A curable composition

Abstract

The present invention relates to a curable composition, comprising: (A) natural asphalt and / or petroleum asphalt; (B) an organic polymer having a reactive silicon-containing group; (C) an adhesion promoter selected from at least one of the following groups: (C1) a silane monomer compound containing an amino group and a silane compound having an alkyl group with 4 or more carbon atoms; (C2) an oligomer obtained by condensation of a silane compound having an amino group and an optionally used other alkoxysilane compound. The cured product obtained by curing the curable composition of the present invention has good tensile physical properties, adhesion strength and water-resistant adhesiveness.

Description

Technical Field

[0001] The present invention relates to a curable composition, in particular a curable composition comprising asphalt and an organic polymer having reactive silicon-containing groups. Background Art

[0002] Asphalt is a brown or blackish-brown organic cementitious material. Due to its excellent adhesiveness, processability, waterproofness and low cost, it is an indispensable material in civil engineering construction and is widely used in road paving materials, roofing materials, sealing materials, vibration damping materials, sound insulation materials, etc. However, due to its own problems of heat flow at high temperatures and cold brittleness at low temperatures, and poor weather resistance, if used for a long time and subjected to the alternating heat and cold of the natural environment, it is easy to cause the waterproof material made of asphalt to crack and leak.

[0003] On the other hand, it is known that an organic polymer containing at least 1 reactive silicon group in the molecule can undergo a curing reaction with moisture (moisture in the air) even at room temperature to obtain a rubbery cured product having good mechanical properties. Such polymers have been disclosed in the literature (Patent Documents 1 and 2) and are industrially produced and widely used in applications such as sealing materials, adhesives, and coatings.

[0004] Citation List

[0005] Patent Documents

[0006] Patent Document 1: JP-A-52-73998

[0007] Patent Document 2: JP-A-11-130931 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] With the continuous development of the construction industry, the application of underground space is becoming more and more extensive. In particular, for underground buildings such as garages, warehouses, and basements near water sources, the ground is relatively more likely to have problems of water seepage and leakage due to the relatively low terrain. If the waterproof material has insufficient water resistance, problems such as water penetration and a decrease in the adhesive interfacial force are likely to occur once it is immersed in water for a long time. Since it is difficult to repair underground construction projects and it is often difficult to find the leakage source, the requirements for waterproof conditions are relatively higher. In addition, the water-resistant adhesiveness of existing waterproof materials to non-inorganic substrates such as metals, plastics, and woods also needs to be improved.

[0010] Therefore, the main object of the present invention is to provide a curable composition having good bond strength and water-resistant adhesiveness.

[0011] Another object of the present invention is to provide a cured product based on the above curable composition.

[0012] Another object of the present invention is to provide an adhesive based on the above curable composition.

[0013] Another object of the present invention is to provide a sealing material based on the above curable composition.

[0014] Another object of the present invention is to provide an asphalt waterproof material based on the above curable composition.

[0015] Another object of the present invention is to provide a waterproof construction method using the above asphalt waterproof material.

[0016] Another object of the present invention is to provide an object based on the above method.

[0017] Solutions for Solving the Problems

[0018] As a result of in-depth research to solve the above problems, the present inventors have found that adding a specific adhesion promoter to a curable composition containing natural asphalt and / or petroleum asphalt and an organic polymer having a reactive silicon-containing group can obtain a product having good tensile strength, bond strength, and water-resistant adhesion, and is particularly suitable as a waterproof material for underground buildings.

[0019] The present invention includes the following technical solutions:

[0020] [1] A curable composition, comprising:

[0021] (A) Natural asphalt and / or petroleum asphalt;

[0022] (B) An organic polymer having a reactive silicon-containing group;

[0023] (C) An adhesion promoter selected from at least one of the following groups:

[0024] (C1) Comprising a silane monomer compound containing an amino group and a silane compound having an alkyl group with 4 or more carbon atoms;

[0025] (C2) Comprising an oligomer obtained by condensation of a silane compound having an amino group and an optionally used other alkoxysilane compound.

[0026] [2] The curable composition according to [1], wherein, in addition to the oligomer, the component (C2) further comprises a silane compound having an alkyl group with 4 or more carbon atoms.

[0027] [3] The curable composition according to [1] or [2], wherein the component (B) has one or more reactive silicon-containing groups represented by the general formula (1):

[0028] -Si(R 1 ) 3-a Xa (1)

[0029] wherein R 1 each independently is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosilyloxy group represented by -OSi(R ’ )3, wherein R ’ each independently is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X each independently represents a hydroxyl group or a hydrolyzable group; a is an integer of 1 to 3.

[0030] [4] The curable composition according to [3], wherein the component (B) has a main chain structure including polyoxypropylene.

[0031] [5] The curable composition according to any one of [1] to [4], wherein the mass ratio of the silane monomer compound containing an amino group in (C1) to the silane compound containing an alkyl group having 4 or more carbon atoms is 1:0.5 to 3.

[0032] [6] A cured product obtained by curing the curable composition according to any one of [1] to [4].

[0033] [7] An adhesive comprising the curable composition according to any one of [1] to [4].

[0034] [8] A sealing material comprising the curable composition according to any one of [1] to [4].

[0035] [9] An asphalt waterproof material comprising the curable composition according to any one of [1] to [4].

[0036]

[10] A waterproof construction method, wherein the method includes applying the asphalt waterproof material as described in [9] to the surface of an object.

[0037]

[11] An object, wherein one surface or a part of the surface of the object is waterproofed by the waterproof construction method described in

[10] .

[0038] Effects of the Invention

[0039] The curable composition according to the present invention can be used to prepare a cured product having good tensile physical properties, bond strength, and water-resistant adhesiveness, especially with a significant improvement in water-resistant adhesiveness. Detailed Embodiments

[0040] The embodiments of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the respective configurations described below, and various modifications can be made within the scope claimed for the invention. Embodiments and examples obtained by appropriately combining the technical means disclosed in different embodiments and examples are also included in the technical scope of the present invention. In addition, all the documents cited in this specification are hereby incorporated by reference in this specification.

[0041] Unless otherwise defined, the technical and scientific terms used in the present invention have the same meanings as those commonly understood by those of ordinary skill in the technical field to which the present invention pertains.

[0042] In the context of describing the present invention (especially in the context of the appended claims), the terms "a", "an", "the", and similar language will be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context.

[0043] In this specification, an "oligomer" refers to a polymer composed of a relatively small number of repeating units, with a relative molecular mass between that of small molecules and high polymers, mostly ranging from several hundred to several thousand, and generally refers to a polymer composed of 5 to 30 repeating units.

[0044] In the present invention, an "alkoxy group" refers to an alkyl group connected to the rest of the compound through an oxygen atom.

[0045] If not specifically restricted, the "silyl group" in the present invention refers to a -SiH3 group derived from silane, where at least one hydrogen atom in the silyl group can be replaced by an organic group (such as an alkyl group containing 1 to 20 carbon atoms and / or a halogen atom). In particular, the silyl group can include a trimethylsilyl group, a triethylsilyl group, etc.

[0046] In this specification, a numerical range represented by "numerical value A to numerical value B" or "numerical value A - numerical value B" refers to a range that includes the endpoint numerical values A and B.

[0047] In this specification, the meaning expressed by "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process. In this specification, "optional" or "optionally" means that the event or situation described next may or may not occur, and this description includes the situation where the event occurs and the situation where the event does not occur.

