WO2019109328A1 - Composition adhésive thermofusible durcissable à l'humidité - Google Patents

Composition adhésive thermofusible durcissable à l'humidité Download PDF

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Publication number
WO2019109328A1
WO2019109328A1 PCT/CN2017/115195 CN2017115195W WO2019109328A1 WO 2019109328 A1 WO2019109328 A1 WO 2019109328A1 CN 2017115195 W CN2017115195 W CN 2017115195W WO 2019109328 A1 WO2019109328 A1 WO 2019109328A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
melt adhesive
moisture curable
curable hot
weight
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PCT/CN2017/115195
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English (en)
Inventor
Wentao Xing
Hui Guo
Yew-Guan LOW
Xueyu QIU
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Henkel Ag & Co. Kgaa
Henkel (China) Co., Ltd.
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Priority to PCT/CN2017/115195 priority Critical patent/WO2019109328A1/fr
Publication of WO2019109328A1 publication Critical patent/WO2019109328A1/fr

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    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/005—Modified block copolymers
    • 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
    • C09J175/02—Polyureas
    • 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

Definitions

  • This invention relates to a moisture curable hot-melt adhesive composition having good bonding strength and improved reworkability, and the use of such adhesive composition in electronics assembly and especially in battery fixing.
  • 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 polyurethane polymer.
  • Polyurethane prepolymers are conventionally obtained by reacting diols with diisocyanates.
  • moisture-curing urethane hot-melt adhesive compositions have certain disadvantages.
  • One disadvantage is the residual monomer content of polyisocyanates, particularly the more volatile diisocyanates.
  • Some moisture-curing urethane hot-melt adhesive compositions may 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 vapor is toxic, irritating and has a sensitizing effect, so that precautionary measures have to be taken in the application process.
  • Another disadvantage is that the reworkability of polyurethane adhesive is always an issue and it is difficult to totally peel off from substrates at room temperature.
  • 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. Upon cooling, the adhesive 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 can offer good cured adhesion, and since there is no isocyanate, there are no concerns about emission of isocyanate monomer vapor.
  • US20150240135A1 discloses a hot-melt adhesive composition
  • a hot-melt adhesive composition comprising at least one silane group-containing thermoplastic polyolefin which is solid at 25°C. and at least one paraffin wax.
  • the final bonding strength is far from satisfactory.
  • US20150225629A1 concerns an adhesive composition comprising a hot-melt adhesive composition comprising at least one thermoplastic poly-a-olefin that is solid at 25°C and silane groups, at least one thermoplastic poly-a-olefin that is solid at 25°C, and that does not contain silane groups, and at least one resin that is tackifying at 25°C.
  • the final bonding strength is far from satisfactory.
  • US8080308B2 provides a moisture curable sealant composition comprising a silane functional poly-a-olefin polymer, a thermoplastic elastomer comprising a silane terminated block copolymer; and a tackifying agent.
  • a moisture curable sealant composition comprising a silane functional poly-a-olefin polymer, a thermoplastic elastomer comprising a silane terminated block copolymer; and a tackifying agent.
  • the reworkability of the adhesive is far from satisfactory.
  • silane reactive hot-melt adhesive composition that has a desirable combination of properties for commercial use including the excellent final bonding strength and good reworkability at room temperature at the same time.
  • the present invention provides a moisture curable hot-melt adhesive composition, comprising:
  • the present invention also provides a method of applying a moisture curable hot-melt adhesive composition comprising:
  • the present invention provides the use of the moisture curable hot-melt adhesive composition, and an article comprising cured products of the moisture curable hot-melt adhesive composition.
  • the moisture curable hot-melt adhesive composition comprises one or more silane modified polymers.
  • the silane modified polymer may comprise more than one terminal silyl groups, and can be represented by the formula
  • R is an organic backbone selected from the group consisting of polyurethane, polyether, polyester, polyacrylate and polyolefin,
  • A is a linkage that links the silane group to R
  • n 0, 1 or 2;
  • x and y are independently a number from 1 to 12;
  • z is an integer larger than 1.
