CURABLE COMPOSITION AND METHOD FOR BONDING SUBSTRATES THEREOF - Patent application

Abstract

Curable compositions, particularly two-component compositions, are described that include a silane-modified polymer, an epoxy resin terminated with an epoxy end group, and a curing agent and a compatibilizer having at least one silane group and at least one epoxy end group. The curable compositions exhibit enhanced adhesive strength and good elongation at break. Methods for applying the curable compositions to the surface of a substrate are also provided.

Description

[Technical field]

[0001] The present disclosure relates to curable compositions, particularly two-part curable compositions, and methods for applying same to the surface of a substrate. The curable compositions exhibit enhanced adhesive strength and good elongation at break. [Background technology]

[0002] Silane-modified polymers (SMPs), also known as silylated polymers, are versatile, high-value industrial resins that have found wide acceptance in a variety of applications. Silane-modified polymer (SMP)-based adhesives / sealants are becoming increasingly popular due to their many advantages, including low VOC, iso-free and bubble-free, and a good balance of performance properties and durability. In particular, SMP-based adhesives exhibit higher bond strengths and are superior to silicone-based adhesives in that they can be overcoated with additional paints or coatings. In addition, SMP-based adhesives are more durable than adhesives formulated with polyurethane prepolymers.

[0003] SMP-based adhesives / sealants are used in a variety of applications, including prefabricated construction (PC), residential decoration, transportation [vehicles, ships, automobiles, aircraft, high-speed rail (HSR)], industrial assembly, and home appliances. However, high adhesive strength is usually required in these applications, especially in transportation, industrial assembly, and home appliances. For example, a significant number of customers are looking for SMP-based adhesives with adhesive strengths of over 5.0 MPa and elongations at break of over 100-150%. Generally, such high requirements on mechanical strength are generally considered to be a big challenge for SMP-based adhesives, since many of the commercially available SMP-based adhesives on the market can only achieve low adhesive strengths of around 3.0-4.0 MPa. Numerous efforts have been made by many researchers to modify factors such as fillers, resin ratios, adhesion promoters, and catalysts, but none of these prior art studies can achieve adhesive strengths as high as 5.0 MPa.

[0004] Without being limited to a particular theory, it is suspected that the poor adhesive strength of existing SMP-based adhesives is due, at least in part, to the lack of chemical bonding between the SMP phase and other phases used in combination with it. Prior art two-component (2K) adhesive compositions are shown in Figure 1, in which the incorporation of various additives (hardeners, catalysts, accelerants, surfactants, etc.) and compatibilizers establishes little or no chemical bonding between the SMP and epoxy phases, such that the resulting blend contains chemically isolated SMP and epoxy phases and therefore exhibits poor cohesiveness and adhesive strength. Summary of the Invention [Problem to be solved by the invention]

[0005] After continued research, the present inventors have surprisingly developed a two-component composition that can achieve one or more of the above goals. In particular, it has been found that when a specific compatibilizer is included in the 2K curable composition of the present application, the adhesive strength can be further increased to a desired level.

[0006] The present disclosure provides unique curable compositions, particularly two-part curable compositions, and methods for applying the curable compositions to the surface of a substrate.

[0007] In a first aspect of the present disclosure, the present disclosure provides a curable composition, particularly at least one silane-modified polymer; at least one epoxy resin terminated with an epoxy end group; A two-part curable composition is provided that includes a curing agent and a compatibilizer having at least one silane / siloxane group and at least one epoxy end group.

[0008] In a second aspect of the present disclosure, the present disclosure provides a method for applying the aforementioned curable composition onto a surface of a substrate, comprising the steps of: (1) combining a silane-modified polymer, an epoxy resin, a curing agent and a compatibilizing agent to form a precursor blend; (2) applying the precursor blend onto a surface of a substrate; and (3) curing the precursor blend or allowing the precursor blend to cure.

[0009] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic diagram of a prior art 2K curable composition. [Diagram 2] FIG. 2 is a schematic diagram of an embodiment of a 2K curable composition described herein. [Diagram 3] FIG. 3 shows a reaction scheme for a hydrosilylation reaction to prepare an SMP, according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

[0012] As disclosed herein, "and / or" means "and, or alternatively." Unless otherwise stated, all ranges are inclusive of the endpoints. Unless otherwise stated, all percentages and ratios are calculated by weight and all molecular weights are number average molecular weights.

[0013] According to various embodiments of the present disclosure, the curable composition of the present disclosure is a "two-component", "two-part" or "two-package" type composition comprising component (A) containing a silane-modified polymer and component (B) having an epoxy resin. In the context of the present disclosure, the terms "part (A)", "component (A)", "silane-modified polymer component (A)" and "silane-modified polymer part (A)" can be used interchangeably and refer to the component containing the silane-modified polymer, and the terms "part (B)", "component (B)", "epoxy resin part (B)" and "epoxy resin component (B)" can be used interchangeably and refer to the component containing the epoxy resin. Components (A) and (B) are transported and stored separately and are combined shortly or immediately before being applied to the surface of the substrate. According to one embodiment of the present disclosure, the curing agent and the compatibilizer are included in either component (A) or component (B). According to a preferred embodiment, the curing agent is included in component (A) and the compatibilizer is included in component (B). Once combined, the reactive groups of each component, such as epoxy end groups in the epoxy resin, silane / siloxane groups in the SMP, amine and imine groups in the curing agent, epoxy end groups / silane / siloxane groups contained in the compatibilizer, and any other reactive groups contained in other additives or reactants, react with each other to establish a chemically integrated combination of SMP-epoxy resin. According to various embodiments of the present disclosure, once combined, the SMP phase is chemically bonded to the epoxy resin via the curing agent and the compatibilizer. Without being limited to a particular theory, an exemplary embodiment of the present disclosure is shown in FIG. 2. It should be noted that while FIG. 2 shows the SMP phase and the epoxy resin phase integrated into the epoxy-SMP phase, it does not mean that the SMP molecules and the epoxy resin molecules are directly covalently bonded, but assumes that the integration of the two phases can be achieved by the action (e.g., synergistic action) of the curing agent and the compatibilizer. A comparison of FIG. 1 and FIG. 2 clearly shows the difference between the chemically integrated combination of the present application and the chemically separated systems of the prior art.Without being limited to a particular theory, it is believed that the incorporation of a specifically designed compatibilizer in the composition of the present disclosure can effectively achieve a chemically integrated combination of SMP-epoxy resin, thereby successfully increasing the adhesive strength of the resulting composition to a level as high as 5.0 MPa while retaining its good elongation properties.

