Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
  • C08L91/08—Mineral waxes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
  • C08G2170/20—Compositions for hot melt adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
  • C08L93/04—Rosin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers

Definitions

• This invention relates to silane reactive hot melt adhesive compositions having improved green strength, the production of such adhesives and the use of such adhesives.
• Hot melt adhesive compositions are solid at room temperature but, upon application of heat, melt to a liquid or fluid state in which molten form they are applied to a substrate. On cooling, the adhesive composition regains its solid form. The hard phase(s) formed upon cooling the adhesive composition impart all of the cohesion (strength, toughness, creep and heat resistance) to the final bond.
• Hot melt adhesive compositions are thermoplastic and can be heated to a fluid state and cooled to a solid state repeatedly. Hot melt adhesive compositions do not include water or solvents.
• Curable or reactive hot melt adhesive compositions are also solid at room temperature and, upon application of heat, melt to a liquid or fluid state in which molten form they are applied to a substrate. On cooling, the adhesive composition regains its solid form. The hard phase(s) formed upon cooling the adhesive composition and prior to curing impart initial or green strength to the bond.
• the adhesive composition will cure by a chemical crosslinking reaction upon exposure to suitable conditions such as exposure to moisture. Before curing the adhesive composition remains thermoplastic and can be remelted and resolidified. Once cured, the adhesive composition is in an irreversible solid form and is no longer thermoplastic.
• the crosslinked adhesive composition provides additional strength, toughness, creep and heat resistance to the final bond.
• Hot melt curable adhesive compositions can provide higher strength and heat resistance compared to non-curable hot melt adhesive compositions.
• the ability of a reactive hot melt adhesive composition to cool so that the solidified but non-crosslinked composition can quickly bond parts together is called green strength.
• An adhesive composition that quickly develops green strength is desirable in commercial operations as it allows bonded parts to be further processed quickly.
• Reactive hot melt adhesive compositions will continue to react with moisture so that strength of the adhesive bond between parts will continue to rise.
• a high cured strength is desirable in commercial operations as it allows stressed parts to be bonded.
• the adhesive composition is melted in the reservoir of roller coating equipment and applied as a thin film by a roller to a substrate. The molten adhesive composition in the roller coating equipment will react with moisture in the air and begin to crosslink.
• composition that crosslinks slowly will have a long working life but will develop strength more slowly, slowing subsequent commercial operations. It can be difficult to find one reactive hot melt adhesive composition that has a commercially desirable combination of green strength, cured strength, working life and stringing
• urethane hot melt compositions consist primarily of isocyanate terminated polyurethane prepolymers containing urethane groups and reactive isocyanate groups that react with surface or atmospheric moisture to chain extend and form a new polyurethane polymer.
• Polyurethane prepolymers are
• isocyanate groups in the polyurethane prepolymer react with moisture from the environment to form a crosslinked irreversible solid bond.
• Moisture-curing urethane hot melt adhesive compositions have certain disadvantages.
• One disadvantage is the residual monomer content of polyisocyanates, more particularly the more volatile diisocyanates.
• Some moisture-curing urethane hot melt adhesive compositions can contain significant amounts of unreacted monomeric diisocyanates.
• At the hot melt application temperature typically at 100°C to 170°C
• monomeric diisocyanates have a considerable vapor pressure and may be partly expelled in gaseous form.
• the isocyanate vapors may be toxic, irritating and have a sensitizing effect, so that precautionary measures have to be taken in the application process.
• Silane reactive hot melt adhesive compositions have been developed to replace isocyanate reactive hot melt compositions.
• Silane reactive hot melt adhesive compositions are also solid at room temperature and, upon application of heat, melt to a liquid or fluid state in which molten form they are applied to a substrate. On cooling, the composition regains its solid form.
