Hardening components

Abstract

The present invention addresses the problem of providing a new curable composition having excellent initial fixing properties. A curable composition comprising: 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group; 10-500 parts by weight of a polyvinylchloride resin (B); and 150-500 parts by weight of calcium carbonate (C), wherein the most frequent size of the polyvinylchloride resin (B) is 0.1-0.5 μm.

Description

[Technical Field]

[0001] The present invention relates to a curable composition. [Background technology]

[0002] It is known that "organic polymers having hydrolyzable silicon groups" have the property of being able to crosslink even at room temperature through the formation of siloxane bonds accompanied by the hydrolysis reaction of the hydrolyzable silicon groups due to moisture, etc., thereby yielding rubber-like cured products. Polyoxyalkylene polymers having hydrolyzable silicon groups are already produced industrially and are widely used as raw material resins for applications such as sealants, adhesives, and paints.

[0003] For example, Patent Document 1 discloses a curable composition comprising 100 parts by weight of an organic polymer having at least one hydrolyzable silicon group in the molecule and 10 to 500 parts by weight of a vinyl resin.

[0004] Patent Document 2 discloses a curable composition containing 100 parts by weight of an organic polymer having at least one hydrolyzable silicon group in the molecule, 10 to 500 parts by weight of a vinyl resin, and 1 to 150 parts by weight of a polymer plasticizer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 63-225654 [Patent Document 2] Japanese Patent Application Publication No. 2-102237 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the above-mentioned conventional techniques are not sufficient from the viewpoint of initial fixation, and there is room for further improvement.

[0007] One embodiment of the present invention has been made in consideration of the above-mentioned problems, and an object of the invention is to provide a novel curable composition that is excellent in initial fixation properties. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have independently discovered that a curable composition containing specific amounts of an organic polymer having a hydrolyzable silicon group, calcium carbonate, and a polyvinyl chloride resin having a specific mode diameter has excellent initial fixation properties, leading to the completion of the present invention.

[0009] That is, a curable composition according to one embodiment of the present invention contains 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 to 500 parts by weight of a polyvinyl chloride resin (B), and 150 to 500 parts by weight of calcium carbonate (C), and the polyvinyl chloride resin (B) has a mode diameter of 0.10 μm to 0.50 μm. [Effects of the Invention]

[0010] According to one embodiment of the present invention, it is possible to provide a novel curable composition that is excellent in initial fixation property. DETAILED DESCRIPTION OF THE INVENTION

[0011] One embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the respective configurations described below, and various modifications are possible within the scope of the claims. Furthermore, embodiments or examples obtained by appropriately combining the technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. All academic literature and patent documents described in this specification are incorporated herein by reference. Furthermore, unless otherwise specified in this specification, the term "A to B" representing a numerical range means "greater than or equal to A (including and greater than A) and less than or equal to B (including and less than B)."

[0012] 1. Technical Concept of One Embodiment of the Present Invention The present inventors have conducted extensive research in order to develop a curable composition having excellent initial fixability, for example, an adhesive having excellent initial fixability.

[0013] Adhesives with excellent initial fixability are sometimes called high-tack adhesives. Adhesives with excellent initial fixability exhibit excellent fixability (adhesion) even immediately after being removed from a container. Therefore, adhesives with excellent initial fixability are suitable for use in the construction of building interiors, for example, when fixing heavy glass plates or decorative panels to vertical surfaces such as wall surfaces.

[0014] The initial fixability of a curable composition can be affected not only by the viscosity of the curable composition but also by its thixotropy. That is, in order to improve the initial fixability of a curable composition, it is necessary to achieve both the viscosity and thixotropy of the curable composition, and simply increasing the viscosity of the curable composition is not sufficient. Therefore, in order to improve the initial fixability of a curable composition, extensive consideration is required both qualitatively and quantitatively.

[0015] As described above, the techniques described in Patent Documents 1 and 2 were insufficient in terms of initial fixation, and there was room for further improvement. In other words, the techniques described in Patent Documents 1 and 2 were not techniques related to Hi-Tack adhesives, and did not provide useful information for developing an adhesive with excellent initial fixation, as desired by the present inventors. Therefore, the present inventors conducted extensive research to develop an adhesive with excellent initial fixation without relying on the techniques described in Patent Documents 1 and 2. As a result, the present inventors independently discovered the following, which led to the completion of the present invention: a curable composition containing specific amounts of an organic polymer having a hydrolyzable silicon group, calcium carbonate, and a polyvinyl chloride resin having a specific mode diameter, each of which exhibits excellent initial fixation.

[0016] [2. Curable composition] A curable composition according to one embodiment of the present invention contains 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 to 500 parts by weight of a polyvinyl chloride resin (B), and 150 to 500 parts by weight of calcium carbonate (C), wherein the polyvinyl chloride resin (B) has a mode diameter of 0.10 μm to 0.50 μm.

[0017] In this specification, the "curable composition according to one embodiment of the present invention" may be referred to hereinafter as the "curable composition", and the "organic polymer (A) having a hydrolyzable silicon group" may be referred to hereinafter as the "organic polymer (A)".

[0018] Because of the above-described structure, the present curable composition has the advantage of excellent initial fixation. Furthermore, because of the above-described structure, the present curable composition also has the advantage of excellent storage stability. Furthermore, because of the above-described structure, the present curable composition can provide a curable composition that is excellent in initial fixation even when the amount of organic polymer (A) is small. Therefore, the present curable composition also has the advantage of being inexpensive and economical.

[0019] [2-1.Organic polymer (A)] The organic polymer (A) is a polymer containing a hydrolyzable silicon group at the molecular end. The hydrolyzable silicon group is a functional group in which a reactive group such as an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, an amide group, or an oxime group is bonded to a silicon group (Si group). The "hydrolyzable silicon group" is also sometimes called a "reactive silicon group," a "crosslinkable silicon group," a "hydrolyzable silyl group," a "reactive silyl group," or a "crosslinkable silyl group."

[0020] Specific examples of hydrolyzable silicon group include, but are not limited to, trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, and (N,N-diethylaminomethyl)diethoxysilyl group.Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, and (methoxymethyl)diethoxysilyl group show high activity, and can obtain cured material with good mechanical properties, so are preferred. Particularly preferred are trimethoxysilyl, (chloromethyl)dimethoxysilyl, and (methoxymethyl)dimethoxysilyl groups because they exhibit high activity. Particularly preferred are methyldimethoxysilyl, methyldiethoxysilyl, and triethoxysilyl groups because they are highly stable. Particularly preferred are methyldiethoxysilyl and triethoxysilyl groups because they are highly safe. Particularly preferred are trimethoxysilyl, triethoxysilyl, and dimethoxymethylsilyl groups because they are easy to produce.

[0021] The organic polymer (A) preferably has an average of 1.2 to 5.0 hydrolyzable silicon groups per molecule, more preferably 1.2 to 4.0, and even more preferably 1.2 to 3.0. When the organic polymer (A) has an average of 1.2 or more hydrolyzable silicon groups per molecule, a curable composition with good curability can be provided. Therefore, the cured product that can be provided by the curable composition has good rubber elasticity, and the cured product has good recovery, durability, and / or creep resistance. The hydrolyzable silicon groups may be located at the main chain terminals or side chain terminals of the organic polymer (A), or may be located at both the main chain terminals and the side chain terminals. In particular, when the hydrolyzable silicon groups are located only at the main chain terminals of the organic polymer (A), the effective network length in the final cured product is increased, making it easier to obtain a rubbery cured product that exhibits high strength, high elongation, and a low elastic modulus.

