Anaerobic hardening 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 for curing the anaerobic curable component. Advantageously, the composition of the present invention is substantially solid and can be used as a screw locking agent.

Description

Technology Field

[0001] The present invention relates to an anaerobic curable composition that can be used in many applications, for example, as a threadlocker. The composition is substantially solid and may be provided in any suitable solid form, such as in the form of a tape or a filament, or as a coating applied to a substrate comprising, for example, a filament or thread made of another material, such as a nylon or polyester thread. The present invention also relates to a method for manufacturing a threaded component and a method for assembling a threaded component. The composition can be easily handled and applied to a threaded member. Background Technology

[0002] Thread-fastening compositions are used to fasten and / or seal threaded parts, such as nuts and bolts, together. Such thread-fastening compositions significantly increase the torque required for the breakage or rotation of the interlocking threaded parts. Conventional thread-fastening compositions often comprise co-reactive adhesive systems, wherein two or more components are mixed, and the resulting composition is then applied to the threaded interlocking surface(s) of a fastener, whereby the components of the thread-fastening composition react and cure thereon. Examples of such co-reactive systems include epoxy resin adhesive compositions.

[0003] Liquid adhesive compositions have long been used in sealing and screw-fastening applications and have become a standard part of assembly production as well as the maintenance of machinery, tools, etc. Among the liquid adhesive compositions commonly used in these applications are anaerobic compositions. These compositions provide excellent screw-fastening and sealing properties when cured. Anaerobic curable compositions applied as screw-fastening compositions to screw-connected parts remain stable (uncured), and thus in liquid form, until they are placed between the fastened screw-connected parts and cured there in the absence of oxygen.

[0004] Anaerobic curing compositions are generally well known. For example, see the literature [RD Rich, "Anaerobic Adhesives" in Handbook of Adhesive Technology, 29, 467-79, A. Pizzi and KL Mittal, eds., Marcel Dekker, Inc., New York (1994)] and the references cited therein. Their uses are numerous, and new application areas are constantly being developed.

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

[0006] Often, anaerobic adhesive systems comprise resin monomers terminated by polymerizable acrylate esters derived according to known urethane chemistry, such as methacrylate, ethyl acrylate, and chloroacrylate esters [e.g., polyethylene glycol dimethacrylate and urethane-acrylate, e.g., U.S. Patent No. 3,425,988 (Gorman)]. Other components typically present in an anaerobic curable adhesive composition include an initiator, such as an organic hydroperoxide, e.g., cumene hydroperoxide, tertian butyl hydroperoxide, etc., an accelerator that increases the curing rate of the composition, and a stabilizer, e.g., quinone or hydroquinone, included to help prevent premature polymerization of the adhesive due to the decomposition of the peroxy compound.

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

[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 saccharin alone or both saccharin and APH.

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

[0010] Compositions suitable for use in pre-coated screw fastening applications are typically applied in a tack-free form, but have an anaerobic curing function in a subsequent stage.

[0011] In some cases, a tack-free form is achieved using a curing mechanism. For example, a first curing mechanism can form a tack-free form to keep the composition in place on the article, while a second curing mechanism is subsequently activated to achieve screw fastening.

[0012] For example, European Patent No. 0 077 659 (Thompson) describes a pre-coated polymerizable fluid for sealing and securing engineering parts. The composition has two curing mechanisms, and two curing reactions occur. The first mechanism is UV photocuring. Since an opacifying agent is dispersed in the fluid, the fluid becomes substantially opaque to radiation. After the fluid is applied to a component, it is exposed to UV radiation, resulting in the formation of a coating that creates a surface layer as a dry, non-stick outer layer. The fluid beneath the film is unaffected by radiation and generally remains in a liquid state. When the component is screwed into another component, the surface layer breaks, and as soon as an anaerobic environment is established when the screwed components are fastened, a second polymerization (e.g., free radical polymerization) is initiated and a second curing reaction occurs. The second polymerization mechanism acts to secure the screws together. In the Thompson patent, only a film is formed by the first polymerization, and the remainder of the composition remains as a fluid beneath the film. Therefore, there is a risk that the film may rupture and the fluid composition may leak during handling of the coated engineering part.

[0013] Similarly, European Patent No. 0 548 369 (Usami) describes a pre-coated adhesive composition for application to a screw-joined contact surface of a screw member, such as a screw. The composition comprises a photo-hardening binder in which a second curable composition is dispersed. The second curable composition comprises a microencapsulated reactive monomer / activator / initiator.

[0014] International Patent Publication WO2004 / 024841 A2 (Haller) describes a curable composition for application to screw-joint articles. The composition comprises a dispersion of (a) a (meth)acrylate functional monomer component; (b) a (meth)acrylate functional oligomer component; (c) a component of a first curing mechanism comprising a photoinitiator component; (e) an amine component; (ii) a component of a second curing mechanism comprising an encapsulated epoxy resin component; and (iii) a thickener component. The photoinitiator component is suitable for achieving first curing by penetrating the depth of the composition applied to the screw-joint article upon irradiation of the composition, thereby forming a binder matrix in which the component of the second curing mechanism is dispersed throughout the matrix.