[0048] In this specification, the terms "some specific / preferred embodiments", "some other specific / preferred embodiments", "some specific / preferred technical solutions", "some other specific / preferred technical solutions", etc. refer to the specific elements (e.g., features, structures, properties, and / or characteristics) related to the described embodiments, which are included in at least one of the embodiments described herein, and may or may not exist in other embodiments. Additionally, it should be understood that the elements may be combined in any suitable manner in various embodiments.

[0049] The term "comprising" and any variations thereof in the specification, claims, and drawings of the present invention are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that comprises a series of steps or units is not limited to the listed steps or units, but optionally further includes steps or units not listed, or optionally further includes other steps or units inherent to these processes, methods, products, or apparatuses.

[0050] <Curable composition>

[0051] In the curable composition of the present invention, the above-mentioned natural asphalt and / or petroleum asphalt as component (A) (or referred to as component (A)), the organic polymer having a reactive silicon-containing group as component (B) (or referred to as component (B)), the specific adhesion promoter as component (C) (or referred to as component (C)), and optional other components. Each of the above components can be used alone or in combination of two or more. Hereinafter, each component will be described in turn.

[0052] <Component (A)>

[0053] The natural asphalt and / or petroleum asphalt used as component (A) of the present invention mainly refers to asphalt obtained by the evolution or processing of underground crude oil. Natural asphalt mainly includes asphalt extracted from asphalt lakes or sandstones containing asphalt, such as rock asphalt. Petroleum asphalt mainly includes the residue after distilling various light oils (such as gasoline, kerosene, diesel) and lubricating oil from petroleum crude oil, or products obtained by further processing, such as straight-run asphalt, oxidized asphalt, solvent asphalt, and cracked asphalt produced by the refining process. However, coal tar pitch produced by coal refining processes is not preferred because it contains harmful benzopyrene and has a strong odor. Component (A) can be used alone or in combination of two or more. The addition of component (A) improves the elongation, moisture permeability, and water-resistant adhesiveness of the cured product. In particular, from the viewpoints of compatibility and dispersion stability with component (A) and other components, especially component (B), straight-run asphalt is preferred.

[0054] Asphaltene is a dark brown amorphous solid and is one of the main chemical components of asphalt, determining the adhesion, viscosity, and temperature stability of asphalt, as well as the hardness, softening point, etc. of asphalt. Generally speaking, when the asphaltene content (i.e., the mass fraction of asphaltene in asphalt) increases, the viscosity and adhesion of asphalt increase, and the hardness and temperature stability improve. In the present invention, the inventors found that using natural asphalt and / or petroleum asphalt with a low asphaltene content (10% by weight or less) in the system of the present invention can reduce the viscosity, which is beneficial to improving the dispersion stability, improving the compatibility with component (B), and at the same time, a curable composition with strong adhesion can also be obtained by combining with component (B) and (C) of the present invention. If the asphaltene content exceeds 10% by weight, it will have an adverse effect on the compatibility. If the asphaltene content is less than 6%, it is very likely to affect the adhesiveness. In the present invention, the asphaltene content is preferably 7.5 to 9.5% by weight, which can ensure good adhesion performance while improving the dispersion stability. In a specific embodiment of the present invention, petroleum asphalt with an asphaltene content of 9.1% by weight is used, such as No. 200 asphalt of China National Petroleum Corporation.

[0055] The content (or usage amount, compounding amount) of component (A) is preferably 1 to 200 parts by weight, more preferably 5 to 80 parts by weight, and still more preferably 10 to 50 parts by weight, relative to 100 parts by weight of component (B). In some specific embodiments of the present invention, the content of component (A) is 20 to 40 parts by weight relative to 100 parts by weight of component (B). If it is less than 1 part by weight, there is a tendency for the elongation rate, moisture permeability, water-resistant adhesiveness, and storage stability to decrease. If it exceeds 200 parts by weight, there is a tendency for the viscosity to increase and the processability to decrease.

[0056] <Component (B)>

[0057] There is no particular limitation on the main chain of the organic polymer having a reactive silicon group as the component (B). Examples of the polymer constituting the main chain of the organic polymer include polyalkylene oxide polymers such as polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer; hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, copolymers of isoprene or butadiene with acrylonitrile and / or styrene, polybutadiene, copolymers of isoprene or butadiene with acrylonitrile and styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; polyester polymers obtained by condensation of dibasic acids such as adipic acid with diols or ring-opening polymerization of lactones; (meth)acrylate polymers obtained by radical polymerization of monomers such as ethyl (meth)acrylate and butyl (meth)acrylate; vinyl polymers obtained by radical polymerization of monomers such as (meth)acrylate, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above organic polymers; polysulfide polymers; polyamide polymers such as nylon 6 obtained by ring-opening polymerization of ε-caprolactam, nylon 6 / 6 obtained by polycondensation of hexamethylenediamine and adipic acid, nylon 6 / 10 obtained by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 obtained by polycondensation of ε-aminoundecanoic acid, nylon 12 obtained by ring-opening polymerization of ε-aminolaurin lactam, and copolyamides having two or more components of the above nylons; polycarbonate polymers manufactured by polycondensation of, for example, bisphenol A and phosgene; diallyl phthalate polymers, etc. It should be noted that in the present invention, the "(meth)acrylate" means "acrylate and / or methacrylate", and the "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid". The same applies to other similar expressions.

[0058] Since polyalkylene oxide polymers have a low glass transition temperature and high moisture permeability, and the resulting cured products have excellent cold resistance and adhesiveness, the main chain is preferably a polyalkylene oxide polymer. In a specific embodiment of the present invention, a main chain structure including polypropylene oxide is adopted.

[0059] The polyoxyalkylene polymer is obtained by ring-opening polymerization of an epoxide. As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method based on an alkali catalyst such as KOH, a polymerization method based on a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623, JP-B-46-27250, JP-B-59-15336, U.S. Patent No. 3,278,457, U.S. Patent No. 3,278,458, U.S. Patent No. 3,278,459, U.S. Patent No. 3,427,256, U.S. Patent No. 3,427,334, U.S. Patent No. 3,427,335, etc. (for example, a zinc hexacyanocobaltate diglyme complex catalyst), a polymerization method using a catalyst containing a polyphosphazene salt disclosed in JP-A-10-273512, a polymerization method using a catalyst containing a phosphazene compound exemplified in JP-A-11-060722, etc. are exemplified, but the synthesis methods are not limited to these.

[0060] The reactive silicon-containing group of the present invention refers to a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a group that can be crosslinked by accelerating the reaction through a silanol condensation catalyst to form a siloxane bond. The hydrolyzable group means a group that reacts with water to generate a hydroxyl group. In some specific embodiments of the present invention, component (B) has one or more reactive silicon-containing groups represented by the general formula (1):

[0061] -Si(R 1 ) 3-a X a (1)

[0062] Wherein each R 1 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosilyloxy group represented by -OSi(R ’ )3, wherein each R ’ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; each X independently represents a hydroxyl group or a hydrolyzable group; and a is an integer of 1 to 3.

[0063] The hydrolyzable group is not particularly limited as long as it is a conventionally known hydrolyzable group, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenoxy group, etc. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenoxy group are preferred, and an alkoxy group is more preferred from the viewpoints of stable hydrolysis and easy handling, and alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are particularly preferred.

[0064] The number of hydrolyzable groups or hydroxyl groups bonded to one silicon atom can range from 1 to 3. When two or more hydrolyzable groups or hydroxyl groups are bonded in the reactive silicon-containing group, these groups can be the same or different.

[0065] From the viewpoint of curability, a in the above general formula (1) is preferably 2 or 3. In particular, when rapid curability of the composition is required, it is preferably 3, and when storage stability of the composition is required, it is preferably 2.