  • the linkage A can be a bond or any structure that covalently join the organic backbone group R to the silane group of the silane modified polymer.
  • 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. More preferably, the silane modified polymer is telechelic or end-functionalized, where most or all the ends are silane modified.
  • the moisture curable 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 surfaces to be bonded.
  • the backbone R for the silane modified polymer is polyolefin, preferably poly ⁇ -olefin, and thus the silane modified polymer is a silane modified poly- ⁇ -olefin.
  • Particularly useful silane modified poly- ⁇ -olefins are either completely amorphous or have a low level of crystallinity. In one embodiment, the degree of crystallinity is no greater than about 25%as determined by X-ray diffraction.
  • Useful silane modified amorphous poly- ⁇ -olefins are derived from amorphous poly- ⁇ -olefin and a silane source.
  • Useful amorphous poly- ⁇ -olefins include homopolymers, copolymers and terpolymers including, e.g., atactic polypropylene, atactic poly-1-butene and combinations thereof.
  • the amorphous poly- ⁇ -olefins can be random or block copolymers.
  • amorphous poly- ⁇ -olefin polymers include, e.g., homogeneous substantially linear ethylene- ⁇ -olefin interpolymers of monomers including, e.g., propylene, 1-butene, 1-pentene, 3-metyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, and 1-undecene; amorphous copolymers with other olefins (e.g., ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene) containing propylene as a main component, amorphous copolymers with other olefins (e.g., ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-oc
  • One example of a useful class of amorphous poly- ⁇ -olefins include copolymers and terpolymers derived from 0%by weight to about 95%by weight ⁇ -olefins having from 4 to 10 carbon atoms, (in other embodiments from 3%by weight to about 95%by weight) , from about 5%by weight to 100%by weight propane (in other embodiments from 5%by weight to about 97%by weight) , and from 0%by weight to about 20%by weight ethane as described, e.g., in U.S. Pat. No. 5,994,474.
  • the silane to be grafted on the amorphous poly- ⁇ -olefin has two or three alkoxy groups attached directly to the silicon and at least one olefinic double bond containing moiety.
  • Suitable examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyldimethylmethoxysilane and vinylmethyldibutoxysilane.
  • the amount silane for grafting on the amorphous poly- ⁇ -olefin is from about 0.1%by weight to about 10%by weight, from about 2%by weight to about 6%by weight, or even from about 3%by weight to about 5%by weight, based on the amorphous poly- ⁇ -olefin.
  • the amorphous poly- ⁇ -olefin has a number average molecular weight (Mn) from about 7,000 to about 14,000, a weight average molecular weight (Mw) from about 35,000 to about 90,000 and a Z average molecular weight (Mz) from about 13,000 to about 33,000, and polydispersity (MWD) from about 4.9 to about 6.2.
  • Silane modified polymers are commercially available, for example, from Momentive Performance Material under the trade name SPUR, from Henkel Corporation under the trade name FLEXTEC, from Kaneka Corporation under the trade name MS polymer and SILYL polymer, and from Evonik Degussa under the trade name of Vestoplast.
  • the silane modified polymer is present in an amount of about 0.5%to about 70%, preferably about 1%to about 60%, more preferably about 3%to about 50%, and in particular about 5%to about 45%, based on the weight of the adhesive composition.
  • anther essential feature of the adhesive composition is the ethylenically unsaturated carboxylic acid graft modified polymer.
  • the ethylenically unsaturated carboxylic acid graft modified polymer can be a block copolymer selected from ABA, ABABA, ABA', ABA'BA, or A'BABA', wherein the blocks A and A'represent a poly (vinylarene) block, wherein block B independently represent an optionally hydrogenated poly (conjugated diene) block which is grafted with an ethylenically unsaturated carboxylic acid.
  • Preferred block copolymers to be used as component (b) are ABA'triblock copolymers comprising an elastomeric block portion B and a thermoplastic block portions A and A'which may be the same or different.