[0014] According to various embodiments of the present disclosure, the curable composition of the present disclosure is a two-component composition that can be an adhesive, a sealant, a coating or a concrete, preferably a 2K adhesive or a 2K sealant. The curable composition of the present disclosure can be applied to the surface of a substrate to form a coating film, a concrete layer or a sealant layer thereof, realizing the functions of physical / chemical protection, sound / heat / radiation barrier, filling material, supporting / transporting / construction structure, decorative layer or sealing / sealing / waterproof layer. Furthermore, when the curable composition of the present disclosure is used as an adhesive, it can be used to bond two or more identical or different substrates together. According to embodiments of the present disclosure, the substrate is at least one member selected from the group consisting of metal, masonry, concrete, paper, cotton, fiberboard, paperboard, wood, woven or nonwoven fabric, elastomer, polycarbonate, phenolic resin, epoxy resin, polyester, polyethylene carbonate, synthetic and natural rubber, silicone and silicone polymer. According to another embodiment of the present disclosure, the substrate is a polymer substrate selected from the group consisting of polymethyl methacrylate, polypropylene carbonate, polybutene carbonate, polystyrene, acrylonitrile-butadiene-styrene resin, acrylic resin, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, polyimide, and copolymers thereof. According to another embodiment of the present disclosure, the substrate is selected from the group consisting of wood, polystyrene, nylon, and acrylonitrile-butadiene-styrene.

[0015] Silane Modified Polymer (SMP) According to various embodiments of the present disclosure, component (A) is a component that includes a silane-modified polymer. The SMP can be a polymer having silane groups. For example, the SMP can be represented by formula I: R 1 m (R 2 O) (3-m) Si-R 7- (polymer main chain)-R 8 -SiR 3 n (R 4 O) (3-n) Formula I wherein the polymeric backbone is derived from a polyol or from at least one polyisocyanate and at least one polyol, and optionally contains at least one -R 9 -SiR 5 s (R 6 O) (3-s) Functionalized with R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups is independently a hydrogen atom or C 1 -C 6 each of m, n, and s represents an integral of 0, 1, or 2; R 7 , R 8 and R 9 Each of is independently a direct bond, -O-, a divalent (C 1 ~C 6 alkylene) group, -O-(C 1 ~C 6 alkylene) group, (C 1 ~C 6 alkylene)-O- group, -O-(C 1 ~C 6 alkylene)-O- group, -N(R N )-(C 1 ~C 6 alkylene) group or -C(=O)-N(R N )-(C 1 ~C 6 alkylene) group, R N is a hydrogen atom or C 1 -C6 Represents an alkyl group.

[0016] According to embodiments of the present disclosure, the polymeric backbone may be derived from a polyether polyol or a polyester polyol.

[0017] In the context of this disclosure, "silane-modified" refers to a compound having a group "R 1 m (R 2 O) (3-m) Si-R 7 -", "-R 8 -SiR 3 n (R 4 O) (3-n) " and "-R 9 -SiR 5 s (R 6 O) (3-s) " refers to the attachment of the silicone-containing substituents (group R 1 -, R 2 O-, R 3 -, R 4 O-, R 5 - and R 6 In practice, the term "silane group" refers to all of these groups, regardless of whether O- actually represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxy group. 1 m (R 2 O) (3-m) Si-R 7 -" and "-R 8 -SiR 3 n (R 4 O) (3-n) " represents a terminal group attached to the end of the SMP, while -R 9 -SiR 5 s (R 6 O) (3-s) represents at least one side group attached to an intermediate repeat unit of the polymer backbone.

[0018] In the context of this disclosure, C 1 -C 6Alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, tert-pentyl, neopentyl, and n-hexyl; 1 -C 6 Alkylene includes methylene, ethylene, propylene, butylene, pentamethylene and hexamethylene.

[0019] According to embodiments of the present disclosure, the polymeric backbone is derived from a polyol and the SMP represented by formula I may be prepared by reacting at least one reactive capping group (such as an allyl group) attached to the polyol (i.e., the polymeric backbone) with a trialkoxysilane group via a hydrosilylation reaction, or by reacting a polyisocyanate with a polyol to form a polyurethane intermediate, i.e., the polymeric backbone, which is then functionalized with a silanizing agent.

[0020] According to a preferred embodiment of the present disclosure, the polyurethane intermediate is a polyurethane chain having an isocyanate end group, and the silanizing agent contains a silane group at one end and an isocyanate-reactive group (such as a hydroxyl or amine group) at the other end. In the context of the present disclosure, the amine group can be a primary or secondary amine group.

[0021] According to another preferred embodiment of the present disclosure, the polyurethane intermediate is a polyurethane chain having a hydroxyl end group, and the silanizing agent includes a silane group at one end and an isocyanate group at the other end.

[0022] In various embodiments, the polyisocyanate compound for preparing the polymeric backbone (polyurethane chain) is an aliphatic, cycloaliphatic, aromatic or heteroaryl compound having at least two isocyanate groups. In a preferred embodiment, the polyisocyanate compound is a C 4 -C 12 Aliphatic polyisocyanates, C containing at least two isocyanate groups 6 -C 15Alicyclic or aromatic polyisocyanates, C containing at least two isocyanate groups 7 -C 15 aromatic aliphatic The polyisocyanate compound may be selected from the group consisting of m-phenylene diisocyanate, 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI), various isomers of diphenylmethane diisocyanate (MDI), carbodiimide modified MDI products, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI, naphthylene-1,5-diisocyanate, isophorone diisocyanate (IPDI), or mixtures thereof. In general, the amount of polyisocyanate compound may vary based on the actual requirements of the SMP and the resulting curable composition. For example, in one exemplary embodiment, the content of the polyisocyanate compound may be 15% by weight to 60% by weight, or 20% by weight to 50% by weight, or 23% by weight to 40% by weight, or 25% by weight to 38% by weight, based on the total weight of the SMP.

