WO2017100750A1 - Adhésif de liaison d'un caoutchouc de silicone liquide - Google Patents

Adhésif de liaison d'un caoutchouc de silicone liquide Download PDF

Info

Publication number
WO2017100750A1
WO2017100750A1 PCT/US2016/066114 US2016066114W WO2017100750A1 WO 2017100750 A1 WO2017100750 A1 WO 2017100750A1 US 2016066114 W US2016066114 W US 2016066114W WO 2017100750 A1 WO2017100750 A1 WO 2017100750A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
silane
allyl
urethane
functional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/066114
Other languages
English (en)
Inventor
Tarek Agag
Paul Wheeler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lord Corp
Original Assignee
Lord Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lord Corp filed Critical Lord Corp
Publication of WO2017100750A1 publication Critical patent/WO2017100750A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • 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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins

Definitions

  • the invention relates to an adhesive suitable for injection and compression molding operations preferably those bonding liquid silicone rubber to polycarbonate, other plastics, and metals.
  • Liquid silicone rubber is used to produce a wide range of parts for many different markets. Some notable segments include medical devices, cookware, electronics, and personal electronic devices. Silicone polymers exhibit many unique properties that other materials cannot achieve, combining rubbery flexibility with excellent thermal stability, durability, low surface energy, biocompatibility, soft feel, etc... Because of its unique performance and relative ease of part manufacturing, the global LSR (silicone) market has seen rapid growth. As the market need for LSR expands, product designs are becoming more sophisticated and require bonding of silicone to other substrates, which can be challenging due to its ultra-low surface energy and chemical resistance.
  • silicone elastomers compared to conventional elastomers, include the following properties: UV resistance, thermal stability, high use temperature, and solvent and ozone resistance.
  • One method of producing silicone parts utilizes a chemical process referred to as addition curing, which is typically catalyzed using platinum complexes.
  • One form of silicone is referred to as LSR (liquid silicone rubber) and is handled in two different containers, one containing vinylated silicon polymer and Pt catalyst, and vinylated silicon polymer and Si-H oligomer in the other. Both are mixed just before use, followed by heating for vulcanization at high temperature.
  • Another form of silicone is referred to as HCR (high consistency rubber).
  • a platinum catalyst via a two-roll mill, is added to a high viscosity silicone matrix containing hydrosilane and vinyl groups.
  • thermoplastic substrate particularly polycarbonate, polyester, and polyamide
  • molding addition-cured silicone onto thermoplastic substrate results in multi material design and performance that combines the best attributes of both substrates.
  • Several techniques are used to modify the surface for improved adhesion, including plasma treatment, mechanical or chemical treatment, and exposure to flames, photons or ion beams.
  • plasma treatment is a commonly used method to improve the wettability and adhesion.
  • Such treatment leads to surface oxidization, increasing its surface energy and creating roughness.
  • there are performance reproducibility issues associated with the use of plasma treatment does not yield a surface that will covalently bond to silicone.
  • an adhesive is provided that is capable of bonding a wide assortment of rigid substrates to liquid silicone rubber (LSR) compounds during the curing step of the rubber.
  • this curing step is initiated in a mold to acquire the desired geometry and can optionally be later finished in a post curing step.
  • the adhesive solves several problems encountered today when using traditional LSR adhesives. Parts can be coated with the single coat adhesive by spray or brush techniques and can sit for several days under normal plant conditions and maintain the capability of bonding the dissimilar materials.
  • the inventive adhesive also provides robust adhesion to the various substrates and optionally doesn't require a plasma treating step to improve the surface for bonding. Removing this step is labor saving and saves the end user both time and money.
  • an adhesive comprising an allyl (urethane) silane, wherein the allyl (urethane) silane comprises at least one allyl- functional group and one silane-functional group connected through a urethane linkage.