  • the thermoplastic, hard blocks A and A' are derived from monomers such as styrene, alpha-methyl styrene, other styrene derivatives such as ortho, meta and para methyl styrene, o-, m-, p-ethyl styrene, o-, m-, p-methoxy styrene, o-, m-, p-isopropyl styrene, p-tert butyl styrene or mixtures thereof.
  • thermoplastic hard blocks A and A' are composed of styrene, optionally mixed with minor amounts of alpha-methyl styrene or paramethyl styrene (amounts of at most 15 wt%, relative to the weight of the block (s) A and A', and has a number average molecular weight of from 4,000 to 20,000, preferably from 5,000 to 10,000 and most preferably from 6,000 to 9,000.
  • the hard block portions A comprise from 20 to 50 %and more preferably from 25 to 40 %of the total weight of the block copolymer.
  • the B block (s) have to be regarded as a soft block, which is derived from conjugated diene monomers of from 4 to 6 carbon atoms or linear alkene monomers of from 2 to 6 carbon atoms.
  • Suitable diene monomers include 1, 2-butadiene, 2-methyl-1, 3-butadiene, 2-methyl-1, 3-pentadiene, 1, 3-octadiene, 1, 3-pentadiene and the like.
  • Suitable alkene monomers include ethylene, propylene, butylenes and the like.
  • the soft block portion B preferably comprises a substantially amorphous polyolefin such as ethylene/propylene polymers, ethylene/butylenes polymers, polybutadiene, polyisoprene or mixtures thereof.
  • the soft block (s) B have been derived from butadiene or isoprene and have been optionally hydrogenated in the initially prepared complete block copolymer. This means that the blocks B have been hydrogenated for more than 90%of the originally present ethylenical unsaturation, whereas the aromatic unsaturation has remained intact for more than 90 %.
  • the proportion of 1, 2 polymerized butadiene units is in the range of from 30 to 80 %and more preferably from 35 to 70 %.
  • the number average molecular weight of the soft block (s) B is typically from 10,000 to 90,000 and preferably from 20,000 to 60,000.
  • the soft block (s) B portion comprises from 20 to 80 %by weight and preferably from 40 to 70 wt%, relative to the weight of the total weight of the block copolymer.
  • the block copolymers may be produced by any well-known block polymerization or co-polymerization procedures including the well-known sequential addition of monomer techniques, incremental addition of monomer technique or coupling technique as illustrated in, for example, U.S. Pat. Nos. 3,251,905; 3,390,207; 3,598,887 and 4,219,627, which are incorporated herein by reference.
  • the ethylenically unsaturated carboxylic acid graft modified block copolymer may be prepared by graft-reacting an ethylenically unsaturated carboxylic acid acid moiety or its derivative onto the hydrogenated block copolymer via a free radically initiated reaction.
  • Suitable monomers which may be grafted include ethylenically unsaturated mono-and polycarboxylic acids and anhydrides containing from about 3 to about 10 carbons.
  • Examples of such monomers are fumaric acid, itaconic acid, citraconic acid, acrylic acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, ethyl -and diethyl -maleic anhydride, chloro -and dichloro -maleic anhydride, phenyl maleic anhydride, itaconic anhydride, methyl itaconic anhydride, aconitic anhydride, nadic anhydride, methyl nadic anhydride, tetrahydrophthalic anhydride or methyl naphthalene tetrahydronaphthalene anhydride.
  • the preferred grafting monomer is maleic anhydride.
  • the grafted polymer will usually contain from 0.1 to 10, preferably 0.2 to 5 percent by weight of graft monomer.
  • the grafting reaction can be carried out in solution or by melt-mixing the base block copolymer and the acid/anhydride monomer in the presence of a free radical initiator. Disclosures for such processes are found in U.S. Pat. Nos. 4,033,888; 4,077,893; and 4,670,173 for solution processes and in U.S. Pat. Nos. 4,427,828; 4,578,429; 4,628,072; and 4,657,971 for melt-mixing processes, all of which are incorporated herein by reference.
  • polymers may be readily prepared by the methods set forth above.
