Method for manufacturing a laminated structure and use thereof

Abstract

Provided is a method for manufacturing a layered structure, an adhesive method, and a technique using the same, using a curable composition that has excellent adhesion between a substrate and a cured product in a low-temperature environment. The method for manufacturing a layered structure according to one embodiment includes: a coating step of applying a curable composition to a substrate; and a curing step of curing the curable composition applied to the substrate at an ambient temperature of 10°C or lower to form a cured product, the curable composition containing (A) and (B) below: (A) an organic polymer having a silicon-containing group capable of being crosslinked by forming a siloxane bond, and (B) a compound having a hydroxyl value of less than 100 mgKOH / g and having an ethylene glycol unit.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a laminated structure and its utilization. Background Technology

[0002] Organic polymers containing at least one reactive silicon group in their molecules are known to have the following properties: even at room temperature, they will form siloxane bonds and undergo cross-linking due to hydrolysis of the reactive silicon group caused by moisture, etc., thereby obtaining a rubber-like cured product.

[0003] These polyoxyethylene polymers and (meth)acrylate polymers with reactive silicon groups have been widely used in sealing materials, adhesives, coatings and other applications.

[0004] For example, Patent Document 1 describes a curable composition comprising: (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking by forming siloxane bonds; (B) 21 to 300 parts by weight of a diester compound obtained from polyethylene glycol and aliphatic monocarboxylic acids and / or alicyclic monocarboxylic acids; and (C) 0.01 to 20 parts by weight of a curing catalyst.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2015 / 098998 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, the existing curable compositions described in Patent Document 1, etc., still have room for improvement when used at low temperatures, from the viewpoint of adhesion to the substrate.

[0010] Therefore, one object of the present invention is to provide a method for manufacturing a laminated structure using a curable composition that also exhibits excellent adhesion to a substrate at low temperatures, an adhesive method, a laminated structure, an adhesive, and a sealing material.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by using a curable composition comprising (A) an organic polymer having silicon-containing groups that can be crosslinked by forming siloxane bonds and (B) a compound having ethylene glycol units and a hydroxyl value of a certain value or less, a laminated structure containing a cured material with excellent adhesion to a substrate can be obtained, thereby completing the present invention.

[0013] Therefore, one aspect of the present invention is a method for manufacturing a laminated structure (hereinafter referred to as "the manufacturing method"), which is a method for manufacturing a laminated structure comprising a substrate and a cured product. The method includes: a coating step, coating a curable composition onto the substrate; and a curing step, curing the curable composition coated on the substrate at an ambient temperature below 10°C to form the cured product. The curable composition contains the following (A) and (B): (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units.

[0014] In addition, one aspect of the present invention is an adhesive method (hereinafter referred to as "this adhesive method"), which includes a step of bonding a substrate to a curable composition at an ambient temperature below 10°C, wherein the curable composition contains the following (A) and (B): (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units.

[0015] In addition, one aspect of the present invention is a laminated structure (hereinafter referred to as "this laminated structure"), which is a laminated structure comprising a metal substrate and a cured product, wherein the cured product is a cured product formed by curing a curable composition containing the following (A) and (B): (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units.

[0016] Furthermore, one aspect of the present invention is an adhesive or sealing material for low-temperature use (hereinafter referred to as "the adhesive" and "the sealing material," respectively), which is an adhesive or sealing material for use in low-temperature environments, the adhesive or sealing material for low-temperature use containing the following (A) and (B): (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units.

[0017] The effects of the invention

[0018] According to one aspect of the present invention, a method for manufacturing a laminated structure using a curable composition that exhibits excellent adhesion to a substrate even at low temperatures, an bonding method, and a technology for utilizing such a structure can be provided. Detailed Implementation

[0019] The following describes one embodiment of the present invention in detail. It should be noted that, unless otherwise specified, in this specification, "A to B" indicating a numerical range means "A or more and B or less". Furthermore, the entire contents of the documents described in this specification are incorporated herein by reference.

[0020] [1. Content of this invention]

[0021] The single-component curable composition described in Patent Document 1 is a curable composition comprising (A) a silicon-containing polymer, (B) a diester compound obtained from polyethylene glycol and aliphatic monocarboxylic acids and / or alicyclic monocarboxylic acids, and (C) a curing catalyst. The curable composition of Patent Document 1 exhibits excellent deep curing properties (i.e., rapid curing to deep regions) and low viscosity, thus possessing advantages such as excellent workability, excellent storage stability, and minimal reduction in curability after storage.

[0022] However, the curing composition described in Patent Document 1 has a problem of poor adhesion to substrates (especially metal substrates) when used in low-temperature environments such as winter construction or use in cold storage.

[0023] Therefore, the inventors conducted in-depth research on methods that can solve the above-mentioned problems, and found that by making the curable composition contain 10 to 200 parts by weight of a compound with a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units, the adhesion to the substrate under low temperature conditions is improved, thereby completing the present invention.

[0024] Previously, it was unknown that compounds containing ethylene glycol units were related to adhesion in low-temperature environments; this is a surprising insight discovered by the inventors for the first time. Furthermore, in compounds containing ethylene glycol units, curable compositions using compounds with high hydroxyl content, such as tetraethylene glycol, experience a phenomenon known as leakage, where liquid seeps to the surface. Therefore, the inventors have discovered for the first time that compounds containing ethylene glycol units with low hydroxyl content are suitable as plasticizers for curable compositions.

[0025] The manufacturing method of a laminated structure using such a curable composition that exhibits excellent adhesion to the substrate even at low temperatures is previously unknown and is extremely useful in various fields where this curable composition is used (e.g., interior panel materials, exterior panel materials, vehicle panel materials, vibration damping materials, sound insulation materials, foaming materials, coatings, spraying materials, adhesives, sealing materials, etc.). It should be noted that although Patent Document 1 mentions "excellent cold resistance," this "cold resistance" primarily refers to "use in low-temperature environments," and Patent Document 1 makes no mention of the "improved adhesion in low-temperature environments" mentioned in this specification.

[0026] Furthermore, if the above-described configuration is adopted, a method for manufacturing laminates can be provided that can be used even in low-temperature environments, thereby contributing to the achievement of Sustainable Development Goals (SDGs) such as Goal 13, "Specific measures to address climate change".

[0027] In this specification, "excellent adhesion at low temperatures" means that the above-described curable composition adheres well to the substrate in an environment below 10°C, preferably below 5°C. Specifically, after the curable composition is cured and bonded to the substrate in an environment below 10°C, preferably below 5°C, the proportion of cohesive failure is higher than that of interfacial failure in the adhesion tests described in the examples.

[0028] [2. Manufacturing method of laminated structure]

[0029] This manufacturing method is a method for manufacturing a laminated structure comprising a substrate and a cured product. The method includes: a coating step, in which a curable composition is coated onto the substrate; and a curing step, in which the curable composition coated onto the substrate is cured at an ambient temperature below 10°C to form the cured product. The curable composition contains the following (A) and (B): (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking through the formation of siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value less than 100 mg KOH / g and having ethylene glycol units. It should be noted that, hereinafter, "(A) the organic polymer having silicon-containing groups capable of crosslinking through the formation of siloxane bonds" is sometimes referred to as "component (A)," and "(B) the compound having a hydroxyl value less than 100 mg KOH / g and having ethylene glycol units" is sometimes referred to as "component (B)." In addition, sometimes "a curable composition containing 100 parts by weight of an organic polymer having a silicon-containing group capable of crosslinking by forming siloxane bonds and 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and having an ethylene glycol unit" is referred to as "this curable composition".

[0030] <2-1. Curable Composition>

[0031] The curable composition which is coated onto the substrate in the coating process comprises 100 parts by weight of component (A) and 10 to 200 parts by weight of component (B).

[0032] ((A) ingredient)

[0033] There are no particular restrictions on the main chain of the organic polymer that constitutes component (A). Examples of polymers constituting the main chain of an organic polymer include: polyoxyethylene, polyoxypropylene, polyoxybutene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers, polyoxypropylene-polyoxybutene copolymers, and other polyoxyolefin polymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, copolymers of polychloroprene, polyisoprene, isoprene or butadiene with acrylonitrile and / or styrene, copolymers of polybutadiene, isoprene or butadiene with acrylonitrile and / or styrene, hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers, and other hydrocarbon polymers; polyester polymers obtained by condensation of dicarboxylic acids such as adipic acid with diols or by ring-opening polymerization of lactones; and (meth)acrylate, butyl methacrylate, etc., obtained by free radical polymerization of monomers. Polyamide polymers, including methacrylate polymers; vinyl polymers obtained by free radical polymerization of monomers such as methacrylates, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in the above-mentioned organic polymers; polysulfide polymers; nylon 6 obtained by ring-opening polymerization of ε-caprolactam; nylon 6-6 obtained by condensation polymerization of hexamethylenediamine and adipic acid; nylon 6-10 obtained by condensation polymerization of hexamethylenediamine and sebacic acid; nylon 11 obtained by condensation polymerization of ε-aminoundecanoic acid; nylon 12 obtained by ring-opening polymerization of ε-aminolaurolactam; and copolyamide polymers containing two or more of the above-mentioned nylon components; polycarbonate polymers, such as those manufactured by condensation polymerization of bisphenol A and phosgene; and diallyl phthalate polymers. It should be noted that in this invention, "(meth)acrylate" refers to "acrylates and / or methacrylates," and "(meth)acrylic acid" refers to "acrylic acid and / or methacrylic acid." The other records also have the same meaning.

[0034] Polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and other saturated hydrocarbon polymers, polyoxyethylene polymers, and (meth)acrylate polymers have low glass transition temperatures, resulting in curing products with excellent physical properties, and are therefore preferred from this perspective.