  • the allyl (urethane) silane comprises [Ri]-CO- NH-R2-Si(OR3)3, wherein Ri comprises at least one alkeneoxy group, and R2 comprises a hydrocarbon chain, preferably where R2 comprises at least three carbon atoms, the alkenoxy group comprises [CH2-CH-CH2-O-], and the silane-functional group comprises an alkoxysilane.
  • the alkoxysilane most preferably comprises [-Si-(OR)3], wherein R comprises an unsaturated hydrocarbon, preferably a methyl or ethyl group.
  • R comprises an unsaturated hydrocarbon, preferably a methyl or ethyl group.
  • the allyl (urethane) silane comprises at least two allyl -functional groups.
  • the allyl (urethane) silane comprises the reaction product of gamma-isocyanate propyl triethoxy silane with trimethylol propane diallyl ether.
  • the adhesive further comprises a phenoxy resin, a carrier fluid, and optionally a catalyst, and in further embodiments a vinyl- functional PDMS, an alkoxylated PDMS, and a blocked isocyanate.
  • the adhesive is provided in a two-part composition comprising: in an A-side:
  • the vinyl-functional PDMS comprises about 3.0% vinyl
  • the alkoxylated PDMS comprises an ethoxylated PMDS
  • the isocyanate-functional silane comprises at least 2 carbon atoms between the urethane and silane functional groups.
  • phenoxy resin comprises a PKHH grade phenoxy resin
  • the primary catalyst comprises at least one of a platinum methylvinylcyclotetrasiloxane complex or platinum chloride (PtCl 2 )
  • the metal acetylacetone comprises zinc acetyl acetonate.
  • the carrier fluid comprises at least one of water, methyl ethyl ketone and xylene.
  • a process for bonding an article comprising, a) providing in a molding cavity a rigid substrate having an adhesive comprising the adhesive described above applied thereto, b) contacting within the molding cavity an elastomeric or thermoplastic material at a temperature and pressure to allow the elastomeric or thermoplastic material to flow and contact a portion of the adhesive-applied section of the rigid substrate, and c) maintaining the temperature and pressure sufficient to solidify the elastomeric or thermoplastic material and form an adhesive bond between the material and the rigid substrate.
  • the elastomeric or thermoplastic material comprises a silicone material
  • the adhesive is capable of forming rubber tearing bonds between the silicone material and the rigid substrate.
  • the rigid substrate comprises at least one of polycarbonate, polyester thermoplastic elastomer, and polyamide.
  • the process comprises at least one of a compression molding operation or an injection molding operation.
  • an adhesive is provided for bonding a variety of rigid substrates to elastomers, plastics, and TPVs.
  • the adhesive is particularly useful for injection and compression molding operations where the adhesive is applied to a substrate and a liquid silicone rubber (LSR) is applied through an injection or compression molding operation.
  • LSR liquid silicone rubber
  • the adhesive provides excellent adhesion to a variety of substrates including polycarbonate, polyester, stainless steel, aluminum, glass, and steel. Further, the range of adhesion to liquid silicone rubbers includes a variety of filled and unfilled, colored or transparent liquid silicone rubber compounds.
  • the adhesive comprises an allyl (urethane) silane.
  • the allyl (urethane) silanes employed in the present provide both silane functionality and terminal unsaturation.
  • mono- di- or tri- allyl (urethane) silanes may be employed, with di-allyl silanes being preferred.
  • the allyl (urethane) silane comprises a mono- or di- silane, with tri-silanes being particularly preferred.
  • the silane and allyl functional groups are separated by at least 4 and most preferably at least 6 carbon atoms.
  • the allyl (urethane) silane comprises at least one allyl-functional group and one silane-functional group connected through a urethane linkage.
  • the preferred allyl-functional groups comprise alkenoxy groups having one carbon atom between the double bond and the oxygen.
  • the allyl (urethane) silane comprises at least two allyl-functional groups.
  • the preferred silane-functional group comprises an alkoxysilane, preferably methoxy or ethoxy.
  • the silane functionality comprises a tri-methoxy or tri-ethoxy silane, and although less preferred, longer chain alkenoxy groups may be used with the present invention.
  • the allyl (urethane) silanes are prepared by reacting an isocyanato-silane in the presence of s catalyst with an allyl- containing alcohol to produce the desired allyl (urethane) silane.