  • Suitable polymers such as maleic anhydride-modified SEBS are also commercially available from Kraton Polymer under the trade name FG 1901 and FG1924; from Asahi Chemical Industry under the trade name M-1911, M-1913 and M-1943; and from TSRC Corp under the trade name Taipol 7131.
  • the ethylenically unsaturated carboxylic acid graft modified polymer is present in an amount of about 0.5%to 60%, preferably 1%to 50%, more preferably about 3%to about 30%, and in particular about 5%to about 25%, by weight of the adhesive composition.
  • the moisture curable hot-melt adhesive composition according to the present invention also contains a tackifying agent which imparts appropriate tack required for a hot-melt adhesive composition.
  • a tackifying agent which imparts appropriate tack required for a hot-melt adhesive composition.
  • Useful tackifying agents have a ring and ball softening point of from about 50°C to about 150°C, in other embodiments from about 80°C to about 120°C.
  • the tackifying agent preferably is free of groups with which the silanol group of the silyated amorphous poly- ⁇ -olefin will react.
  • Suitable tackifying agents include a natural rosin, a modified rosin, a hydrogenated rosin, a glycerol ester of a natural rosin, a glycerol ester of a modified rosin, a pentaerythritol ester of a natural rosin, a pentaerythritol ester of a modified rosin, a pentaerythritol ester of a hydrogenated rosin, a copolymer of a natural terpene, a three dimensional polymer of a natural terpene, hydrogenated derivatives of a copolymer of a hydrogenated terpene, a polyterpene resin, hydrogenated derivatives of a phenol-based modified terpene resin, an aliphatic petroleum hydrocarbon resin, a hydrogenated derivatives of an aliphatic petroleum hydrocarbon resin, an aromatic petroleum hydrocarbon resin, hydrogenated derivatives of an aromatic petroleum hydrocarbon resin, a
  • the end-block resin is a polymer of an aromatic monomer having a polymerizable unsaturated group.
  • aromatic monomer include styrenic monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, methoxystyrene, tertiarybutylstyrene and chlorostyrene, and indene monomers such as indene and methylindene.
  • tackifying agents can be used alone or in combination.
  • the tackifying agent is selected from the group consisting of a pentaerythritol ester of a natural rosin, a pentaerythritol ester of a modified rosin, an end-block resin, a hydrogenated derivatives of an aliphatic petroleum hydrocarbon resin, and combination thereof.
  • ECR 179EX (trade name) manufactured by Tonex Co., Ltd.; Maruka Clear H (trade name) manufactured by Maruzen Petrochemical Co., LTD.; Alcon M100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.; I-MARV S100 (trade name) manufactured by Idemitsu Kosan Co., Ltd.; Clearon K100 (trade name) , Clearon K4090 (trade name) and Clearon K4100 manufactured by YASUHARA CHEMICAL CO., LTD.; ECR 179EX (trade name) and ECR 231C (trade name) manufactured by Tonex Co., Ltd.; Plastolyn R1140 (trade name) , Plastolyn R1125 (trade name) , Regalite C6100L (trade name) and Regalite C8010 (trade name) manufactured by Eastman Chemical Company; and FTR 2140 (trade name) manufactured by Mits
  • Examples of the unhydrogenated tackifying agent include Quintone DX390N (trade name) and Quintone DX395 (trade name) manufactured by ZEON CORPORATION.
  • Examples of the rosin ester resins include KA-100L, KF452, KF454 and KF462 from Guangzhou Komo Co., Ltd. These commercially available tackifying agent can be used alone or in combination.
  • the tackifying agent is present in an amount of about 5%to about 75%, preferably about 20%to about 70%, more preferably about 30%to about 65%, by weight of the adhesive composition.
  • the moisture curable moisture curable hot-melt adhesive composition according to the present invention may further comprise a catalyst.
  • exemplary catalysts includes bismuth compounds such as bismuth carboxylate; organic tin catalysts such as dimethyltin dineodecanoate, dibutyltin oxide and dibutyltin diacetate; titanium alkoxides ( 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.