[0066] As R in the above general formula (1) 1 , examples include: alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, or triorganosiloxanyl groups represented by -OSi(R ’ )3 where each R ’ is methyl, phenyl, etc. Among these, from the viewpoint of raw material utilization rate, methyl is particularly preferred.

[0067] Examples of the reactive silicon-containing group include: trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, methyldimethoxysilyl, etc. From the aspect of high activity and good curability, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl are preferred, more preferably trimethoxysilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl, and further preferably trimethoxysilyl. From the viewpoint of storage stability, dimethoxymethylsilyl and triethoxysilyl are preferred.

[0068] The introduction of the reactive silicon-containing group can be carried out by a known method. Examples of such methods are as follows.

[0069] (I) React an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that is reactive with respect to the functional group (for example, an epoxide containing a saturated group) to obtain an organic polymer having an unsaturated group. Then, react the obtained organic polymer having an unsaturated group with a hydrosilane compound having a reactive silicon-containing group (hydrosilylation).

[0070] (II) React an organic polymer containing an unsaturated group obtained in the same manner as in method (I) with a compound having a mercapto group and a reactive silicon-containing group.

[0071] (III) React an organic polymer having functional groups such as hydroxyl groups, epoxy groups, and isocyanate groups in the molecule with a compound having a functional group reactive with respect to the functional group and a reactive silicon-containing group.

[0072] In the above methods, the method of (I), or the method in (III) of reacting an organic polymer having a hydroxyl group at the end with a compound having an isocyanate group and a reactive silicon-containing group can achieve a high conversion rate in a relatively short reaction time, and is therefore preferred. In addition, since the organic polymer having a reactive silicon-containing group obtained by the method of (I) has a lower viscosity than the organic polymer obtained by the method of (III), a curable composition with good workability can be obtained when using the organic polymer having a reactive silicon-containing group obtained by the method of (I). Moreover, the organic polymer obtained by the method of (II) has a strong odor based on mercapto silane, so the method of (I) is particularly preferred.

[0073] Examples of the hydrosilane compound used in the method of (I) include, but are not limited to, halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, and 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane. Among these, halogenated silanes and alkoxysilanes are particularly preferred, and alkoxysilanes are most preferred because the resulting curable composition has stable hydrolyzability and is easy to operate. Among the alkoxysilanes, methyldimethoxysilane is preferred because it is easily obtainable, and the curable composition containing the resulting organic polymer has high curability, storage stability, elongation characteristics, and tensile strength of the cured product. In addition, trimethoxysilane is particularly preferred from the viewpoints of the curability and resilience of the resulting curable composition.

[0074] Examples of the method of (II) include, but are not limited to, a method of introducing a compound having a mercapto group and a reactive silicon-containing group into the unsaturated bond portion of an organic polymer through a radical addition reaction in the presence of a radical initiator and / or a radical generating source. Examples of the compound having a mercapto group and a reactive silicon-containing group include, but are not limited to, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane.

[0075] Examples of the method of reacting an organic polymer having a hydroxyl group with a compound having an isocyanate group and a reactive silicon group in the method of (III) include, but are not limited to, the method disclosed in Japanese Patent Laid-Open No. 3-47825. Examples of the compound having an isocyanate group and a reactive silicon group include, but are not limited to: γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane, etc.

[0076] The organopolysiloxanes having reactive silicon-containing groups can be used alone or in combination of two or more. Specifically, a mixture of two or more organopolysiloxanes selected from polyoxyalkylene polymers having reactive silicon-containing groups, saturated hydrocarbon polymers having reactive silicon-containing groups, and (meth)acrylate polymers having reactive silicon-containing groups can also be used. The organopolysiloxanes having reactive silicon-containing groups can be of any type, linear or branched. The number average molecular weight (Mn) of the organopolysiloxanes having reactive silicon-containing groups is a value measured by GPC (in terms of polystyrene), preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is less than 1,000, the elongation of the cured product tends to be insufficient. When it exceeds 100,000, the curable composition becomes highly viscous, and thus there is a tendency for the workability to be unsatisfactory. The molecular weight distribution (Mw / Mn) of the organopolysiloxanes having reactive silicon-containing groups measured by GPC is preferably 2 or less, more preferably 1.5 or less, and further preferably 1.4 or less. In order to obtain a rubbery cured product showing high strength, high elongation and low elastic modulus, the number of reactive silicon-containing groups contained in the organopolysiloxane is preferably 1 or more, more preferably 1.1 to 5, further preferably 1.1 to 3, and particularly preferably 1.1 to 2 on average per molecule. When the average number of reactive silicon-containing groups contained in the molecule is less than 1, the curability becomes insufficient and it is difficult to obtain a cured product having good rubber elastic behavior. The reactive silicon-containing groups can be located at the ends of the main chain or side chain of the organopolysiloxane, or can be located at both the ends of the main chain and side chain of the organopolysiloxane. In particular, when the reactive silicon-containing groups are only located at the ends of the main chain, since the effective mesh length in the finally formed cured product becomes longer, it is easy to obtain a rubbery cured product showing high strength, high elongation and low elastic modulus. In a specific embodiment of the present invention, the component (B) is selected from at least one of the following group: a polyoxyalkylene polymer having an average of 1.1 to 5 silicon-containing groups selected from at least one of trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, (methoxymethyl)dimethoxysilyl and methyldimethoxysilyl per molecule and having a number average molecular weight of 1,000 to 100,000. In another specific embodiment of the present invention, the component (B) is selected from at least one of the following group: a polyoxyalkylene polymer having an average of 1.1 to 3 silicon-containing groups selected from at least one of trimethoxysilyl, (methoxymethyl)dimethoxysilyl and methyldimethoxysilyl per molecule and having a number average molecular weight of 2,000 to 50,000.

[0077] Examples of polyoxyalkylene polymers having reactive silicon-containing groups include, for example, polyoxyalkylene polymers proposed in Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 46-12154, Japanese Patent Laid-Open No. 50-156599, Japanese Patent Laid-Open No. 54-6096, Japanese Patent Laid-Open No. 55-13767, Japanese Patent Laid-Open No. 55-13468, Japanese Patent Laid-Open No. 57-164123, Japanese Patent Publication No. 3-2450, U.S. Patent No. 3632557, U.S. Patent No. 4345053, U.S. Patent No. 4366307, U.S. Patent No. 4960844, etc., and polyoxyalkylene polymers proposed in Japanese Patent Laid-Open No. 61-197631, Japanese Patent Laid-Open No. 61-215622, Japanese Patent Laid-Open No. 61-215623, Japanese Patent Laid-Open No. 61-218632, Japanese Patent Laid-Open No. 3-72527, Japanese Patent Laid-Open No. 3-47825, Japanese Patent Laid-Open No. 8-231707, etc. The number average molecular weight (M n ) is 6,000 or more, and the molecular weight distribution (M w / M n ) is 1.6 or less, such as polyoxyalkylene polymers, etc., but are not limited to these. The above polyoxyalkylene polymers having reactive silicon-containing groups can be used alone or in combination of two or more.

[0078] In addition, as another optional embodiment, within the range that does not significantly damage the effects of the present invention, the main chain of the organic polymer having a reactive silicon-containing group may also contain a urethane bond and / or a urea bond.

