Main agent for two pack type curable resin composition having improved storage stability

Abstract

To provide a resin composition for a two pack type curable resin composition having good storage stability even in a high temperature and high humidity environment.SOLUTION: A resin composition for a two component curable resin composition contains 100 pts. wt. of a polyoxyalkylene-based polymer (A), 10 pts. wt. to 400 pts. wt. of surface-treated calcium carbonate (B) having a specific configuration, and 2 pts. wt. to 70 pts. wt. of an epoxy-based compound (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component curable resin composition. Main ingredient Regarding. [Background technology]

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

[0003] The physical properties of the cured product of a polyoxyalkylene polymer having a reactive silicon group can be improved by adding a reactive plasticizer and a filler made of surface-treated calcium carbonate (Patent Document 1).

[0004] Two-component curable resin compositions have the advantage of maintaining storage stability for approximately six months to a year because the two components, the base resin and the curing agent, are kept separate until just before use, and are therefore widely used, particularly as construction sealants. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2011-94134 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the conventional technology, there was room for further improvement in terms of storage stability, such as when the container containing the base agent (resin composition excluding the curing agent) was not tightly sealed and / or when stored in a hot and humid environment, the viscosity of the base agent increased or the base agent gelled.

[0007] One embodiment of the present invention has been made in consideration of the above-mentioned problems, and its object is to provide a two-component curable resin composition having good storage stability even in a high-temperature and high-humidity environment. Main ingredient The objective is to provide the following. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems and have completed the present invention.

[0009] That is, one embodiment of the present invention includes the following configuration. [1] A base agent for a two-component curable resin composition, which is prepared by mixing a base agent and a curing agent, each of which is separate, to form a two-component curable resin composition, the base agent comprising: A method for producing a two-component curable resin composition, comprising: 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group; 10 to 400 parts by weight of calcium carbonate (B) surface-treated with a fatty acid compound; and 2 to 70 parts by weight of an epoxy compound (C), wherein the fatty acid compound contains 12 mol % or less of a fatty acid compound having a hydrocarbon composition having 14 or less carbon atoms in 100 mol % of the fatty acid compound. Main ingredient . [2] The calcium carbonate (B) surface-treated with a fatty acid compound contains colloidal calcium carbonate surface-treated with a fatty acid compound. Main ingredient . [3] The two-component curable resin composition according to [1] or [2], further comprising 0.5 to 10.0 parts by weight of a photocurable substance (D). Main ingredient . [4] The two-component curable resin composition according to any one of [1] to [3], further comprising 1.00 to 20.00 parts by weight of a hollow filler (E). Main ingredient . [5] The method for producing a two-component curable resin composition according to [4], wherein the hollow filler (E) contains glass balloons. Main ingredient . [6] A method for producing a two-component curable resin composition according to any one of [1] to [5], further comprising a phthalate ester compound (F). Main ingredient . [ 7 〕 A method for producing a base agent for a two-component curable resin composition, which is prepared by mixing a base agent and a curing agent, each of which is separate, to form a two-component curable resin composition, the method comprising: A method for producing a two-component curable resin composition, comprising: mixing 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group, 10 to 400 parts by weight of calcium carbonate (B) surface-treated with a fatty acid compound, and 2 to 70 parts by weight of an epoxy compound (C), wherein the fatty acid compound contains 12 mol % or less of a fatty acid compound having a hydrocarbon composition having 14 or less carbon atoms in 100 mol % of the fatty acid compound. Main ingredient Manufacturing method. [8] The method for producing a base agent for a two-component curable resin composition according to [7], wherein the calcium carbonate (B) surface-treated with a fatty acid compound contains colloidal calcium carbonate surface-treated with a fatty acid compound. [9] A method for producing a base resin for a two-component curable resin composition according to [7] or [8], further comprising 0.5 to 10.0 parts by weight of a photocurable substance (D).

[10] A method for producing a base resin for a two-component curable resin composition according to any one of [7] to [9], further comprising 1.00 to 20.00 parts by weight of a hollow filler (E).

[11] The method for producing a base resin for a two-component curable resin composition according to

[10] , wherein the hollow filler (E) contains glass balloons.

[12] A method for producing a base resin for a two-component curable resin composition according to any one of [7] to

[11] , further comprising a phthalate ester compound (F). [Effects of the Invention]

[0010] According to one embodiment of the present invention, a two-component curable resin composition having good storage stability even in a high-temperature and high-humidity environment is provided. Main ingredient This has the effect of providing the following. 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] [For two-component curable resin compositions Main ingredient ] For a two-component curable resin composition according to one embodiment of the present invention Main ingredient teeth, A base agent for a two-component curable resin composition, which is prepared by mixing a base agent and a curing agent, each of which is separate, to form a two-component curable resin composition, The composition contains 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group, 10 to 400 parts by weight of calcium carbonate (B) surface-treated with a fatty acid compound, and 2 to 70 parts by weight of an epoxy compound (C), wherein the fatty acid compound contains 12 mol % or less of fatty acid compounds whose hydrocarbon composition has 14 or less carbon atoms per 100 mol % of the fatty acid compound.

[0013] In this specification, the "two-component curable resin composition" may be referred to as the "curable resin composition" hereinafter, and the "component for a two-component curable resin composition" may be referred to as the "curable resin composition". Main ingredient ", hereinafter " Main ingredient ", and "the two-component curable resin composition according to one embodiment of the present invention Main ingredient ", hereinafter " Main agent according to this embodiment ", "polyoxyalkylene polymer (A) having a reactive silicon group" may be referred to hereinafter as "polyoxyalkylene polymer (A)", and "calcium carbonate surface-treated with a fatty acid compound (B)" may be referred to hereinafter as "surface-treated calcium carbonate (B)".

[0014] Main agent according to this embodiment The two-component curable resin composition has the above-mentioned constitution and therefore has good storage stability even in a high-temperature and high-humidity environment. Main ingredient for In other words, Main agent according to this embodiment can be suitably used as a main component of a two-component curable resin composition.

[0015] [Polyoxyalkylene polymer (A)] The polyoxyalkylene polymer (A) is a polymer having a molecular chain terminal containing a hydrolyzable (crosslinkable) silyl group (i.e., a reactive silicon 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 Si group, and having an alkylene oxide repeating unit as the skeleton.

[0016] Specific examples of reactive 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. From the viewpoint of activity, trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are particularly preferred. From the viewpoint of stability, methyldimethoxysilyl group, methyldiethoxysilyl group, and triethoxysilyl group are particularly preferred. From the viewpoint of safety, methyldiethoxysilyl group and triethoxysilyl group are particularly preferred. Trimethoxysilyl group, triethoxysilyl group, and dimethoxymethylsilyl group are particularly preferred because of their ease of production.

[0017] The polyoxyalkylene polymer (A) preferably has an average of 1.2 to 5.0 reactive silicon groups per molecule, more preferably 1.2 to 4.0 reactive silicon groups, and even more preferably 1.2 to 3.0 reactive silicon groups. When the polyoxyalkylene polymer (A) has an average of 1.2 or more reactive silicon groups per molecule, The main agentcan provide a two-component curable resin composition with good curability. Therefore, the cured product that can be provided by this two-component curable resin composition exhibits good rubber elasticity, and the cured product exhibits good recovery, durability, and / or creep resistance. The reactive silicon group may be located at the main chain terminal or side chain terminal of the polyoxyalkylene polymer (A), or may be located at both the main chain terminal and the side chain terminal. In particular, when the reactive silicon group is located only at the main chain terminal of the polyoxyalkylene polymer (A), the effective network length in the final cured product is increased, which makes it easier to obtain a rubbery cured product that has high strength, high elongation, and a low elastic modulus.