• Silane reactive hot melt adhesive compositions are based on silane modified polymers that comprise moisture reactive silane groups that form siloxane bonds when exposed to moisture such as in the atmosphere. Silane reactive hot melt adhesive compositions offer good cured adhesion and since there is no isocyanate there are no concerns about emission of isocyanate monomer vapor.
• silane reactive hot melt adhesive compositions develop green strength slower than reactive polyurethane hot melt adhesive compositions.
• silane reactive hot melt adhesive composition comprising a silane modified polymer and an effective amount of acidic functional wax develops green strength more quickly and has an extended working life as compared to the same silane modified hot melt adhesive composition without the acidic functional wax.
• One embodiment is directed to a silane reactive hot melt adhesive composition comprising a silane modified polymer, an effective amount of acidic functional wax and a silane adhesion promoter,
• Another embodiment is directed to a method of increasing the development of green strength in a silane reactive hot melt adhesive composition by adding an effective amount of acidic functional wax.
• Another embodiment is directed to a method for bonding materials together which comprises applying the silane reactive hot melt adhesive composition in a molten form to a first substrate, bringing a second substrate in contact with the molten composition applied to the first substrate, and subjecting the applied composition to conditions which will allow the composition to cool and cure to an irreversible solid form, said conditions comprising moisture.
• Another embodiment is directed to an article of manufacture comprising a substrate bonded to cured reaction products of a silane reactive hot melt adhesive composition prepared from a si!ane modified polymer and a controlled range of acidic functional wax.
• the disclosed compounds include any and all isomers and stereoisomers.
• the disclosed materials and processes may be alternately formulated to comprise, consist of, or consist essentially of, any
• the disclosed materials and processes may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants, moieties, species and steps used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objective of the present disclosure.
• silane reactive hot melt adhesive composition has reacted with moisture to produce a cured, thermoset, insoluble material.
• the silane reactive hot melt adhesive composition comprises one or more silane modified polymers.
• the silane modified polymer has an organic backbone, bearing one or more terminal or pendant silane or alkoxylated silane groups.
• the silane groups are hydrolyzed by water to silanol groups, which can condense with each other or with reactive species on the adherent surfaces.
• the silane modified polymer may be prepared with one or more of a variety of polymer backbones such as polyurethane (for example derived from Baycoll 2458 from Bayer), polyether, polyester, polyetherester, polyesterether, polyolefin, polycaprolactone, polyacrylate, polybutadiene,
• polycarbonate polycarbonate, polyacetal, polyester amide, polythioether, polyolefin and the like.
• silane modified polymer backbones for the silane modified polymer include polyurethane and polyether and especially acrylate modified polyether (prepared for instance as described in US Patent No. 6,350,345, the contents of which are incorporated reference).
• the silane modified polymer backbone can be free of silicon atoms.
• the silane modified polymer can be a low modulus silane modified polymer having a Young's modulus for the cured, neat polymer lower than 50 psi; a high modulus silane modified polymer having a Young's modulus for the cured, neat polymer equal or greater than 50 psi; or a combination of low modulus silane modified polymer and high modulus silane modified polymer.
• the silane modified polymer can be represented by the formula
• A is a linkage that links the silane to polymer backbone R;
• n 0, 1 or 2;
• the number of silane groups z will preferably be more than one per molecule (to generate a fully cured network), and more preferably at least two per molecule.
• the silane functional polymer is telechelic or end-functionalized, where most or all the ends are silane functional.
• the silane reactive hot melt adhesive composition cures during exposure to water or moisture, when the silane groups are hydrolyzed to silanol groups which can condense with each other or with reactive species on the adherent surfaces.
• Silane modified polymers are commercially available, for example, from Momentive Performance Material under the trade name SPUR, from Henkel
• the silane modified polymer is advantageously liquid at room temperature to provide more rapid reaction of the silane end groups in the silane reactive hot melt adhesive composition and to aid mobility of the reactive sites and thus increase the potential for covalent reaction with the surface of one or both substrates.