  • bismuth compounds such as bismuth carboxylate
  • organic tin catalysts such as dimethyltin dineodecanoate, dibutyltin oxide and dibutyltin diacetate
  • titanium alkoxides types, available from DuPont
  • the level of catalyst in the moisture curable hot-melt adhesive composition will depend on the type of catalyst used, but can range from about 0.05 to about 5%, advantageously from about 0.1 to about 3%and more advantageously from about 0.1 to about 2%, based on the weight of the adhesive composition.
  • the adhesive composition may optional comprise an adhesion promoter or coupling agent which promotes bonding of the composition to a substrate.
  • 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 gamma-ureid
  • Some exemplary epoxy silane adhesion promoters include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane or beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
  • silane adhesion promoters mercapto group-containing silanes such as gamma -mercaptopropyltrimethoxysilane, gamma -mercaptopropyltriethoxysilane, gamma -mercaptopropylmethyldimethoxysilane, and gamma -mercaptopropylmethyldiethoxysilane; epoxy group-containing silanes such as gamma -glycidoxypropyltrimethoxysilane, gamma -glycidoxypropyltriethoxysilane, gamma -glycidoxypropylmethyldimethoxysilane, beta - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and beta - (3, 4-epoxycyclohexyl) ethyltriethoxysilane; carboxysilanes such as beta -carboxyethyltrie
  • silane coupling agent for example, block isocyanatesilane and silylated polyester
  • the level of adhesion promoter employed can be from 0 to about 10%, preferably about 0.1%to about 5%and more preferably about 0.2%to about 3%based on the total weight of the adhesive composition.
  • the adhesion promoter may act as a crosslinker or, if more reactive to moisture than the silane modified polymer, can also serve as a moisture scavenger.
  • the adhesive composition may optional comprise a non-funtionalized block copolymer different to component (2) of the adhesive composition.
  • non-funtionalized block copolymer examples include triblock styrene-ethylene/butylene-styrene block copolymers (SEBS) and styrene-ethylene/propylene-styrene block copolymers (SEPS) available as KRATON G series and SEPTON 2002 and 2063.
  • triblock copolymers useful in the present invention include hydrogenated polyisoprene/butadiene (SEEPS) having styrene monomer units and hydrogenated conjugated diene monomer available as SEPTON 4033-4055 from Kuraray; and hydrogenated poly-isoprene/butadiene polymers that consists of blocks of styrene monomers and hydrogenated conjugated diene monomer units.
  • SEEPS hydrogenated polyisoprene/butadiene
  • SIBS styrene-isobutylene-styrene block copolymers available from Kaneka, under the trade name SIBSTAR 062T, 073T.
  • SIBS styrene-isobutylene-styrene block copolymers available from Kaneka, under the trade name SIBSTAR 062T, 073T.
  • SIBS styrene-isobutylene-styrene block copolymers available from Kaneka, under the
  • the radial block copolymer comprises a structure of (polystyrene-midblock) X , where X is a residue of a multifunctional coupling agent used in the production of the radial block copolymer, and n is a number equal to or greater than 3 and represents the number of polystyrene-midblock arms appended to X.
  • the number n ranges on average from about 3 up to about 10.
  • the level of non-funtionalized block copolymer employed can be from 0 to about 20%, preferably about 1%to about 15%and more preferably about 5%to about 15%based on the total weight of the adhesive composition.
  • the hot-melt adhesive of the present invention may also comprise up to 3%, preferably about 0.25%to about 1%by weight of an optional antioxidant.
  • an optional antioxidant included herein are the hindered phenols or hindered phenols in combination with a secondary antioxidant such as distearyl thiodipropionate ( "DSTDP” ) or dilauryl thio-dipropionate ( "DLTDP” ) .
  • Hindered phenols as used herein are as phenolic compounds containing sterically bulky radicals in close proximity to the phenolic hydroxyl group thereof.