[0022] The hydrolyzable silicon group can be introduced into the organic polymer by a known method, such as the following methods I to III.

[0023] Method I: An organic polymer having functional groups such as hydroxyl groups is reacted with a compound having an unsaturated group and an active group reactive with the functional group to obtain an organic polymer having unsaturated groups. The resulting organic polymer having unsaturated groups is then reacted with a hydrosilane compound having a hydrolyzable silicon group by hydrosilylation.

[0024] Examples of the compound having an unsaturated group and an active group reactive with the functional group used in Method I include unsaturated group-containing epoxy compounds such as allyl chloride, methallyl chloride, and allyl glycidyl ether.

[0025] Examples of the hydrosilane compound used in Method I include, but are not limited to, halogenated silanes, alkoxysilanes, acyloxysilanes, and ketoximate silanes.

[0026] Examples of halogenated silanes include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.

[0027] Examples of alkoxysilanes include dialkoxysilanes and trialkoxysilanes. More specific examples of alkoxysilanes include trimethoxysilane, triethoxysilane, triisopropoxysilane, 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, diethoxymethylsilane, dimethoxymethylsilane, and phenyldimethoxysilane.

[0028] Examples of acyloxysilanes include methyldiacetoxysilane and phenyldiacetoxysilane.

[0029] Examples of ketoximate silanes include bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate)methylsilane, and the like.

[0030] Among these hydrosilane compounds, from the viewpoints of (a) ease of proceeding of the hydrosilylation reaction and (b) an excellent balance between the storage stability and hydrolysis rate of the obtained reaction product, dialkoxysilanes and trialkoxysilanes are preferred, and dimethoxymethylsilane, trimethoxysilane, and triethoxysilane are more preferred.

[0031] Method II: A method in which a compound having a mercapto group and a hydrolyzable silicon group is introduced into the unsaturated group site of an organic polymer having an unsaturated group obtained in the same manner as in Method I by a radical addition reaction in the presence of a radical initiator and / or a radical generating source.

[0032] Examples of compounds having a mercapto group and a hydrolyzable silicon group used in Method II include, but are not limited to, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane.

[0033] Method III: An organic polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group in the molecule is reacted with a compound having a hydrolyzable silicon group and a functional group reactive with the functional group.

[0034] Among the methods III, examples of the method of reacting an organic polymer having a hydroxyl group with a compound having an isocyanate group reactive to a hydrolyzable silicon group and a hydroxyl group include, but are not limited to, the method disclosed in Japanese Patent Laid-Open No. 3-47825.

[0035] Examples of compounds having an isocyanate group reactive with a hydrolyzable silicon group and a hydroxyl group used in Method III include, but are not limited to, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, and isocyanatemethyldimethoxymethylsilane.

[0036] Among the above-mentioned methods I and III, the method of reacting an organic polymer having a terminal hydroxyl group with a compound having a hydrolyzable silicon group and an isocyanate group reactive with a hydroxyl group is preferred because it can achieve a high conversion rate in a relatively short reaction time. On the other hand, the organic polymer having a hydrolyzable silicon group obtained by method I has a lower viscosity than the organic polymer having a hydrolyzable silicon group obtained by method III, and a curable composition with good workability can be obtained. In addition, the organic polymer having a hydrolyzable silicon group obtained by method II may have a strong odor due to the mercaptosilane. For this reason, method I is particularly preferred.

[0037] The main chain skeleton (also simply referred to as the main chain) of the organic polymer (A) is not particularly limited. Examples of the main chain skeleton of the organic polymer (A) include (a) polyoxyalkylene polymers containing repeating units derived from alkylene oxides, (b) ether / ester block copolymers, (c) vinyl polymers containing repeating units derived from vinyl monomers, and (d) diene polymers containing repeating units derived from diene monomers. Among these, the main chain skeleton of the organic polymer (A) preferably contains a polyoxyalkylene polymer, and more preferably is a polyoxyalkylene polymer. This configuration provides the curable composition with the advantage of exhibiting good adhesion to various types of adherends (sometimes referred to as substrates or adherends).

[0038] Examples of repeating units contained in the polyoxyalkylene polymer include polyoxyethylene units, polyoxypropylene units, and polyoxybutylene units, and preferably polyoxypropylene units. The repeating units contained in the polyoxyalkylene polymer may be (a) one or more types selected from the group consisting of polyoxyethylene units, polyoxypropylene units, and polyoxybutylene units, or (b) one or more types of polyoxyalkylene units other than those in the above group.

[0039] Examples of methods for synthesizing polyoxyalkylene polymers include (a) a polymerization method using an alkali catalyst such as KOH, (b) a polymerization method using a transition metal compound-porphyrin complex catalyst, such as the complex obtained by reacting an organoaluminum compound with porphyrin, as disclosed in Japanese Patent Laid-Open No. 61-215623, and (c) methods disclosed in Japanese Patent Publication Nos. 46-27250, 59-15336, U.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, and 3,427,272. Examples of suitable synthesis methods include, but are not limited to, (a) a polymerization method using a composite metal cyanide complex catalyst (e.g., a zinc hexacyanocobaltate glyme complex catalyst) as disclosed in US Pat. No. 56, US Pat. No. 3,427,334, and US Pat. No. 3,427,335, (b) a polymerization method using a catalyst made of a polyphosphazene salt as disclosed in JP-A-10-273512, and (c) a polymerization method using a catalyst made of a phosphazene compound as disclosed in JP-A-11-060722. Among these synthesis methods, the polymerization method in which an alkylene oxide is reacted with an initiator in the presence of a composite metal cyanide complex catalyst is preferred because it can produce a polymer with a narrow molecular weight distribution.

[0040] The composite metal cyanide complex catalyst is Zn3[Co(CN)6] 2 (zinc hexacyanocobaltate complex), etc. Also usable are catalysts in which alcohols and / or ethers are coordinated as organic ligands to zinc hexacyanocobaltate complexes, etc.

[0041] The initiator is preferably a "compound having at least one active hydrogen group" (hereinafter also referred to as an "active hydrogen-containing compound"). Examples of the active hydrogen-containing compound include (a) alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, and hexanol, and (b) linear and / or branched polyether compounds having a number average molecular weight of 500 to 20,000.

[0042] Examples of the alkylene oxide include ethylene oxide, propylene oxide, and isobutylene oxide.

[0043] The organic polymer (A) in one embodiment of the present invention may be either linear or branched. In one embodiment of the present invention, the organic polymer (A) is preferably a mixture of a linear organic polymer (A1) and a branched organic polymer (A2). This configuration provides the curable composition with the advantage of being able to provide a cured product that is excellent in both high shear strength and high elongation at break, i.e., a cured product (adhesive layer) that is resistant to impact and vibration and has excellent durability. In other words, when the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2), the resulting curable composition can be suitably used as an adhesive that is resistant to impact and vibration and has excellent durability.

[0044] In one embodiment of the present invention, the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2). In this case, the weight ratio of the linear organic polymer (A1) to the branched organic polymer (A2) in the organic polymer (A) (weight of organic polymer (A1) / weight of organic polymer (A2)) is not particularly limited, but is preferably 0.1 to 9.0, more preferably 0.3 to 5.0, even more preferably 0.4 to 4.0, and particularly preferably 1.0 to 3.0. This configuration provides the curable composition with the advantage of providing a cured product that is excellent in both high shear strength and high elongation at break. In other words, it is possible to provide a cured product (adhesive layer) that is resistant to impact and vibration and has excellent durability.