[0018] The reactive silicon group can be introduced into the polyoxyalkylene polymer by a known method, such as the following methods I to III.

[0019] Method I: An organic polymer having functional groups such as hydroxyl groups is reacted with a compound having an active group reactive with the functional group and an unsaturated 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 reactive silicon group by hydrosilylation.

[0020] Examples of the compound having an active group and an unsaturated group that exhibits reactivity and that can be used in Method I include allyl chloride, methallyl chloride, and unsaturated group-containing epoxy compounds such as allyl glycidyl ether.

[0021] Examples of the hydrosilane compound used in Method I include, but are not limited to, halogenated silanes, alkoxysilanes, acyloxysilanes, and ketoximate silanes.

[0022] Examples of halogenated silanes include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane.

[0023] Examples of alkoxysilanes include trimethoxysilane, triethoxysilane, triisopropoxysilane, 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, diethoxymethylsilane, dimethoxymethylsilane, and phenyldimethoxysilane.

[0024] Examples of acyloxysilanes include methyldiacetoxysilane and phenyldiacetoxysilane.

[0025] Examples of ketoximate silanes include bis(dimethylketoximate)methylsilane, bis(cyclohexylketoximate)methylsilane, and the like.

[0026] Among these hydrosilane compounds, trialkoxysilanes are preferred from the viewpoint of hydrolysis property and mildness of reaction, and trimethoxysilane and triethoxysilane are more preferred.

[0027] To obtain a polyoxyalkylene polymer (A) having trimethoxysilyl groups, a preferred method is to synthesize a polymer having triethoxysilyl groups using triethoxysilane as a raw material by the methods described in WO 2007-040143 and JP 2008-285585 A, and then convert the triethoxysilyl groups to trimethoxysilyl groups using methanol. This is because trimethoxysilane is a very unstable compound and can undergo a disproportionation reaction to produce low-boiling, pyrophoric monosilane. Furthermore, trimethoxysilane is difficult to handle and difficult to obtain due to its extremely high risk to the human body, especially the eyes.

[0028] Method II: A method in which a compound having a mercapto group and a reactive 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.

[0029] Examples of compounds having a mercapto group and a reactive silicon group that can be used in Method II include, but are not limited to, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane.

[0030] 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 functional group reactive with this functional group and a reactive silicon group.

[0031] Among the methods in Method III, examples of the method of reacting an organic polymer having a hydroxyl group with a compound having an isocyanate group and a reactive silicon group that are reactive with a hydroxyl group include, but are not limited to, the method disclosed in JP-A-3-47825.

[0032] Examples of compounds having an isocyanate group and a reactive silicon group that can be used in Method III include, but are not limited to, γ-isocyanate propyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, isocyanate methyl trimethoxysilane, isocyanate methyl triethoxysilane, and isocyanate methyl dimethoxymethylsilane.

[0033] When γ-mercaptopropyltrimethoxysilane and γ-isocyanatopropyltrimethoxysilane are used, the disproportionation reaction does not proceed as it does when trimethoxysilane is used, and therefore, Method II or Method III is preferred over Method I, which uses trimethoxysilane.

[0034] On the other hand, the disproportionation reaction does not proceed in a compound having a reactive silicon group represented by the following general formula (1) (hereinafter also referred to as a silane compound): H-(SiR 2 2O) m SiR2 2-R 3 -SiX3···(1) (In the formula, each X independently represents a hydroxyl group or a hydrolyzable group. 2m+2 R 2 R each independently represents a hydrocarbon group. 3 represents a divalent organic group, and m represents an integer of 0 to 19.

[0035] Therefore, when introducing a group in which three hydrolyzable groups are bonded to one silicon atom in Method I, it is preferable to use a silane compound represented by general formula (1). From the viewpoints of availability and cost, it is preferable to use a silane compound represented by general formula (1) in which 2m+2 R 2 are each independently preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and even more preferably a hydrocarbon group having 1 to 4 carbon atoms. 3 is preferably a divalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 8 carbon atoms, and even more preferably a divalent hydrocarbon group having 2 carbon atoms. m is most preferably 1.

[0036] Examples of silane compounds represented by general formula (1) include 1-[2-(trimethoxysilyl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1-[2-(trimethoxysilyl)propyl]-1,1,3,3-tetramethyldisiloxane, and 1-[2-(trimethoxysilyl)hexyl]-1,1,3,3-tetramethyldisiloxane.

[0037] Among the above-mentioned methods I and III, the method of reacting an organic polymer having a terminal hydroxyl group with a compound having an isocyanate group and a reactive silicon 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 reactive silicon group obtained by method I has a lower viscosity than the organic polymer having a reactive silicon group obtained by method III, and a curable resin composition with good workability can be obtained. In addition, the organic polymer having a reactive silicon group obtained by method II may have a strong odor due to the mercaptosilane. For this reason, method I is particularly preferred.

[0038] In one embodiment of the present invention, the repeating units contained in the polyoxyalkylene polymer that forms the main skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene units, polyoxypropylene units, and polyoxybutylene units, and are preferably polyoxypropylene units. In one embodiment of the present invention, the repeating units contained in the polyoxyalkylene polymer are not limited to these, as long as they have a crosslinkable silyl group in the molecule. For example, 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] Examples of double metal cyanide complex catalysts include Zn3[Co(CN)6]2 (zinc hexacyanocobaltate complex), etc. Catalysts in which alcohols and / or ethers are coordinated as organic ligands to zinc hexacyanocobaltate complexes, etc., can also be used.

[0041] The initiator is preferably a "compound having at least two active hydrogen groups" (hereinafter also referred to as "active hydrogen-containing compound"). Examples of the active hydrogen-containing compound include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, and 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 polyoxyalkylene polymer (A) in one embodiment of the present invention may be either linear or branched. The number-average molecular weight (Mn) of the polyoxyalkylene polymer (A) is a value measured by gel permeation chromatography (GPC) (in terms of polystyrene) 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 resin composition tends to have high viscosity, resulting in poor workability. The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) measured by GPC is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.4 or less.

[0044] Commercially available products can also be used as the polyoxyalkylene polymer (A). For example, (a) Kaneka MS Polymer and Kaneka Silyl, both manufactured by Kaneka Corporation, (b) Excestar, both manufactured by AGC Corporation, and (c) GENIOSIL, both manufactured by Wacker, are already manufactured and sold for industrial use and can be easily obtained and used as the polyoxyalkylene polymer (A).