  • the allyl (urethane) silane is present in the adhesive from about 5 to about 95, more preferably about 10 to about 50, and most preferably about 15 to about 30 weight percent based on the dry weight of the adhesive.
  • a vinyl functional siloxane is optionally included in the adhesive.
  • the vinyl functional siloxane of the present invention comprises any siloxane with vinyl functionality, such as trimethyl terminated poly(methylvinyl) siloxane, vinyl terminated polydimethyl siloxane, monovinyl terminated polydimethyl siloxane, trimethyl terminated vinylmethyl-dimethyl polysiloxane copolymer, monovinyldimethyl terminated vinylmethyl-dimethyl polysiloxane copolymer, vinyldimethyl terminated cinylmethyl-dimethyl polysiloxane copolymer, and the like.
  • the vinyl-funcitonal siloxane comprises vinyl-terminated polydimethyl siloxane.
  • the vinyl-functional silane comprises at least 2.0 and preferably about 3.0 % vinyl.
  • the vinyl functional siloxane is present in the adhesive up to about 40, more preferably up to about 30, and most preferably up to about 25 weight percent based on the dry weight of the adhesive.
  • an optional material comprises an alkoxylated PDMS corresponding to the general formula (1 )
  • PE is the monovalent radical— CH 2 — CH 2 — CH 2 — 0(eo v /poO w ) m Z,
  • eo represents ethylene oxide
  • po propylene oxide
  • Z is either hydrogen or a Ci-Ce-alkyl radical
  • v and w are integers greater than or equal to 0, wherein v and w are not simultaneously 0, x is an integer greater than or equal to 0, and y and m are integers greater than or equal to 1 , which are preferably so selected that the molecular weight (number average) of formula (1) does not exceed 30,000 g/mol. and the viscosity of component C) is from 10 to 5000 cSt (25°C).
  • an optional isocyanate-functional silane comprising at least 2 carbon atoms between the urethane and silane functional groups.
  • the isocyanate functional silane comprises a trimethoxy or triethoxy isocyanatopropyl silane.
  • the adhesive further comprises a phenoxy resin.
  • Phenoxy reins are commercially important thermoplastic polymers derived from bisphenols and epichlorohydrin. Their molecular weights are higher, i.e., at least about 45,000, than those of conventional epoxy resins, i.e., 8,000 maximum. They lack terminal epoxide functionality and are therefore thermally stable and can be fabricated by conventional thermoforming techniques.
  • the phenoxies have the same repeat unit as advanced epoxy resins and are classified as polyols or polyhydroxy ethers.
  • Phenoxy resins are prepared by reaction of high purity bisphenol A with epichlorohydrin in a 1 : 1 mole ratio. Solution polymerization may be employed to achieve the molecular weight and processibility needed.
  • a solvent-soluble phenoxy resin is employed for use in a solvent-based adhesive.
  • Solvent-soluble phenoxy resins are known in the art from a number of producers, however particularly suitable examples of phenoxy resins for solvent-based adhesives include the solid PKHH grade sold by Phenoxy Associates or PKHS-40, which is a PKHH grade pre-dissolved in methylethyl ketone (MEK).
  • MEK methylethyl ketone
  • Suitable amine neutralized, carboxylated phenoxy resins are those phenoxy resins which have been carboxylated with lower alkanoic acids having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid and hexanoic acid, which have been amine neutralized, by reaction with ammonia or ammonium hydroxide.
  • the phenoxy resin comprises A suitable example of a phenoxy resin that may be used in the present invention is a polymer of bisphenol "A", specifically, diglycidyl ethers of bisphenol "A". Suitable for use in the present invention as the phenoxy resin is that sold as Phenoxy Resin PKHW-35, and manufactured by Gabriel Performance Products in Ohio, USA.
  • PKHW-35 is an amine-neutralized, carboxylated phenoxy resin in water, and is a waterbome product that is surfactant-free, colloidal in natured with excellent emulsion stability from 0°C. to 55°C, exhibiting a high degree of consistency in viscosity and solids, and having up to 40 percent solids by weight.
  • the phenoxy resin is present in the adhesive from about 10 to about 80, more preferably about 35 to about 68, and most preferably about 50 weight percent based on the dry weight of the adhesive.
  • the adhesive further comprises a catalyst.
  • the catalyst comprises a typical metal hydrosilylation catalyst and used in an amount specified below which is sufficient to effect the cure of the adhesive composition.
  • the catalyst comprises a platinum cyclovinylmethylsiloxane complex.