[0015] U.S. Patent No. 9,181,457 (Attarwala) describes a tack-free drying composition comprising a polymeric matrix and an anaerobic curable component present within the polymeric matrix. In a particularly preferred embodiment, the composition is moisture-curable. The composition is non-flowing at high temperatures and has improved solvent resistance when cured. The composition is useful as a screw-fastening composition and can be formulated as a coating on a carrier substrate, such as a tape, string, or sheet.

[0016] British Patent No. 2,543,756 (Ledwith) describes a screw-fixing composition comprising an anaero-curable component and a curing component for curing said anaero-curable component; wherein the composition is in the form of fluid particulates and has a melting point in the range of 30-100°C. The anaero-curable component may comprise an anaero-curable monomer and a resin component. The composition may be provided in at least two-part form. The anaero-curable component is preferably provided in powder form. Preferably, the resin component is selected from methacrylated polyurethane resin, novolak resin, or higher methacrylated polyester resin. The anaero-curable monomer preferably comprises at least one acrylate or methacrylate ester group. The composition preferably does not contain a solvent. Additionally, said composition is applied to a screw of at least one article such that the composition is fused to the screw by melting; Subsequently, a method for screwing together two screw-joint articles is disclosed, comprising, optionally, after cooling, screwing the two articles together to initiate anaerobic curing of the screw-joint composition to chemically bond the two articles together. An article having the composition applied thereto is also disclosed.

[0017] U.S. Patent Application Publication No. 4,039,705 (Douek) relates to an anaerobic curable pressure-sensitive adhesive stock, such as sheets and tapes, wherein a pressure-sensitive adhesive layer comprising at least one anaerobic resin system can be completely transferred therefrom to one substrate to be bonded to another substrate and can be cured upon activation by a peroxy-initiator and blockage of oxygen. The anaerobic pressure-sensitive adhesive is contained between two different release surfaces, which enables the transfer of the pressure-sensitive adhesive to a substrate to be firmly fixed to another substrate upon curing of the anaerobic curable pressure-sensitive adhesive.

[0018] Although conventional anaerobic threadlockers have received and continue to receive a good response in the market, drawbacks have been observed in certain commercial applications with the use of conventional liquid anaerobic threadlockers, as well as known non-flowable, thixotropic, and anaerobic-based threadlockers. For example, these compositions often do not fully cure through large gaps. Furthermore, due to their anaerobic curing properties, a portion of the adhesive that remains exposed to air when applied to a part will be difficult to cure (unless a secondary curing mechanism is triggered). Consequently, the outer joint line exposed to air on a nut / bolt assembly will often remain liquid unless additional additives and curing measures are taken to ensure curing. As a result, the liquid composition in the outer joint line tends to migrate. In the case of conventional non-flowable compositions where non-flowability depends on the thixotropic and / or rheological properties of the composition, these compositions will flow if the temperature to which they are exposed is sufficiently high. Additionally, the solvent resistance of the cured product (which, as indicated above, has a portion remaining uncured) may be poor, suggesting that its integrity is questionable when environmental interactions occur. This can lead to contamination issues and situations harmful to the surrounding environment.

[0019] Despite the latest technology, it would be desirable to provide an alternative screw fastening system, such as a screw member comprising a tack-free dry screw fastening composition, a method for forming such a screw member, and a method for assembling such a screw member.

[0020] In one aspect, the present invention provides an anaerobic curing composition comprising the following:

[0021] Liquid anaerobic hardening component;

[0022] Solid anaerobic hardening component;

[0023] 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

[0024] A hardening component for hardening an anaerobic hardening component.

[0025] Advantageously, the composition of the present invention is substantially solid and can be used as a screw locking agent.

[0026] The liquid anaerobic curable component may be present in an amount of about 4 wt% to about 44 wt% based on the total weight of the curable composition, suitably about 5 wt% to about 40 wt% based on the total weight of the curable composition, for example about 5 wt% to about 20 wt% 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 wt% based on the total weight of the composition, the composition may be too hard / non-flowing when applied / coated to a substrate and thus may not be able to move sufficiently, for example, into the space between screws that are screwed together, have poor screw-fixing performance, or have poor adhesion performance. If the liquid anaerobic curable component is present in an amount greater than about 44 wt% based on the total weight of the composition, the integrity of the part may be adversely affected, the composition may be too fluid / soft, and, for example, the coating formed by the composition may easily crack when in contact with other surfaces, such as the surface of handling equipment or other substrates, such as other substrates to which the coating may have been applied. If the liquid anaerobic curable component is present in an amount of about 4 wt% to about 44 wt% based on the total weight of the curable composition, this provides a composition that achieves an acceptable balance between screw fastening and / or adhesive performance and a composition that cures to form a coating with sufficient integrity and provide excellent bond strength, wherein integrity is required for the application of the composition to the part to be bonded and bond strength is required for the end-use of the bond.