[0045] [Surface-treated calcium carbonate (B)] The calcium carbonate forming the surface-treated calcium carbonate (B) is not particularly limited, and may be, for example, either (a) colloidal calcium carbonate produced by introducing CO gas into an aqueous slurry of Ca(OH) or (b) heavy calcium carbonate obtained by mechanically crushing and classifying limestone. Since finer particles are more easily obtained, the calcium carbonate forming the surface-treated calcium carbonate (B) is preferably colloidal calcium carbonate. In other words, the calcium carbonate (B) surface-treated with a fatty acid compound preferably contains colloidal calcium carbonate surface-treated with a fatty acid compound, and more preferably is colloidal calcium carbonate surface-treated with a fatty acid compound.

[0046] The BET specific surface area of ​​calcium carbonate forming surface-treated calcium carbonate (B) is 1m 2 / g~100m 2 / g, and 2m 2 / g~80m 2 / g, more preferably 5m 2 / g~50m 2 In this specification, the BET specific surface area of ​​calcium carbonate forming the surface-treated calcium carbonate (B) 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).

[0047] The BET specific surface area of ​​the calcium carbonate that forms the surface-treated calcium carbonate (B) is 1m 2 / g or more, Main ingredient In addition, the BET specific surface area of ​​the calcium carbonate forming the surface-treated calcium carbonate (B) is 100 m 2 / g or less, Main ingredient In this process, the aggregation of the surface-treated calcium carbonate (B) is restricted, Main ingredient The dispersibility of the surface-treated calcium carbonate (B) in the water is improved, and as a result, Main ingredient has good thixotropy.

[0048] Main agent according to this embodiment The content of the surface-treated calcium carbonate (B) in the composition is preferably 10 to 400 parts by weight, more preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight, even more preferably 75 to 175 parts by weight, and particularly preferably 80 to 150 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0049] Main agent according to this embodiment The fatty acid compound of the surface-treated calcium carbonate (B) in the above can also be said to be a surface treatment agent for calcium carbonate. The fatty acid compound is not particularly limited, but suitable examples thereof include one or more compounds selected from the group consisting of fatty acids, salts of fatty acids, derivatives of fatty acids, and salts of derivatives of fatty acids.

[0050] 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.

[0051] The fatty acid compound contains, in 100 mol%, 12 mol% or less of fatty acid compounds whose hydrocarbon composition has 14 or less carbon atoms, preferably 11.0 mol% or less, more preferably 10.0 mol% or less, more preferably 9.0 mol% or less, more preferably 8.0 mol% or less, more preferably 7.0 mol% or less, more preferably 6.0 mol% or less, more preferably 5.0 mol% or less, more preferably 4.0 mol% or less, more preferably 3.0 mol% or less, more preferably 2.0 mol% or less, even more preferably 1.0 mol% or less, particularly preferably 0.5 mol% or less, and most preferably substantially none. In 100 mol%, the fatty acid compound whose hydrocarbon composition has 14 or less carbon atoms may be 0 mol%. When the fatty acid compound contains 12.0 mol% or less of a fatty acid compound having a hydrocarbon composition having 14 or less carbon atoms, based on 100 mol% of the fatty acid compound, Main ingredient During this process, the cohesive strength of the surface-treated calcium carbonate (B) decreases, Main ingredient By reducing the increase in viscosity of Main ingredient The storage stability of the composition is improved.

[0052] When calcium carbonate is surface-treated using a surface treatment agent "a fatty acid compound containing 12 mol % or less of a fatty acid compound having a hydrocarbon composition with 14 or less carbon atoms, based on 100 mol % of the fatty acid compound," the resulting calcium carbonate (i.e., surface-treated calcium carbonate) may contain on its surface "a fatty acid compound containing 12 mol % or less of a fatty acid compound having a hydrocarbon composition with 14 or less carbon atoms, based on 100 mol % of the fatty acid compound." Therefore, one embodiment of the present invention can be rephrased as follows: 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group, 10 to 400 parts by weight of calcium carbonate (B) having a fatty acid compound on its surface, and Contains 2 parts by weight to 70 parts by weight of an epoxy compound (C), The fatty acid compound contains 12 mol% or less of a fatty acid compound having a hydrocarbon composition having 14 or less carbon atoms in 100 mol% of the fatty acid compound. Main ingredient .

[0053] The amount of fatty acid compound used in the surface treatment of calcium carbonate (also referred to as the treatment amount with fatty acid compound) is preferably 0.1 to 40.0 parts by weight, more preferably 0.3 to 30.0 parts by weight, more preferably 0.5 to 20.0 parts by weight, more preferably 0.7 to 15.0 parts by weight, and even more preferably 1.0 to 10.0 parts by weight, relative to 100 parts by weight of calcium carbonate. When the treatment amount of fatty acid relative to calcium carbonate is 0.1 parts by weight or more, the calcium carbonate particles are surface-treated entirely, and the effects of the surface-treated calcium carbonate can be fully exerted, which is preferable. Furthermore, when the treatment amount of fatty acid is 40.0 parts by weight or less, effects proportional to the surface treatment amount are obtained, and the effect of the surface treatment relative to the cost is sufficient, which is preferable.

[0054] The amount of the fatty acid compound attached to the surface of the surface-treated calcium carbonate (i.e., the surface-treated calcium carbonate (B)) (which can also be referred to as the surface-adhesion amount of the fatty acid compound) is preferably the same as or approximately the same as the amount of the fatty acid compound used in the surface treatment. That is, the surface-adhesion amount of the fatty acid compound in the surface-treated calcium carbonate (B) is preferably 0.1 wt % to 40.0 wt %, more preferably 0.3 wt % to 30.0 wt %, more preferably 0.5 wt % to 20.0 wt %, more preferably 0.7 wt % to 15.0 wt %, and even more preferably 1.0 wt % to 10.0 wt % based on 100 wt % of the surface-treated calcium carbonate (B). When the surface-adhesion amount of the fatty acid compound in the surface-treated calcium carbonate (B) is (a) 0.1 wt % or more based on 100 wt % of the surface-treated calcium carbonate (B), the effect of the surface-treated calcium carbonate can be fully exhibited, and (b) 40.0 wt % or less is preferable because the effect is proportional to the amount of surface treatment.

[0055] The amount of fatty acid compounds attached to the surface of the surface-treated calcium carbonate (B) can be measured, for example, by using a differential thermal analyzer (TGD9600, manufactured by ULVAC) by carrying out the following steps (1) to (4) in order: (1) heating calcium carbonates A to G (surface-treated calcium carbonates) and raising the temperature of the surface-treated calcium carbonates from room temperature to 500°C at a rate of 10°C / min; (2) measuring the weight of the surface-treated calcium carbonate when it is at 200°C and the weight of the surface-treated calcium carbonate when it is at 500°C; (3) calculating the loss on heating (%) using the following formula, and the obtained loss on heating (%) is defined as the amount of fatty acid compounds attached (%) in 100% by weight of the surface-treated calcium carbonate.

[0056] Heat loss (%) = [(weight (g) of surface-treated calcium carbonate when the surface-treated calcium carbonate is at 200°C - weight (g) of surface-treated calcium carbonate when the surface-treated calcium carbonate is at 500°C) / weight (g) of surface-treated calcium carbonate when the surface-treated calcium carbonate is at 200°C)] × 100 (4) From the obtained heat loss, the amount of fatty acid compounds in 100 parts by weight of surface-treated calcium carbonate was calculated using the following formula.