[0079] As the organic polymer having a reactive silicon-containing group, polymers from Kaneka such as MS POLYMER TM can be used. For example, MS POLYMER TM S203H, MS POLYMER TM S303H, MS POLYMER TM SAT010, MS POLYMER TM SAX350, MSPOLYMER TM SAX400, MS POLYMER TM SAX575, MS POLYMER TM SAX750, etc. In some specific embodiments of the present invention, MS POLYMER TM SAX350 and / or MS POLYMER TM SAX750 are used. In a specific embodiment of the present invention, MS POLYMER TM SAX350 and MS POLYMER TMMixture of SAX750.

[0080] The weight ratio of component (B) to the total weight of the curable composition can be appropriately adjusted. Considering workability, curability, and cost, this weight ratio is preferably 10 - 30 wt%, more preferably 15 - 20 wt%, and even more preferably 16 - 18 wt%.

[0081] <Component (C)>

[0082] The inventors have found that using a specific type of adhesion promoter (also referred to as an adhesion - imparting agent or a bonding promoter) in the system of the present invention in combination with other components of the present invention is beneficial for obtaining a cured product that can maintain tensile physical properties and bonding strength while enhancing water - resistant adhesion, especially improving water - resistant adhesion to substrates such as metals, plastics, and woods.

[0083] The adhesion promoter (i.e., component (C)) of the present invention belongs to the class of silane coupling agents. Component (C) is selected from at least one of the following (C1) and (C2):

[0084] (C1) includes a silane monomer compound containing an amino group and a silane compound containing an alkyl group with 4 or more carbon atoms;

[0085] (C2) includes an oligomer obtained by condensation of a silane compound having an amino group and an optionally used other alkoxysilane compound.

[0086] In one technical solution of the present invention, the adhesion promoter (C) is selected from (C1), that is, the adhesion promoter includes a silane monomer compound containing an amino group and a silane compound containing an alkyl group with 4 or more carbon atoms. That is to say, in addition to the silane monomer compound containing an amino group and the silane compound containing an alkyl group with 4 or more carbon atoms, (C1) may also have other silane compounds. In a specific embodiment of the present invention, (C1) consists of a silane monomer compound containing an amino group and a silane compound containing an alkyl group with 4 or more carbon atoms.

[0087] In the present invention, the silane monomer compound containing an amino group refers to a small molecule silane compound containing an amino group (which may also be abbreviated as amino silane compound in the present invention), that is, a non-polymeric product (distinguished from the oligomers in the following (Group C2)). Examples of the silane monomer compound containing an amino group include: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, (aminomethyl)dimethoxymethylsilane, (aminomethyl)trimethoxysilane, (phenylaminomethyl)dimethoxymethylsilane, (phenylaminomethyl)trimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, bis(3-trimethoxysilylpropyl)amine, and the like.

[0088] The content of the nitrogen atom in the silane monomer compound containing an amino group is preferably 1 wt% or more, more preferably 3 wt% or more, and particularly preferably 4 wt% or more. The content of the nitrogen atom in the silane monomer compound containing an amino group is preferably 15 wt% or less, and further preferably 8-14 wt%. When the content of the nitrogen atom in the silane monomer compound containing an amino group is 1 mass% or more, the cured product of the curable composition can maintain excellent rubber elasticity for a long time. From the viewpoint of adhesion to porous substrates such as concrete, a silane containing one or more amino groups in one molecule is preferred. In a specific embodiment of the present invention, the silane monomer compound containing an amino group is selected from N-β-aminoethyl-γ-aminopropyltrimethoxysilane and is commercially available. The content (or usage amount, compounding amount) of the silane monomer compound containing an amino group is preferably 1-15 parts by weight, more preferably 2-12 parts by weight, and still more preferably 3-10 parts by weight with respect to 100 parts by weight of the component (B). If the content of the silane monomer compound containing an amino group is less than 1 part by weight, the bonding strength may not meet the requirements. If the content of the silane monomer compound containing an amino group exceeds 15 parts by weight, it is very likely to have an adverse effect on the curing process.

[0089] In the present invention, the inventors found that if only a silane monomer compound containing an amino group is used as an adhesion promoter, although good bonding strength can be obtained, the adhesiveness is insufficient after water immersion. To solve this problem, a silane compound having an alkyl group with 4 or more carbon atoms is also required to be used in combination with the aforementioned silane monomer compound containing an amino group in the present invention. The inventors found that, compared with other types of silane compounds such as isocyanate group-containing silanes and epoxy group-containing silanes, the use of a silane compound having an alkyl group with 4 or more carbon atoms in combination with a specific amount of a silane monomer compound containing an amino group can significantly improve the water-resistant adhesiveness of the cured product, especially for the water-resistant adhesiveness to substrates such as metals and plastics. The silane compound having an alkyl group with 4 or more carbon atoms means that the number of carbon atoms in the alkyl group of the silane compound is 4 or more, preferably 7 or more, and more preferably 8 to 20. The alkyl group may have a branched chain, preferably a straight-chain alkyl group, and specific examples of the alkyl group include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, icosyl, etc., and further preferably decyl, octyl, tetradecyl or octadecyl. The silane compound having an alkyl group with 4 or more carbon atoms is further preferably a hydrolyzable silyl group. Specific examples of the silane compound having an alkyl group with 4 or more carbon atoms include, for example, n-butyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxysilane, n-heptyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltriethoxysilane, n-octadecyltriethoxysilane, n-butylmethyldimethoxysilane, n-pentylmethyldimethoxysilane, n-hexylmethyldimethoxysilane, n-heptylmethyldimethoxysilane, n-octylmethyldimethoxysilane, n-dodecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, n-octylbutyldiethoxysilane, 1,8-bis(trimethoxysilyl)octane, 1,12-bis(trimethoxysilyl)dodecane, 1,8-bis(triethoxysilyl)octane, 1,12-bis(triethoxysilyl)dodecane, 1,8-bis(methyldimethoxysilyl)octane, etc.Further preferably, the silane compound having an alkyl group with 4 or more carbon atoms is selected from one or more of n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-nonyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltrimethoxysilane, n-heptyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltriethoxysilane, n-octadecyltriethoxysilane, n-heptylmethyldimethoxysilane, n-octylmethyldimethoxysilane, n-dodecylmethyldimethoxysilane, and n-octadecylmethyldimethoxysilane. Even further, in order to further improve the water-resistant adhesiveness, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, and n-octadecyltrimethoxysilane are more preferred.

[0090] In the present invention, the content (or usage amount, compounding amount) of (C1) is preferably 2 to 30 parts by weight, more preferably 3 to 20 parts by weight, and even more preferably 5 to 15 parts by weight, based on 100 parts by weight of the component (B). Further, the content of the silane compound having an alkyl group with 4 or more carbon atoms is preferably 1 to 15 parts by weight, more preferably 2 to 12 parts by weight, and even more preferably 3.5 to 10 parts by weight, based on 100 parts by weight of the component (B). If the content of the silane compound having an alkyl group with 4 or more carbon atoms is less than 1 part by weight, the water-resistant adhesiveness may not be improved. If the content of the silane compound having an alkyl group with 4 or more carbon atoms exceeds 15 parts by weight, the curability may be reduced. In some specific embodiments of the present invention, the mass ratio of the silane monomer compound having an amino group to the silane compound having an alkyl group with 4 or more carbon atoms is 1:0.5 to 3, further 1:0.7 to 2.5. In order to further improve the water-resistant adhesiveness, in some specific embodiments of the present invention, the mass ratio of the two is 1:0.8 to 2.

