and found to be 3.01%. The mixture was cooled to 160 ° f and then 15.48 grams of 2-hydroxyethyl acrylate (2HEA) was added with slow stirring. The reactor was again sealed and the mixture was stirred under partial (20 "Hg) vacuum for 1.5 hours and again checked for final% NCO, which was found to be 2.00%. The prepolymer was discharged and stored.
Radiation-curable component C
The radiation curable component (C) is GENOMER1121 (acrylic monomer, molecular weight 208).
Radiation-curable component C1
The radiation curable component C1 was GENOMER1121M (acrylic monomer, molecular weight 222).
Example 1
To prepare the adhesive composition of example 1, 50 grams of prepolymer A, 122 grams of prepolymer B, 23 grams of component (C) (GENOMER 1121, acrylic monomer), 4.94 grams of GENOCURE LTM (photoinitiator), and 0.2 grams of DABCO T-12 (catalyst) were charged to a clean dry reactor at room temperature and then mixed under vacuum for 30 minutes. The resulting adhesive composition was discharged and stored under a blanket of dry nitrogen.
Approximately 15-20 mils of the adhesive composition was applied to the particle board. Initially touching with a gloved finger revealed no surface adhesion and was completely liquid. The coated panels were exposed to ultraviolet radiation from a medium pressure mercury lamp with a power of 300 watts at transmission line speeds of 33, 50 and 100 feet per minute. The adhesive was again touched with a gloved finger and in all three cases the material cured to a non-fluid state and was tacky to the touch, with the viscosity increasing with increasing line speed. A plastic film was applied to the tacky adhesive surface, held in place while inverted, and a tail (tail) was observed when peeling the plastic film, indicating that cohesive bonding occurred. After a period of 7 days under ambient conditions, the film could no longer be removed without being damaged, and the surface tack completely disappeared.
Examples 2 to 8
Each of the adhesive compositions of examples 2-8 was prepared according to the procedure in example 1 using a combination of various moisture curable prepolymers, radiation curable components, and moisture curable radiation curable prepolymers as shown in table 1.
Laminate 1 of each of examples 2-8 was prepared according to the lap shear strength and peel adhesion strength tests described herein by coating each of the adhesive compositions of examples 2-8 onto a first PET substrate and then laminating the coated first substrate with a second substrate. The laminate was then exposed to radiation from a medium pressure mercury lamp with a power of 300 watts per minute at a transport speed of 100 feet per minute.
Laminate 2 of each of examples 2-8 was prepared in the same manner as laminate 1, except that the coated adhesive on the first substrate was first exposed to radiation. The first substrate with the partially cured adhesive composition was then laminated with a second PET substrate.
Laminates 1 and 2 of examples 2-8 were tested according to the lap shear strength test method and peel strength test method described herein and the results are shown in tables 2 and 3 below.
TABLE 1
| By weight% | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Prepolymer A | 25 | 25 | 25 | 82.5 | 82.5 | ||
| Prepolymer B | 61 | 61 | 82.5 | 82.5 | |||
| Prepolymer B2 | 61 | ||||||
| Component (C1) | 11.5 | 11.5 | 15 | 15 | |||
| Component (C) | 11.5 | 15 | 15 | ||||
| Photoinitiator | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 |
| Catalyst and process for preparing same | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Total of | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
TABLE 2T Peel Strength and Lap shear Strength of laminates 1 of examples 2-8
| Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| T peel strength | |||||||
| T1 | 0.51 | 0.00 | 0.31 | 0.00 | 0.00 | 1.27 | 0.88 |
| T2 | 2.54 | 4.26 | 1.33 | 6.89 | 30.25 | 1.79 | 1.97 |
| T3 | 14.05 | 110.68 | 1.71 | 9.88 | 31.51 | 6.62 | 4.66 |
| T4 | 106.42 | 243.67 | 507.77 | 436.66 | 271.92 | 14.02 | 65.73 |
| Lap shear strength | |||||||
| T2 | 45.40 | 0.00 | Not tested | 15.13 | 0.00 | 0.00 | 0.00 |
| T3 | 121.07 | 423.73 | Not tested | 227.00 | 3359.60 | 45.40 | 45.40 |
| T4 | 10911.13 | 13468.67 | Not tested | 151.33 | 4328.13 | 45.40 | 90.80 |
T1: testing immediately after lamination without uv exposure;
t2: testing immediately after ultraviolet exposure;
t3: testing after 24 hours;
t4: the test was carried out after 7 days.
Table 3T-peel strength and lap shear strength of laminate 2 of examples 2-8
| Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| T peel strength | |||||||
| T2 | 1.44 | 2.95 | 0.66 | 1.83 | 13.73 | 0.79 | 1.37 |
| T3 | 10.65 | 107.39 | 1.33 | 2.03 | 8.31 | 2.35 | 2.42 |
| T4 | 24.65 | 302.41 | 77.23 | 115.70 | 28.08 | 31.78 | 46.08 |
| Lap shear strength | |||||||
| T2 | 196.73 | 302.67 | Not tested | 45.40 | 847.47 | 0.00 | 45.40 |
| T3 | 10699.27 | 19400.93 | Not tested | 45.40 | 363.20 | 45.40 | 45.40 |
| T4 | 25030.53 | Failure of the substrate | 46413.93 | 26937.33 | Not tested | 19809.53 | 33459.80 |
The above specification, examples and data describe the invention. Additional embodiments may be made without departing from the spirit and scope of the invention.