[0057] The amount of fatty acid compound in the surface-treated calcium carbonate (parts by weight) = [loss on heating (%) × amount of surface-treated calcium carbonate (parts by weight) / 100].

[0058] The method for producing the surface-treated calcium carbonate (B) 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 conventional methods. The method for producing the surface-treated calcium carbonate (B) is not particularly limited except that a fatty acid compound containing 12 mol % or less of a fatty acid compound having a hydrocarbon composition of 14 or less carbon atoms per 100 mol % of the fatty acid compound is used as a surface treatment agent, and the surface treatment method may be either a wet method or a dry method.

[0059] [Epoxy compounds (C)] Epoxy compound (C) The main agent In addition, it can function as a plasticizer. Main agent according to this embodiment By containing the epoxy compound (C), Main ingredient This has the advantage that the durability of the cured product derived from this is improved.

[0060] The epoxy compound (C) is not particularly limited as long as it has one or more epoxy groups in the molecule. Examples of the epoxy compound (C) include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specific examples of the epoxy compound (C) include epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, epoxy butyl stearate, and 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021P), with bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate being preferred. These compounds may be used alone or in combination of two or more.

[0061] The main agent The content of the epoxy compound (C) in the composition is preferably 1 to 120 parts by weight, more preferably 2 to 100 parts by weight, more preferably 2 to 80 parts by weight, even more preferably 3 to 70 parts by weight, and particularly preferably 5 to 55 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0062] [Photocurable substance (D)] Main agent according to this embodiment It is preferable that the composition further contains a photocurable substance (D). Main agent according to this embodiment When the composition further contains a photocurable substance (D), Main ingredient The photocurable material has the advantage that a film of the photocurable material is formed on the surface of the cured product derived from the above, thereby improving the stickiness and weather resistance of the cured product. Photocurable materials are those whose molecular structure undergoes a chemical change in a fairly short time due to the action of light, resulting in physical changes such as hardening.

[0063] Many photocurable substances (D) are known, including organic monomers, oligomers, resins, and compositions containing them, and any commercially available one can be used. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, and azido resins.

[0064] Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups, such as propylene (or butylene or ethylene) glycol di(meth)acrylate and neopentyl glycol di(meth)acrylate, or oligoesters with a molecular weight of 10,000 or less. Specific examples include special acrylates (bifunctional) such as Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, and Aronix M-245; (trifunctional) Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, and Aronix M-325; and (multifunctional) Aronix M-400. In particular, compounds containing acrylic functional groups are preferred, and compounds containing an average of three or more such functional groups per molecule are preferred. (All of the above Aronix products are products of Toagosei Co., Ltd.)

[0065] Polyvinyl cinnamates are photosensitive resins having a cinnamoyl group as a photosensitive group, and include those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many other polyvinyl cinnamate derivatives.

[0066] Azidated resins are known as photosensitive resins with azide groups as the photosensitive group, and are usually rubber photosensitive solutions to which diazide compounds have been added as photosensitizers. Detailed examples are given in "Photosensitive Resins" (published March 17, 1972, by the Printing Society Publishing Department, pp. 93-106, 117-117). These can be used alone or in mixtures, with a sensitizer added as needed. The effect may be enhanced by adding sensitizers such as ketones or nitro compounds, or accelerators such as amines.

[0067] The main agent The content of the photocurable substance (D) in the composition is preferably 0.5 to 20.0 parts by weight, more preferably 0.1 to 10.0 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A). The main agent When the content of the photocurable substance (D) is within the above range, Main ingredient The present invention provides a two-component curable resin composition that can provide a cured product that is excellent in weather resistance, flexible, and resistant to cracking.

[0068] Hollow Filler (E) Main agent according to this embodiment It is preferable that the composition further contains a hollow filler (E). The hollow filler is a spherical filler that is hollow inside. Main agent according to this embodiment If contains hollow filler, Main ingredient , and Main ingredient The cured product derived from this can be made lighter in weight.

[0069] Examples of the hollow filler (E) include organic balloons and inorganic balloons. Materials for the hollow filler (E) include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. It is particularly preferable that the hollow filler (E) is a glass balloon made of glass.

[0070] The main agentThe content of the hollow filler (E) in the composition is preferably 0.01 to 100.00 parts by weight, more preferably 0.10 to 30.00 parts by weight, and particularly preferably 0.20 to 20.00 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0071] The hollow filler (E) preferably has a volume average particle diameter of 5 μm to 300 μm, more preferably 10 μm to 200 μm, and even more preferably 20 μm to 150 μm. The volume average particle diameter of the hollow filler (E) can be measured by a laser diffraction particle size distribution analyzer.

[0072] Typically, the hollow filler (E) is preferably blended in a volume concentration of 0.2 vol% to 5.0 vol%, more preferably 0.3 vol% to 3.0 vol%, based on 100.0 vol% of the two-component curable resin composition. When the volume concentration of the hollow filler (E) in 100.0 vol% of the two-component curable resin composition is 0.2 vol% or higher, it has the advantage of not feeling rough. When the volume concentration of the hollow filler (E) in 100.0 vol% of the two-component curable resin composition is 5.0 vol% or lower, it has the advantages of (a) improving workability because the viscosity of the two-component curable resin composition is not too high, and (b) not increasing the modulus of the resulting cured product too much, which tends to prevent the basic performance of the two-component curable resin composition from being impaired. Note that "vol%" refers to "volume percent."

[0073] [Phthalate ester compounds (F)] Main agent according to this embodiment The phthalate ester compound (F) may further contain a phthalate ester compound (F). The phthalate ester compound (F) is an ester having phthalic acid as the main skeleton. The phthalate ester compound (F) is The main agent In addition, it can function as a plasticizer. Main agent according to this embodiment If the product further contains a phthalate ester compound (F), Main ingredient has the advantage that it is possible to provide a two-component curable resin composition that can provide a cured product with excellent adhesion.

[0074] The phthalate ester compound (F) is not particularly limited, but examples thereof 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. Preferred examples include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate.

[0075] The main agent The content of the phthalate ester compound (F) in the composition is preferably 0 to 200 parts by weight, more preferably 30 to 170 parts by weight, more preferably 50 to 150 parts by weight, even more preferably 70 to 130 parts by weight, and particularly preferably 90 to 110 parts by weight, in total with the epoxy compound (C) per 100 parts by weight of the polyoxyalkylene polymer (A).

[0076] [Other ingredients] Main agent according to this embodiment may further contain untreated ground calcium carbonate. The main agent If the product further contains untreated ground calcium carbonate, (a) Main ingredient and the Main ingredient The present invention has the advantages that (a) the increase in viscosity of a two-component curable resin composition containing the above-mentioned compound is reduced, and (b) the two-component curable resin composition can provide a cured product having excellent strength.

[0077] The BET specific surface area of ​​untreated ground calcium carbonate is: Main ingredient Since the thixotropy of 2 / g~10.0m 2 / g, and 0.2m 2 / g~8.0m 2 / g, more preferably 0.5m 2 / g~5.0m 2 In this specification, the BET specific surface area of ​​the surface-untreated heavy calcium carbonate 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).