• the amount of silane modified polymer in the composition will depend on its molecular weight and functionality, but will typically be from 20-80 wt %, advantageously 25-60 wt %, and more advantageously from 30-50 wt %, based on the total weight of the adhesive composition.
• the silane reactive hot melt adhesive composition comprises a controlled amount of acidic functional wax.
• acidic functional wax it is meant that the wax includes a functional moiety that is acidic.
• the acidic functional wax can have terminal or pendant acidic functional moieties.
• waxes examples include natural waxes, partially synthetic waxes and fully synthetic waxes.
• Natural waxes are formed through biochemical processes and are products of animal or plant metabolism. Partially synthetic waxes are formed by chemically reacting natural waxes.
• Fully synthetic waxes are prepared by polymerizing low molar mass starting materials such as carbon, methane, ethane or propane. The two main groups of fully synthetic waxes are the Fischer - Tropsch waxes and polyolefin waxes such as polyethylene wax, polypropylene wax and copolymers thereof.
• Acidic functional groups are added to the wax molecule by, for example, grafting synthetic waxes with an acidic moiety such as carboxylic acid or maleic anhydride or by cleavage of the esters and/or oxidation of the alcohols in partially synthetic waxes.
• Acidic functional waxes can have a saponification number (mg
• KOH/gm wax of less than about 90 and more advantageously from about 5 to about 30.
• Some useful acid functional maleated waxes can have about 50 % to about 95 % of maleic anhydride moieties bound to the wax backbone with the remaining with the remaining maleic anhydride content not bound to the wax backbone.
• Acidic functional waxes are available commercially, for example from Clariant Internationa! Ltd, Switzerland; EPChem International Pte Ltd, Singapore; Honeywell International Inc., U.S. and Westlake Chemical Corp, U.S.
• Advantageous acid functional waxes are the maleated polypropylene waxes.
• One useful maleated polypropylene wax is A-C 1325P available from Honeywell International Inc.
• the silane reactive hot melt adhesive composition will contain an effective amount of acid functional wax.
• An effective amount of acid functional wax is the amount of acid functional wax that will increase green strength of a silyl reactive hot melt adhesive composition without deleteriously degrading other properties of that
• the silane reactive hot melt adhesive composition will contain 0.1 % to about 15% of acid functional wax.
• the silane reactive hot melt adhesive composition will contain 0.1% to about 4% of acid functional wax.
• the silane reactive hot melt adhesive composition can optionally comprise tackifier.
• tackifier will depend on the backbone of the silane modified polymer.
• the tackifier choices include natural and petroleum-derived materials and combinations thereof as described in C.W. Paul, "Hot Melt Adhesives,” in Adhesion Science and Engineering-2, Surfaces, Chemistry and Applications, M. Chaudhury and A. V. Pocius eds., Elsevier, New York, 2002, p. 718, incorporated by reference herein.
• Useful tackifier for the adhesive composition of the invention includes natural and modified rosin, aromatic tackifier or mixtures thereof.
• Useful natural and modified rosins include gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, resinates, and polymerized rosin; glycerol and pentaeryth tol esters of natural and modified rosins, including, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified
• rosins and rosin derivatives examples include Sylvalite RE 1 10L, Sylvares RE 1 15, and Sylvares RE 104 available from Arizona Chemical; Dertocal 140 from DRT; Limed Rosin No.1 ,GB-120, and Pencel C from Arakawa Chemical.
• One preferred natural and modified rosin is a rosin ester tackifier such as KE-100, available from Arakawa Chemical Co.
• Another preferred rosin ester tackifier is a Komotac 2110 from Komo Resins.
• Useful aromatic tackifiers include styrenic monomers, styrene, alpha-methyl styrene, vinyl toluene, methoxy styrene, tertiary butyl styrene,
• aromatic hydrocarbon resins that are phenolic-modified aromatic resins, C 9 hydrocarbon resins, aliphatic-modified aromatic C 9 hydrocarbon resins, C 9 aromatic/aliphatic olefin-derived and available from Sartomer and Cray Valley under the trade name Norsolene and from Rutgers series of TK aromatic hydrocarbon resins.