[0091] In another technical solution of the present invention, the adhesion promoter (C) is selected from (C2), which includes the following specific oligomers. The oligomer of the present invention is an alkoxyalkyl oligomer containing an amino group, which is obtained by condensation of a silane compound having an amino group and an optionally used other alkoxysilane compound. That is to say, the oligomer of the present invention can be a silane oligomer obtained by hydrolysis and condensation of a silane compound having an amino group, that is, by condensing only the silyl group of the amino silane, or it can also be a partial hydrolysis and condensation of a silane compound having an amino group and other alkoxysilane compounds. In some specific embodiments of the present invention, the oligomer of the present invention is obtained by hydrolyzing the alkoxy groups of the alkoxysilane and the alkoxy groups of the aminoalkoxysilane to form silanol groups, and then condensing these silanol groups.

[0092] The silane compound having an amino group is preferably selected from aminoalkoxysilanes, i.e., compounds having at least one amino group-containing functional group in one molecule and at least one alkoxy group directly bonded to a silicon atom. Specific examples of the silane compound having an amino group include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, (aminomethyl)dimethoxymethylsilane, (aminomethyl)trimethoxysilane, (phenylaminomethyl)dimethoxymethylsilane, (phenylaminomethyl)trimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, bis(3-trimethoxysilylpropyl)amine, and the like. The above silane compounds having an amino group can be used alone or in combination of two or more. In some specific embodiments of the present invention, the silane compound having an amino group is preferably a compound having one amino group-containing functional group and three alkoxy groups directly bonded to a silicon atom in one molecule. More preferably, the amino group-containing functional group is directly bonded to the silicon atom.

[0093] An alkoxysilane compound refers to a compound in which at least one alkoxy group is directly bonded to a silicon atom. Specific examples of other alkoxysilane compounds in the present invention include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetrapropyl orthosilicate, and tetrabutyl orthosilicate; silanes containing epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; silanes containing vinyl-type unsaturated groups such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, and methacryloxymethyltrimethoxysilane; silanes containing mercapto groups such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane; isocyanurate silanes such as 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate and partial hydrolysis condensates, etc. Each of these can be used alone, or two or more of these can be used in combination.

[0094] In some specific embodiments of the present invention, for further improving the water-resistant adhesiveness, especially for improving the water-resistant adhesiveness to substrates such as metals, plastics, and woods, the oligomer of the present invention is preferably a hydrolysis condensate of monoalkyltrialkoxysilane and aminoalkoxysilane.

[0095] In some specific embodiments of the present invention, specific examples of the oligomer of the present invention include X-40-2651 (Shin-Etsu Chemical Co., Ltd.), MS3301 (JNC Corporation), MS3302 (JNC Corporation), Dynasylan 1146 (Evonik Corporation), etc.

[0096] The content of the oligomer of the present invention is 0.5 to 20 parts by weight, further 1 to 10 parts by weight, and still further 2 to 8 parts by weight relative to 100 parts by weight of the component (B). If the amount of the oligomer is less than 0.5 part by weight, the adhesiveness of the coating film tends to be insufficient, and if its amount is greater than 20 parts by weight, the mechanical properties of the cured product will tend to deteriorate.

[0097] In another technical solution of the present invention, in order to further improve the water-resistant adhesiveness of the cured product, the adhesion promoter includes, in addition to the aforementioned oligomer, the aforementioned silane compound having an alkyl group with 4 or more carbon atoms. In some specific embodiments of the present invention, the content of the aforementioned silane compound having an alkyl group with 4 or more carbon atoms is preferably 1 to 15 parts by weight, more preferably 2 to 12 parts by weight, and still more preferably 3.5 to 10 parts by weight relative to 100 parts by weight of the component (B). In some specific embodiments of the present invention, the mass ratio of the aforementioned oligomer to the silane compound having an alkyl group with 4 or more carbon atoms is 1:0.5 to 4, and further 1:1 to 3.

[0098] <Other components>

[0099] Within the scope of not destroying the effects of the present invention, the curable composition of the present invention may also contain components other than the above components (A) to (C) (other components). Hereinafter, the other components will be described.

[0100] In some specific embodiments of the present invention, a plasticizer is added to the curable composition of the present invention. Known plasticizers are used, and specific examples include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, etc.; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate compounds such as diisononyl 1,2-cyclohexanedicarboxylate; aliphatic polycarboxylate compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributyl acetylcitrate, etc.; unsaturated fatty acid ester compounds such as butyl oleate, methyl acetylricinoleate, etc.; phenyl alkyl sulfonate; phosphate ester compounds such as tricresyl phosphate, tributyl phosphate, etc.; trimellitate compounds; chlorinated paraffin; hydrocarbon oils such as alkyl biphenyl, partially hydrogenated terphenyl, etc.; epoxy plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, etc. In addition, high molecular weight plasticizers can also be used, such as polyalkylene oxide; (meth)acrylate polymers; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester; polyesters obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid and diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol; polyethers obtained by urethanizing the hydroxyl groups of polyether polyols, polyethers obtained by esterifying with carboxylic acids, polyethers obtained by etherifying the terminals; polystyrene such as polystyrene, poly-α-methylstyrene; polybutadiene, polybutene, polyisobutene, butadiene-acrylonitrile, polychloroprene; hydrogenated α-olefins such as hydrogenated polybutadiene oligomers. These components can be used alone or in combination of two or more. The addition of the plasticizer reduces the viscosity of the composition and improves the processability. In addition, the compatibility and dispersion stability of component (A) and component (B) can also be improved. In a specific embodiment of the present invention, the plasticizer is preferably one or more of phthalate, saturated or unsaturated fatty acid ester compounds, phosphate ester compounds, epoxy plasticizers or high molecular weight plasticizers, because they tend to significantly improve the dispersion stability of component (A) and component (B). In particular, diisononyl phthalate is preferred. Based on 100 parts by weight of component (B), the content of the plasticizer is preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight. If the amount is less than 10 parts by weight, the effect of viscosity reduction is small and the processability becomes insufficient; if the amount exceeds 120 parts by weight, sufficient mechanical properties cannot be obtained, for example, the tensile strength of the cured product decreases.

[0101] In the prior art, it is usually necessary to add a certain amount of tackifying resin to improve the compatibility and dispersion stability of component (A) and component (B), and at the same time improve the adhesiveness or sealing property to the substrate. Specific examples of the tackifying resin include terpene resins, aromatic-modified terpenes and hydrogenated terpene resins obtained by hydrogenating them, terpene-phenolic resins obtained by copolymerizing terpenes with phenols, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low-molecular-weight polystyrene-based resins, styrene copolymers, petroleum resins (for example, C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These components can be used alone or in combination of two or more. In the prior art, the amount of the tackifying resin used is usually 1-80 parts by weight, more preferably 2-70 parts by weight, per 100 parts by weight of component (B). If this amount is less than 1 part by weight, the dispersion stability usually tends to decrease; if the addition amount exceeds 80 parts by weight, there is a tendency to increase the viscosity of the system and reduce the processability. Through the combination of components (A) to (C) in the present invention, it is possible to maintain good dispersion stability even when the content of the tackifying resin is less than 1 part by weight (per 100 parts by weight of component (B)) or even without adding the tackifying resin. In a preferred embodiment of the present invention, the tackifying resin is not added to further reduce the cost.

