Anaerobic curing composition

Abstract

An anaerobic curable composition comprising a liquid anaerobic curable component, a solid anaerobic curable component, a solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40° C. to 80° C., and a curing component that cures the anaerobic curable component. Advantageously, the composition of the present invention is substantially solid and can be used as a thread locker.

Description

[Technical Field]

[0001] The present invention relates to an anaerobic curable composition that can be used in many applications, including thread lockers. The composition is substantially solid and can be provided in any suitable solid form, including as a tape, a filament, or as a coating applied to a substrate containing a filament or thread made from another material, such as nylon or polyester yarn. The present invention also relates to a method for preparing threaded components and a method for assembling threaded components. The composition is easy to handle and can be applied to threaded members. [Background technology]

[0002] (A brief explanation of related technologies) Threadlock compositions are used to lock and / or seal threaded components such as nuts and bolts in an interlocking state. Such threadlock compositions significantly increase the torque required to break or rotate the engaged threaded components. Conventional threadlock compositions often include a co-reactive adhesive system in which two or more components are mixed before the resulting composition is applied to the threaded engagement surface of a fastener, where the components in the threadlock composition react and harden. Examples of such co-reactive systems include epoxy resin adhesive compositions.

[0003] Liquid adhesive compositions have long been used in sealing and threadlocking applications and have become a standard part of assembly manufacturing as well as maintenance of machinery, tools, and other equipment. Among the liquid adhesive compositions commonly used in these applications are anaerobic compositions. These compositions provide excellent threadlocking and sealing properties when cured. Anaerobic curing compositions applied to screw parts as threadlocking compositions remain stable (in an uncured state) and are therefore liquid until placed between interlocked screw parts that cure in the absence of oxygen.

[0004] Anaerobic curing compositions are generally well known. See RDRich, “Anaerobic Adhesives” in the Adhesion Technology Handbook, 29, 467-79, edited by A. Pizzi and KLMittal, Marcel Dekker, Inc., New York (1994), and the references cited therein. They have numerous applications, and new applications continue to be developed.

[0005] Anaerobic adhesive systems are stable in the presence of oxygen but polymerize in its absence. Polymerization is often initiated by the presence of free radicals generated from peroxy compounds. Anaerobic adhesive compositions are well known for their ability to remain in a liquid, non-polymerized state in the presence of oxygen and then harden into a solid state when oxygen is removed.

[0006] In many cases, anaerobic adhesive systems contain resin monomers having polymerizable acrylate esters at their termini, such as methacrylate, ethyl acrylate, and chloroacrylate esters. For example, polyethylene glycol dimethacrylate and urethane acrylate (e.g., U.S. Patent No. 3,425,988 (Gorman)) are derived according to known urethane chemistry. Other components typically present in anaerobic curing adhesive compositions include initiators such as organic hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide, accelerators to increase the curing rate of the composition, and stabilizers such as quinone or hydroquinone, which are included to prevent premature polymerization of the adhesive due to the decomposition of peroxy compounds.

[0007] A desirable curing-inducing composition for inducing and accelerating anaerobic curing may, together with maleic acid, comprise one or more toluidines such as saccharin, N,N-diethyl-p-toluidine ("DE-pT") and N,N-dimethyl-o-toluidine ("DM-oT"), and acetylphenylhydrazine ("APH"). See U.S. Patent Nos. 3,218,305 (Krieble), 4,180,640 (Melody), 4,287,330 (Rich), and 4,321,349 (Rich), among others.

[0008] Saccharin and APH are used as standard curing accelerator components in anaerobic adhesive curing systems. In fact, many of the LOCTITE® brand anaerobic adhesive products currently available from Henkel Corporation use either saccharin alone or both saccharin and APH.

[0009] Anaerobic curing adhesive compositions also typically contain chelating agents, such as ethylenediaminetetraacetic acid (EDTA), which are used to sequester metal ions.

[0010] Compositions suitable for use in pre-applied threadlock applications are typically applied in a dry-touch manner but possess anaerobic curing properties in a later stage.

[0011] In some cases, a dry-touch form is achieved using a curing mechanism. For example, a first curing mechanism can form a dry-touch form to hold the composition in place on the article, while a second curing mechanism is later activated to achieve thread locking.

[0012] For example, European Patent No. 0077659 (Thompson) describes a pre-coated polymerizable fluid for sealing and locking engineering parts. The composition has two mechanisms for curing, resulting in two curing reactions. The first mechanism is UV light curing. An opaque agent is dispersed in the fluid, making the fluid substantially opaque to radiation. After the fluid is applied to a part, it is exposed to UV radiation, where a coating is formed, creating a surface layer that is a dry, non-sticky outer layer. The fluid beneath the surface is unaffected by radiation and generally remains in a liquid state. When the parts are screwed into another part, the surface layer breaks, initiating a second polymerization (such as free radical polymerization), and once the screw parts are engaged and an anaerobic environment is established, the second curing reaction occurs. The second polymerization mechanism acts to lock the screws together. In Thompson, only the outer layer is formed in the first polymerization, and the rest of the composition remains liquid beneath the outer layer. Therefore, there is a risk that the outer layer may break during handling of the coated industrial parts, causing the liquid composition to leak out.