[0045] The number-average molecular weight (Mn) of the organic polymer (A) is a value measured by gel permeation chromatography (GPC) (polystyrene equivalent) and is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 35,000. If the number-average molecular weight is (a) less than 1,000, the cured product tends to have insufficient elongation, and (b) if it exceeds 100,000, the curable composition tends to have high viscosity, which can be inconvenient in terms of workability. The molecular weight distribution (Mw / Mn) of the organic polymer (A) measured by GPC is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and most preferably 1.2 or less.

[0046] Commercially available organic polymers (A) can be used. For example, (a) Kaneka MS Polymer and Kaneka Silyl, manufactured by Kaneka Corporation, (b) Excestar, manufactured by AGC Corporation, and (c) GENIOSIL, manufactured by Wacker, are already manufactured and sold for industrial use and can be easily obtained and used as the organic polymer (A).

[0047] The content of the organic polymer (A) in the present curable composition is not particularly limited. The content of the organic polymer (A) in the present curable composition is preferably 10 wt% to 25 wt%, more preferably 11 wt% to 24 wt%, more preferably 12 wt% to 23 wt%, even more preferably 13 wt% to 22 wt%, still more preferably 14 wt% to 21 wt%, and particularly preferably 15 wt% to 20 wt%, based on 100 wt% of the curable composition. This configuration makes the curable composition inexpensive, which has the advantage of being economically excellent.

[0048] [2-2. Polyvinyl chloride resin (B)] In this specification, the term "polyvinyl chloride resin" refers to a resin having 50 mol % or more of structural units derived from vinyl chloride out of 100 mol % of structural units constituting the resin.

[0049] As a result of extensive research, the present inventors have independently discovered the following: (a) when the curable composition contains polyvinyl chloride resin (B), the thixotropy of the curable composition can be improved without a significant increase in the viscosity of the curable composition; and (b) when the curable composition contains polyvinyl chloride resin (B) and calcium carbonate, the curable composition exhibits rheological behavior suitable for a Hi-Tack adhesive over a wide range of organic polymer (A) concentrations.

[0050] The polyvinyl chloride resin (B) may be (a) a vinyl chloride homopolymer composed only of structural units derived from vinyl chloride, or (b) a copolymer of vinyl chloride and a monomer other than vinyl chloride that is copolymerizable with vinyl chloride (hereinafter also referred to as monomer A). The polyvinyl chloride resin (B) may have structural units derived from vinyl chloride and structural units derived from monomer A.

[0051] Examples of the monomer A include vinyl acetate, vinylidene chloride, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, maleic acid, maleic acid esters, and acrylonitrile.

[0052] The degree of polymerization of the polyvinyl chloride resin (B) is not particularly limited, but for example, the average degree of polymerization is preferably 200 to 10,000, more preferably 300 to 4,000.

[0053] In this specification, the "modal diameter of polyvinyl chloride resin (B)" refers to the modal diameter obtained when the particle diameters of primary particles of polyvinyl chloride resin (B) are expressed as a frequency distribution on a volume basis. The "modal diameter" is also sometimes referred to as the "mode diameter." The modal diameter of primary particles of polyvinyl chloride resin (B) can be obtained, for example, by measuring a sample of latex containing polyvinyl chloride resin (B) obtained during the production process of polyvinyl chloride resin (B) using a disc centrifugal particle size distribution analyzer (CPS Disc Centrifuge, manufactured by CPS Instruments). In other words, the "modal diameter of polyvinyl chloride resin (B)" can also be said to be the "modal diameter of primary particles of polyvinyl chloride resin (B) before drying."

[0054] The mode diameter of the polyvinyl chloride resin (B) is 0.10 μm to 0.50 μm, preferably 0.11 μm to 0.48 μm, more preferably 0.12 μm to 0.46 μm, more preferably 0.13 μm to 0.44 μm, more preferably 0.14 μm to 0.42 μm, more preferably 0.15 μm to 0.40 μm, more preferably 0.16 μm to 0.39 μm, even more preferably 0.17 μm to 0.38 μm, and particularly preferably 0.18 μm to 0.37 μm. This configuration provides the curable composition with the advantages of excellent initial fixation and storage stability.

[0055] In particular, when the polyvinyl chloride resin (B) has a mode diameter of 0.50 μm or less, the curable composition has the advantage of having excellent storage stability. This is presumed to be due to the following, but one embodiment of the present invention is not limited to the following presumption: As the mode diameter of the polyvinyl chloride resin (B) increases, the polyvinyl chloride resin (B) aggregates break down during storage of the curable composition, and the broken down polyvinyl chloride resin (B) is more uniformly dispersed throughout the curable composition. Consequently, it is presumed that the larger the mode diameter of the polyvinyl chloride resin (B), the greater the effect of increasing the viscosity of the curable composition due to hydrogen bonding. In other words, it is presumed that the larger the mode diameter of the polyvinyl chloride resin (B), the greater the tendency for the viscosity of the curable composition after storage to increase. On the other hand, as the mode diameter of the polyvinyl chloride resin (B) decreases, the polyvinyl chloride resin (B) is already dispersed in the curable composition in a form similar to primary particles before storage. Consequently, it is presumed that the viscosity change of the curable composition before and after storage is small.

[0056] The method for producing the polyvinyl chloride resin (B) is not particularly limited. Polymerization methods such as emulsion polymerization and fine suspension polymerization are preferably used as the method for producing the polyvinyl chloride resin (B). Among these, emulsion polymerization is more preferably used because it is easy to control the primary particle size of the polyvinyl chloride resin (B) to a small size. Furthermore, the polyvinyl chloride resin (B) can be obtained by drying the latex obtained after polymerization of the polyvinyl chloride resin by spray drying, fluidized bed drying, or the like.

[0057] The content of polyvinyl chloride resin (B) in the curable composition is 10 to 500 parts by weight, preferably 20 to 450 parts by weight, more preferably 30 to 400 parts by weight, more preferably 40 to 350 parts by weight, even more preferably 50 to 300 parts by weight, still more preferably 60 to 250 parts by weight, and particularly preferably 70 to 200 parts by weight, relative to 100 parts by weight of organic polymer (A). This configuration provides the curable composition with the advantage of superior initial fixability.

[0058] [2-3. Calcium carbonate (C)] Calcium carbonate (C) can function as a filler in the curable composition. Examples of fillers include, in addition to calcium carbonate, known general-purpose fillers such as kaolin, aluminum hydroxide, aluminum oxide, fume silica, silica powder, glass filler, carbon black, hollow filler, and barium sulfate. Compared to curable compositions that do not contain calcium carbonate (C) as a filler but contain other general-purpose fillers, the curable composition containing calcium carbonate (C) as a filler has the advantage of being excellent in flexibility and / or adhesion to various adherends. The curable composition may further contain, in addition to calcium carbonate (C), one of the above-mentioned general-purpose fillers other than calcium carbonate (C).