[0035] The glass transition temperature of the organic polymer as component (A) is not particularly limited, but is preferably below 20°C, more preferably below 0°C, and particularly preferably below -20°C. When the glass transition temperature is below 20°C, workability is improved, and the softness and elongation of the cured product are also improved. The above-mentioned glass transition temperature represents the value obtained by DSC measurement.

[0036] Furthermore, polyoxyethylene polymers and (meth)acrylate polymers have high moisture permeability, and single-component compositions containing them exhibit excellent deep curing properties, resulting in excellent adhesion. Therefore, polyoxyethylene polymers and (meth)acrylate polymers are preferred as organic polymers, more preferably polyoxyethylene polymers, and even more preferably polyoxypropylene polymers.

[0037] The reactive silicon groups contained in the organic polymer of the present invention are groups having hydroxyl groups or hydrolyzable groups bonded to silicon atoms, capable of cross-linking by forming siloxane bonds through a reaction accelerated by a silanol condensation catalyst. Here, hydrolyzable groups refer to groups that react with water to generate hydroxyl groups.

[0038] As reactive silicon groups, the following groups represented by general formula (1) can be cited.

[0039] [Chemical Formula 1]

[0040] -SiR 1 3-a X a ···(1)

[0041] In formula (1), R is independently an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, or a triorganosilyloxy group represented by -OSi(R') (where R' is independently a hydrocarbon group with 1 to 20 carbon atoms). X is independently a hydroxyl group or a hydrolyzable group. (a is an integer from 1 to 3)

[0042] The hydrolyzable group is not particularly limited, and any conventionally known hydrolyzable group is acceptable. Examples include halogen atoms, alkoxy groups, acyloxy groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenoxy groups. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoxymate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenoxy groups are preferred. From the viewpoint of mild hydrolysis and ease of operation, alkoxy groups are particularly preferred.

[0043] Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3. When more than two hydrolyzable groups and hydroxyl groups are bonded to a reactive silicon group, they can be the same or different.

[0044] From the viewpoint of curability, a in the above general formula (1) is preferably 2 or 3, especially 3 when rapid curability of the composition is required, and 2 when storage stability of the composition is required.

[0045] Examples of R in the above general formula (1) include: alkyl groups such as methyl and ethyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, aralkyl groups such as benzyl, and triorganosyl siloxy groups represented by -OSi(R') where R' is methyl or phenyl. Among these, methyl is particularly preferred.

[0046] Examples of reactive silicon groups include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl. From the perspective of high reactivity and good curability, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl are preferred, more preferably trimethoxysilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl, and even more preferably trimethoxysilyl. From the viewpoint of storage stability, dimethoxymethylsilyl and triethoxysilyl are preferred. Furthermore, the alcohol generated by the hydrolysis of the reactive silicon group from triethoxysilyl and diethoxymethylsilyl is ethanol, which is preferred from the viewpoint of higher safety.

[0047] The introduction of reactive silicon groups can be carried out by known methods. Examples of such methods are (I) to (III) below.

[0048] (I) An organic polymer having functional groups such as hydroxyl groups is reacted with an organic compound having active groups and unsaturated groups that are reactive to the functional groups (e.g., an epoxy compound containing saturated groups) to obtain an organic polymer having unsaturated groups. Next, the obtained organic polymer having unsaturated groups is reacted with a hydrosilane compound having reactive silicon groups (hydrosilanization).

[0049] (II) React an organic polymer containing unsaturated groups obtained in the same manner as in (I) with a compound having thiol and reactive silicon groups.

[0050] (III) Reacting an organic polymer with functional groups such as hydroxyl, epoxy, and isocyanate groups in its molecule with a compound having a functional group that is reactive to the functional group and a reactive silicon group.

[0051] Of the methods described above, method (I) or method (III), which involves reacting an organic polymer with terminal hydroxyl groups with a compound having isocyanate groups and reactive silicon groups, is preferred because it can achieve a high conversion rate in a shorter reaction time. Furthermore, the organic polymer with reactive silicon groups obtained by method (I) has a lower viscosity than the organic polymer obtained by method (III), and using this organic polymer yields a curable composition with good workability. Additionally, the organic polymer obtained by method (II) has a strong odor derived from mercaptosilanes. From these considerations, method (I) is particularly preferred.

[0052] Examples of hydrogenated silane compounds used in method (I) include, for example, halosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, and 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane; and acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane, but are not limited thereto. Among these, halosilanes and alkoxysilanes are particularly preferred, especially alkoxysilanes, as the resulting curable compositions have mild hydrolytic properties and are easy to handle, and are therefore most preferred. Among alkoxysilanes, methyldimethoxysilane is readily available, and the curable compositions containing the resulting organic polymer exhibit high curability, storage stability, elongation characteristics, and tensile strength, and are therefore preferred. Furthermore, from the viewpoint of the curability and restitution properties of the obtained curable composition, trimethoxysilane is particularly preferred.

[0053] As a method in (II), examples include introducing a compound having a thiol group and a reactive silicon group into the unsaturated bond site of an organic polymer via a free radical addition reaction in the presence of a free radical initiator and / or a free radical generating source, but this is not a limitation. Examples of compounds having a thiol group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, etc., but this is not a limitation.

[0054] As a method in (III) for reacting an organic polymer having hydroxyl groups with a compound having isocyanate groups and reactive silicon groups, examples include the method shown in Japanese Patent Application Publication No. 3-47825, but it is not limited thereto. Examples of compounds having isocyanate groups and reactive silicon groups include, for example, γ-isocyanate-propyltrimethoxysilane, γ-isocyanate-propylmethyldimethoxysilane, γ-isocyanate-propyltriethoxysilane, γ-isocyanate-propylmethyldiethoxysilane, isocyanate-methyltrimethoxysilane, isocyanate-methyldimethoxymethylsilane, isocyanate-methyldiethoxymethylsilane, etc., but it is not limited thereto.

[0055] Silane compounds such as trimethoxysilane, which have three hydrolyzable groups bonded to one silicon atom, sometimes undergo disproportionation reactions. If a disproportionation reaction occurs, unstable compounds such as dimethoxysilane are produced, sometimes making the process difficult. However, γ-mercaptopropyltrimethoxysilane and γ-isocyanate-propyltrimethoxysilane do not undergo such disproportionation reactions. Therefore, when using a group such as trimethoxysilane, where three hydrolyzable groups are bonded to one silicon atom, as the silicon-containing group, method (II) or (III) is preferred.

[0056] On the other hand, silane compounds represented by the following general formula (2) do not undergo disproportionation reactions.

[0057] [Chemical Formula 2]

[0058] H-(SiR 2 2O) m SiR 2 2-R 3 -SiX3···(2)

[0059] In the formula, X is the same as in formula (1). 2m+2 R 2 Each is an independent hydrocarbon group. R 3 It is a divalent organic group. M is an integer from 0 to 19.

[0060] Therefore, in method (I), when introducing a group with three hydrolyzable groups bonded to one silicon atom, it is preferable to use a silane compound represented by general formula (2). From the viewpoint of availability and cost, 2m+2 R 2 Each hydrocarbon group is preferably a hydrocarbon group with 1 to 20 carbon atoms, more preferably a hydrocarbon group with 1 to 8 carbon atoms, and even more preferably a hydrocarbon group with 1 to 4 carbon atoms. From the viewpoint of availability and cost, R 3Preferably, the hydrocarbon group is divalent with 1 to 12 carbon atoms, more preferably divalent with 2 to 8 carbon atoms, and even more preferably divalent with 2 carbon atoms. From the viewpoint of availability and cost, m is preferably 1. Examples of silane compounds represented by general formula (2) include: 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1-[2-(trimethoxysilyl)propyl]-1,1,3,3-tetramethyldisiloxane, 1-[2-(trimethoxysilyl)hexyl]-1,1,3,3-tetramethyldisiloxane, etc.

[0061] The organic polymer containing reactive silicon groups can be either linear or branched. The number-average molecular weight (Mn) of the organic polymer containing reactive silicon groups, as determined by GPC (polystyrene conversion), is preferably 1000 to 100000, more preferably 2000 to 50000, and particularly preferably 3000 to 30000. When the number-average molecular weight is 1000 or higher, the elongation of the cured product increases; when it is 10000 or lower, the workability of the cured composition improves. The molecular weight distribution (Mw / Mn) of the organic polymer containing reactive silicon groups, as determined by GPC, is preferably 2 or lower, more preferably 1.5 or lower, and even more preferably 1.4 or lower.

[0062] From the viewpoint of obtaining a rubber-like cured compound exhibiting high strength, high elongation, and low elastic modulus, the number of reactive silicon groups contained in the organic polymer is preferably 1 or more per molecule, more preferably 1.1 to 5.0, further preferably 1.1 to 3.0, and particularly preferably 1.1 to 2.0. When the number of reactive silicon groups contained in the molecule is 1 or more on average, the curability is improved, and a cured compound with good rubber elastic behavior can be obtained. The reactive silicon groups can be located at the ends of the main chain or the ends of the side chains of the organic polymer, or both. In particular, when the reactive silicon groups are only located at the ends of the main chain, the effective network length in the final cured compound becomes longer, thus making it easier to obtain a rubber-like cured compound with high strength, high elongation, and low elastic modulus.

[0063] The aforementioned polyoxyethylene polymers are essentially polymers having repeating units represented by the following general formula (3).

[0064] [Chemical Formula 3]

[0065] -R 4 -O-···(3)

[0066] In the formula, R 4 It is a straight-chain or branched alkylene group having 1 to 14 carbon atoms.