[0023] According to one embodiment of the present disclosure, the polyol for the polymeric backbone or for preparing the polyurethane backbone is a C 2 -C 16 Aliphatic polyhydric alcohols, C containing at least two hydroxyl groups 6 -C 15 Alicyclic or aromatic polyhydric alcohols, C containing at least two hydroxyl groups 7 -C 15 aromatic aliphatic Polyhydric alcohols, polyester polyols having a molecular weight of 100 to 5,000 and an average hydroxyl functionality of 1.5 to 5.0, poly(C) having a molecular weight of 100 to 5,000 2 -C 10 ) alkylene glycol or multiple (C 2-C 10 ) polyether polyols which are copolymers of alkylene glycols, polycarbonate diols having molecular weights of 100 to 5,000, and combinations thereof, and C 2 -C 10 Polyamines, containing at least two thiol groups 2 -C 10 Polythiol, C containing at least one hydroxyl group and at least one amino group 2 ~C 10Further comonomers may be selected from the group consisting of alkanolamines. According to a preferred embodiment, the polyol is a polyether polyol. In various embodiments, the polyether polyol used as the polyol has a molecular weight of 100 to 5,000 g / mol and has end values ​​of 120, 150, 180, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 450, 500, 550, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 290 , 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, and 5000 g / mol. In various embodiments, the polyether polyols can have an average hydroxyl functionality of 1.5 to 5.0, and can have an average hydroxyl functionality within the range obtained by combining any two of the endpoint values ​​1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and 5.0. According to one preferred embodiment, the polyol has an average kinematic viscosity of 500-1,200 cSt, or 600-1,100 cSt, or 700-1,000 cSt, or 800-950 cSt, or 850-920 cSt, and an OH number of 10-100 mg KOH / g, or 12-90 mg KOH / g, or 15-80 mg KOH / g, or 16-70 mg KOH / g, or 17-60 mg KOH / g, or 18-50 mg KOH / g, or 19-40 mg KOH / g, or 20-30 mg KOH / g, or 25-28 mg KOH / g.According to a preferred embodiment of the present disclosure, the polyether polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(2-methyl-1,3-propane glycol), and any copolymers thereof, such as poly(ethylene oxide-propylene oxide) glycol. According to another preferred embodiment of the present disclosure, the polyether polyol comprises at least one poly(C. 2 -C 10 ) alkylene glycol or copolymers thereof, for example, the polyether polyol may be selected from the group consisting of (methoxy)polyethylene glycol (MPEG), polyethylene glycol (PEG), poly(propylene glycol), polytetramethylene glycol, poly(2-methyl-1,3-propane glycol) or copolymers of ethylene epoxide and propylene epoxide having primary or secondary hydroxyl end groups (polyethylene glycol-propylene glycol).

[0024] According to one embodiment of the present disclosure, the polyether polyol is prepared by polymerization of one or more linear or cyclic alkylene oxides selected from propylene oxide (PO), ethylene oxide (EO), butylene oxide, tetrahydrofuran, 2-methyl-1,3-propane glycol and mixtures thereof with a suitable starter molecule in the presence of a catalyst. Typical starter molecules include compounds having at least one, preferably 1.5 to 3.0, hydroxyl group or one or more primary amine groups in the molecule. Suitable starter molecules having at least one, preferably 1.5 to 3.0, hydroxyl groups in the molecule are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, 1,4-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxymethyl)-cyclohexane, 1,3-bis(hydroxymethyl)-cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethyl The starting molecule having one or more primary amine groups in the molecule can be selected from the group consisting of ethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol and formaldehyde, and Mannich condensation products of phenol, formaldehyde and dialkanolamine, and melamine.The starting molecule having one or more primary amine groups in the molecule can be selected from the group consisting of aniline, EDA, TDA, MDA and PMDA, more preferably from the group consisting of TDA and PMDA, and most preferably TDA.When TDA is used, all isomers can be used alone or in any desired mixture.For example, 2,4-TDA, 2,6-TDA, mixtures of 2,4-TDA and 2,6-TDA, 2,3-TDA, 3,4-TDA, mixtures of 3,4-TDA and 2,3-TDA, and mixtures of all the above isomers can also be used. Catalysts for preparing polyether polyols can include alkaline catalysts such as potassium hydroxide for anionic polymerization, or Lewis acid catalysts such as boron trifluoride for cationic polymerization. Suitable polymerization catalysts can include potassium hydroxide, cesium hydroxide, boron trifluoride, or double cyanide complex (DMC) catalysts such as zinc hexacyanocobaltate or tetraphosphazenium compounds. In preferred embodiments of the present disclosure, the starting polyether polyols include polyethylene, (methoxy)polyethylene glycol (MPEG), polyethylene glycol (PEG), poly(propylene glycol), polytetramethylene glycol, poly(2-methyl-1,3-propane glycol) or copolymers of ethylene epoxide and propylene epoxide with primary or secondary hydroxyl end groups (polyethylene glycol-propylene glycol).

[0025] According to a preferred embodiment of the present disclosure, the amount of polyisocyanate is appropriately selected so that the isocyanate groups are present in a stoichiometric molar amount relative to the total molar amount of hydroxyl groups contained in the polyol and any additional additives or modifiers. According to an embodiment of the present disclosure, the polyurethane intermediate (PU backbone) has an NCO content of 2-50 wt%, preferably 6-49 wt%, preferably 8-25 wt%, preferably 10-20 wt%, more preferably 11-15 wt%, and most preferably 12-13 wt%.