  • hindered phenols include: 1, 3, 5-trimethyl 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene; pentaerythrityl tetrakis-3 (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; pentaerythritol tetrakis (3-lauryl thiodipropionate) ; n-octadecyl-3, 5-di-tert-butyl-4-hydroxyphenol) -propionate; 4, 4'-methylenebis (2, 6-tert-butylphenol) ; 4, 4'-thiobis (6-tert-butyl-o-cresol) ; 2, 6-di-tertbut
  • Preferred antioxidants are SUMILIZER TDP, which is pentaerythritol-tetrakis (beta-lauryl-thio-propionate) , a secondary antioxidant available from Sumitomo Chemical Company and IRGANOX 1010 a hindered phenol primary antioxidant available from BASF Corporation.
  • Other antioxidants include ETHANOX 330, a hindered phenol from Albermarle; SANTOVAR A, a 2, 5-ditert-amyl hydroquinone from Monsanto; and NAVAGARD P a tris (p-nonylphenyl) phosphite from Uniroyal.
  • the moisture curable hot-melt adhesive composition can optionally comprise conventional additives known to a person skilled in the adhesive art.
  • Conventional additives which are compatible with the disclosed adhesive composition may simply be determined by combining a potential additive with the composition and determining if they remain homogenous.
  • suitable additives include, without limitation, toughener, 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 moisture curable hot-melt adhesive composition with desired properties.
  • the level of additives can be from 0 to about 50%, and preferably from about 0.5 to about 30%by weight of the total weight of the adhesive composition.
  • the moisture curable hot-melt adhesive composition comprises,
  • the moisture curable hot-melt adhesive composition is preferably free of water and/or solvent in either the solid and/or molten form.
  • the moisture curable hot-melt adhesive composition can be prepared by mixing the tackifying agent, the ethylenically unsaturated carboxylic acid graft modified polymer 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 silane modified polymer and other reactive components.
  • the moisture curable hot-melt adhesive compositions can be used to bond articles together by applying the hot-melt adhesive composition in heated, 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 moisture curable 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. The phase formed upon cooling of the adhesive composition and prior to curing impart initial or bonding strength to the bond. After solidification the adhesive is exposed to conditions such as surface or atmospheric moisture that crosslink and cure the solidified composition to an irreversible solid form.
  • the present invention relates to the method of applying a moisture curable hot-melt adhesive composition comprising:
  • the resulting adhesive is able to bond to a variety of substrates, such as magnesium-aluminum alloys, a polyamide-6, 6, a polyamide alloy, a polyamide-4, 10 alloy, aluminum, polycarbonate (PC) , Acrylonitrile-Butadiene-Styrene (ABS) , PC-ABS alloys, PC-styrene-acrylonitrile alloys, ink coated glass, and polyethylene terephthalate, polybutylene terephthalate laminated or coated ink-glass.
  • substrates such as magnesium-aluminum alloys, a polyamide-6, 6, a polyamide alloy, a polyamide-4, 10 alloy, aluminum, polycarbonate (PC) , Acrylonitrile-Butadiene-Styrene (ABS) , PC-ABS alloys, PC-styrene-acrylonitrile alloys, ink coated glass, and polyethylene terephthalate, polybutylene terephthalate laminated or coated
  • the adhesive composition can find particular utility in assembly for electronics such as touch panel displays, lap tops, computer and display monitors, cell phone, GPS, electronic watch, and electronic appliance touch panel screens and especially for battery fixing.
  • the present invention provides an article of manufacture comprising the cured products of the moisture curable hot-melt adhesive composition.
  • the article of manufacture includes but not limited to the electronics such as touch panel displays, lap tops, computer and display monitors, cell phone, GPS, electronic watch, and electronic appliance touch panel screens, and the battery contained therein.
  • the moisture curable hot-melt adhesive compositions allow for an excellent repair-rework ability that can be easily and continuously peeled off at room temperature, as well as an excellent bonding strength no less than 0.9 MPa, preferably no less than 1.1 MPa.
  • the testing methods of the reworkability and bonding strength are discussed in the part of “Examples” .
  • the combination of silane modified polymer and ethylenically unsaturated carboxylic acid graft modified polymer offers the cured adhesive an excellent balance of adhesive strength and cohesive strength to various substrates.