[0013] Similarly, European Patent No. 0548369 (Usami) describes a pre-applied adhesive composition for application to threaded contact surfaces of screw members such as screws. This composition comprises a photocurable binder in which a second curable composition is dispersed. The second curable composition comprises a microencapsulated reactive monomer / activator / initiator.

[0014] International patent application WO2004 / 024841A2 (Haller) describes a curable composition for application to threaded articles. The composition comprises a first curing mechanism component comprising (a) a (meth)acrylate-functional monomer component, (b) a (meth)acrylate-functional oligomer component, and (c) a photoinitiator component; and a second curing mechanism component comprising (ii)(e) an amine component and (f) an encapsulated epoxy resin component; and a dispersion of (iii) a thickening agent component. The photoinitiator component is suitable for irradiation of the composition and achieves a first curing over the depth of the composition applied to a threaded article, and a binder matrix is ​​formed using the second curing mechanism component dispersed through the matrix.

[0015] U.S. Patent No. 9,181,457 (Attarwala) describes a dry-touch composition comprising a polymer matrix and an anaerobic curable component present within the polymer matrix. In a particularly preferred form, the composition is moisture-curable. The composition is non-flowing at high temperatures and exhibits improved solvent resistance upon curing. The composition is useful as a threadlock composition and can be formulated as a coating on carrier substrates such as tapes, strings, or sheets.

[0016] British Patent No. 2,543,756 (Ledwith) describes a threadlock composition comprising an anaerobic curable component and a curing component for curing the anaerobic curable component, wherein the composition is in the form of flowable particles and has a melting point in the range of 30 to 100°C. The anaerobic curable component may comprise an anaerobic curable monomer and a resin component. The composition may be provided in at least two-part form. The anaerobic curable component is preferably provided in powder form. Preferably, the resin component is selected from methacrylated polyurethane resin, novolac resin, or higher methacrylated polyester resin. The anaerobic curable monomer preferably comprises at least one acrylate or methacrylate ester group. The composition is preferably solvent-free. Also disclosed is a method for threadlocking two threaded articles together, the method comprising applying the composition to the threads of at least one article and melting it into the threads, then optionally after cooling, screwing the two articles together and initiating anaerobic curing of the threadlock composition to chemically bond the two articles. Articles to which the above composition is applied are also disclosed.

[0017] U.S. Patent Application Publication No. 4,039,705 (Douek) relates to an anaerobically curable pressure-sensitive adhesive stock, such as sheets and tapes, in which a pressure-sensitive adhesive layer comprising at least one anaerobic resin system is completely transferred from one substrate to another and cured by activation with a peroxy initiator and elimination of oxygen. The anaerobic pressure-sensitive adhesive is contained between two different release surfaces, enabling the transfer of the pressure-sensitive adhesive to the substrate, which is firmly fixed to the other substrate upon curing of the anaerobically curable pressure-sensitive adhesive. [Overview of the project] [Problems that the invention aims to solve]

[0018] Conventional anaerobic thread lockers have received favorable reviews in the market but have drawbacks for commercial applications. This is seen in the use of conventional liquid anaerobic thread lockers and known non-fluid thixotropic anaerobic-based thread lockers. For example, such compositions often do not cure completely through large gaps. Also, due to the nature of anaerobic curing, if the portion of the adhesive applied to the part remains exposed to air, curing becomes difficult (in the absence of a triggered secondary curing mechanism). Thus, external bond lines on nut / bolt assemblies that remain exposed to air often remain liquid unless additional additives or curing means are employed to ensure curing. As a result, the liquid composition of the external bond line tends to move. In the case of conventional non-fluid compositions where non-fluidity depends on the thixotropic and / or rheological properties of the composition, these compositions flow when the temperature to which they are exposed is sufficiently high. Furthermore, the solvent resistance of the cured product (which has uncured portions as described above) is low, indicating doubt about its integrity in the event of environmental interactions. This can lead to problems of contamination and dangerous surrounding conditions.

[0019] Despite the state of the art, it is desirable to provide an alternative thread lock system that includes a dry-touch thread lock composition, a method of forming such a threaded member, and a method of assembling such a threaded member.

Means for Solving the Problems

[0020] <Summary> In one aspect, the present invention provides a liquid anaerobic curable component, a solid anaerobic curable component, a solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40°C to 80°C, and a curing component for curing the anaerobic curable component, comprising an anaerobic curable composition.

[0021] Advantageously, the composition of the present invention is substantially solid and can be used as a thread locker.