[0026] The reaction of the polyisocyanate with the polyol may occur in the presence of one or more catalysts capable of promoting the reaction between the isocyanate group and the hydroxyl group. Without being bound by theory, the catalysts include, for example, glycine salts; tertiary amines; tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; morpholine derivatives; piperazine derivatives; chelates of various metals, such as those obtained from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethylacetoacetate, and the like, with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni; acidic metal salts of strong acids, such as ferric chloride and stannic chloride; organic acids with alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and C; tin(II) salts of organic carboxylic acids, such as organotin compounds such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, as well as dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate; bismuth salts of organic carboxylic acids, such as bismuth octanoate, organometallic derivatives of trivalent and pentavalent As, Sb, and Bi, as well as metal carbonyls of iron and cobalt, or mixtures thereof. In general, the content of the catalyst used herein is greater than zero and is up to 3.0% by weight, preferably up to 2.5% by weight, more preferably up to 2.0% by weight, based on the total weight of component (A).

[0027] Silanizing agents used to introduce silane groups into SMPs (especially "R 1 m (R 2 O) (3-m) Si-R 7 -", "-R 8 -SiR 3 n (R 4 O) (3-n) " and "-R 9 -SiR 5 s (R6 O) (3-s) ") can be represented by the formula silane-X, where the X group can be chlorine, hydroxyl, an amine group, an imine group, an isocyanate group, a halogen atom (e.g., chlorine, bromine or iodine), a ketoximato, amino, amido, acid amide, aminoxy, mercapto or alkenyloxy group. Examples of suitable silanizing agents include γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminophenyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane, aminoethylaminomethylmethyldiethoxysilane, (3-aminopropyl)-diethoxy-methylsilane, (3-aminopropyl)-dimethyl-ethoxysilane, (3-aminopropyl)-trimethoxysilane, N-((β- N-((β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-aminopropyldimethylmethoxysilane, N-((β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-((β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(6-aminohexyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, N-((β-aminoethyl)-γ-aminopropylethyldiethoxysilane, and mixtures thereof.

[0028] According to a preferred embodiment of the present disclosure, the polymeric backbone is derived exclusively from polyol, preferably polyether polyol or polyester polyol. The polymeric backbone may be inclusive with two or more end groups, such as hydroxyl, glycidyl, allyl, or combinations thereof. A hydrosilylation reaction may occur between the above end groups of the polyol chain and the X group of the silanizing agent to form an SMP. A mechanistic scheme of the hydrosilylation reaction is shown in FIG. 3, where the silanizing agent is SiH(OC 2H 5 ) 3 It is.

[0029] According to another preferred embodiment of the present disclosure, the polymeric backbone is a polyurethane backbone derived from the reaction of a polyisocyanate with a polyol. The polymeric backbone may be inclusive with two or more end groups, such as hydroxyl or isocyanate groups. A silylation reaction may occur between the end groups of the polyurethane chain and the X group of the silanizing agent to form an SMP.

[0030] According to one embodiment of the present disclosure, the molar content of the silanizing agent is selected such that the SMP has 1.2-4.0, preferably 1.5-3.0, more preferably 1.8-2.5, more preferably 2.0-2.2 silane functional groups.

[0031] In general, the amount of SMP may vary based on the actual requirements of the resulting curable composition. For example, as one exemplary embodiment, the content of SMP may be 10% to 90% by weight, or 10% to 85% by weight, or 10% to 80% by weight, or 10% to 75% by weight, or 10% to 70% by weight, or 10% to 65% by weight, or 20% to 65% by weight, or 20% to 60% by weight, or 12% to 50% by weight, or 14% to 40% by weight, or 15% to 30% by weight, or 17% to 25% by weight, or 18% to 22% by weight, based on the total weight of the curable composition.

[0032] Epoxy Resin In various embodiments of the present disclosure, component (B) comprises an epoxy resin having at least one, and preferably two, epoxy end groups.

[0033] An epoxy resin can be any polymeric material that contains epoxy functionality. Compounds that contain reactive epoxy functionality can vary widely and include polymers that contain epoxy functionality or blends of two or more epoxy resins. Epoxy resins can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and can be substituted. In some embodiments, an epoxy resin can include a polyepoxide. Polyepoxide refers to a compound or mixture of compounds that contain two or more epoxy moieties. Polyepoxides include partially advanced epoxy resins that are the reaction product of a polyepoxide with a chain extender, the reaction product having an average of two or more unreacted epoxide units per molecule. Aliphatic polyepoxides can be prepared from the reaction of epihalohydrins with polyglycols. Other specific examples of aliphatic epoxides include trimethylolpropane epoxide, and diglycidyl-1,2-cyclohexanedicarboxylate. Other compounds include epoxy resins such as, for example, glycidyl ethers of polyhydric phenols (i.e., compounds having an average of two or more aromatic hydroxyl groups per molecule).

[0034] In one embodiment, the epoxy resin utilized in the curable composition of the present disclosure includes a resin made from an epihalohydrin and a phenol or a phenol-type compound. A phenol-type compound includes a compound having an average of two or more aromatic hydroxyl groups per molecule. Examples of phenol-type compounds include dihydroxyphenols, biphenols, bisphenols, halogenated biphenols, halogenated bisphenols, hydrogenated bisphenols, alkylated biphenols, alkylated bisphenols, trisphenols, phenol-aldehyde resins, novolac resins (which are the reaction products of phenols and simple aldehydes, such as formaldehyde), halogenated phenol-aldehyde novolac resins, substituted phenol-aldehyde novolac resins, phenol-hydrocarbon resins, substituted phenol-hydrocarbon resins, phenol-hydroxybenzaldehyde resins, alkylated phenol-hydroxybenzaldehyde resins, hydrocarbon-phenol resins, hydrocarbon-halogenated phenol resins, hydrocarbon-alkylated phenol resins, or combinations thereof. Specifically, phenol-type compounds include resorcinol, catechol, hydroquinone, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, tetrabromobisphenol A, phenol-formaldehyde novolak resins, alkyl-substituted phenol-formaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolic resins, dicyclopentadiene-substituted phenolic resins, tetramethylbiphenol, tetramethyl-tetrabromobisphenol, tetramethyltribromobisphenol, and tetrachlorobisphenol A. In some embodiments, the epoxy resin of the composition can have a functionality of at least 1.5, at least 3, or at least 6.