[0078] Main agent according to this embodiment The content of the surface-untreated heavy calcium carbonate in the composition is preferably 3 to 200 parts by weight, more preferably 5 to 170 parts by weight, more preferably 10 to 150 parts by weight, even more preferably 20 to 120 parts by weight, and particularly preferably 30 to 100 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0079] Main agent according to this embodiment may further comprise a light stabilizer. The main agent When the composition further contains a light stabilizer, Main ingredient has the advantage that it can provide a two-component curable resin composition that can provide a cured product that is reduced in oxidation and deterioration due to light.

[0080] Examples of the light stabilizer include benzotriazole compounds, hindered amine compounds, benzoate compounds, etc. As the light stabilizer, hindered amine compounds are particularly preferred.

[0081] The main agent The content of the light stabilizer in the composition is preferably 0.1 to 10.0 parts by weight, more preferably 0.2 to 5.0 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0082] Main agent according to this embodiment may further contain an ultraviolet absorber. The main agent When the composition further contains an ultraviolet absorber, Main ingredient has the advantage that it can provide a two-component curable resin composition that can provide a cured product with excellent surface weather resistance.

[0083] Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylate compounds, substituted tolyl compounds, and metal chelate compounds, with benzotriazole compounds being particularly preferred as ultraviolet absorbers.

[0084] The main agent The content of the ultraviolet absorber in the composition is preferably 0.1 to 10.0 parts by weight, more preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

[0085] Main agent according to this embodiment may further contain a thixotropic agent (anti-sagging agent) for the purpose of preventing sagging and improving workability.

[0086] The thixotropy-imparting agent is not particularly limited, but examples thereof include polyamide waxes, hydrogenated castor oil derivatives, and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These may be used alone or in combination of two or more.

[0087] Main agent according to this embodiment The content of the thixotropy-imparting agent in the composition is not particularly limited, but is preferably 0.1 to 20.0 parts by weight relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0088] Main agent according to this embodiment may contain a plasticizer other than the epoxy compound (C) and the phthalate ester compound (F).

[0089] Plasticizers other than the epoxy compound (C) and the phthalate ester compound (F) are not particularly limited and include non-phthalate ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; aliphatic polycarboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl esters; phosphate ester compounds; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; and process oils. These may be used alone or in combination of two or more.

[0090] As plasticizers other than the epoxy compound (C) and the phthalate ester compound (F), (a) acrylic compounds, (b) polyoxyalkylene polymers having 0.3 to 1.2 reactive silicon groups per molecule, (c) acrylic polymers having 0.3 to 1.2 reactive silicon groups per molecule, etc. may also be used. Main ingredient The two-component curable resin composition containing (a) and (c) has the effect of improving the contamination resistance of the cured product. In addition, (a) the acrylic compound and (c) the acrylic polymer having 0.3 to 1.2 reactive silicon groups per molecule have the effect of improving the weather resistance of the cured product. These may be used alone or in combination of two or more.

[0091] Main agent according to this embodiment The content of the plasticizer other than the epoxy compound (C) and the phthalate ester compound (F) in the composition is, relative to 100 parts by weight of the polyoxyalkylene polymer (A), preferably 0 to 200 parts by weight, more preferably 30 to 170 parts by weight, more preferably 50 to 150 parts by weight, still more preferably 70 to 130 parts by weight, and particularly preferably 90 to 110 parts by weight, in total, including the epoxy compound (C) and the phthalate ester compound (F).

[0092] The main agent The amount of water (moisture content) in is not particularly limited, but is preferably 0.1% or more because it provides better storage stability. The main agent In 100 parts by weight, the content is preferably 200 ppm to 10,000 ppm, more preferably 500 ppm to 8,000 ppm, further preferably 1,000 ppm to 7,000 ppm, and particularly preferably 1,500 ppm to 6,000 ppm.

[0093] Main agent according to this embodiment may further comprise an adhesion promoter. The main agent When the composition further comprises an adhesion promoter, Main ingredient has the advantage of improving adhesion to the substrate and increasing strength.

[0094] Examples of the adhesion promoter include aminosilane compounds, epoxysilane compounds, isocyanatesilane compounds, acrylicsilane compounds, etc. As the adhesion promoter, aminosilane compounds are particularly preferred.

[0095] Main agent according to this embodiment The content of the adhesion promoter in the composition is preferably 0.1 to 10.0 parts by weight, more preferably 0.2 to 5.0 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer (A).

[0096] Main agent according to this embodiment may further comprise a solvent and / or diluent. The main agent If the product contains a solvent and / or diluent, Main ingredient has the advantage of reducing viscosity and improving workability.

[0097] Examples of the solvent and diluent include low-viscosity liquid compounds such as hydrocarbon compounds, aromatic compounds, alcohols, esters, and silicone oils.

[0098] Main agent according to this embodimentThe content of the solvent and / or diluent in the composition is preferably 0.1 to 20.0 parts by weight, more preferably 0.2 to 10.0 parts by weight, in total, of the solvent and diluent per 100 parts by weight of the polyoxyalkylene polymer (A).

[0099] Main agent according to this embodiment may further comprise an antioxidant. The main agent When the composition further contains an antioxidant, Main ingredient has the advantage that deterioration can be delayed even when stored for a long period of time, and performance can be maintained even when stored under high temperature conditions.

[0100] Examples of the antioxidant include hindered phenol compounds, monophenol compounds, polyphenol compounds, etc. As the antioxidant, hindered phenol compounds are particularly preferred.

[0101] Main agent according to this embodiment The content of the antioxidant in the composition is preferably 0.1 to 10.0 parts by weight, more preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

[0102] Main agent according to this embodiment In addition to the polyoxyalkylene polymer (A), the composition may contain an acrylic polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, etc. The acrylic polymer having a reactive silicon group and the saturated hydrocarbon polymer having a reactive silicon group are The main agent The heat resistance and / or weather resistance of the cured product obtained by the two-component curable resin composition containing the compound can be significantly improved. The main agent When used as a construction sealant and / or industrial sealant, it has the advantage that the life of the sealant can be significantly extended.

[0103] The amount of these used is preferably 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A).

[0104] Main agent according to this embodiment In addition to the above, the composition may contain a flame retardant, a hardening modifier, a lubricant, a pigment, a foaming agent, a mildewproofing material, and the like.

[0105] [For two-component curable resin compositions Main ingredient Manufacturing method] For a two-component curable resin composition according to one embodiment of the present invention Main ingredient The manufacturing method of A method for producing a base agent for a two-component curable resin composition, which is prepared by mixing a base agent and a curing agent, each of which is separate, to form a two-component curable resin composition, the method comprising: The method includes a step of mixing 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group, 10 to 400 parts by weight of calcium carbonate (B) surface-treated with a fatty acid compound, and 2 to 70 parts by weight of an epoxy compound (C), wherein the fatty acid compound contains 12 mol % or less of a fatty acid compound whose hydrocarbon composition has 14 or less carbon atoms, based on 100 mol % of the fatty acid compound.

[0106] In the present specification, "a two-component curable resin composition according to one embodiment of the present invention" means a Main ingredient "The manufacturing method of the present invention" may be hereinafter referred to as "the present manufacturing method."

[0107] The present production method provides a two-component curable resin composition having the above-described configuration, which has good storage stability even in a high-temperature and high-humidity environment. Main ingredient for This has the advantage of being able to provide:

[0108] Hereinafter, each aspect of the present production method will be described. However, other than the details described below, the same applies to the method for producing a two-component curable resin composition. Main ingredient ] The description in the section is incorporated by reference.