[0102] In some specific embodiments of the present invention, an inorganic filler is added to the curable composition of the present invention. The inorganic filler is not particularly limited, and conventionally known inorganic fillers can be widely used. The inorganic filler is not particularly limited, and conventionally known inorganic fillers can be widely used. Examples of the inorganic filler include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, calcined clay, clay, and kaolin; resin powders such as calcium carbonate, dolomite, anhydrous silicic acid, hydrous silicic acid, magnesium carbonate, diatomaceous earth, talc, titanium oxide, bentonite, organic bentonite, iron oxide, aluminum micropowder, zinc oxide, activated zinc white, PVC powder, and PMMA powder; fibrous fillers such as glass fiber, etc. These components can be used alone or in combination of two or more. By adding the inorganic filler, the dispersion stability of the composition and the strength of the cured product are improved. In particular, from the viewpoints of easy handling, availability, and cost, calcium carbonate is preferred. The calcium carbonate can be at least one selected from heavy calcium carbonate, precipitated calcium carbonate, and calcium carbonate subjected to surface treatment of these calcium carbonates. Precipitated calcium carbonate is classified into light calcium carbonate having a major axis of 1 μm or more and colloidal calcium carbonate having an average particle size of 1 μm or less, and any of these two types of calcium carbonate can be used. Among them, colloidal calcium carbonate is preferably used in consideration of obtaining good mechanical properties. Colloidal calcium carbonate subjected to surface treatment can also be used. Examples of the surface treatment agent include fatty acids such as stearic acid, fatty acid esters, modified fatty acids, resin acids such as rosin, paraffin, polyethylene wax, cationic surfactants, etc. Calcium carbonate preferably selected from those subjected to surface treatment, and colloidal calcium carbonate subjected to fatty acid treatment or resin acid treatment is particularly preferred. The average particle size of the heavy calcium carbonate is preferably 0.3 to 10 μm, more preferably 0.7 to 7 μm, particularly preferably 0.7 to 5 μm, and most preferably 1.1 to 4 μm. When it is less than 0.3 μm, there is a tendency that the viscosity of the bituminous waterproofing agent becomes high and the workability deteriorates; heavy calcium carbonate subjected to surface treatment can also be used. The amount of the inorganic filler used is preferably 10 to 500 parts by weight, more preferably 50 to 450 parts by weight, and still more preferably 200 to 400 parts by weight based on 100 parts by weight of the component (B). If it is less than 10 parts by weight, it is likely to have an adverse effect on the dispersion stability and strength. If it exceeds 500 parts by weight, there is a tendency to increase the viscosity of the system and reduce the processability.

[0103] In some specific embodiments of the present invention, a thixotropic agent (or anti-sagging agent) may also be added to the curable composition of the present invention to prevent sagging and improve workability. There is no particular limitation on the thixotropic agent. For example, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, barium stearate, etc. These thixotropic agents can be used alone or in combination of two or more. The amount of the thixotropic agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of component (B).

[0104] In the curable composition of the present invention, a stabilizer can be added. Specific examples of the stabilizer include antioxidants, light stabilizers, and ultraviolet absorbers. If an antioxidant is used, the weather resistance of the cured product can be improved. As the antioxidant, hindered phenols, monophenols, bisphenols, polyphenols can be exemplified, and hindered phenols are particularly preferred, such as Irganox 245. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of component (B). When a light stabilizer is used, photo-oxidative degradation of the cured product can be prevented. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferred. The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, further preferably 0.2 to 5 parts by weight, based on 100 parts by weight of component (B). When an ultraviolet absorber is used, the surface weather resistance of the cured product can be improved. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred. The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, further preferably 0.2 to 5 parts by weight, based on 100 parts by weight of component (B).

[0105] In the present invention, in order to further improve the tensile strength, a small amount of carbon black can be incorporated. Furnace black, lamp black, gas black, channel black, pyrolytic carbon black, acetylene black obtained by the oil furnace method or the gas furnace method can be cited. Considering the availability, carbon black obtained by the mainstream furnace method is preferred. Specific examples of the carbon black can be obtained in the form of commercially available products such as HIBLACK30, HIBLACK10, HIBLACK5L, HIBLACK20L, etc. The carbon black can be used alone or in combination of two or more. The content of the carbon black is preferably 0.1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight, particularly preferably 0.3 to 1 part by weight, based on 100 parts by weight of component (B). In the specific embodiments of the present invention, the amount of carbon black used is small, so it is not considered to belong to the aforementioned inorganic fillers of the present invention.

[0106] In some specific embodiments of the present invention, a dehydrating agent is further added. Examples of the dehydrating agent may include, for example: synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, alkoxysilane compounds (such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.), oxazolidine compounds, isocyanate compounds, etc. In a specific embodiment of the present invention, vinyltrimethoxysilane is used as the dehydrating agent, that is, in this embodiment, in addition to the adhesion promoter (C) of the present invention, the curable composition further contains an additional vinyl silane coupling agent as the dehydrating agent. The content of the dehydrating agent is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of component (B).

[0107] In some specific embodiments of the present invention, a curing catalyst is further added to promote curing. Any silanol condensation catalyst well-known in the art can be used. Specific examples of the silanol condensation catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetra(acetylacetone)titanium, bis(acetylacetone)diisopropoxytitanium, bis(ethoxyacetoacetyl)diisopropoxytitanium; tetravalent organotin compounds such as dimethyltin diacetate, bis(acetylacetone)dimethyltin, dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, bis(2-ethylhexanoic acid)dibutyltin, bis(methylmaleic acid)dibutyltin, bis(ethylmaleic acid)dibutyltin, bis(butylmaleic acid)dibutyltin, bis(octylmaleic acid)dibutyltin, bis(tridecylmaleic acid)dibutyltin, bis(benzylmaleic acid)dibutyltin, dibutyltin diacetate, bis(ethylmaleic acid)dioctyltin, bis(octylmaleic acid)dioctyltin, dimethanol dibutyltin, bis(nonylphenol)dibutyltin, divinyltin oxide, dibutyltin oxide, bis(acetylacetone)dibutyltin, bis(ethylacetylacetone)dibutyltin, reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate, dioctyltin dilaurate, dioctyltin diacetate, bis(acetylacetone)dioctyltin; organoaluminum compound classes such as tris(acetylacetone)aluminum, tris(ethylacetylacetone)aluminum, ethylacetoacetate diisopropoxyaluminum; zirconium compound classes such as tetra(acetylacetone)zirconium; carboxylic acid and / or metal carboxylate; amidine compound; amine compounds such as butylamine, octylamine, di-n-butylamine, laurylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleamide, cyclohexylamine, benzylamine, diethylaminopropylamine and salts formed by them and carboxylic acids. Specific examples involved also include silanol condensation catalysts well-known in the art such as other acidic catalysts and basic catalysts. These catalysts can be used alone or in combination of two or more. The content of the silanol condensation catalyst is preferably 0.01 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (B). If the content is less than 0.01 part by weight, the composition is not easily cured. If the content exceeds 15 parts by weight, there is a tendency for the storage stability and adhesiveness to decrease. Considering the curing performance and storage stability comprehensively, the reaction product of dialkyltin oxide and silicate is preferred, such as U-303.

[0108] Furthermore, in order to adjust various other physical properties of the curable composition or the cured product, various additives can be added to the curable composition of the present invention as needed. Examples of such additives include, for example, flame retardants, radical inhibitors, metal deactivators, ozone deterioration preventives, phosphorus-based peroxide decomposers, lubricants, pigments, foaming agents, solvents, mildew preventives, etc. The various additives can be used alone or in combination of two or more.

[0109] In some specific embodiments of the present invention, in addition to components (A) to (C), the curable composition further includes calcium carbonate, a plasticizer, and a small amount of antioxidant, thixotropic agent, dehydrating agent, and catalyst.

