Multi-liquid hardening composition

Abstract

Provided is a multi-component curable composition containing an agent A and an agent B. Agent A contains a polyoxyalkylene-based polymer (A) having an average of more than one reactive silicon group, represented by general formula (1) below, at one terminal position. Agent B contains a reactive silicon group-containing polyoxyalkylene-based polymer (P) and / or a plasticizer (D), an inorganic filler (E), and water (F). The percentage of the inorganic filler (E) in the total amount of the agent B is 10 wt.% or greater. -SiX3 X represents a hydroxyl group or a hydrolyzable group.

Description

[Technical Field]

[0001] The present invention relates to a multi-component curable composition and a cured product obtained by curing the composition. [Background technology]

[0002] Polyoxyalkylene polymers having silicon groups (hereinafter also referred to as "reactive silicon groups") that have hydroxyl groups or hydrolyzable groups on silicon atoms and can form siloxane bonds through hydrolysis and condensation reactions are known to harden in response to moisture in the surrounding environment, yielding a rubbery cured product. These polymers are used as adhesives, sealants, and fillers, taking advantage of their physical properties.

[0003] However, moisture-curable compositions containing the polymer in question have a problem in that the curing reaction depends on moisture in the air, and curing proceeds from the surface of the applied composition, resulting in insufficient deep curing.

[0004] Therefore, it has been reported that deep curing properties can be improved by constructing a two-component composition in which an organic polymer having a reactive silicon group is the main component and water is used as an auxiliary agent (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-231855 [Overview of the project] [Problems that the invention aims to solve]

[0006] In such two-component compositions, it is desirable to incorporate a curable resin and / or plasticizer into the water-containing auxiliary agent to ensure good mixing of the main component and the auxiliary agent. However, auxiliary agents in such formulations lack stability, and the components tend to separate easily.

[0007] Also, in the line production method that is continuously carried out, such as the assembly of industrial products, when performing adhesive bonding, the adhesive is required to exhibit a certain degree of initial strength in a short time to ensure early fixity.

[0008] Furthermore, it is also required that the mixture is not easily thickened after mixing the main agent and the auxiliary agent, and the usable time is long.

[0009] In view of the above situation, the present invention provides a two-component curable composition containing a main agent containing a polyoxyalkylene polymer having a reactive silicon group and an auxiliary agent containing water, which has good stability of the auxiliary agent, a long usable time after mixing the main agent and the auxiliary agent, and a fast development of initial strength.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that by blending a predetermined ratio of an inorganic filler together with at least one of a polyoxyalkylene polymer having a reactive silicon group and a plasticizer in an auxiliary agent containing water, and further using a polyoxyalkylene polymer having a reactive silicon group with a specific structure as the polyoxyalkylene polymer containing a reactive silicon group to be blended in the main agent, the above problems can be solved, and the present invention has been completed.

[0011] That is, the present invention has, on average, more than 1 at one terminal site, the following general formula (1): -SiX3 (1) (In the formula, X represents a hydroxyl group or a hydrolyzable group.) It relates to a two-component curable composition containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by the formula, the B agent contains at least one of a polyoxyalkylene polymer (P) having a reactive silicon group and a plasticizer (D), an inorganic filler (E), and water (F), and the proportion of the inorganic filler (E) in the total amount of the B agent is 10% by weight or more.

Effects of the Invention

[0012] According to the present invention, there is provided a two-component curable composition containing a main component including a polyoxyalkylene polymer having a reactive silicon group and an auxiliary component containing water, which has good stability of the auxiliary component, a long usable time after mixing the main component and the auxiliary component, and a rapid development of initial strength.

Mode for Carrying Out the Invention

[0013] Embodiments of the present invention will be specifically described below, but the present invention is not limited to these embodiments.

[0014] This embodiment is a two-component curable composition containing at least an A component and a B component. The A component contains at least a polyoxyalkylene polymer (A) having, on average, more than one reactive silicon group represented by a specific formula at at least one terminal site. The B component contains at least one of at least a polyoxyalkylene polymer (P) having a reactive silicon group and a plasticizer (D), an inorganic filler (E), and water (F), and the proportion of the inorganic filler (E) in the total amount of the B component is 10% by weight or more. In addition, the curable composition according to this embodiment does not contain an epoxy resin.

[0015] <<Polyoxyalkylene polymer (A) having a reactive silicon group>> <Reactive silicon group> The polyoxyalkylene polymer (A) has a reactive silicon group. The reactive silicon group refers to a silicon group having a hydroxyl group or a hydrolyzable group on a silicon atom and capable of forming a siloxane bond by a hydrolysis / condensation reaction.

[0016] In this embodiment, the reactive silicon of the polyoxyalkylene polymer (A) is one in which three hydroxyl groups or hydrolyzable groups are bonded to one silicon atom, and is represented by the following general formula (1). -SiX3(1) (In the formula, X represents a hydroxyl group or a hydrolyzable group.) By using reactive silicon groups with such characteristic structures, it is possible to secure a relatively long usable time after mixing agent A and agent B, i.e., the time until the mixture thickens and becomes unsuitable for use (coating), and to obtain the advantage of rapid development of initial strength during bonding.

[0017] Examples of X include hydroxyl groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups such as methoxy and ethoxy groups are more preferred due to their mild hydrolysis and ease of handling, with methoxy and ethoxy groups being particularly preferred. Multiple X groups may be the same or different from each other.

[0018] The reactive silicon groups in the polyoxyalkylene polymer (A) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, and triacetoxysilyl groups. Among these, trimethoxysilyl and triethoxysilyl groups are preferred, and trimethoxysilyl groups are more preferred, as they yield cured products with high rigidity.

[0019] In this embodiment, the polyoxyalkylene polymer (A) has, on average, more than one reactive silicon group at each terminal site. This allows for a relatively long usable time after mixing agent A and agent B, and provides the advantage of rapid development of initial strength during bonding. Furthermore, even if the main agent and auxiliary agent are mixed and applied to the substrate, and then the adherends are bonded together after a certain amount of time has elapsed, good adhesion can be achieved, providing the advantage of a longer working time.

[0020] Having more than one reactive silicon group on average at each terminal site means that the polyoxyalkylene polymer (A) contains polyoxyalkylene molecules having two or more reactive silicon groups at each terminal site. In other words, the polyoxyalkylene polymer (A) may contain only polyoxyalkylene molecules having two or more reactive silicon groups at each terminal site, or it may contain both polyoxyalkylene molecules having two or more reactive silicon groups at each terminal site and polyoxyalkylene molecules having one reactive silicon group at each terminal site. Furthermore, a single polyoxyalkylene molecule may have multiple terminal sites, some having two or more reactive silicon groups and others having one reactive silicon group. In addition, the polyoxyalkylene polymer (A) as a whole may have more than one reactive silicon group on average at each terminal site, but may also contain polyoxyalkylene molecules having terminal sites without reactive silicon groups.

[0021] A terminal region having two or more reactive silicon groups can be represented, for example, by the following general formula (2).

[0022] [ka]

[0023] (In the formula, R 1 ,R 3 Each of these independently represents a divalent carbon-1 to carbon-6 bonding group, R 1 ,R 3 The atom bonded to each adjacent carbon atom is either carbon, oxygen, or nitrogen. 2 ,R 4 Each of these independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. X is as described above for equation (1).

[0024] R 1 , R 3It may be a divalent organic group having 1 to 6 carbon atoms, which may be a hydrocarbon group that may contain an oxygen atom. The number of carbon atoms of the hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. R 1 Specific examples of R 3 include, for example, -CH2OCH2-, -CH2O-, -CH2-. Preferably, it is -CH2OCH2-. R

[0025] R 2 R 4 The number of carbon atoms of the hydrocarbon group of R 2 R 4 is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. Specific examples of R

[0026] According to a particularly preferred embodiment, the terminal moiety represented by the general formula (2) is such that R 1 is -CH2OCH2-, R 3 is -CH2-, and R 2 and R 4 are each a hydrogen atom. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2. However, n is not limited to one value and a plurality of values may be mixed.