[0027] The solid anaerobic curable component may be present in an amount of about 5 wt% to about 45 wt% based on the total weight of the composition, suitably about 10 wt% to about 40 wt% based on the total weight of the curable composition, for example, 15 wt% to about 35 wt% based on the total weight of the curable composition. A composition containing less than about 5 wt% of the solid anaerobic curable component tends to lack cohesive strength and may not be suitable for application on parts. For example, a coating formed by such a composition may easily crack when in contact with other surfaces, such as the surface of handling equipment, or other substrates, such as other substrates to which the coating may have been applied. A composition containing more than about 45 wt% of the solid anaerobic curable component tends to form a coating that is too brittle to be applied to any part to be bonded. When a solid anaerobic curable component is present in an amount of about 5 wt% to about 45 wt% based on the total weight of the composition, this provides a composition that achieves an acceptable balance between screw-fastening and / or adhesive performance (when cured) (when applied as a coating) and a composition that can be applied as a coating with sufficient integrity and strength.

[0028] The solid thermoplastic polyurethane resin may be present in an amount of about 20 wt% to about 75 wt% based on the total weight of the curable composition, suitably about 35 wt% to about 65 wt% based on the total weight of the curable composition, for example about 38 wt% to about 62 wt% based on the total weight of the curable composition. A composition containing less than about 20 wt% of the solid thermoplastic polyurethane component tends to have elastic properties that are insufficient to allow the composition to be properly applied to the parts to be bonded. A composition containing more than about 75 wt% of the solid thermoplastic polyurethane component tends to exhibit poor screw-fastening / adhesion properties. When a solid thermoplastic polyurethane resin is present in an amount of about 20 wt% to about 75 wt% based on the total weight of the curable composition, this provides a composition that achieves an acceptable balance between screw fastening and / or adhesive performance and a composition capable of forming a coating with sufficient elastic properties to allow the composition to be applied to a part to be bonded.

[0029] The curing component for curing the anaerobic curable component may be present in an amount of about 0.1 to about 10 wt% based on the total weight of the curable composition, for example, about 1 to about 5 wt% based on the total weight of the curable composition.

[0030] Suitablely, the liquid anaerobic curable component contains a liquid (meth)acrylate monomer component.

[0031] The liquid (meth)acrylate monomer component may be one or more selected from those having the following chemical formulas:

[0032] H2C=CGCO2R 8 ,

[0033] Here, G is hydrogen, a halogen, or an alkyl group having 1 to 4 carbon atoms, and R 8The group is selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkalyl, alkalyl or aryl groups having 1 to about 16 carbon atoms, any of which may optionally be substituted or interposed with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, sulfone, etc.

[0034] Suitably, the solid anaerobic curable component comprises one or more solid (meth)acrylate monomer components. For example, the solid anaerobic curable component may be the following compound, which is the reaction product of phenyl isocyanate and hydroxyethyl methacrylate (HEMA), i.e., 2-methacryloxyethyl urethane having a melting point of about 70-75°C:

[0035]

[0036] The solid anaerobic curing component may also be a 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). For example: HEMA-IPDI-HEMA having a melting point of about 72-74°C.

[0037]

[0038] HEMA-hMDI-HEMA having a melting point of approximately 75-85°C

[0039]

[0040] HEMA-CHDI-HEMA with a melting point of approximately 75-85°C

[0041]

[0042] There is.

[0043] The solid anaerobic curable component may also be a polyurethane methacrylate resin having a molecular weight of >2000 g·mol and a semicrystalline polyester polyol backbone. An example of such a resin is provided in WO201768196A1, which is a product terminally capped with HEMA following the reaction of a polyol known as Dynacoll 7380 with toluene diisocyanate. These resins have melting points in the range of 50-80°C.

[0044] In addition, novolak vinyl ester resin, which is a reaction product of novolak epoxy resin and methacrylic acid, is used as a solid anaerobic curable component. Examples of these resins and methods of their preparation are disclosed in U.S. Patent No. 9957344. For example, there are the following compounds where n is an integer from 2 to 10, and these compounds have a melting point of about 70-75°C:

[0045]

[0046] Suitably, the hardening component comprises one or more selected from the group consisting of 1-acetyl-2-phenylhydrazine, N,N-dimethyl para-toluidine, N,N-diethyl para-toluidine, N,N-diethanol para-toluidine, N,N-dimethyl ortho-toluidine, N,N-dimethyl meta-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.

[0047] The anaerobic curable composition of the present invention may include a curing accelerator encompassed by the following:

[0048]

[0049] Here, X is CH2, O, S, NR 4 , CR 5 R 6or C=O; R is one or more of hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, or hydroxyalkynyl; and R 1 - R 6 Each is individually selected from hydrogen, halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, or alkalyl; R 7 Silver, hydrogen, or CHR 8 R 9 and, here R 8 and R 9 Each is individually selected from hydrogen, halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, or alkalyl; n is 0 or 1.