Claims (22)
1. A method of making an electronic assembly comprising:
(A) applying an adhesive composition to at least a portion of the first substrate, the adhesive composition comprising a moisture curable radiation curable prepolymer having a moisture curable functional group and a radiation curable functional group; and
(B) contacting the adhesive on the first substrate with at least a portion of a second substrate, at least one of the first and second substrates comprising at least one electronic component prior to application of the adhesive; wherein the moisture curable functional groups on the moisture curable radiation curable prepolymer are selected from isocyanates and combinations thereof.
2. The method of claim1, wherein the adhesive composition further comprises an additional moisture curable prepolymer and/or an additional radiation curable component.
3. The method of claim1, further comprising exposing the adhesive to radiation before or after step (B).
4. The method of claim 2, wherein the moisture-curable prepolymer is selected from the group consisting of aliphatic isocyanate-terminated prepolymers, silanized-terminated prepolymers, and combinations thereof.
5. The method of claim 2, wherein the radiation curable component is selected from monomers, oligomers, and polymers of (meth) acrylates and combinations thereof.
6. The method of claim1, wherein the radiation curable functional groups on the moisture curable radiation curable prepolymer are selected from monomers, oligomers, and polymers of (meth) acrylates and combinations thereof.
7. The method of claim1, wherein the moisture curable radiation curable prepolymer is a reaction product of a moisture curable prepolymer and a radiation curable component.
8. The method of claim1, wherein the first substrate and the second substrate can be the same or different materials and are independently selected from the group consisting of polyethylene, polyethylene terephthalate, polyethylene naphthalate, and combinations thereof.
9. The method of claim1, wherein at least one of the first and second substrates is a flexible substrate.
10. The method of claim1, wherein the electronic component is selected from the group consisting of a light emitting diode, a radio frequency identification tag, an electrochromic display, an electrophoretic display, a battery, a sensor, and a photovoltaic cell.
11. The method of claim1, wherein the electronic component is selected from the group consisting of a high brightness light emitting diode, an organic light emitting diode, and a solar cell.
12. The method of claim1, wherein the adhesive further comprises a photoinitiator.
13. An electronic assembly, comprising:
a first substrate;
a second substrate;
at least one electronic component located between the first and second substrates; and
an adhesive composition comprising a dual cure reaction product of a moisture curable radiation curable prepolymer having a moisture curable functional group and a radiation curable functional group,
wherein at least a portion of the first substrate is bonded to at least a portion of the second substrate by the adhesive composition;
wherein the moisture curable functional groups on the moisture curable radiation curable prepolymer are selected from isocyanates and combinations thereof.
14. The assembly of claim 13, wherein the adhesive composition comprises a dual cure reaction product of a moisture curable radiation curable prepolymer having a moisture curable functional group and a radiation curable functional group with an additional moisture curable prepolymer and/or an additional radiation curable component.
15. The assembly of claim 13, wherein the first substrate and the second substrate are the same or different materials and are independently selected from the group consisting of polyethylene, polyethylene terephthalate, polyethylene naphthalate, and mixtures thereof.
16. The assembly of claim 13, wherein at least one of the first and second substrates is a flexible substrate.
17. The assembly of claim 13, wherein the electronic component is part of a device selected from the group consisting of a light emitting diode, a radio frequency identification tag, an electrochromic display, an electrophoretic display, a battery, a sensor, and a photovoltaic cell.
18. The assembly of claim 13, wherein the electronic component is part of a device selected from a high brightness light emitting diode, an organic light emitting diode, a solar cell.
19. The assembly of claim 13, wherein the adhesive further comprises an additive selected from the group consisting of: antioxidants, photoinitiators, plasticizers, tackifiers, adhesion promoters, non-reactive resins, ultraviolet light stabilizers, catalysts, rheology modifiers, defoamers, biocides, corrosion inhibitors, dehydrating agents, organic solvents, colorants, fillers, surfactants, flame retardants, waxes, reactive plasticizers, thermoplastic polymers, tackifiers, organofunctional silane adhesion promoters, and combinations thereof.
20. A method of making an electronic assembly comprising:
(A) providing an adhesive composition comprising:
(i) a moisture-curable prepolymer; and
(ii) a radiation curable component;
(B) applying the adhesive composition to at least a portion of a first substrate; and
(C) contacting the adhesive on the first substrate with at least a portion of a second substrate, at least one of the first and second substrates comprising an electronic component prior to application of the adhesive;
wherein the moisture curable functional groups on the moisture curable radiation curable prepolymer are selected from isocyanates and combinations thereof.
21. The method of claim 20, wherein the adhesive composition further comprises a photoinitiator.
22. An electronic assembly, comprising:
a first substrate;
a second substrate;
at least one electronic component located between the first and second substrates; and
an adhesive composition comprising the dual cure reaction product of a moisture curable prepolymer and a radiation curable component,
wherein at least a portion of the first substrate is bonded to at least a portion of the second substrate by the adhesive composition;
wherein the moisture curable functional groups on the moisture curable radiation curable prepolymer are selected from isocyanates and combinations thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161510806P | 2011-07-22 | 2011-07-22 | |
| US61/510,806 | 2011-07-22 | ||
| PCT/US2012/047393 WO2013016133A2 (en) | 2011-07-22 | 2012-07-19 | A one-component, dual-cure adhesive for use on electronics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1196391A1 HK1196391A1 (en) | 2014-12-12 |
| HK1196391B true HK1196391B (en) | 2016-06-24 |
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