  • An additional suitable platinum catalyst is available from Gelest, Inc. under the SIP 6830 designation, also known as Karstedt Catalyst, or a COD catalyst such as dichloro(l,5-cyclooctadiene)platinum(II), available from Sigma- Aldrich, Missouri, USA.
  • the catalyst comprises a platinum methylvinylcyclotetrasiloxane complex.
  • An additional suitable platinum catalyst comprises dichloro(l,5-cyclooctadiene)platinumII.
  • the catalyst is present in the adhesive up to about 3.0, more preferably about 0.05 to about 2.0, and most preferably about 0.10 to about 1.5 weight percent based on the dry weight of the adhesive.
  • co-catalysts While typically employed in embodiments where a catalyst is present in the adhesive formulation, co- catalysts may also be employed in adhesive formulations without a primary catalyst.
  • co-catalysts are preferable based on the elements from Groups VIIB, VIII, IB, IIB, IVA or VA of the Periodic Table of the Elements such as manganese, cobalt, nickel, copper, zinc, zirconium germanium, antimony, or bismuth, especially compounds based on an element from the foregoing groups metals, such as bivalent metals, and particularly chelates of metals, or oxides or salts of these metals and especially carbonate salts are preferred. Zinc, bismuth, and antimony are especially preferred metallic elements, with zinc being most preferred.
  • Representative salts of these co-catalyst metals are based on inorganic acids, carboxylic acids, hydroxy carboxylic acids, alcohols, glycols and phenols.
  • Representative carboxylic acids include both mono and dicarboxylic acids containing from 1 to about 20 carbon atoms and include aliphatic and cycloaliphatic saturated or unsaturated acids, and aromatic acids, and include formic, acetic, acrylic, methacrylic. propionic, butyric, hexanoic, octanoic, decanoic, stearic, oleic, eiconsanoic and benzoic acids.
  • Examples of dicarboxylic acids include oxalic, malic, maleic, succinic, sebacic and the various isomeric phthalic acids.
  • Typical hydroxy carboxylic acids preferably contain from 2 to about 20 carbon atoms and include hydroxy acetic, lactic, citric, tartaric, salicylic, and gluconic acids.
  • Inorganic acids or the mineral acids include carbonic acid, halogen acids such as hydrochloric, hydrobromic, and hydriodic acids, nitrogen acids, sulfur acids and phosphorus acids, all of which are known in the art.
  • the alcohols comprise straight chain or branched chain mono- or polyhydroxy alcohols, alkyl substituted or unsubstituted mononuclear or polynuclear mono or polyhydroxy cycloaliphatic alcohols and the like containing from 1 to about 20 carbon atoms.
  • the phenols comprise alkyl substituted or unsubstituted mononuclear or polynuclear mono or polyhydroxy phenols.
  • the carbonates of the aforesaid metals may exist as pure carbonates or as basic carbonates which are believed to be mixtures of the carbonate and the oxide or hydroxide of the metal in a single molecule and include metal carbonates such as basic zinc carbonate, basic copper carbonate and the like.
  • the chelates of the aforesaid metals that may be employed may be based on any metal chelating compounds known in the art but typically comprise beta-diketones such as acetyl acetone to provide the acetyl acetonates of the metals.
  • Metal catalysts that are generally most suitable as cocatalysts are the ones that are soluble in the formulation especially if soluble in the functional compound, e.g. the polyol resin or soluble in the solvent if the formulation uses a solvent.
  • Some specific metal catalysts that may be employed comprise zinc carbonate (basic), zinc acetyl acetonate, zinc acetate, copper acetylacetonate, iron acetyl aeetonate, nickel acetylacetonate, zinc acetate, zinc lactate, and copper acetate.
  • Such suitable metal cocatalysts are generally described by Leiner and Bossert in U. S. Pat. No. 4,395,528.
  • the co-catalyst is present in the adhesive up to about 10, preferably up to about 5, and most preferably about 1.0 to about 3.0 weight percent based on the dry weight of the adhesive.
  • the adhesive further comprises a self-blocked isocyanate. Self-blocked isocyanates are also referred to as internally-blocked isocyanates and commonly comprise dimerized diisocyanates.
  • Bis (cyclic ureas) are blocked aliphatic diisocyanates and are preferred in some embodiments because no by-products are formed upon thermal release of the reactive isocyanate groups. These comprise compounds that can be referred to as self-blocked isocyanates. Examples of these bis-cyclic ureas are described by Ulrich, ACS Symp. Ser. 172 519 (1981), Sherwood, J. Coat. Technol. 54 (689), 61 (1982) and Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 23, p. 584 all of which are incorporated herein by reference.