[0050] Optionally, the curing accelerator is used in combination with at least one co-accelerator selected from the group consisting of amines, amine oxides, sulfonamides, metal sources, acids, and mixtures thereof.

[0051] For example, the co-promoter may be selected from the group consisting of triazine, ethanolamine, diethanolamine, triethanolamine, N,N dimethylaniline, benzene sulfanimide, cyclohexylamine, triethylamine, butylamine, saccharin, N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, acetylphenylhydrazine, maleic acid, and mixtures thereof.

[0052] The curing accelerator may be the following compounds:

[0053]

[0054] Here, R is one or more of hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, or hydroxyalkynyl; R 1 and R 2Each is individually selected from halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, or alkalyl.

[0055] For example, a curing accelerator may be selected from one or more of the following compounds:

[0056]

[0057] Here, R is as defined above.

[0058] The curing accelerator may be the following compounds:

[0059]

[0060] The composition of the present invention may further include an initiator for free radical polymerization, such as a peroxide.

[0061] The initiators for free radical polymerization are cumene hydroperoxide ("CHP"), para-menthan hydroperoxide, t-butyl hydroperoxide ("TBH"), t-butyl perbenzoate, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl 4,4-bis(t-butylperoxy)valerate, p-chlorobenzoyl peroxide, t-butyl cumyl 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-phosphorus, 4-methyl-2,2-di-t-butylperoxypentane, It is one or more selected from the group consisting of t-amyl hydroperoxide, 1,2,3,4-tetramethylbutyl hydroperoxide, and combinations thereof. The initiator of free radical polymerization may include an encapsulated peroxide.

[0062] The composition of the present invention may additionally include a curing accelerator in addition to or instead of those described above. For example, the curing accelerator may include one or more metallocenes, such as ferrocene, suitably n-butyl ferrocene. Advantageously, the presence of the curing accelerator facilitates the curing of the composition of the present invention on a "non-active" or "passive" substrate, such as a plastic substrate.

[0063] Suitably, the composition of the present invention may be provided as a coating applied to a substrate comprising any suitable solid form, such as tape or filament, or a filament or thread made of another material, such as nylon or polyester thread. The tape or filament may be applied by winding, that is, in a manner similar to PTFE tape or screw-sealing cord commonly used to seal connections of pipe structures. It will be recognized that the solid form may exist in a desired pattern or layout, including a stick, tape, filament, gasket, or patch. The composition in the solid form, such as tape or filament, may have sufficient integrity to be handled without breakage. Since the composition in the solid form, such as tape or filament, may be non-sticky and tack-dry, a carrier, such as a release liner, is not required. The composition in the tape or filament form may be self-winding and, being non-sticky and tack-dry, will not adhere to itself. Alternatively, the tape or filament form may comprise an anaerobic curable composition as described herein and one or more release liners. For example, if the temperature at which the composition is to be stored is greater than 40°C, a release liner may be useful because the non-sticky composition may become sticky and adhere to itself at temperatures greater than 40°C. As mentioned above, the composition of the present invention may also be a (solid, tack-free) coating applied to a substrate comprising any suitable solid form, such as a tape form, a filament form, or a filament or thread made of another material, such as a nylon or polyester thread.

[0064] Another aspect of the present invention provides a cured composition formed by curing the curable composition of the present invention claimed herein. Suitably, the curable composition may be cured by exposure to an anaerobic environment. The curable composition may be cured by exposure to an anaerobic environment for a period ranging, for example, from about 1 minute to about 30 minutes, e.g., from about 1 minute to about 20 minutes. Optionally, the curable composition may be cured within a temperature range of about 40°C to about 100°C. For example, the curable composition may be cured within a temperature range of about 40°C to about 100°C by exposure to an anaerobic environment for a period ranging from about 1 minute to about 30 minutes.

[0065] In another aspect, the present invention provides a screw member comprising at least one screw-joining surface, wherein the at least one screw-joining 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 may be applied to the screw-joining surface, for example, by at least partially surrounding the tape, thread, or fiber around the screw-joining 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 may be applied to the screw-joining surface, for example, by at least partially surrounding the coated thread or fiber around the screw-joining surface.

[0066] In another additional aspect, the present invention provides a method for manufacturing a screw-joint member comprising a screw-fixing composition, comprising the following steps: providing at least one screw-joint member comprising at least one screw-joint surface; and applying an anaero-curable composition as described herein to said at least one screw-joint surface. Suitably, the anaero-curable composition is applied to the at least one screw-joint surface as a coating applied to a substrate such as a tape, a filament, or a thread or fiber formed of a different material, for example, the tape, filament, or coated substrate may at least partially surround the perimeter of at least one screw-joint surface of the screw-joint member. Suitably, the anaero-curable composition in the form of a tape, a filament, or a coated substrate may be non-sticky and tack-free, so a carrier, such as a release liner, is not required.