[0035] In some embodiments, the epoxy resins utilized in epoxy component (B) include those resins produced from epihalohydrins and amines. Suitable amines include diaminodiphenylmethane, aminophenol, xylylenediamine, aniline, or combinations thereof.

[0036] In some embodiments, epoxy resins utilized in the epoxy component include those resins produced from epihalohydrins and carboxylic acids. Suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and / or hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, isophthalic acid, methylhexahydrophthalic acid, or combinations thereof.

[0037] In some embodiments, the epoxy resin is an advanced epoxy resin, as described above, which is the reaction product of one or more epoxy resins with one or more phenolic type compounds and / or one or more compounds having an average of two or more aliphatic hydroxyl groups per molecule. Alternatively, the epoxy resin may be a phenolic type compound having a hydrocarbon backbone, preferably C 1 -C 40 It can react with carboxyl-substituted hydrocarbons, which are compounds having a hydrocarbon backbone and one or more carboxyl moieties, preferably two or more, most preferably two. 1 -C 40 The hydrocarbon backbone may be a straight or branched chain alkane or alkene, and optionally contains oxygen. Fatty acids and fatty acid dimers are among the useful carboxylic acid-substituted hydrocarbons. Fatty acids include caproic acid, caprylic acid, capric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, pentadecanoic acid, margaric acid, arachidic acid, and dimers thereof.

[0038] In some embodiments, the epoxy resin is the reaction product of a polyepoxide and a compound containing two or more isocyanate moieties or polyisocyanates. For example, the epoxy resin produced in such a reaction can be an epoxy-terminated polyoxazolidone.

[0039] In one particular embodiment, the epoxy resin component is a blend of a brominated epoxy resin and a phenolic novolac epoxy resin.

[0040] According to various embodiments of the present application, the epoxy resin has a molecular weight of 100 to 20,000 grams per mole (g / mol), or 500 to 15,000 g / mol, or 800 to 12,000 g / mol, or 1,000 to 10,000 g / mol, or 2,000 to 9,000 g / mol, or 3,000 to 8,000 g / mol, or 4,000 to 7,000 g / mol, or 5,000 to 6,000 g / mol. According to various embodiments of the present application, the epoxy resin has an epoxy functionality of 1.2 to 10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6. In general, the amount of epoxy resin may vary based on the actual requirements of the resulting curable composition. For example, in one exemplary embodiment, the epoxy resin content can be 5% to 70% by weight, or 7% to 68% by weight, or 5% to 65% by weight, or 10% to 65% by weight, or 11% to 60% by weight, or 12% to 50% by weight, or 14% to 40% by weight, or 15% to 30% by weight, or 17% to 25% by weight, or 18% to 22% by weight, based on the total weight of the curable composition.

[0041] Hardener According to various embodiments of the present disclosure, curing agents that can be used in the practice of the present disclosure include, among others, aliphatic amines, cycloaliphatic amines, aromatic amines, polyaminoamides, imidazoles, dicyandiamides, epoxy-modified amines, Mannich-modified amines, Michael addition-modified amines, ketimines, acid anhydrides, alcohols, and phenols. According to the most preferred embodiment of the present application, the curing agent is triethylenetetramine (TETA). As one exemplary embodiment, the content of the curing agent is 1% to 8% by weight, or 1% to 5% by weight, or 1.5% to 4% by weight, or 1.8% to 3% by weight, or 1.9% to 2.5% by weight, or 2% to 2.2% by weight, based on the total weight of the curable composition. The curing agent can either be supplied and delivered as a component independent of components A and B, or be contained in components A or B. According to a preferred embodiment of the present disclosure, the curing agent is contained in component A, i.e., as a blend with the SMP.

[0042] Compatibilizer The compatibilizer useful in the curable composition of the present disclosure is particularly characterized in that it contains both a silane group and an epoxy group as described above.

[0043] According to an embodiment of the present disclosure, the compatibilizer may be represented by formula II or a condensation oligomer or polymer thereof: [ka] Here, R 10 teeth, [ka] where * is selected from the group consisting of R 10 represents the bonding site that is bonded to other parts of the compatibilizer. R 11 is C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene, -C 2 -C6 Alkylene-Si(C 1 -C 6 Alkyl) 2- C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkyl) 2 -C 2 -C 6 Alkylene, -C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2 -C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2 -C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkyl) 2 -C 2 -C 6 Alkylene-(O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2 -C 2 -C 6 Alkylene-(O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C6 Alkylene-Si(C 1 -C 6 Alkyl) 2- [O-Si(C 1 -C 6 Alkyl) 2 ] x -C 2 -C 6 Alkylene-(O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 Alkylene, and -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2- [O-Si(C 1 -C 6 Alkoxy) 2 ] x -C 2 -C 6 Alkylene-(O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 alkylene; Here, R 12 and R 13 Each of 、 Also is C 1 -C 6 Alkyl group, C 1 -C 6 Alkoxy group, halogen atom, C 2 -C 6 Arken R group, C 2 -C 6 Alkynyl group, -Si(C 1 -C 4 Alkyl) 3 , -Si(C 1 -C 4 Alkoxy) 3 , -Si-{O-[Si(C 1 -C 4 Alkoxy) 3 ] 3 , -(C 1-C 6 ) alkylene-Si(C 1 -C 4 Alkyl) 3 , -(C 1 -C 6 ) alkylene-Si(C 1 -C 4 Alkoxy) 3 Or -(C 1 -C 6 ) alkylene-Si-{O-[Si(C 1 -C 4 Alkoxy) 3 ] } 3 C optionally substituted with 1 -C 6 represents an alkyl group, t represents an integer of 0, 1, or 2, and x represents an integer of 1 to 100. For example, x is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53 , 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100.