[0067] R in general formula (3)4 Preferably, it is a straight-chain or branched alkylene group with 1 to 14 carbon atoms (more preferably 2 to 4). Examples of repeating units represented by general formula (3) include: -CH2O-, -CH2CH2O-, -CH2CH(CH3)O-, -CH2CH(C2H5)O-, -CH2C(CH3)O-, -CH2CH2CH2CH2O-, etc. The main chain of the polyoxyethylene polymer may consist of only one repeating unit or may contain two or more repeating units. Especially when the above-mentioned curable composition is used as a sealant, etc., the main component of the organic polymer of component (A) is preferably an amorphous polyoxypropylene polymer with low viscosity.

[0068] Examples of methods for synthesizing polyoxyethylene polymers include, but are not limited to, polymerization methods based on alkaline catalysts such as KOH, polymerization methods based on transition metal compound-porphyrin complex catalysts such as the complex obtained by reacting organoaluminum compounds with porphyrins shown in Japanese Patent Application Publication No. 61-215623, polymerization methods based on complex metal cyanide complex catalysts (e.g., zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalysts) shown in Japanese Patent Application Publication No. 46-27250, polymerization methods using catalysts containing polyphosphazene salts exemplified in Japanese Patent Application Publication No. 10-273512, and polymerization methods using catalysts containing phosphazene compounds exemplified in Japanese Patent Application Publication No. 11-060722.

[0069] Examples of polyoxyalkylene polymers with reactive silicon groups include, for example, those with a number-average molecular weight (Mn) of 6000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less, as proposed in Japanese Patent Application Publication No. 8-231707, but these are not limited to these. The aforementioned polyoxyalkylene polymers with reactive silicon groups can be used alone or in combination of two or more.

[0070] The above-mentioned saturated hydrocarbon polymers are polymers that do not contain aliphatic unsaturated bonds. Saturated hydrocarbon polymers can be obtained by the following methods: (1) polymerizing olefins with 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, and isobutene, as the main monomers; or (2) homopolymerizing dienes such as butadiene and isoprene; or copolymerizing the above-mentioned olefins and then hydrogenating them.

[0071] Methods for preparing saturated hydrocarbon polymers with reactive silicon groups are described, for example, in Japanese Patent Application Publication No. 7-53882, but are not limited thereto. The aforementioned saturated hydrocarbon polymers with reactive silicon groups can be used alone or in combination of two or more.

[0072] The monomers constituting the main chain of the aforementioned methacrylate polymers are not particularly limited, and various monomers can be used. Examples of such monomers include: (meth)acrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluene methacrylate, benzyl methacrylate, and 2-ethylhexyl methacrylate. 1-Methoxyethyl ester, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearate, glycidyl acrylate, 2-aminoethyl acrylate, γ-((meth)acryloyloxy)propyltrimethoxysilane, γ-((meth)acryloyloxy)propyldimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, ethylene oxide adducts of methacrylic acid, and other methacrylic acid monomers.

[0073] As the aforementioned (meth)acrylate polymers, the following vinyl monomers can be copolymerized with (meth)acrylate monomers. Examples of such vinyl monomers include styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid and its salts; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, etc. Maleimide monomers such as amines, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and cyclohexyl maleimide; cyano-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pentanoate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

[0074] These monomers can be used individually or in multiple copolymers.

[0075] From the viewpoint of physical properties, polymers formed from (meth)acrylate monomers are preferred as (meth)acrylate polymers, as well as polymers formed from styrene monomers and (meth)acrylate monomers. Polymers formed from (meth)acrylate monomers are more preferred, and polymers formed from acrylate monomers are even more preferred.

[0076] In general construction applications where low viscosity, low modulus, high elongation, weather resistance, and heat resistance of the compound are required, butyl acrylate is preferred as a monomer constituting the (meth)acrylate polymer. On the other hand, in automotive applications where oil resistance is required, copolymers primarily composed of ethyl acrylate are preferred as (meth)acrylate polymers. While these ethyl acrylate-based copolymers exhibit excellent oil resistance, they tend to have slightly poorer low-temperature properties (cold resistance). Therefore, to improve their low-temperature properties, a portion of the ethyl acrylate can be replaced with butyl acrylate. However, since the good oil resistance is compromised as the proportion of butyl acrylate increases, the proportion of butyl acrylate is preferably set to 40% by weight or less, more preferably 30% by weight or less, in applications requiring oil resistance. Furthermore, to improve low-temperature properties without compromising oil resistance, monomers with oxygen introduced into the branched alkyl groups (e.g., 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, etc.) are preferred. However, when alkoxy groups with ether bonds are introduced into the branched chains, the heat resistance of the copolymer tends to decrease. Therefore, when heat resistance is required for the copolymer, the ratio of monomers with oxygen introduced into the branched alkyl groups is preferably set to 40% by weight or less. Depending on the various applications and required objectives, and considering the necessary properties such as oil resistance, heat resistance, and low-temperature characteristics, the ratio of the monomers used can be changed to obtain a suitable polymer. For example, copolymers with excellent balance of properties such as oil resistance, heat resistance, and low-temperature characteristics, such as ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (by weight ratio of 40-50 / 20-30 / 30-20), can be cited as an example. In the present invention, butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethoxyethyl acrylate can be copolymerized with other monomers and then block copolymerized. In this case, it is preferable that the copolymer contains 40% by weight or more of butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethoxyethyl acrylate.

[0077] There are no particular limitations on the synthesis method of (meth)acrylate polymers, and they can be carried out by known methods. However, polymers obtained by conventional free radical polymerization using azo compounds, peroxides, etc., as polymerization initiators generally have a molecular weight distribution greater than 2, resulting in increased viscosity. Therefore, in order to obtain (meth)acrylate polymers with a narrow molecular weight distribution, low viscosity, and a high proportion of crosslinking functional groups at the ends of the molecular chains, living radical polymerization is preferred.

[0078] In the "living radical polymerization method," the "atom transfer radical polymerization method," which uses organohalides or halosulfonyl compounds as initiators and transition metal complexes as catalysts to polymerize (meth)acrylate monomers, in addition to the characteristics of the aforementioned "living radical polymerization method," offers greater design freedom for initiators and catalysts. As a method for manufacturing (meth)acrylate polymers with specific functional groups, it further optimizes the use of halogens or similar substances at the terminal ends, which are more favorable for functional group conversion reactions. This atom transfer radical polymerization method is documented, for example, in Matyjaszewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.), 1995, Vol. 117, p. 5614.

[0079] Methods for preparing (meth)acrylate polymers with reactive silicon groups include, for example, a method using free radical polymerization with a chain transfer agent disclosed in Japanese Patent Application Publication No. 6-211922. Additionally, a method using atom transfer radical polymerization disclosed in Japanese Patent Application Publication No. 9-272714 is also disclosed, but the method is not limited to this. The aforementioned (meth)acrylate polymers with reactive silicon groups can be used alone or in combination of two or more.

[0080] These organic polymers with reactive silicon groups can be used alone or in combination of two or more. Specifically, mixtures of two or more organic polymers selected from polyoxyethylene polymers with reactive silicon groups, saturated hydrocarbon polymers with reactive silicon groups, and (meth)acrylate polymers with reactive silicon groups can also be used.

[0081] Japanese Patent Application Publication No. 11-116763 discloses a method for manufacturing a mixture of an organic polymer having reactive silicon groups, specifically a polyoxyethylene polymer and a (meth)acrylate polymer having reactive silicon groups, but is not limited thereto. A preferred method for manufacturing the (meth)acrylate polymer is, for example, the method of blending a polyoxyethylene polymer having reactive silicon groups into a copolymer whose molecular chain is substantially composed of (meth)acrylate monomer units represented by the following general formula and (meth)acrylate monomer units represented by the following general formula (5).

[0082] [Chemical Formula 4]

[0083] -CH2-C(R 5 (COOR) 6 )-···(4)

[0084] In the formula, R 5 It can be a hydrogen atom or a methyl group. R 6 It is an alkyl group having 1 to 8 carbon atoms.

[0085] [Chemical Formula 5]

[0086] -CH2-C(R 5 (COOR) 7 )-···(5)

[0087] In the formula, R 5 Same as above. R 7 It is an alkyl group with 9 or more carbon atoms.

[0088] R is the general formula (4) above. 6 Examples of such alkyl groups include methyl, ethyl, propyl, n-butyl, tert-butyl, and 2-ethylhexyl, which have 1 to 8 carbon atoms, preferably 1 to 4, and more preferably 1 or 2. It should be noted that R... 6 The alkyl group can be one type or two or more types.

[0089] R, as in the above general formula (5) 7 Examples of such alkyl groups include: nonyl, decyl, lauryl, tridecyl, cetyl, stearyl, docosyl, etc., which have 9 or more carbon atoms, preferably 10 to 30, and more preferably 10 to 20. It should be noted that R... 7 alkyl and R 6 The same situation can be one type or two or more types.

[0090] The molecular chains of the preferred (meth)acrylate polymers described above are substantially formed of monomer units of general formulas (4) and (5). Here, "substantially" means that the total amount of monomer units of general formulas (4) and (5) present in the polymer exceeds 50% by weight. The total amount of monomer units of general formulas (4) and (5) is preferably 70% by weight or more.

[0091] The ratio of the monomer unit of general formula (4) to the monomer unit of general formula (5) by weight is preferably 95:5 to 40:60, more preferably 90:10 to 60:40. Among the preferred (meth)acrylate polymers described above, monomer units other than those of general formulas (4) and (5) can be, for example: (meth)acrylic acid; monomers containing amide groups such as (meth)acrylamide and N-hydroxymethyl(meth)acrylamide; monomers containing epoxy groups such as glycidyl methacrylate; monomers containing amino groups such as diethylaminoethyl methacrylate and aminoethyl vinyl ether; and other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ethers, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc.