[0059] There are no particular limitations on the calcium carbonate (C), and examples include (a) colloidal calcium carbonate produced by introducing CO gas into a water slurry of Ca(OH) , (b) heavy calcium carbonate obtained by mechanically crushing and classifying limestone, and (c) colloidal calcium carbonate (sometimes called precipitated calcium carbonate). Generally, colloidal calcium carbonate and colloidal calcium carbonate have smaller volume average particle diameters than heavy calcium carbonate.

[0060] The BET specific surface area of ​​calcium carbonate (C) is 1m 2 / g~100m 2 / g, and 2m 2 / g~80m 2 / g, more preferably 5m 2 / g~50m 2 / g. It is more preferable that the BET specific surface area of ​​calcium carbonate (C) is 1 m 2 When the BET specific surface area of ​​calcium carbonate (C) is 100 m / g or more, the thixotropy of the curable composition is good. 2 / g or less, aggregation of calcium carbonate (C) particles in the hardenable composition is restricted, and the dispersibility of calcium carbonate (C) in the hardenable composition is improved. As a result, the BET specific surface area of ​​calcium carbonate (C) is 100 m 2 / g or less, the curable composition has good thixotropy. In this specification, the BET specific surface area of ​​calcium carbonate (C) is a value measured using a specific surface area measuring device (Macsorb HM model-1208 manufactured by Mountec Co., Ltd. or Flowsorb II2300 manufactured by Micromeritics).

[0061] The calcium carbonate (C) may be calcium carbonate that has been surface-treated with a surface treatment agent. The surface treatment agent is not particularly limited, but a preferred example is a fatty acid compound. The fatty acid compound is not particularly limited, but a preferred example is one or more selected from the group consisting of fatty acids, fatty acid salts, fatty acid derivatives, and salts of fatty acid derivatives.

[0062] The fatty acid is not particularly limited, but saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, etc. can be preferably used. Specific examples include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alaic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, obsiclic acid, caroleic acid, undecylenic acid, linderic acid, tsuzuic acid, physeteric acid, moristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, asclevic acid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid, erucic acid, brassidic acid, selacholeic acid, ximenic acid, lumecic acid, sorbic acid, linoleic acid, stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate, etc. These may be used alone or in combination of two or more. Of the above fatty acids, palmitic acid, stearic acid, and oleic acid are particularly preferred.

[0063] The method for producing the surface-treated calcium carbonate (C) is not particularly limited, and examples thereof include a method in which the above-mentioned calcium carbonate is surface-treated (coated) with the above-mentioned fatty acid compound, and then powdered through steps such as dehydration, drying, and pulverization according to a conventional method.

[0064] The content of calcium carbonate (C) in the curable composition is 150 to 500 parts by weight, preferably greater than 150 to 500 parts by weight, more preferably 160 to 500 parts by weight, more preferably 170 to 500 parts by weight, even more preferably 180 to 500 parts by weight, even more preferably 190 to 500 parts by weight, particularly preferably 200 to 500 parts by weight, and most preferably 250 to 500 parts by weight, per 100 parts by weight of the organic polymer (A). This configuration provides the curable composition with the advantage of superior initial fixability. Furthermore, by providing calcium carbonate (C) in an amount of 150 parts by weight or more, a curable composition with excellent initial fixability can be obtained, even when the organic polymer (A) content is low (e.g., 25% by weight or less). This results in the advantage of providing an inexpensive curable composition with excellent initial fixability. From the viewpoints of the initial fixability and production costs of the curable composition, the content of calcium carbonate (C) in the present curable composition may be 170 to 450 parts by weight, 180 to 400 parts by weight, 190 to 350 parts by weight, or 200 to 300 parts by weight, relative to 100 parts by weight of the organic polymer (A).

[0065] The present curable composition preferably uses a combination of two or more types of calcium carbonates having different volume average particle sizes as the calcium carbonate (C). The present curable composition preferably contains, as the calcium carbonate (C), for example, (a) calcium carbonate (C1) (e.g., colloidal calcium carbonate or colloidal calcium carbonate) having a volume average particle size of 0.01 μm or more and less than 0.50 μm, and (b) calcium carbonate (C2) (e.g., surface-untreated heavy calcium carbonate) having a volume average particle size of 0.50 μm to 10.00 μm.

[0066] The present curable composition contains, relative to 100 parts by weight of the organic polymer (A), (i) (a) 0 to 300 parts by weight of calcium carbonate (C1) having a volume average particle diameter of 0.01 μm or more and less than 0.50 μm, and (b) 0 to 500 parts by weight of calcium carbonate (C2) having a volume average particle diameter of 0.50 μm to 10.00 μm, (ii) more preferably comprises (a) 0 to 250 parts by weight of calcium carbonate (C1) having a volume average particle diameter of 0.03 μm to 0.40 μm, and (b) 100 to 500 parts by weight of calcium carbonate (C2) having a volume average particle diameter of 0.50 μm to 10.00 μm, (iii) more preferably comprises (a) 0 to 200 parts by weight of calcium carbonate (C1) having a volume average particle diameter of 0.05 μm to 0.20 μm, and (b) 150 to 500 parts by weight of calcium carbonate (C2) having a volume average particle diameter of 0.60 μm to 9.00 μm, (iv) It is particularly preferable that the composition contains (a) 0 to 150 parts by weight of calcium carbonate (C1) having a volume average particle diameter of 0.05 μm to 0.15 μm, and (b) 150 to 500 parts by weight of calcium carbonate (C2) having a volume average particle diameter of 0.70 μm to 5.00 μm. According to this configuration, the curable composition has the advantages of (a) superior initial fixation and (b) ease of handling due to ease of discharge from a storage container. In this specification, the volume-average particle diameter of calcium carbonate (C) is a value obtained by measurement using a laser light diffraction scattering method. The term "volume-average particle diameter" is also synonymous with "d50 particle diameter."

[0067] In the calcium carbonate (C), the ratio of the weight of calcium carbonate (C1) to the weight of calcium carbonate (C2) (weight of calcium carbonate (C1) / weight of calcium carbonate (C2)) is not particularly limited, but is, for example, preferably 1.0 or less, more preferably 0.9 or less, even more preferably 0.8 or less, and particularly preferably 0.7 or less.

[0068] The ratio ((B) / (C)) of the content of the polyvinyl chloride resin (B) to the content of the calcium carbonate (C) in the curable composition is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, even more preferably 0.2 to 0.6, and particularly preferably 0.2 to 0.5. This configuration offers the following advantages: (a) the dischargeability of the curable composition is not impaired; (b) the curable composition has a low specific gravity; and (c) the heat resistance and / or weather resistance of the cured product are not impaired. That is, when (B) / (C) is within the above-mentioned range, the curable composition has the advantage of exhibiting good high-tack adhesiveness. Furthermore, a curable composition having a low specific gravity means that the curable composition is lighter than a curable composition having the same volume. Compared to a curable composition having a high specific gravity, a curable composition having a low specific gravity has the advantage of lower production costs, transportation costs, and storage costs.

[0069] [2-4. Dehydrating Agent (D)] The present curable composition may further contain a dehydrating agent (D) in addition to the organic polymer (A), the polyvinyl chloride resin (B), and the calcium carbonate (C). When the present curable composition contains the dehydrating agent (D), the curable composition has the advantage of excellent storage stability.

[0070] The dehydrating agent (D) is not particularly limited, but is preferably a substance that absorbs water and / or moisture. Examples of the dehydrating agent (D) include vinylsilane compounds, silicate compounds, calcium oxide, zeolite compounds, and methyl orthoformate. Among these, vinylsilane compounds and silicate compounds are preferred as the dehydrating agent (D), and vinylsilane compounds are more preferred. This configuration provides the curable composition with the advantage of having excellent storage stability.