• aromatic tackifiers are alpha-methyl styrene types such as Kristalex 3100, Kristalex 5140 or Hercolite 240, all available from Eastman Chemical Co.
• the tackifier component will usually be present in an amount of from about 20 wt % to about 90 wt %, advantageously from about 25 wt % to about 45 wt %, more advantageously from about 30 wt % to about 40 wt %, based on the total weight of the adhesive composition.
• the rosin tackifier will be present from 0 to 30 wt %,
• the aromatic tackifier will be present from 0 to about 60 wt %, advantageously from about 15 to about 40 wt %, based on the total weight of the adhesive composition.
• the silane reactive hot melt adhesive composition can optionally comprise an acrylic polymer or copolymer (acrylic polymer).
• the acrylic polymer can improve green strength of the cooled hot melt adhesive composition.
• the acrylic polymer can be either a silane-reactive polymer or non-reactive polymer.
• a silane reactive polymer comprises groups such as carboxylic acid, amine, thiol and hydroxyl that react with silane moieties.
• a preferred silane reactive group is carboxylic acid.
• the number of groups should be sufficient such that a significant amount, at least 5%, of the acrylic polymer is grafted to the silane modified polymer via the silane groups.
• a non-silane reactive acrylic polymer does not include groups that are reactive with the silane modified polymer.
• Elvacite 2903 is a solid acrylic copolymer comprising acid and hydroxyl groups, has an acid number 5.2 and hydroxyl number of 9.5.
• the amount of solid acrylic polymer in the adhesive composition will depend on a number of factors, including the glass transition temperature and molecular weight of the acrylic polymer, but will typically be present in an amount of from about 10 to about 45 wt %, based on the total weight of the adhesive composition.
• the silane reactive hot melt adhesive composition can optionally comprise a catalyst.
• a catalyst Suitable curing agents for the silane groups are described in U.S. Patent Publication No. 2002/0084030, and incorporated by reference herein.
• Exemplary catalyst includes bismuth compounds such as bismuth carboxylate; organic tin catalysts such as dimethyltin dineodecanoate, dibutyltin oxide and dibutyltin diacetate; titanium alkoxides (TYZOR® types, available from DuPont); tertiary amines such as bis (2- morpholinoethyl) ether, 2,2'-Dimorpholino Diethyl Ether (DMDEE) and triethylene diamine; zirconium complexes (KAT XC6212, K-KAT XC-A209 available from King Industries, Inc.); aluminum chelates (K-KAT 5218, K-KAT 4205 available from King Industries, Inc.), KR types (available from Kenrich Petro
• the level of catalyst in the silane reactive hot melt adhesive composition will depend on the type of catalyst used, but can range from about 0.05 to about 5 wt %, advantageously from about 0.1 to about 3 wt % and more advantageously from about 0.1 to about 2 wt %, based on the total weight of the adhesive composition.
• the silane reactive hot melt adhesive composition can optionally comprise a moisture scavenger to extend pot life, such as vinyl trimethoxy silane or
• the level of moisture scavenger employed can be from 0 to 3% and preferably from 0 to 2%, based on the total weight of the adhesive composition.
• the adhesive composition can comprise an adhesion promoter or coupling agent which promotes bonding of the composition to a substrate. Examples are described in: Michel J. Owen, "Coupling agents: chemical bonding at interfaces” , in Adhesion Science and Engineering-2, Surfaces, Chemistry and Applications, M.
• Preferred adhesion promoters include organo-silanes which can link the silane-functional polymer to the surface such as amino silanes and epoxy silanes.