[0092] Japanese Patent Application Publication Nos. 1-168764 and 2000-186176, among others, have proposed mixtures of organic polymers consisting of saturated hydrocarbon polymers with reactive silicon groups and (meth)acrylate polymers with reactive silicon groups, but are not limited to these.

[0093] A method for manufacturing a mixture of organic polymers containing (meth)acrylate polymers with reactive silicon functional groups can be employed by polymerizing (meth)acrylate monomers in the presence of organic polymers containing reactive silicon groups. This manufacturing method is specifically disclosed in Japanese Patent Application Publication Nos. 59-78223, 59-168014, 60-228516, and 60-228517, but is not limited thereto.

[0094] On the other hand, the main chain of the organic polymer may contain urethane bonds and / or urea bonds within a range that does not significantly impair the effects of the present invention. The aforementioned urethane bonds and / or urea bonds are bonds containing amide segments represented by general formula (6), which can be formed, for example, by the reaction of isocyanate groups with active hydrogen groups.

[0095] [Chemical Formula 6]

[0096] -NR 8 -C(=O)-···(6)

[0097] In the formula, R 8 It can be an organic group or a hydrogen atom.

[0098] The amide segment has high polarity, therefore, if an organic polymer containing it is used, there is a tendency for the resulting cured product to have increased strength and adhesion to the substrate.

[0099] As an amide segment represented by general formula (6), examples include amide segments formed by the reaction of isocyanate group with hydroxyl group, reaction of isocyanate group with amino group, and reaction of isocyanate group with mercapto group. In addition, segments formed by the reaction of the above-mentioned amide segment containing an active hydrogen atom with an isocyanate group are also included in the amide segments represented by general formula (6).

[0100] An industrially readily available method for manufacturing organic polymers having amide segments and reactive silicon groups can be exemplified by, for instance, manufacturing them by reacting an organic polymer with an active hydrogen-containing group at the end with an excess of a polyisocyanate compound to form a polymer with isocyanate groups at the end of a polyurethane backbone, or simultaneously reacting all or part of the isocyanate groups with the W group of a silicon compound represented by general formula (7).

[0101] [Chemical Formula 7]

[0102] WR 9 -SiR 1 3-a X a ···(7)

[0103] In the formula, R 1 X and a are the same as above. R 9 It is a divalent organic group, more preferably a hydrocarbon group with 1 to 20 carbon atoms. W is a group containing active hydrogen selected from hydroxyl, carboxyl, mercapto, and amino (primary or secondary amino).

[0104] For example, Japanese Patent Application Publication No. 2001-323040 is cited as a related document.

[0105] In addition, examples of organic polymers having amide segments and reactive silicon groups include polymers manufactured by reacting an organic polymer having an active hydrogen group at the end with an isocyanate compound containing a reactive silicon group represented by general formula (8).

[0106] [Chemical Formula 8]

[0107] O=C=NR 9 -SiR 1 3-a X a ···(8)

[0108] In the formula, R 9 R 1X and a are the same as above.

[0109] For example, WO03 / 059981 is a relevant document for this manufacturing method.

[0110] Examples of organic polymers having active hydrogen groups at the ends include: olefinic polymers (polyether polyols) with hydroxyl groups at the ends, polyacrylic acid polyols, polyester polyols, saturated hydrocarbon polymers (polyolefin polyols) with hydroxyl groups at the ends, polythiol compounds, and polyamine compounds. Among these, polyether polyols, polyacrylic acid polyols, and polyolefin polyols are preferred from the perspective of having a low glass transition temperature and excellent cold resistance of the cured product. In particular, organic polymers obtained from polyether polyols have low viscosity, good workability, good deep curing properties of the curing composition, and good adhesion of the cured product, and are therefore especially preferred. Furthermore, cured products obtained from polyacrylic acid polyols and saturated hydrocarbon polymers have good weather resistance and heat resistance, and are therefore more preferred.

[0111] As a polyether polyol, any polyether polyol manufactured in any manufacturing method can be used, but polyether polyols with an average of at least 0.7 hydroxyl groups at the end of each molecule are preferred. Examples of polyether polyols include: polyoxyethylene polymers manufactured using existing alkali metal catalysts; and polyoxyethylene polymers manufactured by reacting an initiator such as a polyhydroxy compound having at least 2 hydroxyl groups with an oxide in the presence of a complex metal cyanide complex or cesium.

[0112] Among the above polymerization methods, the polymerization method using composite metal cyanide complexes can obtain oxidized olefin polymers with lower unsaturation, narrow Mw / Mn ratio, lower viscosity, and high acid resistance and weather resistance, and is therefore preferred.

[0113] Examples of the aforementioned polyacrylic acid polyols include polyols with alkyl methacrylate (co)polymers as the main chain and hydroxyl groups within the molecule. Regarding the synthesis method of this polymer, living radical polymerization is preferred from the perspective of narrow molecular weight distribution and the ability to achieve low viscosity; atom transfer radical polymerization is even more preferred. Furthermore, polymers obtained by continuous bulk polymerization of alkyl acrylate monomers under high temperature and high pressure (obtained via the so-called SGO process) as described in Japanese Patent Application Publication No. 2001-207157 are preferred. Examples include ARUFON UH-2000 manufactured by Toa Synthetic Co., Ltd.

[0114] Examples of the aforementioned polyisocyanate compounds include, for instance, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and phenyl dimethyl diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0115] As for silicon compounds represented by general formula (7), there are no particular limitations, and examples include: amino-containing silanes such as γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, (N-phenyl)-γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, and N-phenylaminomethyltrimethoxysilane; hydroxyl-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto-containing silanes such as γ-mercaptopropyltrimethoxysilane; etc. In addition, as described in Japanese Patent Application Publication No. 6-211879, various α,β-unsaturated carbonyl compounds reacting with silanes containing primary amino groups, or various silanes containing (meth)acryloyl groups reacting with compounds containing primary amino groups, can also be used as silicon compounds represented by general formula (7).

[0116] There are no particular limitations on the isocyanate compounds containing reactive silicon groups represented by general formula (8), and examples include: γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, and diethoxymethylsilylmethyl isocyanate. In addition, as described in Japanese Patent Application Laid-Open No. 2000-119365 (US Patent No. 6046270), compounds obtained by reacting a silicon compound of general formula (7) with an excess of the above-mentioned polyisocyanate compounds can also be used as isocyanate compounds containing reactive silicon groups represented by general formula (8).

[0117] In a preferred embodiment, the organic polymer of component (A) is: having an average of 1.1 to 5 silicon-containing groups selected from trimethoxysilyl, triethoxysilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl per molecule, and having a number-average molecular weight of 1,000 to 100,000, and being selected from at least one of polyoxyolefin polymers, saturated hydrocarbon polymers, and (meth)acrylate polymers. It should be noted that in this preferred embodiment, the above-mentioned limitations on silicon-containing groups and number-average molecular weight modify all polyoxyolefin polymers, saturated hydrocarbon polymers, and (meth)acrylate polymers.

[0118] In a more preferred embodiment, the organic polymer of component (A) is: at least one selected from polyoxyethylene polymers and (meth)acrylate polymers, having an average of 1.1 to 3 silicon-containing groups selected from trimethoxysilyl, (methoxymethyl)dimethoxysilyl, and methyldimethoxysilyl per molecule, and a number-average molecular weight of 2,000 to 50,000. It should be noted that in this more preferred embodiment, the above-mentioned limitations on silicon-containing groups and number-average molecular weight (modifiers) limit the selection to both polyoxyethylene polymers and (meth)acrylate polymers.

[0119] In a further preferred embodiment, the organic polymer of component (A) is a polyoxyethylene polymer having an average of 1.1 to 2 silicon-containing groups selected from trimethoxysilyl and methyldimethoxysilyl per molecule and a number-average molecular weight of 3,000 to 30,000.

[0120] In a particularly preferred embodiment, the organic polymer of component (A) is a polyoxypropylene polymer having an average of 1.1 to 2 methyldimethoxysilyl groups per molecule and a number-average molecular weight of 3,000 to 30,000.

[0121] <(B) Component>

[0122] This curable composition contains a compound with a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units as component (B). Component (B) functions as a so-called plasticizer. By adding component (B), the viscosity, slump properties, and mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Furthermore, when using component (B), the cured product obtained by curing the composition at low temperatures exhibits improved adhesion to the substrate compared to the use of conventional plasticizers.

[0123] Since component (B) contains ethylene glycol units, it is preferable to include polyethylene glycol. Examples of polyethylene glycols included in component (B) include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, and decaethylene glycol. These can be used alone or in combination. Since the viscosity of polyethylene glycol increases with increasing degree of polymerization, diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol are preferred. From the perspectives of good safety, low viscosity, and easy availability, triethylene glycol and tetraethylene glycol are particularly preferred.