[0027] The polyoxyalkylene polymer (A) has more than 1.0 reactive silicon groups on average at one terminal moiety. The average number is more preferably 1.1 or more, even more preferably 1.5 or more, and still more preferably 2.0 or more. Also, it is preferably 5 or less, more preferably 3 or less.

[0028] The number of terminal sites having more than one reactive silicon group in one molecule of polyoxyalkylene polymer (A) is preferably 0.5 or more on average, more preferably 1.0 or more, even more preferably 1.1 or more, and even more preferably 1.5 or more. Furthermore, it is preferably 4 or less, and more preferably 3 or less.

[0029] The polyoxyalkylene polymer (A) may have reactive silicon groups in locations other than the terminals, but it is preferable to have them only in the terminals, as this makes it easier to obtain a rubbery cured product with high elongation and low elastic modulus.

[0030] From the viewpoint of the strength of the cured product, the average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, even more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. Furthermore, from the viewpoint of the elongation of the cured product, it is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less.

[0031] <Main chain structure> There are no particular restrictions on the main chain skeleton of the polyoxyalkylene polymer (A), and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-polyoxybutylene copolymer. Among these, polyoxypropylene is preferred.

[0032] The number-average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000, in terms of polystyrene-equivalent molecular weight in GPC. If the number-average molecular weight is less than 3,000, the amount of reactive silicon groups introduced increases, which may be disadvantageous in terms of manufacturing costs, and if it exceeds 100,000, it tends to become highly viscous, which is disadvantageous in terms of workability.

[0033] The molecular weight of polyoxyalkylene polymer (A) can also be expressed as the end-group-reduced molecular weight, which is determined by directly measuring the end-group concentration of the organic polymer precursor before the introduction of reactive silicon groups by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and considering the structure of the organic polymer (degree of branching determined by the polymerization initiator used). Alternatively, the end-group-reduced molecular weight of polyoxyalkylene polymer (A) can be determined by creating a calibration curve between the number-average molecular weight obtained by general GPC measurement of the organic polymer precursor and the above-mentioned end-group-reduced molecular weight, and then converting the number-average molecular weight obtained by GPC of polyoxyalkylene polymer (A) to the end-group-reduced molecular weight.

[0034] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less. Furthermore, from the viewpoint of improving various mechanical properties such as the durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution of the polyoxyalkylene polymer (A) can be determined from the number-average molecular weight and weight-average molecular weight obtained by GPC measurement.

[0035] Furthermore, the main chain structure of the polyoxyalkylene polymer (A) may be linear or branched. A linear main chain structure is preferable because it allows for a longer usable time after mixing agent A and agent B.

[0036] <Method for synthesizing polyoxyalkylene polymer (A)> Next, we will explain the method for synthesizing polyoxyalkylene polymer (A). A polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon group at each terminal site is preferably obtained by introducing two or more carbon-carbon unsaturated bonds to one hydroxyl group terminal of a hydroxyl group polymer obtained by polymerization, and then reacting it with a reactive silicon group-containing compound that reacts with carbon-carbon unsaturated bonds. This synthesis method is described below.

[0037] (polymerization) For polyoxyalkylene polymers (A), a method is preferred in which an epoxy compound is polymerized on a hydroxyl group-containing initiator using a complex metal cyanide catalyst such as a zinc hexacyanocobaltate grime complex.

[0038] Examples of initiators having hydroxyl groups include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polyoxypropylene monoallyl ether, and polyoxypropylene monoalkyl ether, which have one or more hydroxyl groups.

[0039] Examples of epoxy compounds include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Among these, propylene oxide is preferred.

[0040] (Introduction of carbon-carbon unsaturated bonds) A preferred method for introducing two or more carbon-carbon unsaturated bonds to a single terminal is to react a hydroxyl-terminated polymer with an alkali metal salt, then first react it with an epoxy compound having carbon-carbon unsaturated bonds, and then react it with a halogenated hydrocarbon compound having carbon-carbon unsaturated bonds. This method allows for efficient and stable introduction of reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain by polymerization conditions.

[0041] Preferred alkali metal salts include sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide, with sodium methoxide and potassium methoxide being more preferred. Sodium methoxide is particularly preferred due to its availability.

[0042] The temperature for reacting with the alkali metal salt is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time for reacting with the alkali metal salt is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0043] As epoxy compounds having carbon-carbon unsaturated bonds, in particular, general formula (3):

[0044] [ka]

[0045] (R in the formula) 1 , R 2 The above is the same. Compounds represented by ) can be preferably used. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide are preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.

[0046] The amount of epoxy compound having carbon-carbon unsaturated bonds added can be any amount, taking into consideration the amount of carbon-carbon unsaturated bonds introduced into the polymer and its reactivity. In particular, the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.2 or higher, more preferably 0.5 or higher. It is also preferably 5.0 or lower, and more preferably 2.0 or lower.

[0047] When an epoxy compound having a carbon-carbon unsaturated bond is subjected to a ring-opening addition reaction with a polymer containing a hydroxyl group, the reaction temperature is preferably 60°C or higher and 150°C or lower, and more preferably 110°C or higher and 140°C or lower.

[0048] Examples of halogenated hydrocarbon compounds having carbon-carbon unsaturated bonds include vinyl chloride, allyl chloride, methyl chloride, vinyl bromide, allyl bromide, methyl bromide, vinyl iodide, allyl iodide, and methyl iodide. Due to their ease of handling, allyl chloride and methyl chloride are more preferable.

[0049] There are no particular restrictions on the amount of halogenated hydrocarbon compound having a carbon-carbon unsaturated bond added, but the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.7 or higher, more preferably 1.0 or higher. Furthermore, it is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0050] The reaction temperature for a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is preferably 50°C to 150°C, and more preferably 110°C to 140°C. The reaction time is preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0051] (Introduction of reactive silicon groups) The method for introducing reactive silicon groups is not particularly limited, and known methods can be used. Examples of introduction methods are given below. (i) A method for adding a hydrosilane compound to a polymer having carbon-carbon unsaturated bonds by a hydrosilylation reaction. (ii) A method of reacting a polymer having carbon-carbon unsaturated bonds with a compound (also called a silane coupling agent) having both a group capable of forming a bond in reaction with carbon-carbon unsaturated bonds and a reactive silicon group. Examples of groups capable of forming a bond in reaction with carbon-carbon unsaturated bonds include, but are not limited to, mercapto groups. (iii) A method for reacting a reactive group-containing polymer with a silane coupling agent. Examples of reactive group combinations between the reactive group-containing polymer and the silane coupling agent include, but are not limited to, hydroxyl group and isocyanate group, hydroxyl group and epoxy group, amino group and isocyanate group, amino group and thioisocyanate group, amino group and epoxy group, amino group and α,β-unsaturated carbonyl group (reaction by Michael addition), carboxyl group and epoxy group, unsaturated bond and mercapto group, etc.

[0052] Method (i) is preferred because the reaction is simple, the amount of reactive silicon groups introduced can be easily adjusted, and the physical properties of the resulting reactive silicon group-containing polyoxyalkylene polymer (A) are stable. Methods (ii) and (iii) are preferred because they offer many reaction options and make it easy to increase the rate of reactive silicon group introduction.

[0053] The hydrosilane compounds that can be used by method (i) are not particularly limited, but examples include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, and triacetoxysilane.

[0054] Regarding the amount of hydrosilane compound used, a molar ratio (moles of hydrosilane / moles of carbon-carbon unsaturated bonds) of 0.05 to 10 relative to the carbon-carbon unsaturated bonds in the precursor polymer is preferable from the viewpoint of reactivity, and 0.3 to 2 is more preferable from the viewpoint of economy.