• Some exemplary aminosilane adhesion promoters include 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl-3- aminopropyl)trimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-amino-3,3- dimethylbutyltrimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, 1- butanamino-4-(dimethoxymethylsilyl)-2,2-dimethyl, (N- cyclohexylaminomethyl)triethoxysilane, (N-cyclohexylaminomethyl)- methyldiethoxysilane, (N-phenylaminoethyl)trimethoxysilane, (N-phenylaminomethyl)- methyldimethoxysilane or .
• amino silanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane.
• Some exemplary epoxy silane adhesion promoters include 3- glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane or beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane.
• Other silane adhesion promoters include mercaptosilanes.
• Some exemplary mercaptosilane adhesion promoters include 3- mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane or 3- mercaptopropyltriethoxysilane.
• the level of adhesion promoter employed can be from 0 to 0%, preferably 0.1 to 5% and more preferably 0.2-3%.
• the adhesion promoter, if more reactive to moisture than the silane modified polymer, can also serve as a moisture scavenger.
• silane reactive hot melt adhesive composition comprising aminosilane adhesion promoter and having a ratio (R) of acid functionality to
• aminosilane functionality within a limited range has proven to provide an advantageous combination of green strength, final (cured) strength and working life.
• R is defined as the molar ratio between acid functionality from acid functional wax and amino functionality from aminosilane.
• each maleic anhydride functional group will generate 2 carboxylic acid functionalities. This is due to anhydride chemistry and well known to people in the art.
• R is defined as R1/R2.
• R is greater than 0 and less than about 1.8. More advantageously, R may be in the range of about 0.3 to about 1.2.
• the silane reactive hot melt adhesive composition can optionally comprise conventional additives known to a person skilled in the art.
• Conventional additives which are compatible with a composition according to this invention may simply be determined by combining a potential additive with the composition and determining if they remain homogenous.
• suitable additives include, without limitation, fillers, plasticizers, defoamers, rheology modifiers, air release agents and flame retardants.
• the total level of additives will vary depending on amount of each particular additive needed to provide the silane reactive hot melt adhesive composition with desired properties.
• the level of additives can be from 0 to 50%.
• An exemplary silane reactive hot melt adhesive composition is shown below.
• the silane reactive hot melt adhesive composition is preferably free of water and/or solvent in either the solid and/or molten form.
• the silane reactive hot melt adhesive composition can be prepared by mixing the tackifier, wax and other non-reactive components with heat until homogeneously blended.
• the mixer is placed under vacuum to remove moisture followed by heated mixing of the reactive components.
• the silane reactive hot melt adhesive compositions can be used to bond articles together by applying the hot melt adhesive composition in molten form to a first article, bringing a second article in contact with the molten composition applied to the first article. After application of the second article the silane reactive hot melt adhesive composition is subjected to conditions that will allow it to solidify, bonding the first and second articles. Solidification occurs when the liquid melt is subjected to a temperature below the melting point, typically room temperature. Bonding based on solidification and before cure is referred to as green strength. After solidification the adhesive is exposed to conditions such as surface or atmospheric moisture to cure the solidified composition to an irreversible solid form.
• silane reactive hot melt adhesive compositions are useful for bonding articles composed of a wide variety of substrates (materials), including but not limited to wood, metal, polymeric plastics, glass and textiles.
• substrates materials
• Non-limiting uses include use in the manufacture of footwear (shoes), use in the manufacture of doors including entry doors, garage doors and the like, use in the manufacture of panels, use in bonding
• compositions are determined by the thermal stability of the composition and the heat sensitivity of the substrates. Preferred application temperatures are above 120°C and below 170°C, more preferably below 150°C, and most preferably below 140°C,
• the silane reactive hot melt adhesive compositions may be then applied in molten form to substrates using a variety of application techniques known in the art. Examples includes hot melt glue gun, hot melt slot-die coating, hot melt wheel coating, hot melt roller coating, melt blown coating, spiral spray and the like. In preferred embodiments the hot melt adhesive composition is applied to a substrate using hot melt roller coater or extruded onto a substrate.