[0067] In another additional aspect, the present invention provides a method for assembling screw members, comprising the following steps: providing a first screw member comprising at least one screw surface; applying an anaerobic curable composition as described herein to the at least one screw surface; providing a second screw member capable of matingly engaging with the first screw member; matingly engaging the first and second screw members, thereby exposing the anaerobic curable composition to an anaerobic environment for a sufficient amount of time for the anaerobic curable composition to cure between the first and second screw members.

[0068] A method for manufacturing a tape, thread, or fiber for screw fastening is also provided, comprising the following steps:

[0069] (i) a step of mixing 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, and a solvent;

[0070] (ii) mixing these with a liquid anaerobic curable component, a solid anaerobic curable component, and a curing component for curing the anaerobic curable component; optionally, adding an additive to the mixture;

[0071] (iii) a step of applying the mixture of step (ii) to a mold liner;

[0072] A step of allowing the solvent to evaporate to thereby form a tape, thread, or fiber comprising an anaerobic curable composition and a release liner as described herein. Specific details for implementing the invention

[0073] As summarized 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.

[0074] Definitions and Standard Test Methods

[0075] The term "liquid" means that it is in a liquid state within a temperature range of about 5°C to 30°C, suitably in a liquid state at room temperature and atmospheric pressure.

[0076] The term "solid" means a solid state within a temperature range of about 5°C to 40°C, suitably a solid state at room temperature and atmospheric pressure. A solid state is defined as a state of matter in which the substance is not a fluid and maintains its boundaries without a support, wherein atoms or molecules occupy fixed positions relative to one another and cannot move freely.

[0077] In relation to the present invention, non-stickiness means a tack-free state in which the composition does not peel off or fall off during handling or use. For example, an article to which the composition of the present invention is applied is in a tack-free state. An article to which the composition of the present invention is applied is considered to be in a tack-free state if 20 such articles are placed individually on dry tissue paper for 4 hours and there is no change in the appearance of the tissue.

[0078] The molecular weight disclosed herein is determined according to ISO 13885-1:2008 "Binders for paints and varnishes -- Gel permeation chromatography (GPC) -- Part 1: Tetrahydrofuran (THF) as eluent".

[0079] The melting and re-solidification temperature ranges are measured according to ISO 1137-1:2016 "Plastics - Differential scanning calorimetry (DSC) - Part 1 General Principles".

[0080] Liquid anaerobic hardening component

[0081] Suitablely, the liquid anaerobic curable component contains a liquid (meth)acrylate monomer component.

[0082] The liquid (meth)acrylate components are beta-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, and trimethylolpropane. Triacrylates, pentaerythritol tetraacrylate, phenoxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, cyclohexyl methacrylate, glycerol mono-methacrylate, glycerol 1,3-dimethacrylate, trimethylcyclohexyl methacrylate, methyl triglyceride 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 and methacrylic acid and It may include one or more (meth)acrylate monomers selected from his mixture.

[0083] Preferred liquid (meth)acrylate monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, and methacrylic acid.

[0084] One or more suitable (meth)acrylates are polyfunctional (meth)acrylates, e.g., but not limited to, difunctional or trifunctional (meth)acrylates, e.g., 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, e.g., ethoxylated bisphenol-A (meth)acrylates. ("EBIPMA"), and bisphenol-F mono and di(meth)acrylates, such as ethoxylated bisphenol-F (meth)acrylate, may be selected from.

[0085] For example, the redox curable component may include the following bisphenol A dimethacrylate:

[0086]

[0087] Suitably, the redox curable composition may include ethoxylated bisphenol A di(meth)acrylate.

[0088] Another (meth)acrylate that may be suitable for use in this invention is the silicon (meth)acrylate moiety (“SiMA”) taught and claimed, e.g., by U.S. Patent No. 5,605,999 (Chu), the disclosure of said patent is explicitly incorporated herein by reference.

[0089] Other suitable materials may be selected from polyacrylate esters represented by the following chemical formulas:

[0090]

[0091] Here, R 4 is a radical selected from hydrogen, halogen, or alkyl having 1 to about 4 carbon atoms; q is an integer corresponding to at least 1, preferably 1 to about 4; and X is an organic radical containing at least 2 carbon atoms and having a total bonding ability of q + 1. Regarding the upper limit for the number of carbon atoms of X, monomers are available at essentially all values. However, in practical terms, a general upper limit is about 50, for example, preferably about 30, preferably about 20 carbon atoms.

[0092] For example, X can be an organic radical of the following chemical formula:

[0093]

[0094] Here, Y 1 and Y 2 Each is an organic radical, such as a hydrocarbon group, containing at least two carbon atoms, preferably 2 to about 10 carbon atoms, and Z is an organic radical, preferably a hydrocarbon group, containing at least one carbon atom, preferably 2 to about 10 carbon atoms. Other materials may be selected from the reaction products of di- or tri-alkylolamines (e.g., ethanolamine or propanolamine) and acrylic acid, such as those disclosed in French Patent No. 1,581,361.