[0055] Hydrosilylation reactions are accelerated by various catalysts. Known catalysts such as various complexes of cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium can be used as hydrosilylation catalysts. For example, platinum supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes consisting of chloroplatinic acid with alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2]; platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4]; platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4]; and platinum-phosphite complexes [Pt{P(OPh)3}4] can be used. From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

[0056] Silane coupling agents that can be used by the method of (ii) or (iii) above include, for example, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and mercaptomethyltriethoxysilane, which react with unsaturated bonds; isocyanatesilanes such as 3-isocyanatetopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, isocyanatemethyltrimethoxysilane, and isocyanatemethyltriethoxysilane, which react with hydroxyl groups; epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, and glycidoxymethyltriethoxysilane, which react with hydroxyl groups, amino groups, or carboxyl groups; and 3-aminopropyltrimethoxysilane, 3-A Examples include aminosilanes such as minopropyltriethoxysilane, 3-(2-aminoethyl)propyltrimethoxysilane, 3-(2-aminoethyl)propyltriethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and bis(3-(trimethoxysilyl)propyl)amine; and hydroxyalkylsilanes such as 3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane.

[0057] The main chain of the polyoxyalkylene polymer (A) is composed of ester bonds, or general formula (4), to the extent that the effects of the invention are not impaired. -NR 6 -C(=O)- (4) (In the formula, R 6 The amide segment may include an organic group with 1 to 10 carbon atoms or a hydrogen atom.

[0058] Cured products obtained from curable compositions containing a polyoxyalkylene polymer (A) containing ester bonds or amide segments may have high hardness and strength due to the action of hydrogen bonding, etc. However, polyoxyalkylene polymers (A) containing amide segments, etc., may cleave due to heat, etc. Also, curable compositions containing polyoxyalkylene polymers (A) containing amide segments, etc., tend to have high viscosity. Considering the above advantages and disadvantages, polyoxyalkylene polymers (A) may be used as polyoxyalkylene polymers (A) containing amide segments, etc., or polyoxyalkylene polymers that do not contain amide segments, etc., may be used.

[0059] Examples of amide segments represented by the general formula (4) include those formed by the reaction of an isocyanate group with a hydroxyl group, an amino group with a carbonate, an isocyanate group with an amino group, an isocyanate group with a mercapto group, and so on. Furthermore, amide segments formed by the reaction of an amide segment containing an active hydrogen atom with an isocyanate group are also included in the amide segments represented by the general formula (4).

[0060] A method for producing a polyoxyalkylene polymer (A) containing an amide segment is, for example, to react a polyoxyalkylene having an active hydrogen-containing group at its terminus with an excess polyisocyanate compound to synthesize a polymer having an isocyanate group at its terminus, or simultaneously with its synthesis, the general formula (5): ZR 7 -SiRX3(5) (In the formula, X is the same as above. R 7 A is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group, or a secondary amino group. One method involves reacting the Z group of a silicon compound represented by () with all or part of the isocyanate groups of the synthesized polymer.

[0061] The silicon compound represented by the general formula (5) is not particularly limited, but examples include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, (N-phenyl)-γ-aminopropyltrimethoxysilane, and N-ethylaminoisobutyltrimethoxysilane; hydroxyl group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; and the like. Furthermore, as described in Japanese Patent Publication No. 6-211879 (US Patent No. 5364955), Japanese Patent Publication No. 10-53637 (US Patent No. 5756751), Japanese Patent Publication No. 10-204144 (EP0831108), Japanese Patent Publication No. 2000-169544, and Japanese Patent Publication No. 2000-169545, Michael addition products of various α,β-unsaturated carbonyl compounds and primary amino group-containing silanes, or Michael addition products of various (meth)acryloyl group-containing silanes and primary amino group-containing compounds, can also be used as silicon compounds represented by the general formula (5).

[0062] Furthermore, as a method for producing a polyoxyalkylene polymer (A) containing an amide segment, for example, a polyoxyalkylene having an active hydrogen-containing group at its terminus is given a general formula (6): O=C=NR 7 -SiX3(6) (In the formula, R 7 A method for reacting a reactive silicon group-containing isocyanate compound represented by (where X is the same as described above) can be given.

[0063] The reactive silicon group-containing isocyanate compound represented by the general formula (6) is not particularly limited, but examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, and triethoxymethylsilylmethyl isocyanate.

[0064] When the polyoxyalkylene polymer (A) contains amide segments, the number of amide segments per molecule of the polyoxyalkylene polymer (A) (average value) is preferably 1 to 10, more preferably 1.5 to 5, and particularly preferably 2 to 3. If this number is less than 1, the curability may not be sufficient, and conversely, if it is greater than 10, the polyoxyalkylene polymer (A) may become highly viscous and difficult to handle. To lower the viscosity of the curable composition and improve workability, it is preferable that the polyoxyalkylene polymer (A) does not contain amide segments.

[0065] <<Reactive silicon group-containing (meth)acrylic acid ester polymer (B)>> Agent A may contain a reactive silicon group-containing polyoxyalkylene polymer (A) along with a reactive silicon group-containing (meth)acrylic acid ester polymer (B) (hereinafter also referred to as "(meth)acrylic acid ester polymer (B)"). However, (meth)acrylic acid ester polymer (B) is an optional component and may not be included. The (meth)acrylic acid ester monomers constituting the main chain of polymer (B) are not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylate Nyl, Decyl (meth)acrylate, Dodecyl (meth)acrylate, Phenyl (meth)acrylate, Toluyl (meth)acrylate, Benzyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 3-Methoxybutyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, Stearyl (meth)acrylate, Glycidyl (meth)acrylate, (3-Trimethoxysilyl)propyl (meth)acrylate, (3-Dimethyl Examples of (meth)acrylic acid monomers include toxicmethylsilyl)propyl, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

[0066] The (meth)acrylic acid ester polymer (B) has a reactive silicon group represented by the general formula (1) shown above. The reactive silicon group of the (meth)acrylic acid ester polymer (B) may be the same as or different from the reactive silicon group of the polyoxyalkylene polymer (A).

[0067] The reactive silicon groups in the (meth)acrylic acid ester polymer (B) include, but are not limited to, trimethoxysilyl, triethoxysilyl, tris(2-propenyloxy)silyl, and triacetoxysilyl groups. Among these, trimethoxysilyl and triethoxysilyl groups are more preferred, and trimethoxysilyl groups are even more preferred, as they yield cured products with a high Young's modulus.

[0068] The reactive silicon group equivalent of the (meth)acrylic acid ester polymer (B) is not particularly limited, but is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, and even more preferably 0.6 mmol / g or more. The reactive silicon group equivalent is preferably 2.0 mmol / g or less, and more preferably 1.0 mmol / g or less in terms of suppressing a decrease in the elongation of the cured product. Furthermore, in order to obtain a cured product with high rigidity and a high Young's modulus, the reactive silicon group equivalent is particularly preferably 0.6 mmol / g or more and 1.0 mmol / g or less.

[0069] The (meth)acrylic acid ester polymer (B) preferably contains 40% by weight or more of alkyl (meth)acrylate, which has 1 to 3 carbon atoms in the alkyl group, in the total monomer, as this results in high strength.

[0070] The number-average molecular weight of the (meth)acrylic acid ester polymer (B) is not particularly limited, but is preferably 500 to 50,000 in polystyrene equivalent molecular weight as measured by GPC, more preferably 500 to 30,000, and particularly preferably 1,000 to 10,000.

[0071] Methods for blending (meth)acrylic acid ester polymers (B) and polyoxyalkylene polymers (A) are proposed in Japanese Patent Publication No. 59-122541, Japanese Patent Publication No. 63-112642, Japanese Patent Publication No. 6-172631, and Japanese Patent Publication No. 11-116763, among others. In addition, a method of polymerizing (meth)acrylic acid ester monomers in the presence of a polyoxypropylene polymer having reactive silicon groups can be used.

[0072] When using a (meth)acrylic acid ester polymer (B), the weight ratio (A):(B) of the polyoxyalkylene polymer (A) to the (meth)acrylic acid ester polymer (B) is preferably 95:5 to 50:50, that is, the proportion of (A) is 50% by weight or more and 95% by weight or less. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained.

[0073] <<Polyoxyalkylene polymer (P)>> A polyoxyalkylene polymer (P) having a reactive silicon group can be incorporated into agent B. By incorporating the polyoxyalkylene polymer (P) into agent B, mixing of agent A and agent B can be easily achieved. Both a plasticizer (D) and the polymer (P) may be incorporated into agent B. However, if the plasticizer (D) is incorporated into agent B, the polymer (P) does not need to be incorporated.