[0022] The liquid anaerobic curable component may be present in an amount of about 4% to about 44% by weight based on the total weight of the curable composition, preferably in an amount of about 5% to about 40% by weight based on the total weight of the curable composition, for example, in an amount of about 5% to about 20% by weight based on the total weight of the curable composition. If the liquid anaerobic curable component is present in an amount of less than about 4% by weight based on the total weight of the composition, the composition, when applied / coated to a substrate, may be too rigid / not fluid and therefore not move well. For example, it may not move in the space between mutual threads that are screwed together, resulting in poor thread locking performance or poor adhesive performance. If the liquid anaerobic curable component is present in an amount greater than about 44% by weight based on the total weight of the composition, the integrity of the on-part may be adversely affected, and the composition may be too fluid / soft, for example, the composition may easily rupture when it comes into contact with other surfaces, such as the surface of handling equipment, or other substrates, including other substrates to which the coating may be applied. When the liquid anaerobic curable component is present in an amount of about 4% to 44% by weight based on the total weight of the curable composition, this provides the composition with an acceptable balance between threadlocking and / or adhesive performance, forming a coating with sufficient integrity and resulting in good bond strength upon curing. Integrity is required for the application of the composition to the parts to be bonded, while bond strength is required for the end use of the bond.

[0023] The solid anaerobic curable component is present in an amount of about 5% to about 45% by weight, based on the total weight of the composition, and preferably in an amount of about 10% to about 40% by weight, e.g., 15% to about 35% by weight, based on the total weight of the curable composition. Compositions containing less than about 5% by weight of the solid anaerobic curable component tend to lack cohesiveness and may not be suitable for on-part coating. For example, a coating formed by such a composition may easily rupture upon contact with other surfaces, such as the surface of handling equipment, or other substrates, including other substrates to which the coating may have been applied. Compositions containing more than about 45% by weight of the solid anaerobic curable component tend to form a coating that is too brittle to be applied to the parts to be bonded. When the solid anaerobic curable component is present in an amount of about 5% to about 45% by weight, based on the total weight of the composition, it provides a composition that has an acceptable balance between threadlock and / or adhesive performance (when cured) (when applied as a coating) and provides a composition that can be applied as a coating with sufficient integrity and strength.

[0024] The solid thermoplastic polyurethane resin can be present in an amount of about 20% to about 75% by weight based on the total weight of the composition, and preferably in an amount of about 35% to about 65% by weight based on the total weight of the curable composition, for example, about 38% to about 62% by weight. Compositions containing less than about 20% by weight of solid thermoplastic polyurethane component tend to have insufficient elastomer properties and cannot be properly applied to the parts to be bonded. Compositions containing more than about 75% by weight of solid thermoplastic polyurethane component tend to exhibit poor threadlock / adhesion properties. When the solid thermoplastic polyurethane resin is present in an amount of about 20% to about 75% by weight based on the total weight of the curable composition, this provides the composition with an acceptable balance between threadlock and / or adhesion performance, provides a composition that forms a coating with sufficient elastomer properties, and enables the application of the composition to the parts to be bonded.

[0025] The curing component for curing the anaerobic curing component may be present in an amount of about 0.1 to about 10% by weight based on the total weight of the curable composition, for example, in an amount of about 1 to about 5% by weight based on the total weight of the curable composition.

[0026] Preferably, the liquid anaerobic curing component includes a liquid (meth)acrylate monomer component.

[0027] The liquid (meth)acrylate monomer component is, formula: H2C=CGCO2R 8 One or more may be selected from those having the following characteristics: During the ceremony, G is hydrogen, halogen, or alkyl group having 1 to 4 carbon atoms, and R 8 The group is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, or aryl groups having 1 to about 16 carbon atoms, and may be optionally substituted or interrupted with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, sulfone, etc.

[0028] Preferably, the solid anaerobic curable component comprises one or more solid (meth)acrylate monomer components. For example, the solid anaerobic curable component may be a reaction product of phenyl isocyanate and hydroxyethyl methacrylate (HEMA). [ka] This is a 2-methacryloxylethyl urethane with a melting point of approximately 70-75°C.

[0029] The solid anaerobic curing component may be the reaction product of 2 molar equivalents of HEMA and 1 molar equivalent of a diisocyanate such as isophorone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate) (hMDI), or 1,5-cyclohexyl diisocyanate (CHDI).

[0030] for example, [ka] It is a HEMA-IPDI-HEMA with a melting point of approximately 72-74°C.

[0031] [ka] It is HEMA-hMDI-HEMA with a melting point of approximately 75-85°C.

[0032] [ka] It is HEMA-CHDI-HEMA with a melting point of approximately 75-85°C.

[0033] The solid anaerobic curable component may be a polyurethane methacrylate resin having a semicrystalline polyester polyol main chain with a molecular weight of >2000 g·mol. An example of such a resin is the reaction product of a polyol known as Dynacoll 7380, described in WO201768196A1, with toluene diisocyanate and end-capped with HEMA. These resins have melting points in the range of 50–80°C.

[0034] As a solid anaerobic curable component, novolac vinyl ester resins, which are reaction products of novolac epoxy resin and methacrylate acid, are also useful. Examples of these resins and their preparations are shown in U.S. Patent No. 9,957,344. For example, [ka] In the formula, n is an integer between 2 and 10, and the compound has a melting point of approximately 70 to 75°C.