  • uretdi one- bound self-blocked isophorone diisocyanate which is marketed from Huls Co. under a tradename "IPDI-BF 1540" may be cited.
  • the "internally blocked isocyanates” comprise the dimerized diisocyanates discussed above, however there may be some isocyanate functionalities on the ends of the molecule that are partially blocked or unblocked. These functionalities may react slowly with water and decrease shelf life in aqueous formulations, however the primary "internally blocked” isocyanate functionality remains reactive in the as-applied adhesive formulation and is available for bonding.
  • the self-blocked isocyanate comprises dimeric isocyanates such as dimeric toluene diisocyanate (TDI-uretdione), dimeric methylene diphenyl diisocyanate (MDI-uretdione) or a mixture thereof.
  • dimeric toluene diisocyanate TDI-uretdione
  • MDI-uretdione dimeric methylene diphenyl diisocyanate
  • a mixture thereof is an example of a uretdione of MDI is GRILBOND A2BOND available from EMS-Griitech (Switzerland)
  • an example of a uretdione of TDI is ADOLINK TT available from Rhein Chemie Rheinau GmBH (Mannheim, Germany).
  • the self-blocked isocyanate is present in the adhesive up to about 30, more preferably about 15 to about 25, and most preferably about 20 weight percent based on the dry weight of the adhesive.
  • the adhesive is provided in an aqueous carrier with the optional inclusion of small amounts of co-solvent.
  • the adhesive is provided in a solvent carrier system, though small amounts of water may be present in an emulsion or colloidal mixture.
  • 00S4] In a further embodiment of the present invention, the adhesive is provided in a hydrocarbon-solvent based system.
  • suiiable solvents are solvents which are inert towards isocyanate groups, such as hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, di ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or monoethyl ether acetate, diethylene glycol-ethyl and butyl ether acetate, propylene glycol monomethyl ether acetate, l-methoxyprop-2-yl acetate, 3-methoxy-n-butyl acetate, propylene glycol diacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyciohexanone, lactones such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ - caprolactone and ⁇ -methyl caprolactone, for example,
  • the adhesive compositions of the present invention can optionally contain other well-known additives including plasticizers, fillers, pigments, surfactants, dispersing agents, wetting agents, rheology modifiers, reinforcing agents and the like.
  • the adhesives are applied to the rigid substrate through common application procedures such as spray application, brush application, or a dip process.
  • the adhesive is preferably applied in a uniform wet film and hot air is employed to assist the drying and removal of the carrier fluid.
  • the dry film thickness is targeted for about 0.20-1.0 mils or 5 to 25 microns.
  • Bonded assemblies are prepared using a compression or injection molding process.
  • a mold having two separate cavities is employed.
  • the rigid substrate having the dry adhesive film coating is placed in the preheated mold and the plastic/elastomer to be bonded is placed on top in the cavity.
  • the hot mold is closed and placed in a hydraulic press and clamped under a known pressure. Once cured, the bonded assemblies are removed from the mold. Once the bonded assemblies cooled to room temperature they can be manually and visually tested for bond quality.
  • Injection molding is similar, except the plastic/elastomer is injected into the mold cavity as a liquid and an elevated temperature and pressure are maintained until the assembly is cured and bonded.
  • the adhesive bonds platinum-cured liquid silicone rubber (LSR) to polycarbonate and polyester thermoplastic elastomer without the need for any surface pretreatment process, such as plasma, corona, flame, or solvent treatment.
  • the adhesive is not affected by the addition of colorant to the LSR (4 weight percent pink colorant).
  • the adhesive demonstrates layover performance of at least 3 days, meaning that the plastic parts can be sprayed with this adhesive and stored under ambient conditions for 3 days before LSR molding, and still achieve effective bond strength.
  • the adhesive gives bond strengths that exceed the tear strength of the LSR material.
  • the adhesive has a large processing window in terms of thickness - it is effective at thicknesses ranging from 3 to 20 microns.