[0074] The reactive silicon group-containing polyoxyalkylene polymer (P) may or may not meet the definition of the reactive silicon group-containing polyoxyalkylene polymer (A) described above. The polymer (A) blended into agent A and the polymer (P) blended into agent B may be the same polymer or different polymers.

[0075] The reactive silicon groups in polyoxyalkylene polymers (P) consist of one silicon atom to which one to three hydroxyl groups or hydrolyzable groups are bonded, and can be represented by the following general formula (7). -SiR 5 3-a Ya (7) (In the formula, R 5 (where represents a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms. Y represents a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3.)

[0076] R 5 The number of carbon atoms in the hydrocarbon group represented by is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 5 Specific examples include alkyl groups such as methyl and ethyl groups; alkyl groups having hetero-containing groups such as chloromethyl, methoxymethyl, and 3,3,3-trifluoropropyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. Preferably, it is an alkyl group or an alkyl group having a hetero-containing group, more preferably a methyl group, ethyl group, chloromethyl group, or methoxymethyl group, even more preferably a methyl group or ethyl group, and particularly preferably a methyl group. 5 If multiple instances exist, they may be identical or different from one another.

[0077] Specific examples of Y are the same as the specific examples of X described above, so their description is omitted. Because Y is mildly hydrolyzable and easy to handle, it is preferable that Y be an alkoxy group, more preferably a methoxy group or an ethoxy group, and particularly preferably a methoxy group. If there are multiple Y groups, they may be the same or different from one another.

[0078] a represents 1, 2, or 3, and is preferably 2 or 3. a is particularly preferably 2 because it has a significant effect in suppressing gelation during storage of agent B.

[0079] The reactive silicon group of the polyoxyalkylene polymer (P) is not particularly limited, but examples include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, dimethoxyphenylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, etc. Among these, the dimethoxymethylsilyl group is particularly preferred because it has an excellent effect in suppressing gelation during storage of agent B.

[0080] The polyoxyalkylene polymer (P) may have an average of more than one reactive silicon group per terminal site, or it may have an average of one or fewer reactive silicon groups per terminal site. From the viewpoint of improving the final strength of the resulting cured product, it is preferable that the polymer (P) has an average of more than one reactive silicon group per terminal site. On the other hand, from the viewpoint of the stability of agent B, it is preferable that the polymer (P) has an average of one or fewer reactive silicon groups per terminal site. Furthermore, the lower limit is not particularly limited, but for example, it may have an average of 0.1 or more reactive silicon groups per terminal site.

[0081] The average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (P) is not particularly limited, but may be, for example, around 0.1 to 6, preferably 0.3 to 5, more preferably 0.3 to 2.5, and particularly preferably 0.3 to 1.

[0082] The main chain skeleton of the polyoxyalkylene polymer (P) is not particularly limited, and specific examples include those described above for the polyoxyalkylene polymer (A). Among these, polyoxypropylene is preferred. Furthermore, the main chain skeleton of the polyoxyalkylene polymer (P) may be linear or branched. From the viewpoint of the stability of agent B, it is preferable that the main chain skeleton of the polyoxyalkylene polymer (P) be linear.

[0083] The number-average molecular weight and weight-average molecular weight of the polyoxyalkylene polymer (P) are not particularly limited and are the same as those described above for the polyoxyalkylene polymer (A), so their description is omitted.

[0084] Polyoxyalkylene polymers (P) can be produced by known synthesis methods. Furthermore, the main chain of the polyoxyalkylene polymer (P) may contain ester bonds or amide segments represented by the general formula (4) described above.

[0085] The amount of polyoxyalkylene polymer (P) blended is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0086] <<Silanol condensation catalyst (C)>> The silanol condensation catalyst (C) can promote the condensation reaction of reactive silicon groups in the polyoxyalkylene polymer (A). The silanol condensation catalyst (C) may be incorporated into either agent A or agent B, or both, or into agents other than agents A and B, or it may not be included in the multi-component curable composition according to this embodiment. However, it is preferable that it be incorporated into agent A. By incorporating the silanol condensation catalyst (C) into agent A instead of agent B, hydrolysis of the silanol condensation catalyst (C) can be suppressed, and the development of initial strength after mixing agents A and B can be further improved.

[0087] Examples of silanol condensation catalysts (C) include organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, and alkoxy metals.

[0088] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin oxide, reaction products of dibutyltin oxide with silicate compounds, reaction products of dioctyltin oxide with silicate compounds, and reaction products of dibutyltin oxide with phthalate esters.

[0089] Specific examples of metal carboxylate salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. Various metals can be combined with the following carboxylic acids to form metal carboxylate salts.

[0090] Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butyl biguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0091] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0092] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), and diisopropoxytitanium bis (ethylacetoacetate), as well as aluminum compounds such as aluminum tris (acetylacetonate) and diisopropoxyaluminum ethylacetoacetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

[0093] Other curing catalysts that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0094] The curing catalyst may be used in combination with two or more different catalysts. For example, using the aforementioned amine compound in combination with a carboxylic acid, or with an amine compound in combination with an alkoxy metal, may improve reactivity.

[0095] The amount of silanol condensation catalyst (C) used is preferably 0.001 parts by weight or more and 20 parts by weight or less per 100 parts by weight of polyoxyalkylene polymer (A) [if (meth)acrylic acid ester polymer (B) is used, the total of polyoxyalkylene polymer (A) and (meth)acrylic acid ester polymer (B) is 100 parts by weight. The same applies hereinafter], more preferably 0.01 parts by weight or more and 15 parts by weight or less, and even more preferably 0.01 parts by weight or more and 10 parts by weight or less.

[0096] <<Plasticizer (D)>> The plasticizer (D) is preferably blended into component B. It may be blended into component B only, or into component A and component B separately. Blending the plasticizer (D) can lower the viscosity of the curable composition, making it easier to handle. In particular, blending it into component B facilitates mixing of component A and component B. However, if a polyoxyalkylene polymer (P) is blended into component B, the plasticizer (D) does not need to be blended into component B.

[0097] The plasticizer (D) is not particularly limited, but examples include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; and aliphatic polymethyl acetylate compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitrate. Examples include carboxylic acid ester compounds; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkyl sulfonate phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffin; hydrocarbon oils such as alkyl diphenyl and partially hydrogenated terphenyl; process oils; epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarbonoxylate (E-PS), epoxyoctyl stearate, epoxybutyl stearate, and epoxybenzyl stearate. Polymeric plasticizers can also be used as plasticizer (D). Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol with a number average molecular weight of 500 or more, and polyether plasticizers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc.; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, etc. Among these, polymeric plasticizers are preferred, polyether-based plasticizers are more preferred, and polypropylene glycol is particularly preferred. Only one type of plasticizer (D) may be used, or two or more types may be used in combination.

[0098] The total amount of plasticizer (D) is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0099] <<Inorganic filler (E)>> The inorganic filler (E) is added to at least component B. It may be added to component B only, or to both component A and component B. The addition of the inorganic filler (E) can improve the strength of the cured product, and when added to component B, it also contributes to improving the stability of component B.

[0100] The inorganic filler (E) is not particularly limited, but examples include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium dioxide, fumed silica, wet silica, crystalline silica, fused silica, anhydrous silicic acid, hydrated silicic acid, alumina, carbon black, ferric oxide, aluminum powder, zinc oxide, activated zinc oxide, glass fibers, and filaments. Of these, calcium carbonate, fumed silica, wet silica, and titanium dioxide are preferred. Only one type of inorganic filler (E) may be used, or two or more types may be used in combination.

[0101] The total amount of inorganic filler (E) is preferably 1 to 300 parts by weight, and more preferably 10 to 250 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0102] From the viewpoint of improving the stability of Agent B, the proportion of the inorganic filler (E) contained in Agent B to the total amount of Agent B is set to 10% by weight or more. If it is less than 10% by weight, Agent B becomes unstable, and the polyoxyalkylene polymer (A) and / or plasticizer (D) and water (F) tend to separate during storage of Agent B. The aforementioned proportion is preferably 15% by weight, and more preferably 20% by weight. The upper limit of the aforementioned proportion is preferably 60% by weight or less, more preferably 50% by weight or less, and even more preferably 40% by weight or less.