[0124] As component (B), examples include: triethylene glycol bis(2-ethylhexanoate), diethylene glycol dibutyrate, diethylene glycol dihexanoate, diethylene glycol bis(2-ethylhexanoate), diethylene glycol dioctanoate, diethylene glycol bis(2-propylheptaate), diethylene glycol dicyclohexanoate, triethylene glycol dibutyrate, triethylene glycol dihexanoate, triethylene glycol dioctanoate, triethylene glycol dicyclohexanoate, triethylene glycol di(2-ethylhexanoate) tetraethylene glycol dimethyl ether, tetraethylene glycol dibutyrate, tetraethylene glycol diethylhexanoate ... Diethylene glycol dihexanoate, tetraethylene glycol bis(2-ethylhexanoate), tetraethylene glycol dioctanoate, tetraethylene glycol bis(2-propylheptanoate), tetraethylene glycol dicyclohexanoate, pentaethylene glycol dibutyrate, pentaethylene glycol dihexanoate, pentaethylene glycol bis(2-ethylhexanoate), pentaethylene glycol dioctanoate, pentaethylene glycol bis(2-propylheptanoate), pentaethylene glycol dicyclohexanoate, oligoethylene glycol bis(2-ethylhexanoate), bis(2-(2-butoxyethoxy)ethoxy)methane, etc., but not limited to these.

[0125] Of the components in (B) above, tetraethylene glycol dimethyl ether and triethylene glycol bis(2-ethylhexanoate) are widely used as plasticizers in resins constituting interlayers for laminated glass, and are therefore readily available and particularly preferred. Tetraethylene glycol dimethyl ether is marketed by Andoh Parachemie under the trade name PROGLYDE DMM. Triethylene glycol bis(2-ethylhexanoate) is marketed by OXEA under the trade name OXSOFT 3G8, by Celanese under the trade name WVC 3800, by Dowchemical under the trade name Flexol 3GO, and by Eastman under the trade name Eastman TEG-EHPlasticizer.

[0126] The molecular weight of component (B) is preferably 200 to 10,000, more preferably 200 to 6,000, and even more preferably 200 to 1,000. When the molecular weight of component (B) is 10,000 or less, the viscosity of the curable composition decreases, and it tends to improve workability. In addition, when the molecular weight of component (B) is 200 or more, it exhibits excellent heat resistance.

[0127] (B) The hydroxyl value of component (B) is less than 100 mg KOH / g, preferably less than 80 mg KOH / g, more preferably less than 50 mg KOH / g, and even more preferably less than 10 mg KOH / g. The fewer the hydroxyl groups, the better; for example, it can be 0 mg KOH / g. When the hydroxyl value of component (B) is less than 100 mg KOH / g, the adhesion between the substrate and the cured product at low temperatures is improved. The hydroxyl value of component (B) is determined by 1H NMR measurement using 1,4-bis(trifluoromethyl)benzene as an internal standard, and calculated based on the ratio of the integrated value to the signal from the hydroxyl group.

[0128] Component (B) can be used alone or in combination of two or more. The amount of component (B) is preferably 10 to 200 parts by weight, more preferably 30 to 100 parts by weight, and even more preferably 40 to 90 parts by weight, relative to 100 parts by weight of the organic polymer of component (A). When the amount of component (B) is 20 parts by weight or more, improved adhesion at low temperatures can be obtained. Furthermore, when the amount of component (B) is 200 parts by weight or less, a good balance between the workability of the composition and the strength of the cured product can be achieved.

[0129] (Catalyst solidification)

[0130] In addition to components (A) and (B) described above, this curing composition may also contain a curing catalyst. The curing catalyst functions as a silanol condensation catalyst for component (A). Examples of such curing catalysts include: titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetra(acetylacetone)titanium, diisopropoxydi(acetylacetone)titanium, and diisopropoxydi(acetoacetate)titanium; and dimethyltin diacetate, dimethyl bis(acetylacetone)tin, dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), and bis(methyl maleate). Dibutyltin, bis(ethyl maleate)dibutyltin, bis(butyl maleate)dibutyltin, bis(octyl maleate)dibutyltin, bis(tridecyl maleate)dibutyltin, bis(benzyl maleate)dibutyltin, dibutyltin diacetate, dibutyldimethoxytin, bis(nonylphenoxy)dibutyltin, dibutylenyltin oxide, dibutyltin oxide, dibutylbis(acetylacetone)tin, dibutylbis(ethyl acetoacetate)tin, dibutyltin oxide and silica Dibutyltin compounds, such as reaction products of salt compounds and reaction products of dibutyltin oxide with phthalates; dioctyltin compounds, such as bis(ethyl maleate)dioctyltin, bis(octyl maleate)dioctyltin, dioctyltin dilaurate, dioctyltin diacetate, dioctylbis(acetylacetone)tin, dioctyltin dineodecanate, and reaction products of dioctyltin oxide with silicate compounds; tri(acetylacetone)aluminum, tri(ethyl acetoacetate)aluminum, ethyl acetoacetate... Aluminum compounds such as aluminum diisopropyl ester; zirconium compounds such as tetra(acetylacetone)zirconium; carboxylic acids and / or metal salts of carboxylic acids; and amidine compounds such as 1-(o-tolyl)biguanide, 1-phenylguanide, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and amidine compounds described in WO2008 / 078654.

[0131] As the curing catalyst mentioned above, organotin compounds such as dibutyltin compounds and dioctyltin compounds are preferred. Dibutyltin compounds have a good balance of curing properties and adhesion properties and are widely used. In addition, as dioctyltin compounds, dioctylbis(acetylacetone)tin, dioctyltin dilaurate, dioctyltin dineodecanate, and the reaction products of dioctyltin with silicate compounds are industrially available and are therefore preferred.

[0132] Furthermore, from the viewpoint of improving the deep curing properties of the curable composition and the adhesion of the cured product to the substrate, an amidine compound is preferred as the curing catalyst for component (C), and 1-phenylguanidine is more preferred.

[0133] The amount of curing catalyst as component (C) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the organic polymer of component (A). When the amount of curing catalyst is in the range of 0.01 to 20 parts by weight, the curable composition has excellent curability and a moderate curing time, thus resulting in excellent workability.

[0134] (Plasticizer)

[0135] This curing composition may contain a plasticizer. By including a plasticizer in this curing composition, the physical properties of the cured product can be altered. For example, by incorporating a plasticizer, the elongation and strength of the cured product can be increased.

[0136] Examples of plasticizers include: phthalates (dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc.), non-aromatic diesters (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.), aliphatic esters (butyl oleate, methyl acetylacetonate, etc.), polyalkylene glycol esters (diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, etc.), phosphate esters (tricresyl phosphate, tributyl phosphate, etc.), trimellitic esters, and polystyrene. Ethylene compounds (polystyrene, poly-α-methylstyrene, etc.), polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, chlorinated paraffins, hydrocarbon oils (alkyl biphenyls, partially hydrogenated terphenyls, etc.), process oils, polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), and derivatives formed by converting the hydroxyl groups of polyether polyols to ester groups, ether groups, etc.); epoxy plasticizers (epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives and mixtures thereof, etc.). Polyester plasticizers derived from dicarboxylic acids and diols (such as polyesters derived from sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.); vinyl polymers (obtained by polymerizing vinyl monomers such as acrylic plasticizers through various methods); and cyclohexane dicarboxylic acid ester polymers obtained by hydrogenating phthalic acid esters.

[0137] Specific examples of epoxy plasticizers include: epoxidized soybean oil, epoxidized linseed oil, 4,5-epoxycyclohexane-1,2-dicarboxylic acid di(2-ethylhexyl) ester (E-PS), octyl epoxy stearate, and butyl epoxy stearate. Among the above-mentioned epoxy plasticizers, E-PS is preferred. Using compounds with epoxy groups as plasticizers can improve the resilience of the cured product.

[0138] Acrylic plasticizers can be produced by high-temperature continuous polymerization without the use of solvents and chain transfer agents. Specific examples of acrylic plasticizers include: ARUFON UP-1000, UP-1020, UP-1110 (all manufactured by Toa Synthetic Co., Ltd.), JDX-P1000, JDX-P1010, and JDX-P1020 (all manufactured by Johnson Polymer).

[0139] (Other ingredients)

[0140] Without compromising the effects of the present invention, this curable composition may contain components other than those described above (other components). The other components will be described below.

[0141] Aminosilanes may be added to this curing composition. Aminosilanes are compounds having reactive silicon groups and amino groups in their molecules, and are commonly referred to as tackifiers. When the curing composition containing aminosilanes is used on various substrates, such as inorganic substrates like glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates like vinyl chloride, acrylic acid, polyester, polyethylene, polypropylene, and polycarbonate, aminosilanes exhibit significant improvements in adhesion under both non-priming and priming conditions. The improvement in adhesion to various substrates is particularly significant when using a curing composition containing aminosilanes under non-priming conditions. Furthermore, aminosilanes can function as property modifiers, dispersant modifiers for inorganic fillers, etc. Specific examples of aminosilanes are described in WO2015 / 098998.

[0142] Tackifiers other than aminosilanes may be used in this curable composition. Specific examples of tackifiers other than aminosilanes are described in WO2015 / 098998.

[0143] By further using a silane coupling agent containing an ethylene glycol structure, the deep curing property, one of the effects of the present invention, can be further improved. An example of a silane coupling agent containing an ethylene glycol structure is Shin-Etsu Chemical Co., Ltd., under the trade name X-12-641. When using a silane coupling agent containing an ethylene glycol structure, its amount relative to 100 parts by weight of the organic polymer of component (A) is preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight.

[0144] Antioxidants (anti-aging agents) can be used in this curing composition. Using antioxidants can improve the heat resistance of the cured product. Examples of antioxidants include hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants, with hindered phenolic antioxidants being particularly preferred. Specific examples of antioxidants are described in Japanese Patent Application Publication Nos. 4-283259 and 9-194731. When using antioxidants, their amount relative to 100 parts by weight of the organic polymer in component (A) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight.