[0109] In the step (mixing step) of mixing the polyoxyalkylene polymer (A), calcium carbonate (B), and epoxy compound (C) in the present production method, the method for mixing these components (mixing method) is not particularly limited. Examples of the mixing method include (1) blending the above-mentioned components and kneading them using a mixer, roll, kneader, or the like at room temperature (e.g., 15°C to 30°C) or under heat (e.g., 50°C to 120°C), and (2) dissolving the components in a small amount of a suitable solvent and mixing the resulting solutions.

[0110] The main agent Reduces moisture content, resulting in excellent storage stability Main ingredient Therefore, in this production method, the Main ingredient It is preferable that the method further comprises a step of dehydrating and / or drying the product.

[0111] The main agent The method for dehydrating and / or drying the Main ingredient When the material is a solid such as a powder, a heat drying method or a reduced pressure dehydration method is preferable. Main ingredient When the compound is a liquid, a dehydration method under reduced pressure or a dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is preferred. In addition to these methods, a method using an alkoxysilane compound such as n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methyl silicate, ethyl silicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, or γ-glycidoxypropyltrimethoxysilane is also preferred. Main ingredient Add to Main ingredient It is also possible to dehydrate the compound by reacting it with the water (moisture) in the solution. Main ingredient Add to Main ingredient It is also possible to dehydrate it by reacting it with the water (moisture) in the Main ingredient isocyanate groups and Main ingredientThe water (moisture) in the solution may be reacted with the solution to dehydrate it.

[0112] [Two-component curable resin composition] The two-component curable resin composition according to one embodiment of the present invention is a curable resin composition for two-component curable resin compositions. Main ingredient ] Main ingredient or [for two-component curable resin compositions Main ingredient The manufacturing method described in Main ingredient , including.

[0113] In one embodiment of the present invention, before being made into a two-component curable resin composition, Main ingredient Since the curing agent is stored separately from the curing agent, the curing agent for the two-component curable resin composition is Main ingredient can be stored for a longer period of time and more stably. Main agent according to this embodiment and / or obtained by this manufacturing method Main ingredient can be mixed with a curing agent just before application to prepare a two-component curable resin composition. 。

[0114] [ Hardener] The curing agent is a mixture containing ingredients such as a curing catalyst, a filler, a plasticizer, and water.

[0115] Examples of the curing catalyst include known curing catalysts such as tin compounds such as dibutyltin diacetylacetonate, stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversatate, tin octoate, tin versatate, and tin naphthenate.

[0116] As a curing catalyst for the two-component curable resin composition according to one embodiment of the present invention, tin octoate is preferably used because it is excellent in curing speed and / or durability of the cured product.

[0117] In order to increase 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.

[0118] The filler and plasticizer contained in the curing agent are not particularly limited and may be any known filler and plasticizer.

[0119] The curing agent can be produced by a conventional method, such as (1) blending components such as a curing catalyst, a filler, a plasticizer, and water, and mixing the components at room temperature or under heat using a mixer, roll, or kneader, or (2) dissolving the components in a small amount of a suitable solvent and mixing the resulting solutions.

[0120] [Color Master] The two-component curable resin composition according to one embodiment of the present invention may further include a color master. By including a color master in the two-component curable resin composition, the color of the produced cured product can be adjusted as desired.

[0121] The color master may be a commercially available product. Specific examples of the color master include, but are not limited to, a paste-like mixture containing a pigment such as tin oxide, carbon black, titanium oxide, or red iron oxide, a filler such as calcium carbonate or kaolin, and a plasticizer. The pigment, filler, and plasticizer contained in the color master are not particularly limited and may be any known material. Furthermore, each of the pigment, filler, and plasticizer may be used alone or in combination of two or more.

[0122] The amount of the color masterbatch used is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A).

[0123] [Cured product] A cured product can be obtained by curing the two-component curable resin composition according to one embodiment of the present invention. The cured product obtained by curing the two-component curable resin composition according to one embodiment of the present invention is also one embodiment of the present invention.

[0124] The method for producing a cured product according to one embodiment of the present invention is not particularly limited, but specifically, a cured product can be obtained, for example, by sequentially performing the following operations (1) and (2): (1) The two-component curable resin composition is molded into a 3 mm thick sheet using, for example, a polyethylene mold, taking care to prevent air bubbles, to obtain a sheet sample; (2) The sheet sample produced in (1) is left to stand at 23°C and 50% RH (relative humidity) for 3 days, and then left to stand at 50°C and 50% RH for a further 4 days, thereby obtaining a sheet-like cured product.

[0125] The cured product according to one embodiment of the present invention has the above-described configuration and therefore has the advantage of excellent tensile properties such as 100% stress (modulus), strength at break (breaking strength), and elongation at break (elongation at break). [Example]

[0126] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. <Material> The materials used in the examples and comparative examples are as follows.

[0127] [Polyoxyalkylene polymer (A)] As the polyoxyalkylene polymer (A), Kaneka MS Polymer S810 manufactured by Kaneka Corporation was used.

[0128] Kaneka MS Polymer S810 is a polyoxyalkylene polymer containing approximately two methyldimethoxysilyl groups per molecule as reactive silicon groups and polyoxypropylene units in the main chain. Kaneka MS Polymer S810 has a number average molecular weight (Mn) of 26,000.

[0129] [Surface-treated calcium carbonate (B)] Colloidal calcium carbonate was treated with a fatty acid compound, which is a mixture of multiple fatty acids, and used as calcium carbonates A to G. Calcium carbonates A to G are surface-treated calcium carbonates. For calcium carbonates A to G, (a) the composition of each fatty acid contained in 100 mol% of the fatty acid compound, (b) the BET specific surface area (m 2 / g), and (c) the amount of fatty acid compound attached are shown in Table 1. Colloidal calcium carbonate was used as calcium carbonate H without any surface treatment. The BET specific surface area (m 2 / g) are shown in Table 1.

[0130] [Table 1]

[0131] In Table 1, C indicates the number of carbon atoms in each fatty acid, and if the fatty acid has unsaturated bonds, the number of unsaturated bonds is also listed.

[0132] The amount of fatty acid compound attached to each of calcium carbonates A to G was measured using a differential thermal analyzer (TGD9600, manufactured by ULVAC Corporation) by carrying out the following steps (1) to (3) in order: (1) calcium carbonates A to G (surface-treated calcium carbonates) were heated, and the temperature of the surface-treated calcium carbonates was increased from room temperature to 500°C at a rate of 10°C / min; (2) the weight of the surface-treated calcium carbonate when it was at 200°C and the weight of the surface-treated calcium carbonate when it was at 500°C were measured; (3) the loss on heating (%) was calculated using the following formula, and the obtained loss on heating (%) was defined as the surface adhesion amount (wt%) of fatty acid compound per 100 wt% of the surface-treated calcium carbonate. Heat loss (%) = [(weight (g) of surface-treated calcium carbonate when the surface-treated calcium carbonate is at 200°C - weight (g) of surface-treated calcium carbonate when the surface-treated calcium carbonate is at 500°C) / weight (g) of surface-treated calcium carbonate when the surface-treated calcium carbonate is at 200°C)] × 100 [Heavy calcium carbonate] The heavy calcium carbonate used was LM2200 manufactured by DONGGUAN LIMAO CHEMICAL CO., LTD. This heavy calcium carbonate had no surface treatment and a BET specific surface area of ​​1.1 m 2 / g.