[0103] <<Water(F)>> Water (F) is added to agent B. By adding water (F), the hydrolysis reaction of the reactive silicon groups of the polyoxyalkylene polymer (A) is promoted when agent A and agent B are mixed, resulting in better development of initial strength. In addition, since water (F) is added to agent B, deterioration of the storage stability of agent A, which contains the polyoxyalkylene polymer (A), can be avoided.

[0104] The amount of water (F) added is preferably 0.1 parts by weight or more and 10 parts by weight or less, more preferably 0.1 parts by weight or more and 5 parts by weight or less, even more preferably 0.1 parts by weight or more and 3 parts by weight or less, and particularly preferably 0.1 parts by weight or more and 2.5 parts by weight or less, per 100 parts by weight of polyoxyalkylene polymer (A). If water exceeding the upper limit is added, the adhesion to the substrate may decrease. Furthermore, the proportion of water (F) in the total amount of agent B is preferably 0.5 to 30% by weight. Within this range, mixing of agent A and agent B can be easily achieved. Preferably, it is 1 to 20% by weight, and more preferably 3 to 15% by weight.

[0105] <<Fatty Acid Amide (G)>> Agent A preferably further contains a fatty acid amide (G) so as to satisfy the viscosity characteristics described later. As the fatty acid amide, fatty acid amide wax can be used, which is commercially available as a thixotropic agent, thickener, anti-settling agent, anti-dripping agent, etc.

[0106] Commercially available fatty acid amide waxes include powdered fatty acid amide wax components and pre-swelled types in which fatty acid amide wax is paste-formed in a solvent. Other products may also be compounded with other thixotropic components. Examples of commercially available products include Disparon® manufactured by Kusumoto Kasei Co., Ltd. and products from ARKEMA.

[0107] The amount of fatty acid amide (G) added is preferably 0.1 parts by weight or more and 15 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less, even more preferably 1 part by weight or more and 8 parts by weight or less, and particularly preferably 2 parts by weight or more and 6 parts by weight or less, per 100 parts by weight of polyoxyalkylene polymer (A).

[0108] <<Other additives>> In addition to polyoxyalkylene polymers (A), (meth)acrylic acid ester polymers (B), polyoxyalkylene polymers (P), silanol condensation catalysts (C), plasticizers (D), inorganic fillers (E), water (F), and fatty acid amides (G), additives such as organic fillers, adhesion promoters, anti-sagging agents, antioxidants, light stabilizers, UV absorbers, tackifying resins, and other resins may be added to the curable composition. Furthermore, various additives may be added to the curable composition as needed to adjust the various physical properties of the curable composition or cured product. Examples of such additives include solvents, diluents, photocurable substances, oxygen-curable substances, surface modifiers, silicates, curing modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, and foaming agents.

[0109] <Adhesion-enhancing agent> Adhesion-imparting agents can be added to the curable composition. As adhesion-improving agents, silane coupling agents and reaction products of silane coupling agents can be added.

[0110] Specific examples of silane coupling agents include amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl)aminomethyltrimethoxysilane; as well as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, and γ-iso Examples include isocyanate group-containing silanes such as cyanate-propylmethyldimethoxysilane, α-isocyanate-methyltrimethoxysilane, and α-isocyanate-methyldimethoxymethylsilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In addition, condensates of various silane coupling agents, such as condensates of amino group-containing silanes and condensates of amino group-containing silanes and other alkoxysilanes, and reaction products of various silane coupling agents, such as reaction products of amino group-containing silanes and epoxy group-containing silanes and reaction products of amino group-containing silanes and (meth)acrylic group-containing silanes, can also be used.

[0111] The above adhesion-improving agents may be used individually or in combination of two or more types. Reaction products of various silane coupling agents can also be used.

[0112] The amount of adhesion promoter used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A).

[0113] (Solvents, diluents) A solvent or diluent may be added to the curable composition. While not particularly limited, the solvent and diluent can include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, etc. When using a solvent or diluent, to address the issue of air pollution when the composition is used indoors, the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and particularly preferably 250°C or higher. The solvent or diluent may be used alone or in combination of two or more.

[0114] <Drip-preventing agent> The curable composition may contain, if necessary, anti-sagging agents to prevent sagging and improve workability. While not particularly limited, examples of anti-sagging agents include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used individually or in combination of two or more.

[0115] The amount of anti-slip agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of polyoxyalkylene polymer (A).

[0116] <Antioxidant> Antioxidants (anti-aging agents) can be used in the curable composition. Using antioxidants can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in Japanese Patent Publication No. 4-283259 and Japanese Patent Publication No. 9-194731.

[0117] The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0118] <Light stabilizer> Light stabilizers can be used in the curable composition. Using a light stabilizer can prevent photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds, but hindered amine-based compounds are particularly preferred.

[0119] The amount of light stabilizer used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0120] <UV absorber> UV absorbers can be used in the curable composition. Using UV absorbers can improve the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate compounds, but benzotriazole-based compounds are particularly preferred, and examples include commercially available products such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all manufactured by BASF).

[0121] The amount of UV absorber used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0122] (Property modifier) The curable composition may contain property modifiers to adjust the tensile properties of the resulting cured product. While not particularly limited, examples of property modifiers include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; arylalkoxysilanes such as diphenyldimethoxysilane and phenyltrimethoxysilane; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes. By using these property modifiers, the hardness of the curable composition can be increased or decreased, resulting in increased elongation at break. These property modifiers may be used individually or in combination of two or more.

[0123] In particular, compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis have the effect of reducing the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that produce trimethylsilanol are especially preferred. Examples of compounds that produce compounds having a monovalent silanol group in their molecule upon hydrolysis include silicon compounds that are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol and produce silane monool upon hydrolysis. Specifically, examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

[0124] The amount of property modifier used is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A).

[0125] <Adhesive-granting resin> A tackifying resin may be added to the curable composition to enhance adhesion or bonding to the substrate, or as needed. There are no particular restrictions on the tackifying resin used; commonly used resins can be used.

[0126] Specific examples include terpene resins, aromatically modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenated products, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used individually or in combination of two or more types.

[0127] The amount of tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 5 to 30 parts by weight, per 100 parts by weight of polyoxyalkylene polymer (A).

[0128] <<Curable composition>> The curable composition according to this embodiment comprises, as agent A, a polyoxyalkylene polymer (A), an arbitrary acrylic ester polymer (B), a silanol condensation catalyst (C), an arbitrary plasticizer (D), an arbitrary inorganic filler (E), etc., and as agent B, a polyoxyalkylene polymer (P), at least one of the plasticizer (D), an inorganic filler (E), water (F), etc., and it is preferable to prepare it as a multi-component type by mixing agent A and agent B before use.

[0129] Agent B may contain either a polyoxyalkylene polymer (P) or a plasticizer (D), or both. By combining a polyoxyalkylene polymer (P) with a plasticizer (D) in Agent B, the stability of Agent B containing the polyoxyalkylene polymer (P) can be improved. This effect is particularly pronounced when a polymer corresponding to polyoxyalkylene polymer (A) is used as the polyoxyalkylene polymer (P).

[0130] Agent A was measured using a rheometer at 23°C with a shear rate of 5 × 10⁻⁶. -3 The viscosity at (1 / sec) is preferably 15,000 Pa·s or higher. Within this range, the mixture of agent A and agent B can maintain its shape when applied. The viscosity value is more preferably 20,000 Pa·s or higher, even more preferably 25,000 Pa·s or higher, and particularly preferably 30,000 Pa·s or higher. The upper limit is not particularly limited, but may be, for example, 100,000 Pa·s or less, or 70,000 Pa·s or less.

[0131] Agent B was measured using a rheometer at 23°C with a shear rate of 5 × 10⁻⁶. -3 The viscosity at (1 / sec) is preferably 15,000 Pa·s or higher. Within this range, agent B does not separate, and high stability can be ensured. The viscosity value is more preferably 20,000 Pa·s or higher, even more preferably 25,000 Pa·s or higher, and particularly preferably 30,000 Pa·s or higher. The upper limit is not particularly limited, but for example, it may be 50,000 Pa·s or less, or 40,000 Pa·s or less.