• viscosity of the silane reactive hot melt adhesive composition should be 5,000 to 20,000 cps at 250°F.
• Stringiness - Visual evaluation of adhesive composition strings extending between a recently coated substrate and the roller coating apparatus Desirably, stringiness of the silane reactive hot melt adhesive composition should be no greater than moderate.
• final strength of the silane reactive hot melt adhesive composition should be greater than 60 psi at room temperature and greater than 20 psi at 180 °F.
• Green Strength by TLS - Lap shear bonds were made and tested as described above, but were tested largely uncured a short time (2 hours to one week) after bonding. This test characterizes the ability of the bonded structure to survive handling in manufacture prior to full cure. Hot melts have the advantage of high strength in the green state which minimizes working inventory.
• CPT Green Strength by Cantilever Pull Test
• One substrate is roll coated with 10 grams/foot 2 of molten adhesive.
• the second specimen is placed on the coated specimen so that there is a 3 inch by 2 inch overlap area and the overlapping area is lightly pressed.
• the bonded substrates are allowed to sit for a short time (typically 5 minutes, 10 minutes or 1 hour) to allow the adhesive to solidify.
• One substrate is fixed and an increasing force is applied in the thickness direction
• A-C 1325P a maleated polypropylene wax available from Honeywell International Inc. The manufacturer states that A-C 1325P has 78% bound maleic anhydride; a saponification number of 18 mg KOH/gm wax; and a viscosity of 1600 cps at 190°C.
• A-C 596P a maleated polypropylene wax available from Honeywell International Inc. The manufacturer states that A-C 596P has 85% bound maleic anhydride; a saponification number of 50 mg KOH/gm wax; and a viscosity of 150 cps at 190 D C.
• MAX 951 is a low modulus silane terminated polyether, commercially available from Kaneka Corp.
• DMDEE is a bis (2-morpholinoethyl) ether available from VWR Inc.
• Elvacite 2903 is a solid acrylic polymer, available from Ineos Acrylics.
• KE-100 is a hydrogenated rosin ester, available from Arakawa Chemical Co.
• Kristalex 3100 is an alpha-methyl styrene tackifier, available from Eastman Chemical Co.
• Silquest A-174 is a moisture scavenger, available from Momentive Performance Materials.
• Silquest A1110 is an adhesion promoter, available from Momentive Performance Materials.
• KBM503 is an adhesion promoter, available from Shin Etsu Silicone.
• A515 is an air release agent, available from BYK Chemie.
• Samples of silane reactive hot melt adhesive compositions were prepared according to the following table.
• Sample A is a comparative example with no acid functionalized wax.
• the air release agent, acrylic polymer and tackifiers were combined, heated to 305 °F and stirred until homogeneous. Vacuum was applied to remove any water and the temperature was lowered to 280 °F. When the temperature reached 280 °F the silane modified polymer was added and vacuum mixed until homogeneous.
• the 3-methacryloxypropyltrimethoxysilane and adhesion promoter were added and vacuum mixed until homogeneous.
• the catalyst was added and vacuum mixed until homogeneous.
• the final adhesive was poured into a container, cooled to room temperature and sealed under nitrogen. Sample (wt %)
• Viscosity (cps @ 6763 14050 8325 10250 8925 9700
• Samples of silane reactive hot melt adhesive compositions were prepared according to the following table.
• Sample A is a comparative example with no acid functionalized wax.
• Viscosity (cps @ 250° F) 6763 6413 8250
• AC596P used in samples 6 and 7 is a maleated polypropylene wax with a saponification number of 50 mg KOH/g wax.
• AC596P has a higher maleic anhydride content than the AC1325P wax used in samples 1-5.
• HPL high pressure laminate
• CRS is cold rolled steel.
• PB is particle board.
• SMC is sheet molding composite.

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