[0145] A light stabilizer can be used in this curable composition. Using a light stabilizer prevents photo-oxidative degradation of the cured product. Examples of light stabilizers include benzotriazole light stabilizers, hindered amine light stabilizers, and benzoate light stabilizers, with hindered amine light stabilizers being particularly preferred. When using a light stabilizer, its amount relative to 100 parts by weight of the organic polymer in component (A) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight. Specific examples of light stabilizers are described in Japanese Patent Application Publication No. 9-194731.

[0146] Ultraviolet absorbers can be used in this curable composition. Using ultraviolet absorbers improves the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, substituted toluene-based ultraviolet absorbers, and metal chelate-based ultraviolet absorbers, with benzotriazole-based ultraviolet absorbers being particularly preferred. When using ultraviolet absorbers, their amount relative to 100 parts by weight of the organic polymer in component (A) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight. It is preferable to use a combination of phenolic antioxidants and / or hindered phenolic antioxidants, hindered amine light stabilizers, and benzotriazole-based ultraviolet absorbers.

[0147] One or more fillers may be added to this curable composition. Examples of fillers include: fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica, hydrated silica, and reinforcing fillers such as carbon black; fibrous fillers such as glass fibers and filaments; heavy calcium carbonate, colloidal calcium carbonate (e.g., colloidal calcium carbonate surface-treated with fatty acids), magnesium carbonate, diatomaceous earth, sintered clay, clay, talc, titanium dioxide (e.g., rutile titanium dioxide), bentonite, organobentonite, iron oxide, aluminum micropowder, flint powder, zinc oxide, active zinc oxide, hollow spheres made of white sand, glass microhollow spheres, organic microhollow spheres made of phenolic resin or vinylidene chloride resin, PVC powder, PMMA powder, and other resin powders. When using fillers, their amount relative to 100 parts by weight of component (A) is preferably 1 to 250 parts by weight, more preferably 10 to 200 parts by weight.

[0148] When a high-strength cured product is desired, it is preferable to primarily use a filler selected from fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica, hydrated silica, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and active zinc oxide. When using the above-mentioned filler, its amount relative to 100 parts by weight of the organic polymer of component (A) is preferably 1 to 200 parts by weight.

[0149] Furthermore, when a cured material with low strength and high elongation at break is desired, it is preferable to primarily use a filler selected from titanium dioxide, heavy calcium carbonate, magnesium carbonate, talc, iron oxide, zinc oxide, and hollow spheres of Shirasu sand. When using the above-mentioned filler, its amount is preferably 5 to 200 parts by weight relative to 100 parts by weight of the organic polymer of component (A).

[0150] Generally, the larger the specific surface area of ​​calcium carbonate, the greater the improvement in the tensile strength, elongation at break, and adhesion of the cured product. When using calcium carbonate, it is preferable to use a combination of surface-treated fine calcium carbonate and heavy calcium carbonate, which have large particle sizes. The particle size of surface-treated fine calcium carbonate is preferably 0.5 μm or less, and its surface treatment is preferably fatty acid treatment or fatty acid salt treatment. Furthermore, the particle size of the large-particle calcium carbonate is preferably 1 μm or more. Untreated calcium carbonate can also be used as the large-particle calcium carbonate.

[0151] Tackifiers may be added to this curable composition. There are no particular limitations on the tackifier; any tackifier that is commonly used at room temperature, whether solid or liquid, can be used. Examples of tackifiers include: styrene copolymers and their hydrogenates (especially styrene block copolymers and their hydrogenates), phenolic resins, modified phenolic resins (e.g., cashew oil-modified phenolic resins, tall oil-modified phenolic resins, etc.), terpene phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene resins, DCPD resins, and petroleum resins. Examples of styrene-based block copolymers and their hydrogenated derivatives include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), and styrene-isobutylene-styrene block copolymers (SIBS). These tackifiers can be used alone or in combination of two or more. When using a tackifier, its amount relative to 100 parts by weight of the organic polymer in component (A) is preferably 5 to 1000 parts by weight, more preferably 10 to 100 parts by weight.

[0152] In this curable composition, a thixotropic agent (anti-drip agent) may be added as needed to prevent dripping and improve workability. There are no particular limitations on the thixotropic agent; examples include polyamide waxes, hydrogenated castor oil derivatives, and metallic soaps such as calcium stearate, aluminum stearate, and barium stearate. Furthermore, when using rubber powder with a particle size of 10 to 500 μm as described in Japanese Patent Application Publication No. 11-349916 or organic fibers as described in Japanese Patent Application Publication No. 2003-155389 as the thixotropic agent, a curable composition with high thixotropic properties and good workability can be obtained. These thixotropic agents can be used alone or in combination of two or more. When using a thixotropic agent, its amount is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the organic polymer in component (A).

[0153] A dehydrating agent may be added to this curing composition. Examples of dehydrating agents include: synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, and alkoxysilane compounds (e.g., n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, etc.). azole compounds (e.g., ethyl-2-methyl-2-(3-methylbutyl)-1,3- (e.g., azoles, isocyanate compounds, etc.) When using a dehydrating agent, its amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the organic polymer of component (A).

[0154] Examples and properties of photocurable substances, fillers, thermally expandable hollow microparticles, flake-like or granular substances, hollow spheres, cured particles, silicates, property modifiers, compounds having epoxy groups and not containing silicon atoms, photocurable substances, oxygen-curable substances, phosphorus plasticizers, flame retardants, solvents, etc., that may be used in this curing composition are described in WO2015 / 098998.

[0155] For the purpose of adjusting the various properties of the cured composition or cured product, additives other than those mentioned above may be added to the cured composition as needed. Examples of such additives include: curing modifiers, free radical inhibitors, metal passivators, ozone deterioration inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, termite repellents, and mildew inhibitors. These additives may be used alone or in combination of two or more. Specific examples of additives are described, for example, in Japanese Patent Application Publication Nos. 4-69659, 7-108928, 63-254149, 64-22904, and 2001-72854.

[0156] <2-2. Substrate>

[0157] The substrate can be, for example, metal, paper, stone, plastic, ceramic, tile, rubber, urethane, etc., preferably metal, plastic, or tile, and more preferably metal. Conventional curable compositions tend to have reduced adhesion to metals at low temperatures; therefore, if the substrate is metal, the effect of the curable composition used in this manufacturing method can be further enhanced. The metal is not particularly limited and can be, for example, aluminum, iron, copper, silver, nickel, zinc, tin, stainless steel, their alloys, or oxides. Among these metals, aluminum and stainless steel are preferred.

[0158] The application of the aforementioned substrate is not particularly limited, and it can be, for example, a substrate for interior panels, a substrate for exterior panels, a substrate for vehicle panels, or a substrate for exterior ceramic tiles. Among these, from the viewpoint of intended use in low-temperature environments, substrates for interior panels, exterior panels, or vehicle panels are preferred.

[0159] <2-3. Coating Process>

[0160] This manufacturing method includes a coating step of applying a curable composition containing components (A) and (B) to a substrate. By including components (A) and (B) in the curable composition, the cured product exhibits excellent adhesion to the substrate even at low temperatures below 10°C.

[0161] The method for performing the above coating process is not particularly limited and can be carried out by known methods. The coating of this curable composition onto the substrate can be performed using, for example, rollers, doctor blades, trowels, etc. Furthermore, the shape of the coated curable composition is not particularly limited and can be coated into any shape, such as rectangles, squares, pentagons, or beads.

[0162] The ambient temperature for performing the above coating process is not particularly limited; it can be room temperature or a low temperature. Preferably, it is performed at 10°C or below, more preferably at 5°C or below. The lower limit of the ambient temperature is not particularly limited; in practice, it can be -20°C or above. According to the curing composition used in this manufacturing method, even at low temperatures below 10°C, the increase in viscosity can be suppressed, thus facilitating coating onto the substrate.

[0163] <2-4. Curing Process>

[0164] This manufacturing method includes a curing step that cures the curable composition at an ambient temperature below 10°C. In this curing step, the curable composition becomes a cured product and adheres to the substrate. As mentioned above, conventional curable compositions are difficult to cure at low temperatures. However, according to this manufacturing method, even when the curing step is performed at a low temperature such as below 10°C, the curable composition can be sufficiently cured and fully adhered to the substrate.

[0165] In the above curing process, the ambient temperature is preferably below 10°C, more preferably below 5°C. There is no particular limitation on the lower limit of the ambient temperature; in practice, it can be above -20°C.

[0166] There are no particular limitations on the method for carrying out the above curing process, and it can be carried out by known methods. The above curing process can be carried out using, for example, a dryer, refrigerator, freezer, low-temperature warehouse, or outdoors on days with low temperatures. In addition, there are no particular limitations on the time for carrying out the above curing process, which can be, for example, 1 day to 10 days, preferably 3 days to 7 days.

[0167] [3. Bonding method]

[0168] This bonding method includes a step of bonding a substrate to a curable composition containing the following (A) and (B) at an ambient temperature below 10°C: (A) 100 parts by weight of an organic polymer containing silicon groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and containing ethylene glycol units.

[0169] This bonding method is a method of bonding the above-described substrate to the above-described curable composition. Therefore, in other words, this bonding method can also be referred to as the bonding step included in this manufacturing method.

[0170] According to this bonding method, the curable composition can be bonded to the substrate even at low temperatures, resulting in a laminated structure with good adhesion.

[0171] The curing composition in this bonding method is described in [2. Method for manufacturing laminated structures].

[0172] [4. Layered Structure]

[0173] This laminated structure is a laminated structure comprising a metal substrate and a cured product, wherein the cured product is a cured product formed by curing a curable composition containing the following (A) and (B): (A) 100 parts by weight of an organic polymer having silicon-containing groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and having ethylene glycol units.