[0132] Furthermore, from the viewpoint of facilitating the mixing of agent A and agent B, it is preferable that the difference between the viscosity values ​​of agent A and agent B, measured using a rheometer at 23°C and a shear rate of 64 (1 / sec), is small. Specifically, it is preferable that the value calculated by determining the higher and lower viscosity values ​​of agent A and agent B at a shear rate of 64 (1 / sec), and then using the formula [(higher viscosity value - lower viscosity value) / (higher viscosity value)] × 100, is 50% or less. More preferably, it is 40% or less, even more preferably 30% or less, and particularly preferably 20% or less.

[0133] The curable composition according to this embodiment may be cured at room temperature or by heat curing after mixing agent A and agent B. The heating temperature is not particularly limited, but 40°C or higher is preferred, 60°C or higher is more preferred, and 80°C or higher is even more preferred. However, if the temperature exceeds 100°C, the water in agent B may evaporate, which can cause void formation, so a heating temperature of less than 100°C is preferred.

[0134] When preparing Agent A, it is preferable to either dehydrate and dry any water-containing components beforehand before mixing, or to dehydrate them by reducing pressure during the mixing process.

[0135] For dehydration and drying, suitable methods include heat drying for solid materials such as powders, and vacuum dehydration or dehydration using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc., for liquid materials. Alternatively, a small amount of isocyanate compound may be added and the isocyanate group may be reacted with water to dehydrate the material. Oxazolidine compounds such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may also be added and reacted with water to dehydrate the material.

[0136] In addition to these dehydration and drying methods, storage stability can be further improved by adding lower alcohols such as methanol and ethanol, or alkoxysilane compounds. Examples of such alkoxysilane compounds include methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0137] The amount of dehydrating agent, particularly the alkoxysilane compound, used is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A).

[0138] <<Surface treatment of the substrate>> The curable composition according to this embodiment can exhibit good adhesion to various substrates such as plastics, metals, and composite materials. Furthermore, when used as an adhesive for non-polar materials such as polypropylene or engineering plastics with rigid molecular chains such as polyphenylene sulfide, the substrate can be pre-treated by known methods to enhance adhesion to these substrates and obtain stable adhesive strength. For example, surface treatment techniques such as sanding, flame treatment, corona discharge, arc discharge, and plasma treatment can be used. Plasma treatment is preferred because it causes less damage to the substrate and provides stable adhesion. These surface treatments are also effective in removing mold release agents that remain on the substrate surface after molding.

[0139] The curable composition according to this embodiment exhibits the desired physical properties after a long curing (curing) process following the joining of adherends, while also having the characteristic of rapid strength development. For this reason, the curable composition according to this embodiment can be suitably used for joining adherends in a continuously performed line production system.

[0140] The conditions for the final curing (curing) process for the curable composition to exhibit its desired physical properties are not particularly limited, but examples include a temperature of 5 to 90°C and a curing time of 24 hours to 1 week.

[0141] <<Application>> The curable composition is suitable for use as an adhesive composition and can be used as a sealing material for buildings, ships, automobiles, and roads, as well as an adhesive, sealant, and waterproofing material for joining panels in buses, trailers, trains, etc. This curable composition is also suitable for joining dissimilar materials such as aluminum-steel, steel-composite materials, and aluminum-composite materials. When joining dissimilar materials, it is preferable to cover the joint with a sealer to prevent corrosion. As the sealer, a polymer having reactive silicon groups as shown in this application can be used. Preferably, the curable composition is used as an adhesive in automobile parts such as vehicle panels, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical parts, and various machine parts.

[0142] The following sections list preferred embodiments of this disclosure, but the present invention is not limited to these sections. [Item 1] A multi-component curable composition comprising agent A and agent B, Agent A is present in an average of more than one unit per terminal site, as shown in the general formula (1): -SiX3(1) (In the formula, X represents a hydroxyl group or a hydrolyzable group.) It contains a polyoxyalkylene polymer (A) having a reactive silicon group represented by , Agent B contains at least one of a polyoxyalkylene polymer (P) having a reactive silicon group and a plasticizer (D), an inorganic filler (E), and water (F). The proportion of inorganic filler (E) in the total amount of component B is 10% by weight or more. Multi-component curable composition. [Item 2] The multi-component curable composition according to item 1, wherein agent A further contains a silanol condensation catalyst (C). [Item 3] The polyoxyalkylene polymer (A) has a linear main chain structure, and is a multi-component curable composition according to item 1 or 2. [Item 4] A multi-component curable composition according to any one of items 1 to 3, wherein the reactive silicon group of the polyoxyalkylene polymer (P) is a dimethoxymethylsilyl group. [Item 5] A multi-component curable composition according to any one of items 1 to 4, wherein the proportion of inorganic filler (E) in the total amount of component B is 60% by weight or less. [Item 6] A multi-component curable composition according to any of items 1 to 5, wherein the proportion of water (F) in the total amount of component B is 0.5 to 30% by weight. [Item 7] Agent B was measured using a rheometer at a shear rate of 5 × 10⁻⁶. ―3 A multi-component curable composition according to any of items 1 to 6, wherein the viscosity at (1 / sec) is 15,000 Pa·s or more. [Item 8] A multi-component curable composition according to any one of items 1 to 7, wherein, at a shear rate of 64 (1 / sec) measured using a rheometer, the viscosity of component A and component B, where (higher viscosity - lower viscosity) / (higher viscosity) × 100 is 50% or less. [Item 9] A multi-component curable composition according to any one of items 1 to 8, wherein the terminal portion of the polyoxyalkylene polymer (A) has a structure represented by the general formula (2). [Item 10] A multi-component curable composition according to any one of items 1 to 9, which is a two-component curable composition consisting of agent A and agent B. [Item 11] A cured product obtained by mixing agent A and agent B in a multi-component curable composition described in any of items 1 to 10 and curing it. [Examples]

[0143] The present invention will be specifically described below with reference to examples, but these examples are not intended to limit the present invention.

[0144] The number-average molecular weight in the examples is the GPC molecular weight measured under the following conditions. Liquid delivery system: Tosoh HLC-8120GPC Column: Tosoh TSK-GEL H type Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40℃

[0145] The molecular weights in the examples, calculated using end-group ratios, were determined by determining the hydroxyl value according to the measurement method of JIS K 1557 and the iodine value according to the measurement method of JIS K 0070, taking into account the structure of the organic polymer (degree of branching determined by the polymerization initiator used).

[0146] The average number of carbon-carbon unsaturated bonds introduced to each terminal of the polymer (Q) shown in the examples was calculated using the following formula. (Average number of introduced groups) = [Unsaturated group concentration of polymer (Q) determined from iodine value (mol / g) - Unsaturated group concentration of precursor polymer (P) determined from iodine value (mol / g)] / [Hydrogen group concentration of precursor polymer (P) determined from hydroxyl value (mol / g)].

[0147] The average number of silyl groups introduced per terminal of polymer (A) shown in the example was calculated by NMR measurement.

[0148] (Synthesis Example 1) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 28,500 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and then 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. As a result, polyoxypropylene having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that this polymer has an average of 2.0 carbon-carbon unsaturated bonds introduced at each terminal site. To 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, 72 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution on a platinum basis) was added, and 2.2 parts by weight of trimethoxysilane were slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted trimethoxysilane was removed by distillation under reduced pressure to obtain a linear reactive silicon-containing polyoxypropylene polymer (A-1) having an average of 1.6 trimethoxysilyl groups at one terminal site, an average of 3.2 trimethoxysilyl groups per molecule, and a number-average molecular weight of 28,500.