[0044] As used herein, the terms "condensation oligomer" and "condensation polymer" refer to an oligomeric or polymeric compound obtained by condensing two or more compounds represented by formula II, particularly through the condensation of silane groups. For example, the compatibilizer can be a condensation oligomer or condensation polymer represented by formula III: [ka] Here, R 10 , R 11and R 13 is as defined above, and r represents an integer from 1 to 50, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

[0045] According to the most preferred embodiment of the present disclosure, the compatibilizer is selected from any one of the following compounds: [ka] Here, x is an integer from 1 to 100, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 , 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100, [ka] where R' is C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene, -C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkyl) 2 -C 2 -C 6 Alkylene, -(CH 2 -C 2 -C 6 Alkylene-Si(C1 -C 6 Alkyl) 2 -C 2 -C 6 Alkylene, -C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2 -C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2 -C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkyl) 2 -C 2 -C 6 Alkylene-(O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkyl) 2 -[O-Si(C 1 -C 6 Alkyl) 2 ] x -C 2 -C 6 Alkylene-(O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 Alkylene, -(CH 2 -O)-C 2 -C 6 Alkylene-Si(C 1 -C 6 Alkoxy) 2 -[O-Si(C 1 -C 6Alkoxy) 2 ] x -C 2 -C 6 Alkylene-O-CH 2 )-CH(OH)-CH 2 -NH-C 2 -C 6 alkylene, and R is a hydrogen atom. 、 Also is C 1 -C 6 Alkyl group, C 1 -C 6 Alkoxy group, halogen atom, C 2 -C 6 Alkenyl group, C 2 -C 6 Alkynyl group, -Si(C 1 -C 4 Alkyl) 3 , -Si(C 1 -C 4 Alkoxy) 3 , -Si-{O-[Si(C 1 -C 4 Alkoxy) 3 ] 3 , -(C 1 -C 6 ) alkylene-Si(C 1 -C 4 Alkyl) 3 , -(C 1 -C 6 ) alkylene-Si(C 1 -C 4 Alkoxy) 3 Or -(C 1 -C 6 ) alkylene-Si-{O-[Si(C 1 -C 4 Alkoxy) 3 ] } 3 C optionally substituted with 1 -C 6 Alkyl groupand y represents an integer of 1 to 50, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50.

[0046] As an exemplary embodiment, the content of the compatibilizer is 1% to 20% by weight, 1% to 15% by weight, or 1.5% to 14% by weight, or 1.8% to 13% by weight, or 2% to 12% by weight, or 3% to 11% by weight, or 4% to 10% by weight, or 5% to 9% by weight, or 6% to 8% by weight, or 6.5% to 7% by weight, based on the total weight of the curable composition. The compatibilizer can be supplied and delivered as a component independent of components A and B, or can be contained in components A or B. According to a preferred embodiment of the present disclosure, the curing agent is contained in component B, i.e., as a blend with the epoxy resin.

[0047] According to preferred embodiments of the present disclosure, the amounts of SMP, epoxy resin, curing agent and compatibilizer are selected such that, inter alia, the molar ratio of total epoxy functional groups to total amine functional groups can be in the range of 1:0.95 to 0.95:1, the molar ratio of epoxy silane compatibilizer to epoxy resin can be 1:10 to 1:1, and the molar ratio of total epoxy groups (including epoxy groups in the epoxy resin and compatibilizer) to total SMP resin can be 1:100 to 5:1.

[0048] Additives In various embodiments of the present disclosure, the curable composition comprises a catalyst, vinyl-Si[O—(C 1 -C 4(A) alkyl], chain extenders, crosslinkers, tackifiers, phthalates, non-aromatic dibasic and phosphate esters, polyesters of dibasic acids with dihydric alcohols, polypropylene glycol and its derivatives, plasticizers such as polystyrene, rheology modifiers, antioxidants, fillers such as calcium carbonate, kaolin, talc, silica, titanium dioxide, aluminum silicate, magnesium oxide, zinc oxide and carbon black, colorants, pigments, surfactants, solvents such as hydrocarbons, acetates, alcohols, ethers and ketones, diluents, flame retardants, anti-slip agents, antistatic agents, preservatives, biocides, UV stabilizers, thixotropic agents, anti-sagging agents such as hydrogenated castor oil, organic bentonite, calcium stearate, and combinations of two or more thereof. These additives are used in known manners and amounts. These additives can be delivered and stored as separate components and can be incorporated into the polyurethane composition shortly before or immediately before the combination of components (A) and (B). Alternatively, these additives can be contained in either components (A) and (B) if they are chemically inert towards reactive groups such as epoxy groups, amino groups, and silane groups.

[0049] The above catalyst refers to a catalytic material that can further accelerate or enhance the interaction between reactive groups such as epoxy groups, amino groups and silane groups. It is also known as a curing catalyst, and can be used independently or in combination of two or more. Representative catalysts include dibutyltin dilaurate, dibutyltin acetoacetate, titanium acetoacetate, titanium ethyl acetoacetate complex and tetraisopropyl titanate, bismuth carboxylate, zinc octoate, blocked tertiary amine, zirconium complex, combination of tin composition with silicic acid amine and Lewis acid catalyst adduct.

[0050] According to a preferred embodiment of the present disclosure, the curable composition of the present disclosure does not contain an aminosilane compound as described above. According to another preferred embodiment of the present disclosure, the curable composition of the present disclosure does not contain a hydroxyl silane compound. According to various aspects of the present application, it has been possible to improve the adhesive strength while maintaining the elongation ratio.

[0051] Once combined, the silane modified polymer, epoxy resin, hardener, and compatibilizer react with each other and gradually cure to form the target layer or structure. The curing process can be carried out at a temperature of, for example, 0°C or more, preferably 20°C or more, more preferably 60°C or more, and most preferably 80°C or more, and simultaneously 300°C or less, preferably 250°C or less, more preferably 200°C or less, and most preferably 180°C or less. The curing process can be carried out, for example, at a pressure of, for example, desirably 0.01 bar or more, preferably 0.1 bar or more, and more preferably 0.5 bar or more, and simultaneously desirably 1000 bar or less, preferably 100 bar or less, and more preferably 10 bar or less. The curing process can be carried out for a predetermined period of time sufficient to cure the SMP-epoxy composition. For example, the curing time can be desirably 1 minute or more, preferably 10 minutes or more, and more preferably 100 minutes or more, and simultaneously desirably 24 hours or less, preferably 12 hours or less, and more preferably 8 hours or less.