[0035] Preferably, the curing component contains one or more selected from the group consisting of 1-acetyl-2-phenylhydrazine, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-diethanol-p-toluidine, N,N-dimethyl-o-toluidine, N,N-dimethyl-m-toluidine, indoline, 2-methylindoline, isoindoline, indole, 1,2,3,4-tetrahydroquinoline, 3-methyl-1,2,3,4-tetrahydroquinoline, 2-methyl-1,2,3,4-tetrahydroquinoline, and 1,2,3,4-tetrahydroquinoline-4-carboxylic acid.

[0036] The anaerobic curable composition of the present invention

Chemical formula

[0037] Optionally, the curing accelerator described above may be used in combination with at least one co-accelerator, such as a co-accelerator selected from the group consisting of amines, amine oxides, sulfonamides, metal sources, acids, and mixtures thereof.

[0038] For example, the co-promoter may be selected from the group consisting of triazine, ethanolamine, diethanolamine, triethanolamine, N,N-dimethylaniline, benzenesulfanimide, cyclohexylamine, triethylamine, butylamine, saccharin, N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, acetylphenylhydrazine, maleic acid, and mixtures thereof.

[0039] The hardening accelerator is [ka] That's fine. During the ceremony, R is one or more of hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, or hydroxyalkynyl. R 1 and R 2 Each of these is individually selected from halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, or alkaryl.

[0040] For example, a hardening accelerator is [ka] You may choose one or more from the above. In the formula, R is as defined above.

[0041] The hardening accelerator is [ka] That's fine.

[0042] The composition of the present invention may further contain a free radical polymerization initiator such as a peroxide. Free radical polymerization initiators include cumene hydroperoxide ("CHP"), paramentane hydroperoxide, t-butyl hydroperoxide ("TBH"), t-butyl perbenzoate, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, 4,4-bis(t-butylperoxy)butyl valerate, p-chlorobenzoyl peroxide, t-butylcumyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl The free radical polymerization initiator is one or more selected from the group consisting of peroxyhex-3-in, 4-methyl-2,2-di-t-butylperoxypentane, t-amyl hydroperoxide, 1,2,3,4-tetramethylbutyl hydroperoxide, and combinations thereof. The free radical polymerization initiator may include an encapsulated peroxide.

[0043] The compositions of the present invention may further include, in addition to or instead of the above, a curing accelerator. For example, the curing accelerator may include one or more metallocenes, such as ferrocene, and preferably n-butylferrocene. Advantageously, the presence of the curing accelerator promotes the curing of the compositions of the present invention on "inactive" or "passive" substrates, such as plastic substrates.

[0044] Preferably, the compositions of the present invention may be provided in any suitable solid form, including a coating applied to a substrate, which may include a tape, a filament, or a filament or thread made from another material such as nylon or polyester yarn. The tape or filament can be applied by winding, i.e., in a similar manner to current PTFE tapes or thread sealing cords used to seal joints in piping. It will be understood that the solid form may be a desired pattern or layout including sticks, tapes, filaments, gaskets, or patches. The composition in solid form, such as in tape or filament form, may have sufficient integrity to be handled without breaking. The composition in solid form, such as in tape or filament form, is non-sticky and dry-touch, and therefore does not require a carrier such as a release liner. The composition in tape or filament form is non-sticky and dry-touch, and therefore can be wound on itself and does not adhere to itself. Alternatively, the tape or filament form may include the anaerobic curable composition and one or more release liners described herein. For example, if the temperature at which the composition is stored exceeds 40°C, a release liner may be useful because at temperatures above 40°C, the non-sticky composition may become sticky and adhere to itself. As described above, the compositions of the present invention may also be in any suitable solid form, including a (solid, dry-touch) coating applied to a substrate containing a tape, a filament, or a filament or yarn made from another material, such as nylon or polyester yarn.

[0045] Another aspect of the present invention provides a cured composition formed by curing a curable composition of the present invention as claimed herein. Preferably, the curable composition can be cured by exposure to an anaerobic environment. The curable composition can be cured, for example, by exposure to an anaerobic environment for a period of time ranging from about 1 to 30 minutes, for example, from about 1 to about 20 minutes. Optionally, the curable composition can be cured within a temperature range of about 40°C to about 100°C. For example, the curable composition can be cured by exposure to an anaerobic environment within a temperature range of about 40°C to about 100°C for a period ranging from about 1 to about 30 minutes.

[0046] In another embodiment, the present invention provides a threaded member comprising at least one threaded surface, wherein at least one threaded surface comprises an anaerobic curable composition as described herein. For example, the anaerobic curable composition may be in the form of a tape or a filament. Alternatively, it may be in the form of a composition applied / coated to a thread made of a different material. The tape, thread, or fiber can be applied to the threaded surface, for example, by wrapping the tape, thread, or fiber at least partially around the threaded surface. For example, the anaerobic curable composition may be coated onto a thread or fiber made of a different material to form a coated thread or fiber. The coated thread or fiber can be applied to the threaded surface, for example, by wrapping the coated fiber thread at least partially around the threaded surface.