[0149] (Synthesis Example 2) Using a polyoxypropylene triol with a number-average molecular weight of approximately 3,000 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene with terminal hydroxyl groups, a number-average molecular weight of 25,630 (terminal group equivalent molecular weight of 17,440), and a molecular weight distribution Mw / Mn = 1.21. 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and then 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. As a result, polyoxypropylene having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that this polymer has an average of 2.0 carbon-carbon unsaturated bonds introduced at each terminal site. To 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, 72 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution based on platinum) was added, and 2.9 parts by weight of trimethoxysilane were slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted trimethoxysilane was removed by distillation under reduced pressure to obtain a branched-chain reactive silicon-containing polyoxypropylene polymer (A-2) having an average of 1.6 trimethoxysilyl groups at one terminal site, an average of 4.8 trimethoxysilyl groups per molecule, and a number-average molecular weight of 25,630.

[0150] (Synthesis Example 3) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 28,500 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was mixed and stirred into the resulting hexane solution, and after removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. To 100 parts by weight of the obtained polyoxypropylene, 72 ppm of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 1.1 parts by weight of trimethoxysilane were slowly added dropwise while stirring. The mixed solution was reacted at 90°C for 2 hours, and then the unreacted trimethoxysilane was removed under reduced pressure to obtain a linear reactive silicon-containing polyoxypropylene polymer (P-1) having an average of 0.8 trimethoxysilyl groups at each terminal site, an average of 1.6 trimethoxysilyl groups per molecule, and a number-average molecular weight of 28,500.

[0151] (Synthesis Example 4) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 28,500 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.0 molar equivalent of sodium methoxide in a 28% methanol solution was added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, methanol was removed by adding 0.28 molar equivalents of sodium methoxide in a methanol solution, and then 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups to allyl groups. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. As a result, polyoxypropylene having a terminal structure with two or more carbon-carbon unsaturated bonds was obtained. It was found that this polymer has an average of 2.0 carbon-carbon unsaturated bonds introduced at each terminal site. To 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, 36 ppm of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 1.9 parts by weight of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted dimethoxymethylsilane was removed by distillation under reduced pressure to obtain a linear reactive silicon-containing polyoxypropylene polymer (P-2) having an average of 1.6 dimethoxymethylsilyl groups at one terminal site, an average of 3.2 dimethoxymethylsilyl groups per molecule, and a number-average molecular weight of 28,500.

[0152] (Synthesis Example 5) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 28,500 (end-group equivalent molecular weight of 17,700) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was mixed and stirred into the resulting hexane solution, and after removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. To 100 parts by weight of the obtained polyoxypropylene, 36 ppm of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 1.0 part by weight of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted dimethoxymethylsilane was removed by distillation under reduced pressure to obtain a linear reactive silicon group-containing polyoxypropylene polymer (P-3) having an average of 0.8 dimethoxymethylsilyl groups at each terminal site, an average of 1.6 dimethoxymethylsilyl groups per molecule, and a number-average molecular weight of 28,500.

[0153] (Synthesis Example 6) Using polyoxypropylene glycol with a number-average molecular weight of approximately 2,000 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate grime complex catalyst to obtain polyoxypropylene with a number-average molecular weight of 14,600 (end-group equivalent molecular weight of 9,100) and a molecular weight distribution Mw / Mn = 1.21, with hydroxyl groups at both ends. 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. To 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was mixed and stirred into the resulting hexane solution, and after removing the water again by centrifugation, the hexane was removed by defloration under reduced pressure. To 100 parts by weight of the obtained polyoxypropylene, 36 ppm of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 1.7 parts by weight of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted dimethoxymethylsilane was removed by distillation under reduced pressure to obtain a linear reactive silicon group-containing polyoxypropylene polymer (P-4) having an average of 0.75 dimethoxymethylsilyl groups at each terminal site, an average of 1.5 dimethoxymethylsilyl groups per molecule, and a number-average molecular weight of 14,600.

[0154] (Synthesis Example 7) A polyoxypropylene glycol with a number-average molecular weight of approximately 4,800 (end-group molecular weight of 3,000) and a molecular weight distribution Mw / Mn = 1.21 was mixed with 1.2 molar equivalents of sodium methoxide in a 28% methanol solution to its hydroxyl groups. After removing the methanol by vacuum defoliation, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene and the reaction was carried out at 130°C for 2 hours. To 100 parts by weight of the resulting unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by vacuum defoliation. To 100 parts by weight of the obtained polyoxypropylene, 36 ppm of platinum divinyldisiloxane complex (a solution of isopropanol at 3% by weight in terms of platinum) was added, and 3.8 parts by weight of dimethoxymethylsilane were slowly added dropwise while stirring. After reacting the mixed solution at 90°C for 2 hours, the unreacted dimethoxymethylsilane was removed by distillation under reduced pressure to obtain a linear reactive silicon group-containing polyoxypropylene polymer (P-5) having an average of 0.25 dimethoxymethylsilyl groups at each terminal site, an average of 0.5 dimethoxymethylsilyl groups per molecule, and a number-average molecular weight of 4,800.

[0155] (Synthesis Example 8) Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate-grime complex catalyst to obtain polyoxypropylene oxide with a number-average molecular weight of 7,800 (end-group equivalent molecular weight of 5,000) and a molecular weight distribution Mw / Mn = 1.21. 1.2 molar equivalents of sodium methoxide in a 28% methanol solution were added to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After removing methanol by vacuum defoliation, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene and the reaction was carried out at 130°C for 2 hours. 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water. After removing the water by centrifugation, another 300 parts by weight of water was added to the resulting hexane solution and stirred. After removing the water again by centrifugation, the hexane was removed by vacuum defoliation. To 100 parts by weight of the obtained polyoxypropylene, 36 ppm of platinum divinyldisiloxane complex (a solution of isopropanol equivalent to 3% by weight of platinum) was added, and 1.6 parts by weight of dimethoxymethylsilane was slowly added dropwise while stirring. The mixed solution was reacted at 90°C for 2 hours, and then the unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a linear reactive silicon group-containing polyoxypropylene polymer (P-6) having a dimethoxymethylsilyl group at only one end, with an average of 0.8 dimethoxymethylsilyl groups per molecule and a number-average molecular weight of 7,800.

[0156] (Example 1) 100 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 was mixed with 1 part by weight of Nocrack CD (antioxidant, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) and 1 part by weight of Adeka Stab AO-60 (antioxidant, manufactured by ADEKA Corporation) as stabilizers, 13 parts by weight of Actcol P-23 (polypropylene glycol, manufactured by Mitsui Chemicals, Inc.) as a plasticizer (D), 40 parts by weight of CCR-S10 (colloidal calcium carbonate, manufactured by Shiraishi Industries Co., Ltd.) and 0.05 parts by weight of Asahi Thermal (carbon black, manufactured by Asahi Carbon Co., Ltd.) as fillers (E), and 2.5 parts by weight of Crayvallac SL (fatty acid amide wax, manufactured by ARKEMA) as a rheology control agent using a planetary mixer, and dehydrated by reduced pressure heating at 120°C for 1 hour. The obtained composition was cooled, and 3 parts by weight of A-171 (vinyltrimethoxysilane, manufactured by Momentive) as a dehydrating agent, 2 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter, and 0.2 parts by weight of Neostan U-810 (dioctyl tin dilaurate, manufactured by Nitto Chemical Co., Ltd.) as a silanol condensation catalyst (C) were mixed to obtain agent A. Next, 10.3 parts by weight of polypropylene glycol with a number average molecular weight of 14,600 was used as a plasticizer (D), 1.3 parts by weight of CCR-S10 (colloidal calcium carbonate, manufactured by Shiraishi Industries Co., Ltd.), 1.2 parts by weight of AEROSIL R-202 (hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.), 2 parts by weight of R-820 (titanium dioxide, manufactured by Ishihara Industries Co., Ltd.), and 1.5 parts by weight of water (F) were mixed using a planetary mixer to obtain agent B.

[0157] (viscosity) The viscosities of the obtained components A and B were measured using a parallel disc plate with a diameter of 20 mm as a jig, with a gap set to 0.3 mm, at 23°C, and with a shear rate of 5 × 10⁻⁶. -3 The viscosity was measured at (1 / sec) and 64 (1 / sec), respectively. A TA Instruments rheometer (DHR-2) was used. The results are shown in Table 1.