[0110] The curable composition of the present invention may or may not contain an epoxy resin. Relative to 100 parts by weight of component (A), the content of the epoxy resin in the curable composition of the present invention is less than 5 parts by weight, preferably 3 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.5 part by weight or less. In some preferred embodiments of the present invention, the curable composition does not contain an epoxy resin, so that the cured product has good weather resistance (especially ultraviolet resistance), and the cured product can also have good adhesiveness to other substrates (such as plastics, wood, etc.) except for inorganic substrates (such as tiles and concrete). At the same time, the curable composition also has more excellent storage stability.

[0111] By selecting and adjusting the amount of components in the present invention, the cured product obtained from the curable composition of the present invention has good tensile physical properties, bond strength, and water-resistant adhesiveness, especially a significant improvement in water-resistant adhesiveness. The curable composition of the present invention is applied in a strip shape to a mortar base material and cured at 23 °C and a relative humidity of 50% for 7 days. Then, it is immersed in water at 23 °C for 7 days. The adhesiveness is evaluated by a hand-peeling experiment, and there are differences in the adhesion state (cohesive failure rate) between the adhesive and the mortar. In some preferred specific embodiments of the present invention, the cohesive failure rate (or called the agglomeration failure rate) is 80% or more. In addition, the cured product obtained by curing the curable composition of the present invention also has good bond strength and water-resistant adhesiveness to substrates of metals, woods, or polymer materials other than inorganic materials (such as tiles, concrete, etc.) (measured by the above method).

[0112] <Preparation of curable composition>

[0113] The curable composition of the present invention can be a one-component composition prepared by mixing all components and curing by moisture in the air. In addition, the curable composition of the present invention can also be a two-component composition prepared by mixing a curing catalyst and other components (such as filler, plasticizer, water, etc.) to prepare the first composition, and separately mixing component (A), component (B), component (C), and other components as needed to prepare the second composition, and mixing the first composition and the second composition before use. In addition, the curable composition of the present invention can also be a multi-component composition prepared by separately preparing more than three compositions and mixing these compositions before use. From the aspect of workability, a one-component composition is preferred.

[0114] When preparing the curable composition of the present invention in the form of a single-component composition, for components containing moisture, it is preferably used after pre-dehydration and drying, or dehydrated by reduced pressure or the like during kneading. When dehydrating or drying a solid such as powder, a heat drying method or a reduced pressure dehydration method is preferred. When dehydrating or drying a liquid, a reduced pressure dehydration method or a method using a dehydrating agent is preferred. If a plasticizer is added to the curable composition, the component (A) and the plasticizer can be premixed first, and then mixed and kneaded with the component (B) and other components as required, such as optional inorganic fillers, a small amount of carbon black, and antioxidants. After that, reduced pressure dehydration is carried out, followed by cooling, and then optional diluents, dehydrating agents, component (C) (bonding promoter), etc. are added. Finally, a curing catalyst is added and kneaded to obtain the curable composition of the present invention, which is beneficial to obtaining a composition with high stability.

[0115] There is no particular limitation on the preparation method of the curable composition of the present invention. Conventional methods such as blending the above components and using a mixer, roll, kneader, etc. for kneading at normal temperature or heating, or using a small amount of solvent to dissolve the components and mixing them can be adopted.

[0116] <Cured product>

[0117] When the curable composition of the present invention is exposed to the atmosphere, a three-dimensional network structure will be formed due to the action of moisture, and it will cure into a cured product with rubber-like elasticity.

[0118] <Use>

[0119] As for the use of the curable composition of the present invention, there is no particular limitation, and it can be effectively used as a waterproof asphalt material, a sealing material, an adhesive, etc. for construction and civil engineering. In particular, since this composition has no odor and is excellent in bonding strength and water-resistant adhesiveness, it is preferably used as an underground waterproof material. The present invention further provides a waterproof construction method, which includes applying the curable composition of the present invention to the surface of an object, such as applying the curable composition of the present invention to the surface of concrete or mortar for underground construction or underground buildings, and exposing it to the atmosphere to cure into a cured waterproof coating with rubber-like elasticity, which can maintain adhesive durability and waterproofness for a long time. Any method can be used to coat the curable composition of the present invention, such as using a brush, a trowel, a roll, a sprayer, etc. to coat it. Especially when coating a large area, from the perspective of coating efficiency, it is preferred to use a roll or a spraying machine for coating.

[0120] The present invention further provides an object, wherein one surface or a part of the surface of the object is subjected to waterproof treatment by using the foregoing waterproof construction method of the present invention. Further, the object includes artificial structures. Further, the artificial structures include ground buildings and their accessories, structures built on water such as ships, underwater structures, etc. The parts of the artificial structures applicable to the present invention are not limited, and construction can be carried out where waterproofing is required, such as roofs, balconies, open corridors, roads, exterior walls, etc. where waterproofing is required; underground parts (such as underground passages, tunnels), etc., where waterproof treatment of groundwater is required; bathrooms, kitchens, toilets, sinks, sewage tanks, etc., where waterproofing of domestic water is required; heat storage layers, swimming pools, waste liquid treatment tanks, landfills, etc., where waterproofing of industrial water is required. Further preferably, considering the excellent water-resistant adhesiveness of the present invention, it is preferred to use the curable composition of the present invention for waterproof treatment of underground structures.

[0121] The present invention is further illustrated by the following examples, but is not limited thereto.

[0122] Examples

[0123] Example 1

[0124] 30 parts by weight of straight-run asphalt (manufactured by China National Petroleum Corporation, trade name No. 200 asphalt, asphaltene content: 9.1% by weight) and 90 parts by weight of plasticizer diisononyl phthalate (manufactured by Shanghai Huishuo Company) were first mixed to obtain a premix. Then it was mixed with the following composition: 100 parts by weight of a polymer having methyldimethoxysilyl group and a polyoxypropylene main chain (manufactured by Kaneka Corporation, MS POLYMER TM SAX350), 80 parts by weight of calcium carbonate (manufactured by Maruo Corporation, product number KALFINE 200A), 280 parts by weight of calcium carbonate (manufactured by Omya Corporation, product number Omya-1T), 1 part by weight of carbon black (manufactured by Orion Corporation, product number Hiblack 30), 1 part by weight of antioxidant (manufactured by BASF Corporation, product number Irganox 245), 2 parts by weight of thixotropic agent (manufactured by Arkema Corporation, product number SL). The obtained mixture was subjected to reduced-pressure dehydration at 120°C for 2 hours and cooled to below 50°C, then 3 parts by weight of vinyltrimethoxysilane (manufactured by Momentive Performance Materials Inc., product number A-171) as a dehydrating agent and 4 parts by weight of oligomer-type adhesion promoter (manufactured by Evonik Industries AG, product number Dynasylan 1146) were added. Finally, 3 parts by weight of bis(triethoxysiloxy)dibutyltin (manufactured by Nitto Kasei Co., Ltd., trade name: NEOSTAN U-303) as a curing catalyst was added and kneaded to obtain a curable composition. The composition was sealed in a moisture-proof cartridge in a substantially water-free state.

[0125] Example 2

[0126] Change the 4 parts by weight of the oligomer-type adhesion promoter in Example 1 to 4 parts by weight of an amino group-containing silane monomer compound (manufactured by Momentive, product number A-1120) and 7 parts by weight of a silane compound having an alkyl group with 4 or more carbon atoms (manufactured by Evonik, product number Dynasylan OCTMO). The rest is the same as in Example 1.

[0127] Example 3

[0128] Change the 4 parts by weight of the oligomer-type adhesion promoter in Example 1 to 4 parts by weight of the oligomer-type adhesion promoter and 7 parts by weight of a silane compound having an alkyl group with 4 or more carbon atoms (manufactured by Evonik, product number Dynasylan OCTMO). The rest is the same as in Example 1.