[0052] The uncured blend of components A and B can be applied to one or more substrates by a batch or continuous process. The uncured blend can be applied by techniques such as gravity casting, vacuum casting, automated pressure gelling (APG), vacuum pressure gelling (VPG), injection, filament winding, infusion (e.g., lay-up injection), transfer molding, preplasing, dipping, coating, potting, encapsulation, spraying, brushing, and the like. EXAMPLES

[0053] Some embodiments of the present invention will now be described in detail in the following examples. However, the scope of the present disclosure is of course not limited to the formulations described in these examples. Rather, the examples are merely illustrative of the present disclosure.

[0054] Information on the raw materials used in the examples is listed in Table 1 below. [Table 1]

[0055] Preparation example: Preparation of SMP Voranol™ 4000LM (4000 g) was heated at room temperature with N 2 The mixture was added to a guarded three-neck flask and heated at 110° C. under nitrogen flow for 4 hours. After the material in the flask was cooled to 80° C., T12 (2.0 g) and IPDI (296.4 g) were added and the flask was further heated at 80° C. for 4 hours. SCA-3303 (156.93) was then added to the flask and the mixture was heated at 80° C. for 4 hours. After the reaction, the resulting SMP was transferred to a sealed bottle for further characterization, formulation, and testing.

[0056] Comparative Examples 1 and 2 and Inventive Examples 3 to 8 Different two-part curable compositions were prepared according to the formulations listed in Table 2, where Examples 1 and 2 are comparative examples that do not contain a compatibilizer specifically selected according to the present disclosure, and the SMP resins were prepared in the preparation examples above.

[0057] As can be seen from Table 2, Part A contains SMP resin, hardener, dehumidifier, and optionally further contains plasticizer and filler, while Part B contains epoxy resin, epoxy silane compatibilizer, tin catalyst. Part A and Part B were prepared separately by mixing their contents in separate speed mixers at a stirring speed of 2,000 rpm / min. Part A and Part B were combined and thoroughly mixed in a speed mixer at a stirring speed of 1,000 rpm / min for 20 seconds and 1,500 rpm / min for 20 seconds, then further mixed in a vacuum mixer at a pressure of 0.2 KPa at 1,000 rpm / min for 2 minutes, and finally mixed in a speed mixer at 2,000 rpm / min for 20 seconds. After the above mixing steps, the resulting blend was either directly characterized or applied to the surface of a substrate to produce a film sample.

[0058] The samples prepared in the examples were characterized by the following techniques.

[0059] A. The SMP prepared in the above preparation examples was characterized by gel permeation chromatography (GPC) using the following conditions and parameters, GPC was performed using an Agilent 1200 model chromatograph equipped with two mixed D columns (7.8 x 300 mm) and an Agilent refractive index detector, the column temperature was 35 °C, the detector temperature was 35 °C, the flow rate was 1.0 mL / min, the mobile phase was tetrahydrofuran, and the injection volume was 50 μL. The detection data was collected and analyzed using Agilent GPC software based on a calibration curve obtained using PL polystyrene narrow standards with molecular weights of 316,500 to 316,580 g / mol (part number: 2010-0101).

[0060] The Mn of the SMP was measured to be 21,662 and the Mw to be 41,081, so the PDI can be calculated to be 1.90.

[0061] B. Mechanical properties of samples prepared in Examples 1-8 according to ASTM D1708-06A. The cured films of any of the examples were die-cut into dog-bone shaped specimens according to the procedure introduced in ASTM D1708-06A. The specimens were clamped in an Instron 5566 instrument and stretched at a constant rate of 50 mm / min. The load at yield (if any), the maximum load carried by the specimen during the test, the load at break, and the elongation at break (elongation between grips) were recorded. The shear strength of the specimens was also measured with the Instron 5566 instrument with a bonded area of ​​2.5 cm x 2.5 cm. The measurement results are also summarized in Table 2. [Table 2]

[0062] Comparative Example 2 does not contain a compatibilizer and exhibits an adhesive strength of 2.7 MPa, which is very similar to most SMP-based adhesives available on the market, and such poor adhesion cannot fully meet the requirements of many customers in home appliances. As introduced in the previous paragraph, home appliance adhesives are required to have an adhesive strength of more than 5.0 MPa while maintaining an elongation at break of about 100% so that thinner frame areas can be realized. Some industrial assembly customers also frequently require SMP adhesives with higher adhesive strengths for typical substrates such as gaivanized steel and stainless steel.

[0063] Comparing the inventive examples with the comparative examples, it is clear that the introduction of the epoxy silane compatibilizer can significantly increase the tensile strength (to levels above 5.0 MPa) and shear strength while maintaining the elongation at break at approximately 100%, making the SMP-based products of the present disclosure more competitive and differentiated in the marketplace.