  • the cured adhesives possess a suitable adhesive strength to the substrate so as to firmly bind to the substrate after curing and render removable when an external force is applied on the adhesives.
  • the cured adhesives exhibit a cohesive strength sufficient to be intact when the external force is applied until the adhesive is completely removed from the substrate. Therefore, the cured products of the adhesive composition can be removed from the bonded substrate in an adhesive failure mode.
  • the adhesive composition preferably is applied in the form of a melt at temperatures from about 50°C to about 200°C, from about 65°C to about 180°C, or even from about 75°C to about 160°C
  • the adhesive composition can be applied using a wide variety of application techniques including, e.g., spray application, extrusion, dispensing, roll coating, and combinations thereof.
  • the bonding strength of the adhesives was tested and evaluated by the following procedure.
  • Bonding strength F / [25.4 ⁇ (W1 + W2) ] (MPa)
  • Vestoplast 206 used as silane modified polymer is a silane modified poly- ⁇ -olefin commercially available from Evonik Degussa (China) Co., Ltd.
  • SEBS 7131 used as the ethylenically unsaturated carboxylic acid graft modified polymer is a maleic anhydride graft modified styrene anhydride -ethylene /butylene –styrene (SEBS) copolymer, commercially available from Taiwan Synthetic Rubber Corp. (TSRC) , Taiwan under the trade name TAIPOL SEBS 7131, grafted with 1.38 wt%maleic anhydride.
  • SEBS maleic anhydride graft modified styrene anhydride -ethylene /butylene –styrene
  • FG 1901 used as the ethylenically unsaturated carboxylic acid graft modified polymer copolymer is a copolymer of maleic anhydride graft modified SEBS copolymer, commercially available from Kraton Polymer, under the trade name Kraton FG 1901, containing 30 wt%polystyrene block content and grafted with 1.7 wt%maleic anhydride.
  • MP-10 is amino group-modified SEBS copolymer commercially available from Asahi Kasei Chemicals Corporation, under the trade name Tuftec MP10.
  • Septon 2063 is a styrene-ethylene-propylene-styrene (SEPS) copolymer commercially available from Kuraray Co., Ltd.
  • SEPS styrene-ethylene-propylene-styrene
  • Regalite C8010 used as tackifying agent is a hydrogenated hydrocarbon resin commercially available from Eastman Chemical Company.
  • KA 100L used as tackifying agent is a rosin resin commercially available from Guangdong Komo Co., Ltd.
  • Plastolyn R1140 and R1125 used as tackifying agent is a hydrocarbon resin commercially available from Eastman Chemical Company.
  • DBTDL used as catalyst is dibutyl tin dilaurate, commercially available from Sinopharm Chemical Reagent Co., Ltd.
  • U220H used as catalyst is dibutyltin acetylacetonate, commercially available from Nitto Kasei Co., Ltd.
  • Eastoflex E1060 used as toughener is an amorphous polyolefin commercially available from Eastman Chemical Company.
  • Irganox 1010 used as antioxidant is pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) commercially available from BASF Corporation.
  • SIVO 202 used as silane coupling agent is a multifunctional aminosilane commercially available from Evonik Degussa (China) Co., Ltd.
  • Alink35 used as silane coupling agent is 3-isocyanatopropyltrimethoxysilane (CAS 15396-00-6) , commercially available from Momentive Performance Materials.
  • Example (Ex. ) 1 The adhesive composition of Example (Ex. ) 1 was prepared by sequentially charging the following components into a Z blade mixer manufactured by Shuenn Diing Machine Corporation that had been preheated to 160°C and equipped with vacuum: 3.00g SEBS 7131, 12.41g Septon 2063, 0.5g Irganox 1010 and 15.70g Regalite C8010. The materials were mixed for 20 minutes and then 12.57g KA 100L, 23.66g Plastolyn R1140 were added and mixed for 10 minutes. Vacuum was started and kept for 10 minutes to remove water, and 30.66g Vestoplast 206, 1.00 g Alink35 and 0.5 g U220H were then added to the mixer under vacuum and mixed for 10 minutes. The speed of mixing was controlled at 50 rpm during the whole preparation process. Then the adhesive composition was taken out to a 30mL plastic cartridge with aluminium foil sealed for testing.