[0129] Example 4

[0130] Change the 7 parts by weight of the silane compound having an alkyl group with 4 or more carbon atoms (manufactured by Evonik, product number Dynasylan OCTMO) in Example 2 to 5 parts by weight. The rest is the same as in Example 2.

[0131] Example 5

[0132] Change the 7 parts by weight of the silane compound having an alkyl group with 4 or more carbon atoms (manufactured by Evonik, product number Dynasylan OCTMO) in Example 2 to 3 parts by weight. The rest is the same as in Example 2.

[0133] Example 6

[0134] Change the 100 parts by weight of the polymer having methyldimethoxysilyl group and a polyoxypropylene main chain (manufactured by Kaneka, MS POLYMER TM SAX350) in Example 2 to 50 parts by weight of the polymer having methyldimethoxysilyl group and a polyoxypropylene main chain (manufactured by Kaneka, MS POLYMER TM SAX350) and 50 parts by weight of the polymer having methyldimethoxysilyl group and a polyoxypropylene main chain (manufactured by Kaneka, MSPOLYMER TM SAX750). Change the amount of the curing catalyst from 3 parts by weight to 2 parts by weight. The rest is the same as in Example 2.

[0135] Comparative Example 1

[0136] Change the 4 parts by weight of the oligomer-type adhesion promoter in Example 1 to 4 parts by weight of an amino group-containing silane monomer compound (manufactured by Momentive Performance Materials Inc., product number A-1120). The rest is the same as in Example 1.

[0137] Comparative Example 2

[0138] Change the 4 parts by weight of the oligomer-type adhesion promoter in Example 1 to 7 parts by weight of a silane compound having an alkyl group with 4 or more carbon atoms (manufactured by Evonik Industries AG, product number Dynasylan OCTMO). The rest is the same as in Example 1.

[0139] Comparative Example 3

[0140] Do not add 30 parts by weight of straight-run asphalt (manufactured by China National Petroleum Corporation, trade name No. 200 asphalt, asphaltene content is 9.1% by weight), and at the same time change the 100 parts by weight of the polymer having methyldimethoxysilyl group and a polyoxypropylene main chain (manufactured by Kaneka Corporation, MS POLYMER TM SAX350) to 130 parts by weight of the polymer having methyldimethoxysilyl group and a polyoxypropylene main chain (manufactured by Kaneka Corporation, MS POLYMER TM SAX350). The rest is the same as in Example 1.

[0141] The types and amounts of the components in the curable compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1 below. It should be noted that the unit of the component amounts shown in Table 1 below is parts by weight.

[0142] (Characteristic Evaluation)

[0143] The tensile physical properties and water-resistant adhesiveness of the curable compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were measured and evaluated. The results are shown in Table 1 below.

[0144] <Tensile Physical Properties>

[0145] The curable composition was filled into a 3-mm-thick polyethylene template in a manner that no bubbles would enter, cured at 23°C and 50% relative humidity for 3 days, and then further cured at 50°C for 4 days to obtain a cured product. According to JIS K 6251, a No. 7 dumbbell-shaped test piece was punched from the obtained cured product, and a tensile test (tensile speed: 200 mm / minute, 23°C, 50% relative humidity) was carried out to measure the moduli (M50, M100) at 50% and 100% elongation, the strength at break (TB), and the elongation at break (%). The results are shown in Table 1.

[0146] <Initial Adhesion and Water-Resistant Adhesiveness>

[0147] The curable composition was applied to a concrete substrate (produced by Nantong Bibo New Material Technology Co., Ltd.: GBT-113477, 70×70×20 mm) in strips and cured at 23 °C and a relative humidity of 50% for 7 days. A 90° hand-peeling test was conducted on the cured product, and the adhesiveness was evaluated based on the cohesive failure rate at the bonding interface (initial adhesiveness). The results are shown in Table 1. Then, it was immersed in water at 23 °C for 7 days. After taking it out of the water, a 90° hand-peeling test of the cured product was also conducted, and the adhesiveness was evaluated based on the cohesive failure rate at the bonding interface (water-resistant adhesiveness). The results are shown in Table 1 for water-resistant adhesiveness. The evaluation criteria are as follows:

[0148] A: The cohesive failure rate is 80% or more.

[0149] B: The cohesive failure rate is more than 50% and less than 80%.

[0150] C: The cohesive failure rate is more than 5% and less than 50%.

[0151] D: Interface failure is 100%.

[0152] As can be seen from Table 1, Examples 1 to 6 of the present invention have good tensile physical properties. Compared with Comparative Examples 1 to 3, Examples 1 to 6 of the present invention have a significant improvement in water-resistant adhesiveness. In Comparative Example 3, natural asphalt and / or petroleum asphalt were not used, resulting in not only insufficient water-resistant adhesiveness but also a significant decrease in elongation at break. Comparing Example 1 and Example 3, the combined use of an oligomer (Dynasylan 1146) and a silane compound containing an alkyl group with 4 or more carbon atoms (Dnasylan OCTMO) can further improve the water-resistant adhesiveness.

[0153] Table 1

[0154]

[0155]

Claims

1. A curable composition, characterized in that, It includes: (A) Natural asphalt and / or petroleum asphalt; (B) An organic polymer having reactive silicon-containing groups; (C) An adhesion promoter of the following (C1) or (C2): (C1) Comprising a silane monomer compound containing an amino group and a silane compound containing an alkyl group having 4 or more carbon atoms; (C2) Comprising an oligomer obtained by condensation of a silane compound having an amino group and an optionally used other alkoxysilane compound, In addition to the oligomer, the component (C2) further comprises a silane compound containing an alkyl group having 4 or more carbon atoms, Relative to 100 parts by weight of the (B) organic polymer, it contains 20 to 40 parts by weight of the (A) asphalt, In the case of containing the (C1) adhesion promoter, relative to 100 parts by weight of the (B) organic polymer, it contains 2 to 15 parts by weight of the (C1) adhesion promoter, and the mass ratio of the silane monomer compound containing an amino group to the silane compound containing an alkyl group having 4 or more carbon atoms in the (C1) is 1:0.8 to 2, In the case of containing the (C2) adhesion promoter, relative to 100 parts by weight of the (B) organic polymer, the silane compound containing an alkyl group having 4 or more carbon atoms is 1 to 15 parts by weight, and the mass ratio of the oligomer to the silane compound containing an alkyl group having 4 or more carbon atoms is 1:1 to 3.

2. The curable composition according to claim 1, characterized in that, The component (B) has one or more reactive silicon-containing groups represented by the general formula (1): -Si(R 1 ) 3-a X a (1) wherein R 1 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosilyloxy group represented by -OSi(R ’ )3, wherein R ’ each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X each independently represents a hydroxyl group or a hydrolyzable group; and a is an integer of 1 to 3.

3. A cured product, characterized in that, It is cured from the curable composition according to claim 1 or 2.

4. An adhesive, characterized in that, It includes the curable composition according to claim 1 or 2.

5. A sealing material, characterized in that, It includes the curable composition according to claim 1 or 2.

6. An asphalt waterproof material, characterized in that, It includes the curable composition according to claim 1 or 2.

7. A waterproof construction method, characterized in that, The method includes applying the asphalt waterproof material according to claim 6 to the surface of an object.

8. An object, characterized in that, A waterproof treatment is performed on one surface or a partial surface of the object by the waterproof construction method according to claim 7.

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