[0047] In yet another aspect, the present invention provides a method for manufacturing a screw member comprising a threadlock composition, comprising providing at least one screw member comprising at least one threaded surface, and applying the anaerobic curable composition described herein to at least one threaded surface. Preferably, the anaerobic curable composition is applied to at least one threaded surface as a coating applied to a substrate such as a tape, filament, or thread-like or fibrous material formed from different materials, for example, the tape, filament, or coated substrate can be wrapped at least partially around at least one threaded surface of the screw member. Preferably, the anaerobic curable composition in the form of a tape, filament, or coated substrate is non-sticky, dry to the touch, and does not require a carrier such as a release liner.

[0048] In yet another aspect, the present invention provides a method for assembling a screw member, comprising providing a first screw member having at least one threaded surface, applying the anaerobic curable composition described herein to at least one threaded surface, providing a second screw member that can be fitted with the first screw member, fitting the first and second screw members together, thereby exposing the anaerobic curable composition to an anaerobic environment for a time sufficient for the anaerobic curable composition to cure between the first and second screw members.

[0049] The following steps, (i) Mix at least one solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40°C to 80°C with a solvent. (ii) Mix a liquid anaerobic curable component, a solid anaerobic curable component, and a curing component that cures the anaerobic curable component, and optionally add an additive to the mixture. (iii) Apply the mixture from step (ii) to the release liner. (iv) The present invention also provides a method for producing a threadlock tape, yarn, or fiber, comprising evaporating the solvent to form a tape, yarn, or fiber comprising the anaerobic curing composition and release liner described herein. [Modes for carrying out the invention]

[0050] <Detailed explanation> As outlined above, the present invention provides an anaerobic curable composition comprising a liquid anaerobic curable component, a solid anaerobic curable component, a solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40°C to 80°C, and a curing component for curing the anaerobic curable component.

[0051] <Definitions and Standard Test Methods> The term "liquid" refers to a liquid state within a temperature range of approximately 5°C to 30°C, preferably at room temperature and atmospheric pressure.

[0052] The term "solid" refers to a solid state within a temperature range of approximately 5°C to 40°C, preferably a solid state at room temperature and atmospheric pressure. The solid state is defined as a state of matter in which matter is not a fluid, maintains its boundaries without support, and atoms or molecules occupy fixed positions relative to each other and cannot move freely.

[0053] In relation to the present invention, "tack-free" means dry touch, meaning that the composition does not peel off during handling or use. For example, articles to which the composition of the present invention is applied are dry touch. Articles to which the composition of the present invention is applied are considered dry touch if 20 articles are placed individually on dry tissue paper for 4 hours and there is no change in the appearance of the tissue.

[0054] The molecular weights disclosed herein are determined according to ISO 13885-1:2008, "Binders for paints and varnishes - Gel permeation chromatography (GPC) - Part 1: Tetrahydrofuran (THF) as an eluent."

[0055] The melting and resolidification temperature ranges were measured according to ISO 1137-1:2016 "Plastics - Differential scanning calorimetry (DSC) - Part 1 General principles".

[0056] <Liquid anaerobic curing component> Preferably, the liquid anaerobic curing component includes a liquid (meth)acrylate monomer component.

[0057] Liquid (meth)acrylate components include β-carboxyethyl acrylate, isobornyl acrylate, n-octyl acrylate, n-decyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, ethoxylated phenyl monoacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isooctyl acrylate, n-butyl acrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate It may contain one or more (meth)acrylate monomers selected from methyl methacrylate, pentaerythritol tetraacrylate, phenoxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, cyclohexyl methacrylate, glycerol monomethacrylate, glycerol 1,3-dimethacrylate, trimethylcyclohexyl methacrylate, methyl triglycol methacrylate, isobornyl methacrylate, trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, hydroxybutyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, glycerol methacrylate, glycidyl methacrylate, methyl methacrylate, methacrylic acid, and mixtures thereof.

[0058] Preferred liquid (meth)acrylate monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, and methacrylic acid.

[0059] One or more suitable (meth)acrylates may be selected from, but are not limited to, di- or tori-functional (meth)acrylates such as polyethylene glycol di(meth)acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate ("TRIEGMA"), tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di-(pentamethylene glycol) dimethacrylate, tetraethylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol di(meth)acrylate, and bisphenol-A mono and di(meth)acrylates such as ethoxylated bisphenol-A(meth)acrylate ("EBIPMA"), and bisphenol-F mono and di(meth)acrylate polyfunctional (meth)acrylates such as ethoxylated bisphenol-F(meth)acrylate.

[0060] For example, the redox curing component is bisphenol A dimethacrylate. [ka] It can include...

[0061] Suitablely, the redox-curable composition may contain ethoxylated bisphenol A di(meth)acrylate.

[0062] Further (meth)acrylates suitable for use herein include silicone (meth)acrylate portions ("SiMA") as taught and claimed by U.S. Patent No. 5,605,999 (Chu), whose disclosure is expressly incorporated herein by reference.

[0063] Other suitable materials may be selected from polyacrylate esters represented by the following formula:

[0064] [ka] During the ceremony, R 4 is a group selected from hydrogen, halogens, or alkyls having 1 to about 4 carbon atoms; q is an integer equal to at least 1, preferably 1 to about 4; and X is an organic group containing at least 2 carbon atoms with a total bond capacity of q+1. Regarding the upper limit of the number of carbon atoms in X, there are monomers that can function at essentially any value. However, in practice, the common upper limit is about 50 carbon atoms, preferably 30, and most preferably about 20.