[0095] Suitable oligomers having (meth)acrylate functional groups may also be used. Examples of such (meth)acrylate-functionalized oligomers include those having the following chemical formulas:

[0096]

[0097] Here, R 5 is hydrogen, an alkyl having 1 to about 4 carbon atoms, a hydroxyalkyl having 1 to about 4 carbon atoms, or

[0098]

[0099] Represents a radical selected from; where R 4 is a radical selected from hydrogen, a halogen, or an alkyl having 1 to about 4 carbon atoms; R 6 Silver hydrogen, hydroxyl, or

[0100]

[0101] It is a radical selected from; m is an integer corresponding to at least 1, for example, 1 to about 15 or more than that, preferably 1 to about 8; n is an integer corresponding to at least 1, for example, 1 to about 40 or more than that, preferably about 2 to about 10; and p is 0 or 1.

[0102] Typical examples of acrylic acid ester oligomers corresponding to the above chemical formulas 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.

[0103] While difunctional and other polyacrylate esters, particularly the polyacrylate esters described in the previous paragraph, may be preferred, monofunctional acrylate esters (esters containing one acrylate group) may also be used.

[0104] Suitable compounds may be selected from cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, t-butylaminoethyl methacrylate, cyanoethyl acrylate, and chloroethyl methacrylate.

[0105] Another class of useful substances is the reaction product of polyisocyanates with (meth)acrylate-functionalized, hydroxyl- or amino-containing substances in suitable proportions that convert each isocyanate group into a urethane or ureido group.

[0106] The (meth)acrylate urethane or urea ester formed in this way may contain hydroxy or amino functional groups in its non-acrylate portion. Suitable (meth)acrylate esters for use may be selected from those of the following chemical formulas:

[0107]

[0108] Here, X is --O-- and

[0109]

[0110] Selected from; here R 9 is selected from hydrogen or lower alkyls having 1 to 7 carbon atoms; R 7 is selected from hydrogen, halogens (e.g., chlorine), or alkyls (e.g., methyl and ethyl radicals); R 8 It is a divalent organic radical selected from alkylene, phenylene, and naphthylene having 1 to 8 carbon atoms.

[0111] These groups react appropriately with polyisocyanates to produce monomers of the following chemical formula:

[0112]

[0113] Here, n is an integer from 2 to about 6; B is a polyvalent organic radical selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, alkaryl and heterocyclic radicals (both substituted and unsubstituted), and combinations thereof; R 7 , R 8 and X have the meaning given above.

[0114] Depending on the properties of B, these (meth)acrylate esters having urea or urethane links may have a molecular weight that classifies them into the oligomer class (e.g., about 1,000 g / mol to about 5,000 g / mol) or a molecular weight that classifies them into the polymer class (e.g., more than about 5,000 g / mol).

[0115] Other unsaturated reactive monomers and oligomers, such as styrene, maleimide, vinyl ether, allyl, allyl ether, and those mentioned in US6844080B1 (Kneafsey et al.), may be used. Vinyl resins such as those mentioned in US6433091 (Xia) may also be used. Methacrylate or acrylate monomers containing these unsaturated reactive groups may also be used.

[0116] Of course, combinations of these (meth)acrylates and other monomers can also be used.

[0117] Solid anaerobic hardening component

[0118] The anaerobic curable composition of the present invention comprises a solid anaerobic curable component. The solid anaerobic curable component may be a solid (meth)acrylate resin. Suitably, the solid (meth)acrylate resin is selected from the list of suitable (meth)acrylate components listed above.

[0119] Solid thermoplastic polyurethane resin

[0120] 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, located at 17 Carre del Gran Vial, Montmelo, Barcelona 08160, Spain.

[0121] Examples

[0122] An anaerobic curable composition as provided in Table 1 was formulated into a tape form.

[0123]

[0124]

[0125] The polyurethane methacrylate resin used is a reaction product in which a flexible methylene ether diol is reacted with a molar excess of toluene diisocyanate and subsequently terminal-capped with HEMA. "Amt" = amount.

[0126] The composition of Table 1 was prepared as follows:

[0127] Solid thermoplastic polyurethane components 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 of each composition were immersed overnight in ethyl acetate and then mixed and dissolved in a Speedmixer DAC150.147. Subsequently, the remaining components were added, and mixing was continued until each component was dissolved. In the case of compositions containing microencapsulated peroxide or methacrylate, the encapsulated component would not dissolve, and mixing was continued until the microencapsulated component formed a dispersion in the solution. Subsequently, each solution was cast onto a siliconized polyester release liner (HiFi SR4-122, 75 micrometers thick) using an Elcometer 4340 automatic film coater maintained at a coating plate temperature of 30°C. After coating, the ethyl acetate was allowed to evaporate from the heated coating plate. A tack-free drying film was obtained.