[0174] This laminated structure can fully bond the substrate and the cured material even in low-temperature environments, making it a preferred choice for interior panels, exterior panels, vehicle panels, etc.

[0175] In one embodiment of the present invention, the laminated structure is obtained by the present manufacturing method.

[0176] The curing composition in this laminated structure is described in [2. Method for manufacturing laminated structures].

[0177] [5. Adhesives and sealants]

[0178] This adhesive and this sealing material are adhesives or sealing materials for use in low-temperature environments at ambient temperatures below 10°C. The adhesives or sealing materials for low-temperature environments contain the following (A) and (B): (A) 100 parts by weight of an organic polymer containing silicon groups capable of crosslinking by forming siloxane bonds, and (B) 10 to 200 parts by weight of a compound having a hydroxyl value of less than 100 mg KOH / g and containing ethylene glycol units.

[0179] This adhesive and sealant contain components that enable them to bond to substrates at low temperatures, thus allowing for use over a wide temperature range.

[0180] In addition to the curable composition described above, this adhesive and sealant may also contain any known components that are commonly found in adhesives or sealants. Furthermore, this adhesive and sealant may be any of the single-component, two-component, or multi-component formulations.

[0181] This adhesive can be used for, for example, interior panel adhesives, exterior panel adhesives, tile adhesives, stone adhesives, ceiling finish adhesives, floor finish adhesives, wall finish adhesives, vehicle panel adhesives, and adhesives for assembling electrical / electronic / precision equipment. Additionally, this sealant can be used for, for example, direct-fit glass sealants, multi-pane glass sealants, SSG construction method sealants, and construction joint sealants in buildings.

[0182] The curing composition in this adhesive and sealing material is described in reference to [2. Method for manufacturing laminated structures].

[0183] [6. Others]

[0184] This invention is not limited to the embodiments described above. Various modifications can be made within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included within the technical scope of this invention. That is, one aspect of this invention is as follows.

[0185] <1> A method for manufacturing a laminated structure, comprising a substrate and a cured material, the method comprising:

[0186] The coating process involves applying the curable composition to the aforementioned substrate; and

[0187] The curing process involves curing the curable composition coated on the substrate at an ambient temperature below 10°C to form the cured product.

[0188] The above-mentioned curable composition contains the following (A) and (B):

[0189] (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds.

[0190] (B) 10 to 200 parts by weight of compounds with a hydroxyl value of less than 100 mg KOH / g and containing an ethylene glycol unit.

[0191] <2> According to the manufacturing method of the stacked structure described in <1>, wherein,

[0192] The molecular weight of (B) above is 200 to 10,000.

[0193] <3> The manufacturing method of the laminated structure according to <1> or <2>, wherein,

[0194] The above-mentioned curable composition further comprises an organotin compound as a curing catalyst.

[0195] <4> The method for manufacturing a laminated structure according to any one of <1> to <3>, wherein,

[0196] The above coating process is carried out at an ambient temperature below 10°C.

[0197] <5> A method for manufacturing a laminated structure according to any one of <1> to <4>, wherein,

[0198] The aforementioned substrate is metal.

[0199] <6> A method for manufacturing a laminated structure according to any one of <1> to <5>, wherein,

[0200] The aforementioned substrate is a substrate for interior panels, a substrate for exterior panels, or a substrate for vehicle panels.

[0201] <7> An adhesive method, the method comprising:

[0202] The process of bonding a substrate to a curing composition at an ambient temperature below 10°C.

[0203] The curable composition contains the following (A) and (B):

[0204] (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds.

[0205] (B) 10 to 200 parts by weight of compounds with a hydroxyl value of less than 100 mg KOH / g and containing an ethylene glycol unit.

[0206] <8> A laminated structure comprising a metal substrate and a cured material, wherein,

[0207] The cured product described above is a cured product obtained by curing a curable composition containing the following (A) and (B):

[0208] (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds.

[0209] (B) 10 to 200 parts by weight of compounds with a hydroxyl value of less than 100 mg KOH / g and containing an ethylene glycol unit.

[0210] <9> An adhesive or sealant for use in low-temperature environments, which is used at ambient temperatures below 10°C.

[0211] The adhesives or sealants used in low-temperature environments described above contain the following (A) and (B):

[0212] (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds.

[0213] (B) 10 to 200 parts by weight of compounds with a hydroxyl value of less than 100 mg KOH / g and containing an ethylene glycol unit.

[0214] Example

[0215] The present invention will now be described in more detail based on embodiments, but the present invention is not limited to these embodiments.

[0216] [Synthesis example 1]

[0217] Using a mixture of polyoxypropylene triol (molecular weight approximately 3000) and polyoxypropylene glycol (molecular weight approximately 3000) as initiators, propylene oxide was polymerized using a zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst to obtain polyoxypropylene with a number average molecular weight of approximately 19700 (the liquid delivery system used was an HLC-8120GPC manufactured by Tosoh Corporation, the chromatographic column used was a TSK-GEL H type manufactured by Tosoh Corporation, and THF was used as the solvent; the molecular weight of polystyrene was determined accordingly). Next, a methanol solution containing 1.2 equivalents of NaOMe relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene was added. The methanol was removed by distillation, and allyl chloride was further added to convert the terminal hydroxyl groups to allyl groups. 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene were mixed with 300 parts by weight of n-hexane and 300 parts by weight of water, and the water was removed by centrifugation to obtain a hexane solution. 300 parts by weight of water were further mixed and stirred into the obtained hexane solution, and the water was removed again by centrifugation. Then, the hexane was removed by vacuum devolatilization. This yielded a polyoxypropylene with allyl-terminated ends and a number-average molecular weight of approximately 19,700 based on GPC-converted polystyrene. Relative to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, 150 ppm of an isopropanol solution containing 3 wt% platinum of a vinylsiloxane platinum complex was used as a catalyst, and reacted with 1.3 parts by weight of methyldimethoxysilane at 90°C for 2 hours to obtain a silyl-containing organic polymer (A-1) with an average of approximately 1.7 methyldimethoxysilyl groups per molecule.

[0218] [Synthesis example 2]

[0219] Polypropylene glycol with a molecular weight of approximately 15,000 was used as an initiator, and propylene oxide was polymerized using a zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst to obtain polypropylene oxide with a number average molecular weight of approximately 30,000 (determined by the same method as described above). Next, a methanol solution containing 1.2 equivalents of NaOMe relative to the hydroxyl groups of the hydroxyl-terminated polypropylene oxide was added, the methanol was removed by distillation, and allyl chloride was further added to convert the terminal hydroxyl groups to allyl groups. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred relative to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide. The water was removed by centrifugation, and 300 parts by weight of water were further mixed into the resulting hexane solution and stirred. The water was removed again by centrifugation, and then the hexane was removed by vacuum devolatilization. Thus, polypropylene oxide with allyl groups at the end and a number average molecular weight of approximately 30,000 based on GPC polystyrene was obtained. Relative to 100 parts by weight of the obtained allyl-terminated polyoxypropylene, a solution of isopropanol containing 3 wt% platinum of vinylsiloxane platinum complex at 150 ppm was reacted with 0.96 parts by weight of methyldimethoxysilane at 90 °C for 2 hours to obtain a polyoxypropylene polymer (p-1) having an average of about 1.6 methyldimethoxysilyl groups per molecule.

[0220] A mixed solution containing 122g of n-butyl acrylate, 29g of methyl methacrylate, 30g of stearate methacrylate, 9g of 3-methacryloyloxypropylmethyldimethoxysilane, and 46g of isobutanol was prepared in a flask, further dissolving 2.6g of azobisisobutyronitrile (AIB) as a polymerization initiator. In a separable flask equipped with a stirrer, thermometer, and nitrogen inlet, 88g of isobutanol was added, and the mixture was heated to 105°C. Nitrogen gas was bubbled into the flask to purge the system, and then, while stirring, the monomer mixture was added dropwise over 4 hours for a further 2-hour post-polymerization. The resulting acrylic polymer p-2 containing methyldimethoxysilane was a 60% solids isobutanol solution with a number-average molecular weight (Mn) of 18000 based on GPC (same as above) for polystyrene. Based on the amount and average molecular weight of 3-methacryloyloxypropylmethyldimethoxysilane, an average of 2.0 methyldimethoxysilane molecules were introduced per molecule of the acrylic polymer (p-2).

[0221] The methyl dimethoxysilyl-terminated polyoxypropylene polymer (p-1) obtained above was mixed with an isobutanol solution of an acrylic polymer (p-2) containing methyl dimethoxysilyl at a solids ratio (weight ratio) of 70 / 30. Isobutanol was then devolatilized using a rotary evaporator under heating at 110°C and reduced pressure to obtain an organic polymer (A-2) containing silyl with a solids concentration of over 99%.

[0222] 〔Material〕

[0223] ((A) ingredient)

[0224] • Organic polymers containing silane (A-1) and (A-2): using compounds synthesized in the synthesis examples (component (B)).

[0225] • Tetraethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), hydroxyl value: 0.06 mg KOH / g, molecular weight: 222.3

[0226] ·OXSOFT 3G8: Triethylene glycol di(2-ethylhexanoate) (manufactured by OXEA), molecular weight: 402.6

[0227] Plasthall 190: Bis(2-(2-butoxyethoxy)ethoxy)methane (manufactured by Hallstar), hydroxyl value: 2.58 mg KOH / g, molecular weight: 336.5

[0228] (Other liquid compounds (liquid compounds that do not belong to component (B))

[0229] Tetraethylene glycol: Manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl value: 614 mg KOH / g

[0230] • Dipropylene glycol monopropyl ether: DOWANOL DPnP (manufactured by Andoh Parachemie)

[0231] • Polypropylene glycol: Molecular weight 2000 (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.), hydroxyl value: 56 mg KOH / g

[0232] • Diisononyl phthalate: DINP (manufactured by J-PLUS)

[0233] (Other ingredients)

[0234] Colloidal calcium carbonate: Bai Yanhua CCR (manufactured by Baishi Kogyo Co., Ltd.)