[0071] Examples of vinylsilane compounds that can be used as the dehydrating agent (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinyldimethylpropoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldipropoxysilane, vinyldiethylmethoxysilane, vinyldiethylethoxysilane, vinyldiethylpropoxysilane, vinylpropyldimethoxysilane, vinylpropyldiethoxysilane, vinylpropyldipropoxysilane, vinyldipropylmethoxysilane, vinyldipropylethoxysilane, vinyldipropylpropoxysilane, methyl silicate, methyl silicate condensates, ethyl silicate, and ethyl silicate condensates. Among these, the vinylsilane compound that can be used as the dehydrating agent (D) is preferably a condensate of vinyltrimethoxysilane and ethyl silicate, and more preferably vinyltrimethoxysilane. This configuration provides the curable composition with the advantage of being even more excellent in storage stability.

[0072] The content of the dehydrating agent (D) in the present curable composition is not particularly limited. The content of the dehydrating agent (D) in the present curable composition is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight, and even more preferably 4 to 6 parts by weight, relative to 100 parts by weight of the organic polymer (A). This configuration has the advantage that the curable composition has better storage stability.

[0073] The amount of water (moisture content) in the present curable composition is not particularly limited, but a smaller amount is preferable because it results in better storage stability. The amount of water (moisture content) in the present curable composition is preferably 200 ppm to 10,000 ppm, more preferably 500 ppm to 8,000 ppm, even more preferably 1,000 ppm to 7,000 ppm, and particularly preferably 1,500 ppm to 6,000 ppm, per 100 parts by weight of the curable composition.

[0074] [2-5. Other ingredients] In addition to the above-mentioned components, the curable composition may contain other components as needed. The other components are not particularly limited, but examples thereof include the following substances: plasticizers, anti-sagging agents (sometimes called thixotropic agents), adhesion promoters, antioxidants, photocurable materials, hollow fillers, light stabilizers, solvents and / or diluents, ultraviolet absorbers, flame retardants, curing modifiers, lubricants, colorants, foaming agents, and mildew inhibitors.

[0075] Examples of plasticizers include epoxy compounds, phthalate ester compounds, and polyether compounds. Epoxy compounds include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Phthalate ester compounds include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, and bisbutylbenzyl phthalate. Polyether compounds include polyoxypropylene diol, polyethylene glycol, polyoxybutylene glycol, and copolymers of ethylene oxide and propylene oxide. These plasticizers may be used alone or in combination. When the present curable composition contains a plasticizer, the curable composition has the advantage of excellent adhesion to various adherend materials.

[0076] Examples of anti-sagging agents include polyamide waxes; hydrogenated castor oil and hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging agents may be used alone or in combination of two or more. When the curable composition contains an anti-sagging agent, the curable composition has the advantage of preventing sagging during application, i.e., improving the workability of the curable composition.

[0077] Examples of adhesion promoters include aminosilane compounds, epoxysilane compounds, isocyanatesilane compounds, and acrylicsilane compounds. Aminosilane compounds are preferred as adhesion promoters, with 3-(2-aminoethylamino)propyltrimethoxysilane being particularly preferred. These adhesion promoters may be used alone or in combination of two or more. When the curable composition contains an adhesion promoter, the curable composition has the advantage of improving adhesion to the adherend and increasing the strength of the cured product.

[0078] Examples of antioxidants include hindered phenol compounds, monophenol compounds, and polyphenol compounds. Hindered phenol compounds are particularly preferred as antioxidants. These antioxidants may be used alone or in combination of two or more. When the curable composition contains an antioxidant, it has the advantages of (a) retarding deterioration of the curable composition even when the curable composition is stored for a long period of time, and (b) maintaining the performance of the curable composition even when the curable composition is stored under high-temperature conditions.

[0079] Examples of the curing catalyst include organotin compounds, metal carboxylates, amine compounds, carboxylic acids, and alkoxy metals.

[0080] Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, a reaction product of dibutyltin oxide with a silicate compound, a reaction product of dioctyltin oxide with a silicate compound, and a reaction product of dibutyltin oxide with a phthalate ester.

[0081] Specific examples of the metal carboxylate include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, etc. As the metal carboxylate, salts obtained by appropriately combining the following carboxylic acids with various metals can also be used.

[0082] Specific examples of the amine compound include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; nitrogen-containing heterocyclic compounds such as pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine, and diphenylguanidine; biguanides such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide; amino group-containing silane coupling agents; and ketimine compounds.

[0083] Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

[0084] Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis(acetylacetonate) and diisopropoxytitanium bis(ethylacetoacetate); aluminum compounds such as aluminum tris(acetylacetonate) and diisopropoxyaluminum ethylacetoacetate; and zirconium compounds such as zirconium tetrakis(acetylacetonate).

[0085] Other curing catalysts (also called silanol condensation catalysts) that can be used include fluorine anion-containing compounds, photoacid generators, and photobase generators.

[0086] To enhance the activity of the curing catalyst, an amine compound may be used in combination with the curing catalyst, such as known amine compounds such as octylamine, decylamine, laurylamine, oleylamine, and di-n-octylamine.

[0087] Examples of colorants include pigments such as tin oxide, carbon black, titanium oxide, and red iron oxide.

[0088] [2-6.Initial fixation] The curable composition has excellent initial fixability. The method for measuring the initial fixability of the curable composition will be described in detail in the Examples.

[0089] The initial fixability of the curable composition is preferably greater than 100 g, more preferably 150 g or greater, more preferably 200 g or greater, more preferably 250 g or greater, more preferably 300 g or greater, more preferably 350 g or greater, more preferably 400 g or greater, even more preferably 450 g or greater, and particularly preferably 500 g or greater. This configuration has the advantage that the curable composition can be more suitably used as a high-tack adhesive.

[0090] [2-7. Manufacturing method] The method for producing the curable composition is not particularly limited. The curable composition can be produced (prepared) by mixing the organic polymer (A), polyvinyl chloride resin (B), calcium carbonate (C), and optionally the dehydrating agent (D) and other components. The order in which the organic polymer (A), polyvinyl chloride resin (B), calcium carbonate (C), and optionally the dehydrating agent (D) and other components are mixed is not particularly limited. Each component may be mixed one by one, or multiple components may be mixed simultaneously. The mixing device used to produce the curable composition is not particularly limited, and a known mixing device such as a three-roll mill can be used.

[0091] The curable composition does not need to be stored in a completely sealed state. When the curable composition is to be stored for a long period of time, it is preferable to store the curable composition in a sealed container such as a cartridge. The cartridge is not particularly limited, but an aluminum cartridge is a suitable example.

[0092] [3. Cured product] A cured product can be obtained by curing the present curable composition. The cured product obtained by curing the present curable composition also represents one embodiment of the present invention. A cured product according to one embodiment of the present invention is a cured product obtained by curing the curable composition described in the section [2. Curable Composition] above. For example, by exposing the present curable composition to air at room temperature, the curable composition reacts with moisture in the air and cures, thereby obtaining a cured product according to one embodiment of the present invention.