[0128] The material properties of the uncured films formed from the compositions of Table 1 were evaluated after solvent evaporation. The percentage 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.

[0129]

[0130] The films of Examples 1 to 5 show that although the elongation of the film may vary significantly, the film maintains integrity and also provides excellent adhesive performance when cured.

[0131] The screw-fixing performance of each film formed from the composition of the present invention specified in Table 1 was evaluated according to ISO 10964 using an M10 nut and a bolt. The thickness of the film was determined. In the case of films containing microencapsulated components, the thickness of the film was measured at a point where the microcapsules were not dominant. The composition of the present invention was applied to an M10 bolt, and a screw-coupling assembly was formed with an M10 nut that could be mated to the M10 bolt. After maintaining the screw-coupling assembly at room temperature (20°C to 25°C) for 24 hours, the fracture strength and preveil strength of the cured composition were measured. The results for each composition on various substrates are provided in Table 3.

[0132]

[0133] The composition of Table 4 was prepared in the same manner as the composition of Table 1.

[0134]

[0135] Compositions 6 and 7 were formulated into tapes according to the above method for compositions 1 to 5.

[0136] The screw-fixing performance of each composition in Table 4 was evaluated according to ISO 10964 using M10 nuts and bolts. The composition of the present invention was applied to an M10 bolt, and a screw-coupled assembly was formed with an M10 nut that could be mated to the M10 bolt. After maintaining the screw-coupled assembly at room temperature (20°C to 25°C) for 24 hours, the fracture strength and prevail strength of the cured composition were measured. The results for each composition on various substrates are provided in Table 5.

[0137]

[0138] The elongation and tensile strength characteristics of the tape formed from the composition of Table 4 were also evaluated.

[0139]

[0140] The film can also be used to structurally bond the mating assembly. Tensile strength was determined for the film prepared according to Example 1 in accordance with ISO 4587. The results are presented as the average value from the presented series of test specimens, along with the standard deviation. In the 0.5" overlap area test, the film was cut into pieces covering the bonding area and placed on a test coupon. Then, a mating coupon was placed on top, the test specimen was secured, and the sample was placed in an oven heated to 80°C for a period of 20 minutes. Subsequently, the test specimen was removed and left at room temperature for 24 hours prior to testing. Test results were obtained for stainless steel (Grade SUS 304), polycarbonate, and acrylonitrile butadiene styrene (ABS).

[0141] Stainless steel / Stainless steel 5.1 ± 0.2 MPa (cohesive fracture)

[0142] Polycarbonate / Polycarbonate 8.0 ± 0.5MPa (Substrate destruction)

[0143] ABS / ABS 4.8 ± 0.7MPa (cohesion breakdown)

[0144] The results demonstrate excellent adhesion, especially in the case of plastics.

[0145] The words “comprising / including” and “having / accompanying”, when used herein in connection with the present invention, are used to specify the presence of the mentioned feature, integer, step, or component, but do not exclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.

[0146] It is recognized that specific features of the invention described in the context of separate embodiments for clarity may also be provided in combination as a single embodiment. Conversely, various features of the invention described in the context of a single embodiment for brevity may also be provided separately or in any suitable sub-combination.