[0065] For example, X may be an organic group as shown in the following formula.

[0066] [ka] During the ceremony, Y 1 and Y 2 Each of them is an organic group such as a hydrocarbon group containing at least two carbon atoms, preferably two to about ten carbon atoms, and Z is an organic group, preferably a hydrocarbon group containing at least one carbon atom, preferably two to about ten carbon atoms.

[0067] Other monomers may be selected from reaction products of di- or tri-alkylolamines (e.g., ethanolamine or propanolamine) with acrylic acid, as disclosed in French Patent No. 1,581,361.

[0068] Suitable oligomers having (meth)acrylate functional groups may also be used. Examples of such (meth)acrylate-functionalized oligomers include those having the following general formula:

[0069] [ka] In the formula, R 5 This includes hydrogen, alkyl groups having 1 to about 4 carbon atoms, hydroxyalkyl groups having 1 to about 4 carbon atoms, or

[0070] [ka] It is a base selected from, R 4 R is a group selected from hydrogen, halogens, or alkyl groups having 1 to about 4 carbon atoms; 6 is hydrogen, hydroxyl or

[0071] [ka] And, m is an integer at least equal to 1, e.g., 1 to about 15 or greater, preferably 1 to about 8; n is an integer at least equal to 1, e.g., 1 to about 40 or greater, preferably about 2 to about 10; and p is 0 or 1.

[0072] Typical examples of acrylic acid ester oligomers corresponding to the above general formula include di-, tri-, and tetraethylene glycol dimethacrylate; di(pentamethylene glycol) dimethacrylate; tetraethylene glycol diacrylate; tetraethylene glycol di(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate; butylene glycol dimethacrylate; neopentyl glycol diacrylate; and trimethylolpropane triacrylate.

[0073] Di- and other polyacrylate esters, particularly those described in the previous paragraph, are preferred, but monofunctional acrylate esters (esters containing one acrylate group) can also be used.

[0074] Suitable compounds can be selected from cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethyl acrylate, and chloroethyl methacrylate.

[0075] Another useful class of materials is the reaction product of (meth)acrylate-functionalized, hydroxyl, or amino-containing materials with polyisocyanates in appropriate ratios to convert all isocyanate groups to urethane or ureid groups, respectively.

[0076] The (meth)acrylate urethane or urea ester thus formed may contain a hydroxyl or amino functional group in its non-acrylate portion. Suitable (meth)acrylate esters for use are those of the formula

[0077] [ka] During the ceremony, X is -O- and

[0078] [ka] Selected from, R 9 R is selected from hydrogen or lower alkyl having 1 to 7 carbon atoms; 7 R is selected from hydrogen, halogen (e.g., chlorine) or alkyl (e.g., methyl and ethyl groups), 8 This is a divalent organic group selected from alkylenes, phenylenes, and naphthylenes having 1 to 8 carbon atoms.

[0079] These groups, upon appropriate reaction with polyisocyanates, produce monomers of the following general formula.

[0080] [ka] In the formula, n is an integer between 2 and about 6; B is a polyvalent organic group selected from both substituted and unsubstituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl and heterocyclic groups and combinations thereof; R 7 , R 8 And X corresponds to the meanings described above.

[0081] Depending on the properties of B, these (meth)acrylate esters having urea or urethane bonds may have molecular weights that are oligomer class (e.g., about 1,000 g / mol to about 5,000 g / mol) or polymer class (e.g., about 5,000 g / mol or more).

[0082] Styrene, maleimide, vinyl ethers, allyl, allyl ethers, and other unsaturated reactive monomers and oligomers such as those described in US6844080B1 (Kneafsey et al.) can be used. Vinyl resins described in US6433091 (Xia) can also be used. Methacrylate or acrylate monomers containing these unsaturated reactive groups can also be used.

[0083] Of course, these (meth)acrylates can also be used in combination with other monomers.

[0084] <Solid anaerobic curing components> The anaerobic curable composition of the present invention comprises a solid anaerobic curable component. The solid anaerobic curable component may be a solid (meth)acrylic resin. Preferably, the solid (meth)acrylate resin is selected from the list of suitable (meth)acrylate components listed above.

[0085] <Solid thermoplastic polyurethane resin> The anaerobic curable composition of the present invention comprises a solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40°C to 80°C. Suitable solid thermoplastic polyurethane resins include Pearlbond® 100, Pearlbond® 106, Pearlbond® 120, Pearlbond® 122, Pearlbond® 180, Pearlstick® 5712, Pearlstick® 5714, and Pearlstick® 40-70 / 08, which are commercially available from Lubrizol, Carrer del Gran Vial, 17, 08160 Montmelo, Barcelona, ​​Spain. [Examples]

[0086] The anaerobic curing compositions shown in Table 1 were formulated in tape form. [Table 1]

[0087] The polyurethane methacrylate resin used is a reaction product of a flexible methylene ether diol reacted with a molar excess of toluene diisocyanate, and then end-capped with HEMA. "Amt" = quantity.