[0093] [4.Applications] The present curable composition can be suitably used as an adhesive composition, for example, as a one-component adhesive. Because the present curable composition has excellent initial fixation, it can be particularly suitably used as a high-tack adhesive. Therefore, the present curable composition and an adhesive according to one embodiment of the present invention described below can be particularly suitably used in the fields of automobile bodies and parts, bodies and parts of large vehicles such as trucks and buses, train cars and parts, aircraft parts, ship parts, containers, electrical and electronic parts, home appliances, various machine parts, mirrors, various decorative panels, sashes, and other building materials.

[0094] [5. Adhesive] An adhesive according to one embodiment of the present invention comprises the curable composition described in the section [2. Curable Composition] above. Because the adhesive according to one embodiment of the present invention has the above-described configuration, it has excellent initial fixation. Therefore, the adhesive according to one embodiment of the present invention can be particularly suitably used as (a) a one-component adhesive and / or (b) a high-tack adhesive. The curable composition itself can be used as the adhesive according to one embodiment of the present invention.

[0095] An embodiment of the present invention may have the following configuration.

[0096] [1] A curable composition comprising 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 to 500 parts by weight of a polyvinyl chloride resin (B), and 150 to 500 parts by weight of calcium carbonate (C), wherein the polyvinyl chloride resin (B) has a mode diameter of 0.10 μm to 0.50 μm.

[0097] [2] The curable composition according to [1], further comprising 2 to 10 parts by weight of a dehydrating agent (D).

[0098] [3] The curable composition according to [1] or [2], wherein the ratio ((B) / (C)) of the content of the polyvinyl chloride resin (B) to the content of the calcium carbonate (C) is 0.2 to 0.8.

[0099] [4] The curable composition according to any one of [1] to [3], wherein the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2).

[0100] [5] The curable composition according to any one of [1] to [4], wherein the content of the calcium carbonate (C) is 250 to 500 parts by weight per 100 parts by weight of the organic polymer (A).

[0101] [6] The curable composition according to any one of [1] to [5], wherein the calcium carbonate (C) comprises calcium carbonate (C1) having a volume average particle diameter of 0.05 μm to 0.15 μm and calcium carbonate (C2) having a volume average particle diameter of 0.70 μm to 5.00 μm, and the ratio of the weight of the calcium carbonate (C1) to the weight of the calcium carbonate (C2) (weight of the calcium carbonate (C1) / weight of the calcium carbonate (C2)) is 1.0 or less.

[0102] [7] A cured product obtained by curing the curable composition according to any one of [1] to [6].

[0103] [8] An adhesive comprising the curable composition according to any one of [1] to [6]. [Example]

[0104] Hereinafter, one embodiment of the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

[0105] <Material> The materials used in the examples and comparative examples are as follows.

[0106] (Organic polymer (A)) Organic polymer A1: an organic polymer obtained in Synthesis Example 1 described below Organic polymer A2: an organic polymer obtained in Synthesis Example 2 described below (Polyvinyl chloride resin (B)) Polyvinyl chloride resin (B1): a polyvinyl chloride resin obtained in Synthesis Example 3 described below Polyvinyl chloride resin (B2): a polyvinyl chloride resin obtained in Synthesis Example 4 described below Polyvinyl chloride resin (B3): a polyvinyl chloride resin obtained in Synthesis Example 5 described below (Calcium carbonate (C)) Calcium carbonate (C1): Neolight SP (Takehara Chemical Industry Co., Ltd., colloidal calcium carbonate (volume average particle size 0.08 μm)) Calcium carbonate (C2); Omya 1T (Omyacarb, heavy calcium carbonate (d50 particle size 2.00 μm)) (Dehydrating agent (D)) A-171: Momentive, vinyltrimethoxysilane (plasticizer) Polyoxypropylene diol (molecular weight approximately 3000) (Anti-sagging agent) Disparlon 308; manufactured by Kusumoto Chemicals, a hydrogenated castor oil derivative (antioxidant) Irganox 1010: BASF hindered phenolic antioxidant Nocrac NS-6: Hindered phenol antioxidant manufactured by Ouchi Shinko Chemical Industry (tackifier) A-1120: Momentive, 3-(2-aminoethylamino)propyltrimethoxysilane (curing catalyst) U303: Nitto Kasei, dibutyltin compound MSCAT02: Dibutyltin compound manufactured by Nippon Chemical Industry Co., Ltd. (coloring agent) R820: Ishihara Industries, titanium oxide <Evaluation method> The evaluation methods used in the examples and comparative examples will be explained below.

[0107] (initial fixity) The initial fixability of the curable compositions obtained in the examples and comparative examples was measured by carrying out the following (1) to (4) in this order: (1) A curable composition was applied to one surface of aluminum plate A to a thickness of 3 mm; (2) The aluminum plate A was fixed so that the plate surface was parallel to the vertical direction; (3) Another aluminum plate B, 100 mm long x 25 mm wide x 3 mm thick, was brought into close contact with aluminum plate A via the curable composition applied to aluminum plate A, so that the plate surfaces of aluminum plate B and aluminum plate A were parallel (i.e., a laminate was obtained in which aluminum plate B - curable composition - aluminum plate A were laminated horizontally in this order). At this time, (a) the adhesion between aluminum plate B and aluminum plate A was achieved by manually pressing aluminum plate B against the curable composition on aluminum plate A, and (b) of the 100 mm long length of aluminum plate B, the lower 75 mm was brought into close contact with aluminum plate A, while the upper 25 mm was not brought into close contact with aluminum plate A; (4) Within 5 seconds of bringing aluminum plate B into close contact with aluminum plate A, a spring scale was placed 25 mm above aluminum plate B, which was not in close contact with aluminum plate A, and the spring scale was pulled up. The maximum stress (g) indicated by the spring balance was taken as the initial fixity.

[0108] (Method for evaluating storage stability) For the curable compositions obtained in the Examples and Comparative Examples, the viscosity of the curable composition was measured immediately after preparation (specifically, within 7 days after preparation) using a Brookfield viscometer at 2 rpm, and the initial viscosity (mPa·s) was recorded. The curable composition was filled into a 330 ml paper aluminum cartridge. The cartridge filled with the curable composition was stored in a dryer set at 50°C for 4 weeks. The viscosity of the curable composition after storage was measured using a Brookfield viscometer at 2 rpm, and the viscosity after storage (mPa·s) was calculated. The viscosity change (%) was calculated using the following formula. Viscosity change (%) = viscosity after storage (mPa·s) / initial viscosity (mPa·s) × 100. When the viscosity change was less than 200%, the storage stability was evaluated as excellent, and when the viscosity change was 200% or more, the storage stability was evaluated as poor. The curable compositions obtained in the examples and comparative examples were stored in sealed plastic containers after preparation in each example and comparative example until evaluation of storage stability was carried out.

[0109] (Method for measuring dumbbell physical properties) The curable composition was filled into a 3 mm thick sheet mold at 23°C and 50% relative humidity. The curable composition in the sheet mold was cured for 3 days at 23°C and 50% relative humidity, and the resulting cured product was then aged in a 50°C dryer for 4 days to obtain a sheet-like cured product. The resulting cured product was punched into a No. 3 dumbbell-shaped test piece in accordance with JIS K 6251. Using the resulting test piece, a tensile test (tensile speed 200 mm / min) was performed using an autograph at 23°C and a relative humidity of 50%, and the 100% elongation modulus, stress at break (tensile strength TB), and elongation at break (EB) were measured.