[0133] [Epoxy compounds (C)] The epoxy compounds used were Sanso Cizer E-PS manufactured by New Japan Chemical Co., Ltd. and JDH22E manufactured by ZHEJIANG JIAAO ENPROTECH STOCK CO., LTD. Both are bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate.

[0134] [Photocurable substance (D)] As the photocurable material, Aronix M309 manufactured by Toagosei Co., Ltd., which is trimethylolpropane triacrylate, was used.

[0135] Hollow Filler (E) As the hollow filler, H25 manufactured by SINOSTEEL MAANSHAN NEW MATERIAL TECHNOLOGY Co., LTD., which is a hollow glass filler with a volume average particle size of 95 μm, was used.

[0136] [Phthalate esters (F)] As the phthalate ester (F), DIDP manufactured by J-Plus Co., Ltd. or DINP manufactured by J-Plus Co., Ltd. was used. DIDP is diisodecyl phthalate, and DINP is diisononyl phthalate.

[0137] [UV absorber] As the ultraviolet absorber, Tinuvin 326 manufactured by BASF, a benzotriazole-based compound, was used.

[0138] [Light stabilizer] As the light stabilizer, Tinuvin 770 manufactured by BASF, which is a hindered amine compound, was used.

[0139] [Thixotropic agent] As the thixotropic agent, Disparlon 308 manufactured by Kusumoto Chemicals Co., Ltd., which is a hydrogenated castor oil derivative, was used.

[0140] [Hardening agent] (a) 3.0 parts by weight of Neostan U-28 (trade name, manufactured by Nitto Kasei Co., Ltd.), a tin octoate curing catalyst, (b) 0.6 parts by weight of laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.), (c) 6.4 parts by weight of diisodecyl phthalate (manufactured by J-Plus Corporation), (d) 5.0 parts by weight of ASP170 (trade name, manufactured by BASF), a kaolin, and (e) 15 parts by weight of LM2200, a heavy calcium carbonate, were weighed out. The weighed raw materials were dispersed in a homogenizer for 5 minutes, and the resulting mixture was used as the curing agent.

[0141] [Color Master] (a) 5.0 parts by weight of titanium oxide (tipake R-820, product name, manufactured by Ishihara Sangyo Kaisha, Ltd.) as a white pigment, (b) 4.0 parts by weight of DIDP as a plasticizer, and (c) 0.1 parts by weight of carbon black (manufactured by Asahi Carbon Co., Ltd.) as a black pigment were weighed out. The weighed raw materials were dispersed using a triple paint roll, and the resulting mixture was used as a color master.

[0142] <Evaluation method> The evaluation methods used in the examples and comparative examples will be explained below.

[0143] [For two-component curable resin compositions Main ingredient viscosity] ≪Initial viscosity≫ For two-component curable resin compositions Main ingredientAfter manufacturing, the product is stored in a temperature-controlled room at 23°C and 50% RH. Main ingredient The mixture was left to stand for one day. Main ingredient The viscosity of each of the above was measured at 2 rpm using a BS type viscometer (manufactured by Tokimec Co., Ltd., rotor No. 7) and recorded as the initial viscosity (Pa·s). The results are shown in Table 2 or 3.

[0144] [Viscosity increase rate after storage at 50℃ 85%RH] For two-component curable resin compositions Main ingredient The samples were left at 50°C and 85% RH (relative humidity). Main ingredient and placed in a temperature-controlled room at 23°C and 50% RH (relative humidity). Main ingredient The mixture was left to stand for 5 hours. Main ingredient The viscosity of each of the two-component curable resin compositions was measured at 2 rpm using the same device as above, and the viscosity (Pa·s) after storage at 50°C and 85% RH was recorded. Main ingredient The ratio (%) of the viscosity after storage at 50°C and 85% RH to the initial viscosity was calculated, and this was taken as the viscosity increase rate (%) after storage at 50°C and 85% RH. The results are shown in Table 2 or 3. Note that, as a result of being left under conditions of 50°C and 85% RH, Main ingredient If the viscosity could not be measured due to gelation or hardening, this was noted in Table 2 or 3.

[0145] [Method of manufacturing the cured product] For each of the two-component curable resin compositions obtained in the examples and comparative examples Main ingredient A two-component curable resin composition was prepared by mixing 100 parts by weight of the curing agent, 10 parts by weight of the curing agent, and 3 parts by weight of the color master using a centrifugal mixer called Awatori Rentaro manufactured by Thinky Corporation. The obtained two-component curable resin composition was molded into a 3 mm thick sheet using a polyethylene mold, taking care to prevent air bubbles, to prepare a sheet specimen. The sheet specimen was left at 23°C and 50% RH for 3 days, and then left at 50°C and 50% RH for a further 4 days. A cured product was produced using this method.

[0146] [Tensile properties of cured product] The resulting cured product was punched into a No. 3 dumbbell shape to prepare test specimens. Using these test specimens, a tensile test (tensile speed: 200 mm / min) was conducted at 23°C (50% RH) to measure the 100% stress (modulus), strength at break (breaking strength), and elongation at break (elongation at break). The results are shown in Tables 2 and 3.

[0147] <Examples and Comparative Examples> Example 1 100 parts by weight of polyoxyalkylene polymer (A) (Kaneka MS Polymer S810), 115 parts by weight of surface-treated calcium carbonate (B) (Calcium Carbonate A), 20 parts by weight of epoxy compound (C) (E-PS), 3.0 parts by weight of photocurable material (D) (M309), 10.00 parts by weight of hollow filler (E) (H25), 80 parts by weight of phthalate ester compound (F) (DIDP), 50 parts by weight of heavy calcium carbonate (LM2200), 1.0 part by weight of ultraviolet absorber (Tinuvin 326), 1.0 part by weight of light stabilizer (Tinuvin 770), and 3.0 parts by weight of thixotropic agent (Disparlon 308) were weighed and mixed with a metal spatula for 3 minutes. This mixture was kneaded using a three-roll paint roller at room temperature (25°C) to produce a two-component curable resin composition. Main ingredient The obtained Main ingredient The initial viscosity and viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0148] Example 2 The same method as in Example 1 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate B. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity of the product, the viscosity increase rate after storage at 50°C and 85% RH, and the Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0149] Example 3 The same method as in Example 1 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate C. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity, viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0150] Example 4 The same method as in Example 1 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate D. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity, viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0151] (Comparative Example 1) The same method as in Example 1 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate E. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity, viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0152] (Comparative Example 2) The same method as in Example 1 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate F. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity, viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0153] (Comparative Example 3) The same method as in Example 1 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate G. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity, viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0154] (Reference example 1) The same method as in Example 1 was used except that surface-untreated calcium carbonate H was used instead of surface-treated calcium carbonate (B). Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity, viscosity increase rate after storage at 50°C and 85% RH, and Main ingredient The tensile properties of the cured product containing the compound were measured. The results are shown in Table 2.