  • the adhesive shows favorable spraying characteristics that allow it to be easily applied with an air powered spray gun. These attributes include low viscosity, fast drying time, good wetting of polymer surfaces, and homogeneous consistency.
  • the adhesive is prepared by mixing 9 parts of A side and 1 part of B side.
  • both sides should be mixed very well to make sure the mixtures are homogenous.
  • thermoplastic materials were gathered from various suppliers, and selected as substrates. These materials will be referred to by their generic designations: polycarbonate (PC), flame-retardant polycarbonate (PCFR), thermoplastic elastomer (TPE), and polyamide (PA). Stainless steel (304) with polished and grit blasted surface finishes was also included in this experiment.
  • LSR Low-strength Rubber
  • the substrate was masked with Kapton tape such that only half of the test plaque would receive adhesive.
  • adhesive was applied to the section with VDI-26 finish.
  • Adhesives were applied with a Binks Model 95 siphon feed HVLP spray gun to a thickness of 10 to 15 microns. Immediately after spraying, parts were dried in a hot air convection oven at 50°C for 15 minutes. After removing from the oven, parts were stored at 21 °C / 50% RH for up to 4 hours before overmolding with LSR.
  • the A and B sides of the silicone were mixed in a mixer at low speed for five minutes.
  • the substrate was overmolded with LSR in a Wabash MPI G30H-18-BX compression press that was heated to 125°C.
  • three pieces of substrate were placed into a 150 mm x 150 mm x 5 mm mold, along with 150 grams of LSR.
  • the parts were then molded at 20 tons of pressure for 5 minutes. After 5 minutes, parts were carefully removed and allowed to cool to room temperature before being separated with a utility knife. Strips 25 mm wide were cut into the LSR for peel testing.
  • failure mode analysis is key to understanding product performance and bonding mechanism.
  • the test area is a 25 mm strip that is approximately 45 mm long. Failure mode is reported as a percentage of this area based on its state after testing is carried out. Failure modes were divided into four categories, each one is described below: • Thick Rubber Retention: the entire thickness of the silicone rubber is intact. This is the most desirable failure mode and means that the strength of the adhesive exceeds the strength of the silicone.
  • Thin Rubber Retention a thin layer of rubber is retained on the substrate. This means that the silicone rubber itself failed, but failed at a layer that is close to the adhesive interphase. This failure mode can be influenced by the performance of the adhesive, and can be caused, for example, if the adhesive retards or interrupts the silicone curing mechanism. A small amount ( ⁇ 20%) of thin rubber failure is normal and unavoidable in this test method.
  • the first test evaluated the effectiveness of each adhesive on three different representative LSR's of similar durometer from three major silicone producers. Each LSR was mixed, per the manufacturer recommendation, at a 50:50 ratio of A to B and cured via addition reaction catalyzed by platinum. The same process conditions (125°C for 5 minutes) were also used for all three silicones. Bonding data is shown below:
  • PC polycarbonate
  • PCFR flame-retardant polycarbonate
  • TPE thermoplastic elastomer
  • SUS stainless steel
  • the adhesive system was successful in bonding multiple platinum-cured silicones to multiple substrates that do not require special surface preparation techniques such as plasma or flame treatment, and does not have the same application limitations as typical silane primers.
  • a mold was constructed to accept 1" x 2.5" x 0.060" coupons (25.4mm x 63.5mm x 1.5mm), and overmold it with a strip of liquid silicone.
  • approximately half of the surface area of coupons of polycarbonate were sprayed with adhesive per the conditions in the table listed below. These coupons were overmolded with a LSR and tested 24 hours later in 90 degree peel at 300 mm/min. Peak peel values were recorded.
  • Example 1 The above-adhesive was mixed, applied, bonded and tested as described in Example 1.
  • the self-blocked isocyanate, A2 Bond arrives as a dispersion in glycol ether, and the phenoxy resin and zinc acetylacetonate arrive as dispersion in water. All these materials are separated above to illustrate the individual components.
  • the adhesive was employed to bond three different LSR materials to a polycarbonate substrate.
  • the adhesive produced rubber-tearing bonds (100%R) in all three trials, demonstrating a robust bond between the LSRs and the polycarbonate substrate.