[0088] The compositions in Table 1 were prepared as follows. Solid thermoplastic polyurethane urethane components of each composition, having molecular weights ranging from 40,000 g / mol to 100,000 g / mol and melting points ranging from 40°C to 80°C, were immersed overnight in ethyl acetate and then mixed and dissolved in a Speedmixer DAC150.147. The remaining components were then added, and mixing continued until each component was dissolved. For compositions containing microencapsulated peroxides or methacrylates, the encapsulated components did not dissolve, and mixing continued until the microencapsulated components formed a dispersion in the solution. Next, each solution was cast onto a silicone-treated polyester release liner (HiFi SR4-122, 75 microns thick) using an Elcometer 4340 automatic film coater maintained at a coating plate temperature of 30°C. After coating, the ethyl acetate was evaporated from the heated coating plate. A dry-touch film was obtained.

[0089] The material properties of the uncured films formed from the compositions in Table 1 were evaluated after solvent evaporation. The elongation of each film was measured according to ASTM D882-02. The tensile breaking strength of each film was measured according to ASTM D882-09. [Table 2]

[0090] Examples 1-5 demonstrate that while the films maintain their integrity and exhibit excellent adhesive properties upon curing, their elongation can change significantly.

[0091] The threadlocking performance of each film formed from the compositions of the present invention specified in Table 1 was evaluated with M10 nuts and bolts according to ISO 10964. The film thickness was measured. For films containing microencapsulated components, the thickness of such films was measured at a point where the microcapsules were not visible. The compositions of the present invention were applied to M10 bolts, and the threaded assemblies were formed with M10 nuts that could mate with the M10 bolts. The threaded assemblies were held at room temperature (20°C to 25°C) for 24 hours before measuring the breaking strength and dominant strength of the cured compositions. The results for each composition on various substrates are shown in Table 3.

[0092] [Table 3]

[0093] The compositions in Table 4 were prepared using the same method as the compositions in Table 1. [Table 4]

[0094] Compositions 6 and 7 were formulated as tapes according to the methods described above for compositions 1 to 5.

[0095] In accordance with ISO 10964, the threadlocking performance of each composition in Table 4 was evaluated using M10 nuts and bolts. The compositions of the present invention were applied to M10 bolts, and the threaded assemblies were formed with M10 nuts that could be mated with the M10 bolts. The threaded assemblies were held at room temperature (20°C to 25°C) for 24 hours before measuring the fracture strength and dominant strength of the cured compositions. The results for each composition on various substrates are shown in Table 5.

[0096] [Table 5]

[0097] The elongation and tensile strength properties of tapes formed from the compositions shown in Table 4 were also evaluated. [Table 6]

[0098] The film can also be used to structurally join mating assemblies. Tensile strength was determined according to ISO 4587 for films manufactured according to Example 1. Results are shown as the mean value, including the standard deviation within the set of test specimens shown. For the 0.5-inch overlap area test, the film was cut into pieces to cover the bonding area and placed on the test coupon. The mating coupon was then placed on top, the test specimen was secured with clamps, and placed in an oven heated to 80°C for 20 minutes. The test specimen was then removed and left at room temperature for 24 hours before testing. Test results were obtained for stainless steel (grade SUS304), polycarbonate, and acrylonitrile butadiene styrene (ABS).

[0099] Stainless steel / Stainless steel 5.1±0.2MPa (cohesive failure) Polycarbonate / Polycarbonate 8.0±0.5MPa (Base material defect) ABS / ABS 4.8±0.7MPa (cohesive failure)

[0100] When used in reference to the present invention, the terms “contains / includes” and “have / includes” are used to identify the presence of a described feature, integer, step, or component, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.

[0101] For clarity, certain features of the present invention described in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, for brevity, various features of the present invention described in the context of a single embodiment may also be provided separately or in any suitable subcombination.

Claims

1. Liquid anaerobic curing component, Solid anaerobic curing components, A solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40°C to 80°C, and A threadlock anaerobic curable composition comprising a curing component that cures one or more components selected from the group consisting of the liquid anaerobic curable component and the solid anaerobic curable component, The liquid anaerobic curing component contains one or more liquid (meth)acrylate monomer components, The solid anaerobic curing component contains one or more solid (meth)acrylate monomer components, A threadlock anaerobic curable composition comprising one or more curing components selected from the group consisting of 1-acetyl-2-phenylhydrazine, N,N-dimethylparatoluidine, N,N-diethylparatoluidine, N,N-diethanolparatoluidine, N,N-dimethylorthotoluidine, N,N-dimethylmetatoluidine, indoline, 2-methylindoline, isoindoline, indole, 1,2,3,4-tetrahydroquinoline, 3-methyl-1,2,3,4-tetrahydroquinoline, 2-methyl-1,2,3,4-tetrahydroquinoline, and 1,2,3,4-tetrahydroquinoline-4-carboxylic acid.