[0235] • Heavy calcium carbonate: Whiton SB (manufactured by White Stone Calcium Co., Ltd.)

[0236] Pigment: Tipaque R820 (manufactured by Ishihara Sangyo Co., Ltd.)

[0237] • Thixotropic agent: Disparlon 6500 (manufactured by Kusumoto Chemical Co., Ltd.)

[0238] • Light stabilizer: Tinuvin 770 (manufactured by BASF Japan)

[0239] • UV absorber: Tinuvin 326 (manufactured by BASF Japan)

[0240] • Dehydrating agents: A171, vinyltrimethoxysilane (manufactured by Momentive Performance Materials)

[0241] • Tackifiers: A1120, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials)

[0242] • Curing catalyst: NEOSTANN U220H (manufactured by Nitto Kasei Corporation)

[0243] [Example 1]

[0244] The organic polymer containing silyl group (A-1), tetraethylene glycol dimethyl ether, diisononyl phthalate, colloidal calcium carbonate, heavy calcium carbonate, pigment, thixotropic agent, light stabilizer, and ultraviolet absorber are mixed in the proportions recorded in Table 1. After thorough mixing, the mixture is dispersed by passing it through a three-roll coating mill three times.

[0245] Next, the mixture was dehydrated under reduced pressure at 120°C for 2 hours and then cooled to below 50°C. Then, the dehydrating agent, thickener, and curing catalyst were added according to the proportions listed in Table 1 and the mixture was kneaded. The kneading was carried out until the mixture was substantially free of moisture. Finally, the mixture was sealed in a moisture-proof container to obtain a single-component curable composition.

[0246] [Example 2]

[0247] A single-agent curable composition was obtained in the same manner as in Example 1, except that an organic polymer containing silane (A-2) was used instead of an organic polymer containing silane (A-1).

[0248] [Example 3]

[0249] Using OXSOFT 3G8 as component (B), the amounts of each component were set to the proportions recorded in Table 1. Otherwise, a single-agent curable composition was obtained in the same manner as in Example 1.

[0250] [Example 4]

[0251] The amounts of each component were set to the proportions recorded in Table 1. Otherwise, a single-agent curable composition was obtained in the same manner as in Example 3.

[0252] [Example 5]

[0253] Using Plasthall 190 as component (B), the amounts of each component were set to the proportions recorded in Table 1. Otherwise, a single-agent curable composition was obtained in the same manner as in Example 1.

[0254] [Comparative Example 1]

[0255] Using tetraethylene glycol instead of component (B), and setting the amounts of each component to the proportions listed in Table 1, a single-agent curable composition was obtained in the same manner as in Example 1.

[0256] [Comparative Example 2]

[0257] Using dipropylene glycol monopropyl ether instead of component (B), and setting the amounts of each component to the proportions listed in Table 1, a single-agent curable composition was obtained in the same manner as in Example 1.

[0258] [Comparative Example 3]

[0259] Using polypropylene glycol instead of component (B), and setting the amounts of each component to the proportions listed in Table 1, a single-agent curable composition was obtained in the same manner as in Example 1.

[0260] [Comparative Example 4]

[0261] By replacing component (B) with diisononyl terephthalate and setting the amounts of each component as described in Table 1, a single-agent curable composition was obtained in the same manner as in Example 1.

[0262] [Physical Property Evaluation]

[0263] (Determination of hydroxyl value)

[0264] 1,4-bis(trifluoromethyl)benzene was used as an internal standard for 1H NMR determination, and the hydroxyl value of component (B) was calculated based on the integral value of the signal from the hydroxyl group.

[0265] The apparatus and measurement conditions are described below.

[0266] Device Name: Bruker Japan AVANCE III HD500 NMR Device

[0267] Solvent: Deuterated chloroform

[0268] Measurement conditions: Pulse angle 90°, relaxation time 30 seconds

[0269] (Surface curing time)

[0270] The curable composition was spread to a thickness of approximately 3 mm using a spatula at 23°C and 50% RH. The small spatula was brought into contact with the surface of the mixture at regular intervals to confirm the time until the mixture no longer adhered to the spatula.

[0271] (Adhesion properties under low-temperature curing)

[0272] Anodized aluminum, electrolytically colored aluminum, and the curing composition, after being placed overnight in a dryer set at 5°C, were transported to a constant temperature chamber at 23°C and 50% RH. The curing composition was then spread onto each substrate to form a rectangle approximately 30 mm long, 15 mm wide, and 10 mm thick, and pressed to ensure tight adhesion to the substrate. It was immediately placed back into the 5°C dryer and removed after 7 days. A test was conducted to peel the cured material by hand at a 90-degree angle. The adhesion between the substrate and the cured material was evaluated after peeling.

[0273] (Adhesion properties at room temperature)

[0274] All were evaluated in the same way as the above (adhesion under low temperature curing) in a constant temperature chamber at 23°C and 50% RH.

[0275] <Evaluation of Adhesion>

[0276] After the peel test, the damage state of the cured product was observed, and any cases of cohesive failure (CF), interfacial failure (AF), and uncured (M) were evaluated. In Table 1 below, 100% cohesive failure is defined as CF, 100% interfacial failure as AF, and uncured product as M100. Alternatively, for example, a case with 40% cohesive failure, 40% interfacial failure, and 20% of the cured composition being uncured is defined as C40A40M20. Cohesive failure refers to the destruction of the cured product itself; a higher proportion of cohesive failure generally indicates better adhesion of the cured product to the substrate. On the other hand, interfacial failure refers to the destruction of the bond between the cured product and the substrate; a higher proportion of interfacial failure generally indicates poorer adhesion of the cured product to the substrate. Furthermore, "leakage" refers to the seepage of liquid cured composition to the surface of the cured product.

[0277] The composition of the single-component curable compositions in Examples 1-5 and Comparative Examples 1-4 is shown in Table 1. In addition, the results of the surface curing time and adhesion test in Examples 1-5 and Comparative Examples 1-4 are shown in Table 2.

[0278] [surface

[0279]

[0280] Table 2

[0281]

[0282] 〔result〕

[0283] According to Table 1, in terms of peel test results and any aspect at room temperature and low temperature, the cured products of Examples 1-5 showed a high proportion of cohesive failure. On the other hand, the cured product of Comparative Example 1 completely leaked. Furthermore, although the cured products of Comparative Examples 2 and 3 showed cohesive failure at room temperature, they showed interfacial failure at low temperature. Additionally, Comparative Example 4 did not cure at low temperature. Based on the above results, the present curable composition exhibits excellent adhesion to substrates under any conditions at room temperature and low temperature.

[0284] Industrial applicability

[0285] According to this manufacturing method, a laminated structure with sufficient adhesion even in low-temperature environments can be obtained, which can be preferably used in fields such as interior panel materials, exterior panel materials, vehicle panel materials, vibration damping materials, sound insulation materials, foaming materials, coatings, spraying materials, adhesives, and sealing materials.

Claims

1. A method for manufacturing a laminated structure, comprising a substrate and a cured material, the method comprising: The coating process involves applying the curable composition to the substrate. as well as The curing process involves curing the curable composition coated on the substrate at an ambient temperature below 10°C to form the cured product. The substrate is a metal substrate. The curable composition contains the following (A) and (B): (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds. (B) 40-60 parts by weight of a compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit, wherein the compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit is tetraethylene glycol dimethyl ether or bis(2-(2-butoxyethoxy)ethoxy)methane.

2. The method for manufacturing a laminated structure according to claim 1, wherein, The molecular weight of (B) is 200~10000.

3. The method for manufacturing a laminated structure according to claim 1, wherein, The curable composition further comprises an organotin compound as a curing catalyst.

4. The method for manufacturing a laminated structure according to claim 1, wherein, The coating process is carried out at an ambient temperature below 10°C.

5. The method for manufacturing a laminated structure according to claim 1, wherein, The substrate is a substrate for interior panels, a substrate for exterior panels, or a substrate for vehicle panels.

6. An adhesive bonding method, the method comprising: The process of bonding a substrate to a curing composition at an ambient temperature below 10°C. The substrate is a metal substrate. The curable composition contains the following (A) and (B): (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds. (B) 40-60 parts by weight of a compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit, wherein the compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit is tetraethylene glycol dimethyl ether or bis(2-(2-butoxyethoxy)ethoxy)methane.

7. A laminated structure comprising a metal substrate and a cured material, wherein, The cured product is a cured product obtained by curing a curable composition containing the following (A) and (B): (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds. (B) 40-60 parts by weight of a compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit, wherein the compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit is tetraethylene glycol dimethyl ether or bis(2-(2-butoxyethoxy)ethoxy)methane.

8. An adhesive or sealant for metal substrates used in low-temperature environments, which is applied at ambient temperatures below 10°C. The adhesive or sealant for low-temperature environments contains the following (A) and (B): (A) 100 parts by weight of an organic polymer containing silicon-containing groups capable of crosslinking through the formation of siloxane bonds. (B) 40-60 parts by weight of a compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit, wherein the compound with a hydroxyl value less than 100 mg KOH / g and having an ethylene glycol unit is tetraethylene glycol dimethyl ether or bis(2-(2-butoxyethoxy)ethoxy)methane.

Images