Landscapes

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

Abstract

La présente invention concerne un adhésif comprenant un allyl(uréthane)silane, dans lequel l'allyl(uréthane)silane comprend au moins un groupe fonctionnel allyle et un groupe fonctionnel silane connectés à travers une liaison uréthane. De préférence, l'allyl(uréthane)silane comprend du [R1]-CO-NH-R2-Si(OU3)3, Ri comprenant au moins un groupe alcèneoxy, et R2 comprenant une chaîne hydrocarbure, préférablement où R2 comprend au moins trois atomes de carbone, le groupe alcèneoxy comprend du [CH2-CH-CH2-O-], et le groupe fonctionnel silane comprend un alcoxysilane. L'alcoxysilane comprend idéalement du [-Si-(OR)3], R comprenant un groupe hydrocarbure insaturé, préférablement un groupe méthyle ou éthyle.
PCT/US2016/066114 2015-12-11 2016-12-12 Adhésif de liaison d'un caoutchouc de silicone liquide Ceased WO2017100750A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201562266173P 2015-12-11 2015-12-11
US201562266197P 2015-12-11 2015-12-11
US62/266,173 2015-12-11
US62/266,197 2015-12-11

Publications (1)

Publication Number Publication Date
WO2017100750A1 true WO2017100750A1 (fr) 2017-06-15

Family

ID=57882121

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/066114 Ceased WO2017100750A1 (fr) 2015-12-11 2016-12-12 Adhésif de liaison d'un caoutchouc de silicone liquide

Country Status (1)

Country Link
WO (1) WO2017100750A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021016514A1 (fr) * 2019-07-25 2021-01-28 Lord Corporation Adhésif en une partie pour uréthanes thermoplastiques
US20210299394A1 (en) * 2018-05-09 2021-09-30 Fisher & Paykel Healthcare Limited Medical components with thermoplastic moldings bonded to substrates
CN117779479A (zh) * 2023-12-19 2024-03-29 万华化学集团股份有限公司 一种柔软高剥离强度透湿的有机硅革及其制备方法
WO2025023144A1 (fr) * 2023-07-26 2025-01-30 信越化学工業株式会社 Composé silicium organique, composant contenant un substrat traité en surface par ce composé silicium organique, préimprégné, carte de circuit imprimé, et liquide de traitement pour tissu de verre
US12281242B2 (en) 2018-12-03 2025-04-22 Lord Corporation Adhesive for castable urethanes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395528A (en) 1981-03-02 1983-07-26 M&T Chemicals Inc. Catalyst composition and curable polymer compositions containing same
US20080108767A1 (en) * 2004-09-09 2008-05-08 Daikin Industries, Ltd. Fluorine-Containing Compound Having Hydrolyzable Metal Alkoxide Moiety, Curable Fluorine-Containing Polymer Prepared From The Same Compound, And Curable Fluorine-Containing Resin Composition Comprising The Same Polymer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395528A (en) 1981-03-02 1983-07-26 M&T Chemicals Inc. Catalyst composition and curable polymer compositions containing same
US20080108767A1 (en) * 2004-09-09 2008-05-08 Daikin Industries, Ltd. Fluorine-Containing Compound Having Hydrolyzable Metal Alkoxide Moiety, Curable Fluorine-Containing Polymer Prepared From The Same Compound, And Curable Fluorine-Containing Resin Composition Comprising The Same Polymer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Kirk-Othmer Encyclopedia of Chemical Technology", vol. 23, pages: 584
SHERWOOD, J. COAT. TECHNOL., vol. 54, no. 689, 1982, pages 61
ULRICH, ACS SYMP. SER., vol. 172, 1981, pages 519