2. The composition according to claim 1, wherein a liquid anaerobic curing component is present in an amount of 4% to 44% by weight based on the total weight of the composition.

3. The composition according to claim 1 or 2, wherein a solid anaerobic curing component is present in an amount of 5% to 45% by weight based on the total weight of the composition.

4. The composition according to any one of claims 1 to 3, wherein a solid thermoplastic polyurethane resin is present in an amount of 20% to 75% by weight based on the total weight of the composition.

5. The composition according to any one of claims 1 to 4, wherein the curing component is present in an amount of 0.1 to 10% by weight based on the total weight of the curable composition.

6. The liquid (meth)acrylate monomer component is, formula: H ２ C=CGCO ２ R ８ 、 (In the formula, G is hydrogen, halogen, or alkyl group having 1 to 4 carbon atoms, and R ８ (The group is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, or aryl groups having 1 to 16 carbon atoms, and may be optionally substituted or interrupted with one or more selected from the group consisting of silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, and sulfone.) The composition according to claim 5, wherein one or more are selected from those having the following characteristics.

7. The composition according to any one of claims 1 to 6, further comprising a free radical polymerization initiator.

8. The composition according to claim 7, wherein the free radical polymerization initiator is one or more selected from the group consisting of cumene hydroperoxide ("CHP"), paramentane hydroperoxide, t-butyl hydroperoxide ("TBH"), t-butyl perbenzoate, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, 4,4-bis(t-butylperoxy)valerate butyl, p-chlorobenzoyl peroxide, t-butylcumyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-in, 4-methyl-2,2-di-t-butylperoxypentane, t-amyl hydroperoxide, 1,2,3,4-tetramethylbutyl hydroperoxide, and combinations thereof.

9. The composition according to claim 7 or 8, wherein the free radical polymerization initiator comprises an encapsulated peroxide.

10. The composition according to any one of claims 1 to 9, further comprising a curing accelerator.

11. The curing accelerator is one or more metallocenes and / or 【Chemistry 1】 (In the formula, X is CH ２ , O, S, NR ４ , CR ５ R ６ or C=O, and R is one or more of hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, or hydroxyalkynyl, and R １ -R ６ is individually selected from hydrogen, halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, or aralkyl, and R ７ is hydrogen or CHR ８ R ９ wherein, in the formula, R ８ and R ９ are individually selected from hydrogen, halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, or aralkyl, and n is 0 or 1) The composition according to claim 10, which is a curing accelerator represented by .

12. The composition according to any one of claims 1 to 11, provided in the form of a tape, a filament, or a coated substrate.

13. A composition according to any one of claims 1 to 11, provided as a coating on a yarn or fiber.

14. A tape comprising the anaerobic curing composition according to any one of claims 1 to 13 and one or more release liners.

15. A screw member comprising at least one screw surface, wherein at least one screw surface comprises the anaerobic curable composition according to any one of claims 1 to 13.

16. The screw member according to claim 15, wherein the anaerobic curing composition is in the form of a tape, a filament, or a coated substrate.

17. The screw member according to claim 16, wherein an anaerobic curing composition in the form of a tape, filament, or coated substrate is applied to the screw surface by wrapping the tape at least partially around the screw surface.

18. A method for manufacturing a screw member containing a threadlocking composition, a. Provide at least one threaded member including at least one threaded surface, b. A method comprising applying the anaerobic curable composition according to any one of claims 1 to 12 to at least one screw surface.

19. The method for manufacturing a screw member according to claim 18, wherein the anaerobic curing composition is in the form of a tape, a filament, or a coated substrate.

20. A method for manufacturing a screw member according to claim 18, wherein an anaerobic curable composition in the form of a tape, a filament, or a coated substrate is at least partially wrapped around at least one threaded surface of the screw member.

21. A method for assembling screw components, (a) Provide a first threaded member having at least one threaded surface, (b) Apply the anaerobic curable composition according to any one of claims 1 to 13 to at least one screw surface, (c) Provide a second screw member that can be fitted with the first screw member, A method comprising fitting first and second screw members together, thereby exposing the anaerobic curable composition to an anaerobic environment for a time sufficient for the anaerobic curable composition to harden between the first and second screw members.

22. The method according to claim 21, wherein the anaerobic curing composition is in the form of a tape, a filament, or a coated substrate.

23. The method according to claim 22, wherein an anaerobic curable composition in the form of a tape, filament, or coated substrate is at least partially wrapped around at least one screw face.

24. The following steps, (i) Mix at least one solid thermoplastic polyurethane resin having a molecular weight in the range of 40,000 g / mol to 100,000 g / mol and a melting point in the range of 40°C to 80°C with a solvent. (ii) A mixture of a liquid anaerobic curable component as defined in claim 1, a solid anaerobic curable component as defined in claim 1, and one or more selected from the group consisting of the liquid anaerobic curable component and the solid anaerobic curable component, and optionally adding an additive to the mixture. (iii) Apply the mixture from step (iii) to the release liner. (iv) A method for producing a threadlock tape, comprising the step of evaporating a solvent, wherein the tape comprises the anaerobic curing composition and a release liner according to any one of claims 1 to 11.

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