[0110] (shear strength) Two sheets of SUS304 stainless steel, degreased with acetone, were used as adherends. The curable composition was applied to one of the adherends at a thickness of 50 μm and an area of ​​25 mm × 25 mm at 23°C and 50% relative humidity. Immediately after application, the other adherend was attached to the adherend with the curable composition interposed therebetween. The adherends were left at 85°C and 85% relative humidity for three days to allow the curable composition between the adherends to cure. The resulting adherends were subjected to a tensile shear test (tensile speed: 50 mm / min) using an autograph to measure the stress at break (TB).

[0111] (Synthesis Example 1) (Preparation of Organic Polymer (A1)) Propylene oxide was polymerized using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator in the presence of a zinc hexacyanocobaltate glyme complex catalyst. This polymerization yielded a terminal hydroxyl-containing polyoxypropylene (P-1) with a number-average molecular weight of 25,500 and a molecular weight distribution (Mw / Mn) of 1.26. Next, a methanol solution containing 28% (w / w) sodium methoxide was added to the reaction solution containing the resulting polyoxypropylene (P-1). The sodium methoxide methanol solution was added to the reaction solution in an amount of 1.2 molar equivalents of sodium methoxide per molar equivalent of the terminal hydroxyl groups of the resulting polyoxypropylene (P-1). Methanol was then removed from the resulting reaction solution by vacuum devolatilization. Subsequently, allyl chloride was added to the reaction solution in an amount of 1.5 molar equivalents of allyl chloride per molar equivalent of the terminal hydroxyl groups of polyoxypropylene (P-1), thereby converting the terminal hydroxyl groups to allyl groups. Subsequently, unreacted allyl chloride was removed from the reaction solution by devolatilization under reduced pressure, yielding crude polyoxypropylene. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed from the resulting mixture by centrifugation to obtain a hexane solution. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polyoxypropylene. Through these operations, polyoxypropylene (Q-1) having allyl groups at its terminals was obtained. A platinum divinyldisiloxane complex solution (3 wt. % isopropanol solution in terms of platinum) was added to polyoxypropylene (Q-1) so that 50 μl of the platinum divinyldisiloxane complex solution (3 wt. % isopropanol solution in terms of platinum) was used per 500 g of polyoxypropylene. While stirring the resulting mixture, 4.5 g of dimethoxymethylsilane was slowly added dropwise to the mixture. The resulting mixture was reacted at 100°C for 2 hours, and then unreacted dimethoxymethylsilane was removed from the mixture by distillation under reduced pressure to obtain a linear organic polymer (A1), which was polyoxypropylene having dimethoxymethylsilyl groups at its terminals. The number-average molecular weight of the organic polymer (A1) was 25,500, and it was found that the organic polymer (A1) had an average of 0.7 dimethoxymethylsilyl groups at each terminal and an average of 1.4 dimethoxymethylsilyl groups per molecule.

[0112] (Synthesis Example 2) (Preparation of Organic Polymer (A2)) Propylene oxide was polymerized using polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator in the presence of a zinc hexacyanocobaltate glyme complex catalyst. This polymerization yielded terminal hydroxyl-containing polyoxypropylene (P-2) with a number-average molecular weight of 16,400 and a molecular weight distribution (Mw / Mn) of 1.31. Next, a methanol solution containing 28% (w / w) sodium methoxide was added to the reaction solution containing the resulting polyoxypropylene (P-2). The sodium methoxide methanol solution was added to the reaction solution in an amount of 1.2 molar equivalents of sodium methoxide per molar equivalent of the terminal hydroxyl groups of the resulting polyoxypropylene (P-2). Methanol was then removed from the resulting reaction solution by vacuum devolatilization. Subsequently, allyl chloride was added to the reaction solution in an amount of 1.5 molar equivalents of allyl chloride per molar equivalent of the terminal hydroxyl groups of polyoxypropylene (P-2), converting the terminal hydroxyl groups to allyl groups. Subsequently, unreacted allyl chloride was removed from the reaction solution by devolatilization under reduced pressure, yielding crude polyoxypropylene. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, and then the water was removed from the resulting mixture by centrifugation to obtain a hexane solution. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polyoxypropylene. Through these operations, polyoxypropylene (Q-2) having allyl groups at its terminals was obtained. A platinum divinyldisiloxane complex solution (3 wt. % isopropanol solution in terms of platinum) was added to polyoxypropylene (Q-1) so that 50 μl of the platinum divinyldisiloxane complex solution (3 wt. % isopropanol solution in terms of platinum) was used per 500 g of polyoxypropylene. While stirring the resulting mixture, 8.9 g of dimethoxymethylsilane was slowly added dropwise to the mixture. The resulting mixture was reacted at 100°C for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain organic polymer (A2), a branched polyoxypropylene having dimethoxymethylsilyl groups at its terminals. The number-average molecular weight of organic polymer (A2) was 16,400, and it was found that organic polymer (A2) had an average of 0.7 dimethoxymethylsilyl groups at each terminal and an average of 2.1 dimethoxymethylsilyl groups per molecule.

[0113] (Synthesis Example 3) (Preparation of Polyvinyl Chloride Resin (B-1)) A pre-degassed, jacketed, 300 L stainless steel pressure vessel equipped with a stirrer was charged with 100 kg of vinyl chloride monomer, 100 kg of ion-exchanged water, 175 g of myristic acid, 1.3 L of 28% (w / w) aqueous ammonia solution, 85 g of sodium formaldehyde sulfoxylate (Rongalit), 1.5 g of ferrous sulfate, and 2.5 g of 2-sodium ethylenediaminetetraacetate. The mixture was then heated to 47.6 °C, and polymerization was carried out by continuously adding tert-butyl hydroperoxide, previously adjusted to 0.3% (w / w), to the mixture. From the monomer-to-polymer conversion rate of 5% to 70%, 7.8 kg of a 10.8 wt% aqueous ammonium myristate solution was continuously added to the mixture, and polymerization was continued until the polymerization pressure dropped by 0.15 MPa from the initial pressure (0.62 MPa). The remaining monomers in the mixed solution were then recovered from the mixed solution to obtain a latex containing vinyl chloride resin. The mode diameter of the vinyl chloride resin in the obtained latex was 0.18 μm. The obtained latex was passed through a 100-mesh sieve to remove coarse particles, and the passed solution was spray-dried to obtain polyvinyl chloride resin (B-1).

[0114] (Synthesis Example 4) (Preparation of Polyvinyl Chloride Resin (B-2)) A latex containing a vinyl chloride resin was obtained by the same procedure as in Production Example 1, except that the amount of myristic acid charged in the pressure vessel was changed to 70 g. The mode diameter of the vinyl chloride resin in the obtained latex was 0.37 μm. The obtained latex was passed through a 100-mesh sieve to remove coarse particles, and the passed solution was spray-dried to obtain a polyvinyl chloride resin (B-2).

[0115] (Synthesis Example 5) (Preparation of polyvinyl chloride resin (B-3)) A 300L jacketed stainless steel pressure vessel equipped with a stirrer was charged with 100 kg of ion-exchanged water, 790 g of linear sodium dodecylbenzenesulfonate, 270 g of stearyl alcohol, 270 g of stearic acid, and 60 g of t-butyl peroxyneododecanoate. The vessel was then degassed. Next, 100 kg of vinyl chloride monomer was added to the vessel, and the mixed solution in the vessel was homogenized for 30 minutes. The mixed solution was then heated to 44.5°C to initiate polymerization. Polymerization continued until the polymerization pressure dropped 0.05 MPa from the initial pressure. The remaining monomer was then recovered from the mixed solution to obtain a vinyl chloride resin-containing latex. The mode diameter of the vinyl chloride resin in the resulting latex was 1.0 μm. The resulting latex was passed through a 100-mesh sieve to remove coarse particles, and the passed solution was spray-dried to obtain polyvinyl chloride resin (B-3).