Claims

Claim 1 An anaerobic curable composition comprising: a liquid anaerobic curable component comprising 4 wt% to 44 wt% of a liquid (meth)acrylate monomer component based on the total weight of the composition; a solid anaerobic curable component comprising 5 wt% to 45 wt% of one or more solid (meth)acrylate monomer components based on the total weight of the composition; and 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, comprising 20 wt% to 75 wt% based on the total weight of the composition. A curing component comprising one or more selected from the group consisting of 1-acetyl-2-phenylhydrazine, N,N-dimethyl para-toluidine, N,N-diethyl para-toluidine, N,N-diethanol para-toluidine, N,N-dimethyl ortho-toluidine, N,N-dimethyl meta-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. Claim 2 A composition according to claim 1, wherein the curing component is present in an amount of 0.1 to 10 wt% based on the total weight of the curable composition. Claim 3 The composition of claim 1, wherein the liquid (meth)acrylate monomer component is one or more selected from those having the following chemical formula: H2C=CGCO2R 8 ,where G is hydrogen, a halogen, or an alkyl group having 1 to 4 carbon atoms, and R 8 The element is an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkalyl, alkalyl or aryl having 1 to 16 carbon atoms, and any of these may optionally be substituted or interposed with a silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, sulfone, or any combination thereof. Claim 4 A composition according to claim 1, further comprising a free radical polymerization initiator. Claim 5 In paragraph 4, the free radical polymerization initiator is cumene hydroperoxide ("CHP"), para-menthan hydroperoxide, t-butyl hydroperoxide ("TBH"), t-butyl perbenzoate, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl 4,4-bis(t-butylperoxy)valerate, p-chlorobenzoyl peroxide, t-butyl cumyl 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-phosphorus, A composition selected from the group consisting of 4-methyl-2,2-di-t-butylperoxypentane, t-amyl hydroperoxide, 1,2,3,4-tetramethylbutyl hydroperoxide and any combination thereof. Claim 6 A composition according to claim 4, comprising a peroxide encapsulated with a free radical polymerization initiator. Claim 7 A composition according to claim 1, further comprising a curing accelerator. Claim 8 In claim 7, the composition comprises a curing accelerator of one or more metallocenes; and / or a curing accelerator of the following formula: Here, X is CH2, O, S, NR 4 , CR 5 R 6 or C=O and; R is hydrogen, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, or hydroxyalkynyl; R 1 - R 6 Each is individually selected from the group consisting of hydrogen, halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, and alkalyl; R 7 Silver, hydrogen, or CHR 8 R 9 and, here R 8 and R 9 Each is individually selected from the group consisting of hydrogen, halogen, amino, carboxyl, nitro, alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, and alkalyl; n is 0 or 1. Claim 9 A composition according to claim 1, in the form of a tape, a filament, or a coated substrate. Claim 10 A composition that is a coating on a thread or fiber in claim 1. Claim 11 A tape comprising an anaerobic curable composition according to claim 1 and one or more release liners. Claim 12 A screw member comprising at least one screw joint surface, wherein the at least one screw joint surface comprises an anaerobic curable composition according to claim 1. Claim 13 In claim 12, a screw member in which the anaerobic curable composition is in the form of a tape, a filament, or a coated substrate. Claim 14 A screw member according to claim 13, wherein an anaerobic curable composition is applied to the screw joint surface. Claim 15 A method for manufacturing a screw-coupling member comprising a screw-fixing composition, comprising the following steps: (a) providing at least one screw-coupling member comprising at least one screw-coupling surface; and (b) applying an anaerobic curable composition according to claim 1 to the at least one screw-coupling surface. Claim 16 In claim 15, the method wherein the anaerobic curable composition is in the form of a tape, a filament, or a coated substrate. Claim 17 A method according to claim 15, wherein the anaerobic curable composition at least partially surrounds the perimeter of at least one screw joint surface of the screw joint member. Claim 18 A method for assembling screw members comprising the following steps: (a) providing a first screw member comprising at least one screw joint surface; (b) applying an anaerobic curable composition according to claim 1 to the at least one screw joint surface; (c) providing a second screw member capable of matingly engaging with the first screw member; (d) matingly engaging the first and second screw members; and (e) 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. Claim 19 In paragraph 18, a method in which the anaerobic curable composition is in the form of a tape, a filament, or a coated substrate. Claim 20 A method according to claim 19 in which the anaerobic curable composition at least partially surrounds the circumference of at least one screw joint surface. Claim 21 The following steps: (a) mixing 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, and a solvent; (b) mixing the product of step (a) with a liquid anaerobic curable component, a solid anaerobic curable component, and 1-acetyl-2-phenylhydrazine, N,N-dimethyl para-toluidine, N,N-diethyl para-toluidine, N,N-diethanol para-toluidine, N,N-dimethyl ortho-toluidine, N,N-dimethyl meta-toluidine, indoline, 2-methylindoline, isoindoline, indole, 1,2,3,4-tetrahydroquinoline, 3-methyl-1,2,3,4-tetrahydroquinoline, A method for manufacturing a tape for screw fastening, comprising: (c) mixing a curing component selected from the group consisting of one or more of 2-methyl-1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroquinoline-4-carboxylic acid; (c) applying the mixture of step (b) to a release liner; and (d) allowing the solvent to evaporate to thereby form a tape comprising an anaerobic curable composition and a release liner, wherein the product of step (b) comprises a liquid anaerobic curable component comprising 4 wt% to 44 wt% of a liquid (meth)acrylate monomer component based on the total weight of the product; and a solid anaerobic curable component comprising 5 wt% to 45 wt% of one or more solid (meth)acrylate monomer components based on the total weight of the product. A method comprising 20 wt% to 75 wt% of a solid thermoplastic polyurethane resin based on the total weight of the composition. Claim 22 An anaerobic curable composition according to claim 1, comprising 5 wt% to 40 wt% of a liquid anaerobic curable component based on the total weight of the composition; 10 wt% to 40 wt% of a solid anaerobic curable component based on the total weight of the composition; and 35 wt% to 65 wt% of a solid thermoplastic polyurethane resin based on the total weight of the composition. Claim 23 An anaerobic curable composition according to claim 22, comprising 5 wt% to 20 wt% of a liquid anaerobic curable component based on the total weight of the composition; 15 wt% to 35 wt% of a solid anaerobic curable component based on the total weight of the composition; and 38 wt% to 62 wt% of a solid thermoplastic polyurethane resin based on the total weight of the composition. Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete

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