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210299394A1 (en) * 2018-05-09 2021-09-30 Fisher & Paykel Healthcare Limited Medical components with thermoplastic moldings bonded to substrates
US12281242B2 (en) 2018-12-03 2025-04-22 Lord Corporation Adhesive for castable urethanes
WO2021016514A1 (fr) * 2019-07-25 2021-01-28 Lord Corporation Adhésif en une partie pour uréthanes thermoplastiques
CN114207074A (zh) * 2019-07-25 2022-03-18 洛德公司 热塑性聚氨酯用单组分粘合剂
US12600887B2 (en) 2019-07-25 2026-04-14 Lord Corporation One-part adhesive for thermoplastic urethanes
WO2025023144A1 (fr) * 2023-07-26 2025-01-30 信越化学工業株式会社 Composé silicium organique, composant contenant un substrat traité en surface par ce composé silicium organique, préimprégné, carte de circuit imprimé, et liquide de traitement pour tissu de verre
JP2025018184A (ja) * 2023-07-26 2025-02-06 信越化学工業株式会社 有機ケイ素化合物、有機ケイ素化合物で表面処理された基材を含む物品、プリプレグ、プリント配線基板、およびガラスクロス処理液
CN117779479A (zh) * 2023-12-19 2024-03-29 万华化学集团股份有限公司 一种柔软高剥离强度透湿的有机硅革及其制备方法

Similar Documents

Publication Publication Date Title
EP3583149B1 (fr) Compositions d'adhésif à base de résines greffées
US9862867B2 (en) Alkoxy-functional organopolysiloxane resin and polymer and related methods for forming same
US20110237740A1 (en) Blend of silylated polyurethane containing polydiorganosiloxane and silylated polyurethane and substrates containing same and process of making said substrates
KR101519459B1 (ko) 오르가닐 옥시실란 말단을 가진 폴리머를 기반으로 하는 가교성 물질
JP5251732B2 (ja) シリコーン粘着剤組成物
WO2017100750A1 (fr) Adhésif de liaison d'un caoutchouc de silicone liquide
JP5594991B2 (ja) 接着性シリコーンゴム組成物
US9850349B2 (en) Multicomponent room temperature-curable organopolysiloxane composition, cured product of said composition, and molded product comprising said cured product
CN108291020A (zh) 包含环氧化合物和带有烷氧基甲硅烷基的预聚物的粘合剂体系及其应用
US7338996B2 (en) Primer for silicone rubber
JP4618451B2 (ja) トリアジンチオール基及びアルケニル基を有するオルガノポリシロキサン及びその製造方法、並びに当該オルガノポリシロキサンを含有する接着用プライマー組成物
KR20080077971A (ko) 2-파트 경화성 조성물 및 그로부터 얻은폴리우레탄-폴리실록산 레진 혼합물
TW200808909A (en) Room temperature-curable organopolysiloxane composition
KR20140007866A (ko) 라미네이트 및 그의 대전 방지 또는 감소 방법
WO2017053402A1 (fr) Composition adhésive et procédé de collage
JP3235382B2 (ja) 粘着性接着剤組成物
US10428183B2 (en) Room temperature-curable resin composition containing an aluminum chelate compound
JP3476368B2 (ja) 室温硬化性オルガノポリシロキサン組成物
US12365799B2 (en) Oil-bleed self-bonding liquid silicone rubber composition
EP4660218A1 (fr) Organopolysiloxane à teneur en groupe hydroxyle ainsi que procédé de fabrication de celui-ci, composition durcissable comprenant cet organopolysiloxane, agent de revêtement, et article revêtu
CN114430758A (zh) 氟硅橡胶层叠体的制造方法以及氟硅橡胶层叠体
JPS6035017A (ja) 反応射出成形によって造形ポリマー成分を製造する方法に使用するための液体有機ポリイソシアネート組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16829448

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16829448

Country of ref document: EP

Kind code of ref document: A1