[0116] (Examples 1 to 3 and Comparative Examples 1 and 2) A curable composition was prepared as follows. First, the components shown in Table 1, excluding the dehydrating agent (D), anti-sagging agent, adhesion promoter, and curing catalyst, were weighed out in the weight parts shown in Table 1. The weighed components were then subjected to a three-roll mill to obtain a uniform dispersion paste. The dispersion paste was then dehydrated at 120°C for 2 hours under reduced pressure. After confirming that the moisture content of the dispersion paste had reached 500 ppm or less, the dispersion paste was cooled until its temperature reached 50°C or less. The remaining components were then added to the dispersion paste, and the resulting mixture was subjected to stirring and degassing to obtain a curable composition. The resulting curable composition was filled into an aluminum cartridge. The initial fixability and storage stability of the resulting curable composition were evaluated using the methods described above. The results of the initial fixability are shown in Table 1. The curable compositions obtained in Examples 1 to 3 are curable compositions according to one embodiment of the present invention and are also adhesives according to one embodiment of the present invention.

[0117] Regarding storage stability, the curable compositions of Examples 1 to 3 and Comparative Example 1 had excellent storage stability with a viscosity change of less than 200%. On the other hand, the curable composition of Comparative Example 2 had poor storage stability with a viscosity change of 200% or more.

[0118] [Table 1] As shown in Table 1, the curable compositions of Examples 1 to 3, which contain specific amounts of an organic polymer (A), a polyvinyl chloride resin (B) having a mode diameter of 0.1 μm to 0.5 μm, and calcium carbonate (C), respectively, were found to have excellent initial fixability. Furthermore, Example 2, in which the ratio ((B) / (C)) of the content of polyvinyl chloride resin (B) to the content of calcium carbonate (C) was 0.8 or less, was found to have superior initial fixability compared to Example 3, in which (B) / (C) was 1.1. On the other hand, the curable compositions of Comparative Examples 1 and 2, which contain a polyvinyl chloride resin (B) having a mode diameter of 1.0 μm, were found to have inferior initial fixability.

[0119] The curable composition of Comparative Example 2 has poor storage stability, and therefore is considered to be unsuitable for adhesive applications in which, after the curable composition is produced, it is (a) transported and stored in a store for a long period of time.

[0120] Examples 4 to 8 A curable composition was prepared as follows. First, the components shown in Table 2, excluding the dehydrating agent (D), anti-sagging agent, adhesion promoter, and curing catalyst, were weighed out in the weight parts shown in Table 2. The weighed components were then subjected to a three-roll mill to obtain a uniform dispersion paste. The dispersion paste was then dehydrated at 120°C for 2 hours under reduced pressure. After confirming that the moisture content of the dispersion paste had reached 500 ppm or less, the dispersion paste was cooled until its temperature reached 50°C or less. The remaining components were then added to the dispersion paste, and the resulting mixture was subjected to stirring and degassing to obtain a curable composition. The resulting curable composition was filled into an aluminum cartridge. The initial fixability and storage stability of the resulting curable composition were evaluated using the methods described above. Furthermore, the dumbbell physical properties and shear strength of the cured product of the curable composition were evaluated using the methods described above. The results of the initial fixability, dumbbell physical properties, and shear strength are shown in Table 1. The curable compositions obtained in Examples 4 to 8 are curable compositions according to one embodiment of the present invention, and are also adhesives according to one embodiment of the present invention.

[0121] Regarding storage stability, the curable compositions of Examples 4 to 8 had a viscosity change of less than 200%, and were therefore excellent in storage stability.

[0122] [Table 2] As shown in Table 2, the curable compositions of Examples 4 to 8 were also found to have excellent initial fixation properties, similar to Examples 1 to 3. Here, in the curable compositions of Examples 4, 7, and 8, the organic polymer (A) was a mixture of a linear organic polymer (A1) and a branched organic polymer (A2). In the curable composition of Example 5, the organic polymer (A) was solely the linear organic polymer (A1), while in the curable composition of Example 6, the organic polymer (A) was solely the branched organic polymer (A2). As shown in Table 2, compared to the cured product obtained from the curable composition of Example 5, the cured products obtained from the curable compositions of Examples 4, 7, and 8 were found to have excellent dumbbell physical properties, 100% elongation modulus, and shear strength at break. Furthermore, compared to the cured product obtained from the curable composition of Example 6, the cured products obtained from the curable compositions of Examples 4, 7, and 8 were found to have excellent dumbbell physical properties, elongation at break. In other words, compared to the cured products obtained from the curable compositions of Examples 5 and 6, it was found that the cured products obtained from the curable compositions of Examples 4, 7, and 8 were able to achieve both excellent 100% elongation modulus and shear strength in the dumbbell properties, and excellent breaking strength in the shear strength. [Industrial Applicability]

[0123] According to one embodiment of the present invention, a novel curable composition having excellent initial fixation properties can be provided, which can be suitably used in the fields of automobile bodies and parts, bodies and parts of large vehicles such as trucks and buses, train cars and parts, aircraft parts, ship parts, containers, electric and electronic parts, home appliances, various machine parts, mirrors, various decorative panels, sashes, and other building materials.

Claims

1. The composition comprises 100 parts by weight of an organic polymer (A) having a hydrolyzable silicon group, 10 to 500 parts by weight of a polyvinyl chloride resin (B), and 150 to 500 parts by weight of calcium carbonate (C), the mode diameter of the polyvinyl chloride resin (B) is 0.10 μm to 0.50 μm; the organic polymer (A) is a polymer containing the hydrolyzable silicon group at a molecular end, The curable composition, wherein the organic polymer (A) has an average of 1.2 to 5.0 hydrolyzable silicon groups per molecule.

2. The curable composition according to claim 1, further comprising 2 to 10 parts by weight of a dehydrating agent (D).

3. 3. The curable composition according to claim 1, wherein a ratio ((B) / (C)) of a content of the polyvinyl chloride resin (B) to a content of the calcium carbonate (C) is 0.2 to 0.

8.

4. The curable composition according to any one of claims 1 to 3, wherein the organic polymer (A) is a mixture of a linear organic polymer (A1) and a branched organic polymer (A2).

5. The curable composition according to any one of claims 1 to 4, wherein the content of the calcium carbonate (C) is 250 parts by weight to 500 parts by weight per 100 parts by weight of the organic polymer (A).

6. The calcium carbonate (C) includes calcium carbonate (C1) having a volume average particle diameter of 0.05 μm to 0.15 μm and calcium carbonate (C2) having a volume average particle diameter of 0.70 μm to 5.00 μm, 6. The hardenable composition according to claim 1, wherein a ratio of a weight of the calcium carbonate (C1) to a weight of the calcium carbonate (C2) (weight of the calcium carbonate (C1) / weight of the calcium carbonate (C2)) is 1.0 or less.

7. A cured product obtained by curing the curable composition according to any one of claims 1 to 6.

8. An adhesive comprising the curable composition according to any one of claims 1 to 6.

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