Claims

1. 1. A curable composition comprising: at least one silane-modified polymer; at least one epoxy resin terminated with an epoxy group; the composition further comprises a curing agent and a compatibilizer having at least one silane group and at least one epoxy end group; The content of the compatibilizer is 4% by weight to 5% by weight based on the total weight of the curable composition; The content of the epoxy resin is 18% by weight to 22% by weight based on the total weight of the curable composition; and A curable composition, wherein the compatibilizer is a compound represented by formula II: 【Chemistry 1】 (In the formula, R １０ but, 【Chemistry 2】 where * represents a binding site; R １１ But, C ２ -C ６ Alkylene, -(CH ２ -O)-C ２ -C ６ Alkylene, -C ２ -C ６ Alkylene-Si(C １ -C ６ Alkyl) ２ -C ２ -C ６ Alkylene, -(CH ２ -O)-C ２ -C ６ Alkylene-Si(C １ -C ６ Alkyl) ２ -C ２ -C ６ Alkylene, -C ２ -C ６ Alkylene-Si(C １ -C ６ Alkoxy) ２ -C ２ -C ６ Alkylene, -(CH ２ -O)-C ２ -C ６ Alkylene-Si(C １ -C ６ Alkoxy) ２ -C ２ -C ６ Alkylene, -(CH ２ -O)-C ２ -C ６ Alkylene-Si(C １ -C ６ Alkyl) ２ -C ２ -C ６ Alkylene-(O-CH ２ )-CH(OH)-CH ２ -NH-C ２ -C ６ Alkylene, -(CH ２ -O)-C ２ -C ６ Alkylene-Si(C １ -C ６ Alkoxy) ２ -C ２ -C ６ Alkylene-(O-CH ２ )-CH(OH)-CH ２ -NH-C ２ -C ６ Alkylene, -(CH ２ -O)-C ２ -C ６ Alkylene-Si(C １ -C ６ Alkyl) ２ -[O-Si(C １ -C ６ Alkyl) ２ ] ｘ -C ２ -C ６ Alkylene-(O-CH ２ )-CH(OH)-CH ２ -NH-C ２ -C ６ Alkylene, and -(CH ２ -O)-C ２ -C ６ Alkylene-Si(C １ -C ６ Alkoxy) ２－ [O-Si(C １ -C ６ Alkoxy) ２ ] ｘ -C ２ -C ６ Alkylene-(O-CH ２ )-CH(OH)-CH ２ -NH-C ２ -C ６ alkylene; R １２ and R １３ Each of the groups is independently a hydrogen atom, or C １ -C ６ Alkyl group, C １ -C ６ Alkoxy group, halogen atom, C ２ -C ６ Alkenyl group, C ２ -C ６ Alkynyl group, —Si(C １ -C ４ Alkyl) ３ , -Si(C １ -C ４ Alkoxy) ３ , -Si-{O-[Si(C １ -C ４ Alkoxy) ３ ]} ３ , -(C １ -C ６ ) alkylene-Si(C １ -C ４ Alkyl) ３ , -(C １ -C ６ ) alkylene-Si(C １ -C ４ Alkoxy) ３ Or - (C １ -C ６ ) alkylene-Si-{O-[Si(C １ -C ４ Alkoxy) ３ ]} ３ C optionally substituted with １ -C ６ represents an alkyl group, t represents an integer of 0, 1, or 2, and x represents an integer of 1 to 100).

2. 2. The curable composition according to claim 1, wherein the curable composition is a two-component curable composition comprising component A and component B, the silane-modified polymer and the curing agent being contained in component A, and the epoxy resin and the compatibilizer being contained in component B.

3. 2. The curable composition of claim 1, wherein the silane-modified polymer is represented by Formula I: R １ ｍ (R ２ O) （３－ｍ） Si-R ７ - (polymer master lock) - R ８ -SiR ３ ｎ (R ４ O) （３－ｎ） Formula I wherein the polymeric backbone is derived from a polyol or from at least one polyisocyanate and at least one polyol, and optionally contains at least one -R ９ -SiR ５ ｓ (R ６ O) （３－ｓ） and R １ , R ２ , R ３ , R ４ , R ５ , and R ６ Each of the groups is independently a hydrogen atom or C １ -C ６ each of m, n, and s represents an integer of 0, 1, or 2; R ７ , R ８ and R ９ Each of is independently a direct bond, —O—, a divalent (C １ ~C ６ alkylene) group, —O—(C １ ~C ６ alkylene) group, (C １ ~C ６ alkylene)-O- group, -O-(C １ ~C ６ alkylene)-O- group, -N(R Ｎ )-(C １ ~C ６ alkylene) group or -C(=O)-N(R Ｎ )-(C １ ~C ６ alkylene) group, R Ｎ is a hydrogen atom or C １ -C ６ The curable composition of claim 1 , wherein the alkyl group is an alkyl group.

4. The curable composition of claim 3 , wherein the polymeric backbone is derived from a polyether polyol, a polyester polyol, or a copolymer thereof.

5. the polymeric backbone is derived from a polyol or from at least one polyisocyanate and at least one polyol; The polyisocyanate contains at least two isocyanate groups. ４ -C １２ Aliphatic polyisocyanates, C containing at least two isocyanate groups ６ -C １５ Alicyclic or aromatic polyisocyanates, C containing at least two isocyanate groups ７ -C １５ araliphatic polyisocyanates, and any combination thereof; The polyol comprises at least two hydroxyl groups. ２ -C １６ Aliphatic polyhydric alcohols, C containing at least two hydroxyl groups ６ -C １５ Alicyclic or aromatic polyhydric alcohols, C containing at least two hydroxyl groups ７ -C １５ 4. The curable composition of claim 3, wherein the curable composition is selected from the group consisting of araliphatic polyhydric alcohols, polyester polyols having a molecular weight of 100 to 5,000 and an average hydroxyl functionality of 1.5 to 5.0, polyether polyols having a molecular weight of 100 to 5,000 and an average hydroxyl functionality of 1.5 to 5.0, and combinations thereof.

6. 2. The curable composition of claim 1, wherein the curing agent is selected from the group consisting of aliphatic amines, cycloaliphatic amines, aromatic amines, polyaminoamides, imidazoles, dicyandiamide, epoxy modified amines, Mannich modified amines, Michael addition modified amines and ketimines.

7. The epoxy resin is glycidyl ethers of ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycol, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane, glycidyl ethers of hydrogenated bisphenol A, F or A / F, 2. The curable composition of claim 1, wherein the glycidyl ether is selected from the group consisting of bisphenol A resins, bisphenol AP resins, bisphenol F resins, bisphenol K resins, phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolic resins, dicyclopentadiene substituted phenolic resins, and combinations thereof.

8. A method for applying the curable composition according to any one of claims 1 to 7 onto a surface of a substrate, comprising the steps of: (1) combining the silane modified polymer, the epoxy resin, the curing agent, and the compatibilizer to form a precursor blend; (2) applying the precursor blend to a surface of a substrate; (3) curing the precursor blend or allowing the precursor blend to cure.

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