[0155] [Table 2]

[0156] The results shown in Table 2 reveal the following: Main ingredient The two-component curable resin compositions of Examples 1 to 4, which are one embodiment of the present invention, do not gel even when stored for 4 weeks under conditions of 50°C and 85% RH. Main ingredient On the other hand, the two-component curable resin compositions of Comparative Examples 1 to 3, which are outside the scope of the present invention and contain surface-treated calcium carbonate (B) with a fatty acid compound containing more than 12 mol% of a fatty acid having 14 or less carbon atoms (C) in 100 mol% of the fatty acid compound, have good storage stability even under high-temperature and high-humidity conditions. Main ingredient When stored under conditions of 50°C and 85% RH, the two-component curable resin compositions of Comparative Examples 1 to 3 gelled within 4 weeks. Main ingredientIt can be said that the storage stability of the two-component curable resin composition of Reference Example 1, which does not contain surface-treated calcium carbonate but contains surface-untreated calcium carbonate H, is poor in a high-temperature and high-humidity environment. Main ingredient It can be seen that the cured product provided by has a small elongation at break.

[0157] Example 5 100 parts by weight of polyoxyalkylene polymer (A) (Kaneka MS Polymer S810), 140 parts by weight of surface-treated calcium carbonate (B) (calcium carbonate D), 30 parts by weight of epoxy compound (C) (JDH22E), 4.5 parts by weight of photocurable material (D) (M309), 15.00 parts by weight of hollow filler (E) (H25), 80 parts by weight of phthalate ester compound (F) (DINP), 30 parts by weight of heavy calcium carbonate (trade name: LM2200), 1.0 part by weight of ultraviolet absorber (Tinuvin 326), 1.0 part by weight of light stabilizer (Tinuvin 770), and 3.0 parts by weight of thixotropic agent (Disparlon 308) were weighed and mixed with a metal spatula for 3 minutes. This mixture was kneaded at room temperature (25°C) using a three-roll paint roller to obtain a two-component curable resin composition. Main ingredient The obtained Main ingredient The initial viscosity and the viscosity increase rate after storage at 50°C and 85% RH were measured. The measurement results are shown in Table 3.

[0158] Example 6 A two-component curable resin composition was prepared in the same manner as in Example 5, except that the amount of epoxy compound (C) (JDH22E) was changed to 50 parts by weight and the amount of phthalate ester compound (F) (DINP) was changed to 60 parts by weight. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity and the viscosity increase rate after storage at 50°C and 85% RH were measured. The measurement results are shown in Table 3.

[0159] Comparative Example 4 The same method as in Example 5 was used except that the epoxy compound (C) (JDH22E) was not used and the amount of the phthalate ester compound (F) (DINP) was changed to 110 parts by weight. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity and the viscosity increase rate after storage at 50°C and 85% RH were measured. The measurement results are shown in Table 3.

[0160] (Comparative Example 5) The same method as in Comparative Example 4 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate G. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity and the viscosity increase rate after storage at 50°C and 85% RH were measured. The measurement results are shown in Table 3.

[0161] (Comparative Example 6) The same method as in Example 5 was used except that the surface-treated calcium carbonate (B) was changed from calcium carbonate A to calcium carbonate G. Main ingredient Next, in the same manner as in Example 1, Main ingredient The initial viscosity and the viscosity increase rate after storage at 50°C and 85% RH were measured. The measurement results are shown in Table 3.

[0162] [Table 3]

[0163] The results shown in Table 3 reveal the following: Main ingredient In other words, the viscosity increase was suppressed to a level that allowed the viscosity to be measured even after storage for two weeks under conditions of 50°C and 85% RH. Main ingredientOn the other hand, the two-component curable resin compositions of Comparative Examples 4 and 5, which do not contain the epoxy compound (C) and are outside the scope of the present invention, have good storage stability even under high temperature and high humidity conditions. Main ingredient When stored under conditions of 50°C and 85% RH, the viscosity increased to the point where it was no longer possible to measure the viscosity within two weeks. Main ingredient The storage stability of the two-component curable resin composition of Comparative Example 6, which is outside the scope of the present invention and contains surface-treated calcium carbonate (B) with a fatty acid compound containing more than 12 mol% of a fatty acid having 14 or less carbon atoms (C) in 100 mol% of the fatty acid compound, is poor in high-temperature and high-humidity environments. Main ingredient When stored under conditions of 50°C and 85% RH, the viscosity increased to the point where it could not be measured within 2 weeks. Main ingredient It can be said that the storage stability of the composition is poor in a hot and humid environment. [Industrial Applicability]

[0164] According to one embodiment of the present invention, a two-component curable resin composition having good storage stability even in a high-temperature and high-humidity environment is provided. Main ingredient Therefore, one embodiment of the present invention can be suitably used in fields such as sealing materials, adhesives, pressure-sensitive adhesives, waterproofing materials, waterproof coating materials, mold release agents, vibration-proofing materials, vibration-damping materials, sound-proofing materials, foam materials, paints, and spray materials for buildings, ships, automobiles, roads, etc.

Claims

1. 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group, 10 to 400 parts by weight of calcium carbonate (B) surface-treated with a fatty acid compound, and Call Contains 2 to 70 parts by weight of an epoxy compound (C), The fatty acid compound has a hydrocarbon composition of carbon number of 100 mol % of the fatty acid compound. A two-component curable resin composition containing 12 mol% or less of a fatty acid compound having a molecular weight of 14 or less. Resin composition.

2. The calcium carbonate (B) surface-treated with a fatty acid compound is The two-component curable resin composition according to claim 1, which contains treated colloidal calcium carbonate. Resin composition for products.

3. 10.0 parts by weight of a photocurable substance (D) 3. A resin composition for use in the two-component curable resin composition according to 2.

4. The composition of any one of claims 1 to 5, further comprising 1.00 to 20.00 parts by weight of a hollow filler (E).

4. A resin composition for use in the two-component curable resin composition according to any one of claims 3 to 3.

5. The two-component composition according to claim 4, wherein the hollow filler (E) contains glass balloons. A resin composition for use in a curable resin composition.

6. The composition according to any one of claims 1 to 5, further comprising a phthalate ester compound (F). A resin composition for use in the above-mentioned two-component curable resin composition.

7. A curable resin obtained by mixing the resin composition for the two-component curable resin composition with a curing agent.

7. The resin composition according to claim 1, wherein the cured product obtained by curing the resin composition has an elongation at break of 300% or more. A resin composition for use in the two-component curable resin composition according to any one of claims 1 to 14.

8. The resin composition for a two-component curable resin composition according to any one of claims 1 to 7 is included. A two-component curable resin composition.

9. 100 parts by weight of a polyoxyalkylene polymer (A) having a reactive silicon group, 10 to 400 parts by weight of calcium carbonate (B) surface-treated with a fatty acid compound, and Call and mixing 2 to 70 parts by weight of an epoxy compound (C), The fatty acid compound has a hydrocarbon composition of carbon number of 100 mol % of the fatty acid compound. A two-component curable resin composition containing 12 mol% or less of a fatty acid compound having a molecular weight of 14 or less. A method for producing a resin composition.

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