[0158] (Stability of Agent B) The obtained solution B was filled into sample bottles and left to stand at 40°C for two weeks. The separation of water was visually confirmed. If separation did not occur, it was labeled "stable"; if separation occurred, it was labeled "separated." The results are shown in Table 1.

[0159] (Mixing method) The A and B compounds prepared in Example 1 were filled into a two-component mixing cartridge (manufactured by Nordson Co., Ltd.) in a ratio of A:B = 10:1 (by weight) or 10:1 (by volume). The A and B compounds were mixed using a static mixer with an element diameter of 10 mm and 24 elements to obtain the mixture.

[0160] (Leather stretching time) Under conditions of 23°C and 50% relative humidity, the mixture was filled into a mold approximately 5 mm thick using a spatula, and the time it took to flatten the surface was defined as the curing start time. The curing time was measured by touching the surface with a spatula and determining the time until no more of the composition adhered to the spatula, which was defined as the skinning time. The results are shown in Table 1.

[0161] (Pot Life) To measure the pot life of the aforementioned mixture, viscosity measurements were performed using a rheometer. A parallel disc plate with a diameter of 20 mm was used as the jig, with a gap set to 0.3 mm, and measurements were taken at 23°C with a shear rate of 10 (1 / sec). The time it took for the viscosity to double compared to the initial viscosity was defined as the pot life. A rheometer (DHR-2) manufactured by TA Instruments was used. The results are shown in Table 1.

[0162] (Shear test (after 30 minutes)) The steel plate (SS400) used as the adherend was polished with #400 sandpaper and degreased with heptane. After applying the mixture to one adherend, the other adherend was immediately bonded to it so that the bonding area was 25 mm × 12.5 mm and the thickness was 0.5 mm. This bonding time was taken as the start time, and after being left for 30 minutes under 23°C and 50% RH conditions, the shear bond strength was measured at a test speed of 10 mm / min. The results are shown in Table 1.

[0163] (Example 2) Except for replacing the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 with the reactive silicon group-containing polyoxypropylene polymer (A-2) obtained in Synthesis Example 2, and changing the formulation as shown in Table 1, Agents A and B were prepared in the same manner as in Example 1, and each was evaluated. The results are shown in Table 1.

[0164] (Examples 3-5) Agents A and B were prepared in the same manner as in Example 2, except that the reactive silicon group-containing polyoxypropylene polymers (P-4) to (P-6) obtained in Synthesis Examples 6 to 8 were used instead of the plasticizer (D), polypropylene glycol, and each was evaluated. The results are shown in Table 1.

[0165] (Comparative Examples 1-3) Except for changing the reactive silicon-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 to the reactive silicon-containing polyoxypropylene polymers (P-1) to (P-3) obtained in Synthesis Examples 3 to 5, and changing the formulation as shown in Table 1, agents A and B were prepared in the same manner as in Example 1, and each was evaluated. The results are shown in Table 1. In Comparative Examples 2 and 3, Neostan S-1 (dioctyl tin bistriethoxysilicate, manufactured by Nitto Chemical Co., Ltd.) was used as the silanol condensation catalyst (C).

[0166] [Table 1]

[0167] Table 1 shows that the multi-component curable compositions of Examples 1-5, which use a polyoxyalkylene polymer (A) having an average of more than one reactive silicon group at each terminal site, and in which the reactive silicon group is a trimethoxysilyl group, exhibit a large ratio of pot life to skinning time, and also show high shear strength values ​​30 minutes after bonding, indicating good initial strength development. From the above, it can be seen that the multi-component curable compositions of Examples 1-5 have a long usable time after mixing the main component and auxiliary component, and exhibit rapid initial strength development. Among these examples, Example 1, which uses a polyoxyalkylene polymer (A) with a linear main chain structure, is particularly excellent in that it has a long usable time after mixing the main component and auxiliary component. On the other hand, in Comparative Example 1, a multi-component curable composition using a polyoxyalkylene polymer having an average of one or fewer reactive silicon groups at each terminal site in component A, exhibited insufficient shear strength 30 minutes after bonding. Comparative Example 2, a multi-component curable composition in which the reactive silicon group of the polyoxyalkylene polymer incorporated in Agent A is a dimethoxymethylsilyl group, also exhibited insufficient shear strength 30 minutes after bonding. Furthermore, in Comparative Example 3, a multi-component curable composition in which a polyoxyalkylene polymer having an average of one or fewer reactive silicon groups at each terminal site in Agent A, and in which the reactive silicon groups are dimethoxymethylsilyl groups, also exhibited insufficient shear strength 30 minutes after bonding.

[0168] (Examples 6-7, Comparative Examples 4-5) Agent B was prepared in the same manner as in Example 1, except that the formulation was changed as shown in Table 2.

[0169] (Stability of Agent B) The obtained solution B was filled into sample bottles and left to stand at 40°C for two weeks. The separation of water was visually checked. If separation did not occur, it was labeled "stable"; if separation occurred, it was labeled "separated". The results are shown in Table 2.

[0170] (viscosity) The viscosity of the obtained agent B was measured using a parallel disc plate with a diameter of 20 mm as a jig, with a gap set to 0.3 mm, at 23°C, and with a shear rate of 5 × 10⁻⁶. -3 The viscosity was measured at (1 / sec) and 64 (1 / sec), respectively. A TA Instruments rheometer (DHR-2) was used. The results are shown in Table 2.

[0171] [Table 2]

[0172] Table 2 shows that the B agents of Examples 6-7, which contain 10% by weight or more of inorganic filler (E), exhibit good stability, while the B agents of Comparative Examples 4-5, which contain less than 10% by weight of inorganic filler (E), exhibit insufficient stability.

Claims

1. A multi-component curable composition comprising agent A and agent B, Agent A is present in more than one unit on average at each terminal site, as shown in the general formula (1): -SiX ３ (1) (In the formula, X represents a hydroxyl group or a hydrolyzable group.) The product contains a polyoxyalkylene polymer (A) having a reactive silicon group represented by , and a silanol condensation catalyst (C), Agent B contains at least one of a polyoxyalkylene polymer (P) having a reactive silicon group and a plasticizer (D), an inorganic filler (E), and water (F), but does not contain a silanol condensation catalyst (C). The proportion of inorganic filler (E) in the total amount of component B is 10% by weight or more. Multi-component curable composition.

2. The multi-component curable composition according to claim 1, wherein the polyoxyalkylene polymer (A) has a linear main chain structure.

3. The multi-component curable composition according to claim 1 or 2, wherein the reactive silicon group of the polyoxyalkylene polymer (P) is a dimethoxymethylsilyl group.

4. The multi-component curable composition according to claim 1 or 2, wherein the proportion of inorganic filler (E) in the total amount of agent B is 60% by weight or less.

5. The multi-component curable composition according to claim 1 or 2, wherein the proportion of water (F) in the total amount of agent B is 0.5 to 30% by weight.

6. Agent B was measured using a rheometer at a shear rate of 5 × 10⁻⁶. ―３ The multi-component curable composition according to claim 1 or 2, wherein the viscosity at (1 / sec) is 15,000 Pa·s or more.

7. The multi-component curable composition according to claim 1 or 2, wherein, at a shear rate of 64 (1 / sec) measured using a rheometer, the viscosity of component A and the viscosity of component B, where (higher viscosity - lower viscosity) / (higher viscosity) × 100 is 50% or less.

8. The terminal portion of the polyoxyalkylene polymer (A) is general formula (2): 【Chemistry 1】 (In the formula, R １ , R ３ Each of these independently represents a divalent bonding group with 1 to 6 carbon atoms, R １ , R ３ The atom bonded to each adjacent carbon atom is either carbon, oxygen, or nitrogen. ２ , R ４ Each of the following independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer from 1 to 10. X represents a hydroxyl group or a hydrolyzable group.) A multi-component curable composition according to claim 1 or 2, having a structure represented by ).

9. The multi-component curable composition according to claim 1 or 2, which is a two-component curable composition comprising agent A and agent B.

10. A cured product obtained by mixing agent A and agent B in the multi-component curable composition according to claim 1 or 2 and curing it.

Images