  • Example 1 The adhesive composition of Example 1 was tested according to the test methods of bonding strength and reworkability set forth above.
  • Examples 1 to 10 according to the present invention possessed excellent binding strength (0.9 MPa or higher) and sufficient reworkability (score 4 or higher) . It was also confirmed in Comparative Examples 1 to 2 that the compositions containing conventional thermoplastics such as SEPS and amino group-grafted SEBS copolymer instead of the maleic acid anhydride graft modified block copolymer could not provide satisfactory reworkability at room temperature and the bonding strength at same time.
  • conventional thermoplastics such as SEPS and amino group-grafted SEBS copolymer instead of the maleic acid anhydride graft modified block copolymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition adhésive thermofusible durcissable à l'humidité, comprenant un polymère modifié par silane, un polymère modifié par greffage d'acide carboxylique éthyléniquement insaturé, et un agent collant. La composition adhésive thermofusible durcissable à l'humidité fournit un produit durci présentant une résistance de liaison améliorée et une excellente aptitude au refaçonnage à température ambiante.
PCT/CN2017/115195 2017-12-08 2017-12-08 Composition adhésive thermofusible durcissable à l'humidité WO2019109328A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4023729A1 (fr) 2020-12-30 2022-07-06 Bostik SA Composition adhésive silylée présentant une adhérence améliorée sur des substrats métalliques
WO2023272543A1 (fr) * 2021-06-30 2023-01-05 Dow Global Technologies Llc Durcissement de polymères à fonction anhydride avec des époxy-silanes
WO2023003714A1 (fr) * 2021-07-22 2023-01-26 Corning Incorporated Films, stratifiés et procédés de fabrication de compositions
WO2023060257A1 (fr) * 2021-10-08 2023-04-13 Synthomer Adhesive Technologies Llc Adhésif durcissable à base de résine à fonction silane

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Publication number Priority date Publication date Assignee Title
WO1996010615A1 (fr) * 1994-09-30 1996-04-11 Dupont Canada Inc. Film adhesif a durcissement module comprenant du silane et des polymeres greffes par acide
US6121354A (en) * 1998-11-19 2000-09-19 Bostik, Inc. High performance single-component sealant
US20140027056A1 (en) * 2012-07-24 2014-01-30 Henkel Corporation Reactive hot melt adhesive
CN104981527A (zh) * 2013-01-24 2015-10-14 汉高知识产权控股有限责任公司 反应性热熔性粘合剂

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Publication number Priority date Publication date Assignee Title
WO1996010615A1 (fr) * 1994-09-30 1996-04-11 Dupont Canada Inc. Film adhesif a durcissement module comprenant du silane et des polymeres greffes par acide
US6121354A (en) * 1998-11-19 2000-09-19 Bostik, Inc. High performance single-component sealant
US20140027056A1 (en) * 2012-07-24 2014-01-30 Henkel Corporation Reactive hot melt adhesive
CN104981527A (zh) * 2013-01-24 2015-10-14 汉高知识产权控股有限责任公司 反应性热熔性粘合剂

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4023729A1 (fr) 2020-12-30 2022-07-06 Bostik SA Composition adhésive silylée présentant une adhérence améliorée sur des substrats métalliques
WO2022144169A1 (fr) 2020-12-30 2022-07-07 Bostik Sa Composition adhésive silylée ayant une adhérence améliorée sur des substrats métalliques
WO2023272543A1 (fr) * 2021-06-30 2023-01-05 Dow Global Technologies Llc Durcissement de polymères à fonction anhydride avec des époxy-silanes
WO2023003714A1 (fr) * 2021-07-22 2023-01-26 Corning Incorporated Films, stratifiés et procédés de fabrication de compositions
WO2023060257A1 (fr) * 2021-10-08 2023-04-13 Synthomer Adhesive Technologies Llc Adhésif durcissable à base de résine à fonction silane

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