Moisture-curable resin composition, adhesive, sealing agent, and cured object

Abstract

The present invention relates to a moisture-curable resin composition comprising the following (A), (B), (C), and (D) components. The (A) component is an oxyalkylene polymer having a hydrolyzable silyl group. The (B) component is a biomass filler. The (C) component is a filler surface-treated with a C12-C18 fatty acid. The (D) component is a metal catalyst.

Description

Moisture-curable resin composition, adhesive, sealant, and cured product

[0001] The present invention relates to a moisture-curable resin composition having excellent curability and stable adhesive performance, and to an adhesive, a sealant, and a cured product obtained from the moisture-curable resin composition.

[0002] Conventionally, reactive polymers having hydrolyzable or hydroxyl groups have been used in moisture-curing adhesives and sealants, and organotin compounds have been widely used as curing catalysts. However, there are concerns that the use of organotin compounds will be restricted due to changes in regulations. Furthermore, silicone compounds used in conventional reactive polymers contain low-molecular-weight siloxanes that cause contact failure, limiting their applications. For this reason, the use of modified silicone compounds that do not contain low-molecular-weight siloxanes, such as those described in Patent Document 1, is becoming more widespread.

[0003] Japanese Patent Application Publication No. 2006-143985

[0004] However, modified silicone compounds that do not use an organotin catalyst have problems such as a slower curing rate compared to curable resin compositions that use an organotin catalyst.

[0005] Furthermore, adhesives and sealants are required to have stable adhesive performance. As an indicator of stable adhesive performance, the state of failure when an external force is applied to break the adhesive or sealant after bonding it to an adherend is used. If the failure state is interfacial failure, which occurs at the interface between the adherend and the adhesive or sealant, it is considered undesirable because variations in the interfacial state lead to large variations in adhesive strength. On the other hand, if the failure state is cohesive failure, which occurs within the adhesive or sealant, it is considered to have stable adhesive performance.

[0006] Adhesives and sealants are required to have the cohesive failure for stable adhesive performance, and also to have durability (heat resistance, oil resistance) as a performance of adhesives and sealants. However, when they are exposed to a solvent such as oil, which has a high affinity with modified silicone compounds, for a long time, or when they are subjected to a long-term thermal history, the failure state becomes interfacial failure, resulting in an unstable adhesive state.

[0007] Therefore, an object of the present invention is to obtain a moisture-curable resin composition that does not contain low-molecular-weight siloxane, that cures stably without the use of an organotin catalyst, that exhibits cohesive failure after adhesion, and that can maintain the cohesive failure state even after heat resistance and oil resistance tests.

[0008] As a result of extensive research, the present inventors have discovered a moisture-curable resin composition having a novel composition that can achieve the above-mentioned object. The gist of the present invention is as follows: [1] A moisture-curable resin composition comprising the following components (A), (B), (C), and (D): Component (A): an oxyalkylene polymer having a hydrolyzable silyl group; Component (B): a biomass filler; Component (C): a filler that has been surface-treated with a fatty acid having carbon atoms of 12 to 18; and Component (D): a metal catalyst.

[0009] [2] The moisture-curable resin composition according to [1], wherein the component (D) is a zinc catalyst.

[0010] [3] The moisture-curable resin composition according to [1] or [2], wherein the component (C) is a filler surface-treated with at least one fatty acid selected from the group consisting of palmitic acid, stearic acid, and octadecenoic acid.

[0011] [4] The moisture-curable resin composition according to any one of [1] to [3], wherein the component (C) is ground calcium carbonate surface-treated with a fatty acid having a carbon number of C12 to C18.

[0012] [5] The BET specific surface area of ​​the component (C) is 10,000 cm ２ / g or more, [1] to [4]. The moisture-curable resin composition according to any one of [1] to [4].

[0013] [6] The moisture-curable resin composition according to any one of [1] to [5], further comprising a plasticizer as component (E).

[0014] [7] The moisture-curable resin composition according to [6], wherein the component (E) contains a castor oil-modified fatty acid ester.

[0015] [8] The moisture-curable resin composition according to any one of [1] to [7], further comprising a non-surface-treated filler as component (C2).

[0016] [9] An adhesive comprising the moisture-curable resin composition according to any one of [1] to [8].

[0017]

[10] A sealant comprising the moisture-curable resin composition according to any one of [1] to [8].

[0018]

[11] A cured product obtained by curing the moisture-curable resin composition according to any one of [1] to [8].

[0019] The present invention provides a moisture-curable resin composition that does not contain low-molecular-weight siloxane, which has good curability even without containing an organotin catalyst, and which causes stable cohesive failure after adhesion.

[0020] The details of the present invention are described below. In this specification, "X to Y" is used to mean that the numerical values ​​(X and Y) before and after it are included as the lower limit and upper limit, and means "at least X but not more than Y."

[0021] The present invention relates to a moisture-curable resin composition comprising components (A), (B), (C), and (D).

[0022] The component (A) used in the present invention is an oxyalkylene polymer having a hydrolyzable silyl group. The oxyalkylene polymer referred to in the present invention refers to a polymer whose main chain comprises an oxyalkylene skeleton (such as polyethylene glycol, polypropylene glycol, polytrimethylene glycol, or polytetramethylene glycol). The hydrolyzable silyl group in the component (A) may be bonded to the end and / or side chain of the oxyalkylene polymer, but is preferably bonded to the end in order to achieve a stable cohesive failure state. Furthermore, the component (A) is preferably liquid at 25°C from the viewpoint of ease of handling. These components (A) may be used alone or in combination of two or more.

[0023] The hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxide group, a ketoximate group, an amino group, an amide group, an aminooxy group, and an alkenyloxide group. From the viewpoint of curability, an alkoxy group is preferred.

[0024] Examples of the alkoxy group include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, tert-butoxy, phenoxy, and benzyloxy groups, but from the viewpoint of achieving both displacement tracking and resin strength, methoxy and ethoxy groups are preferred, methoxy is more preferred, and trimethoxy is most preferred. These alkoxy groups may be used alone or in combination of different types.

[0025] The viscosity of the component (A) at 23°C is preferably 1 to 500 Pa·s, more preferably 20 to 200 Pa·s, and most preferably 30 to 80 Pa·s. If the viscosity is 1 Pa·s or higher, the moisture-curable resin composition has good workability, and if the viscosity is 500 Pa·s or lower, there is no risk of workability being reduced even when the component (A) is mixed with the components (B) and (C). The viscosity of the component (A) is a value measured in accordance with JIS K1557.

[0026] Commercially available products of the component (A) include, but are not limited to, SAT010, SAX115, SAT030, SAT200, SAT350, SAT400, SAX220, SAX510, SAX530, SAX575, SAX580, SAX710, SAX720, SAX725, SAX750, SAX770, S203, S303, S203 H, S303H, S943S, S911S, MA440, MA447, MA451, MA903, MA903M, MA904, S943, MAX923, MAX951, SAX520, etc. (manufactured by Kaneka Corporation), ES-S2410, ES-S2420, ES-S3430, ES-S3610, ES-S3630 (manufactured by Asahi Glass Co., Ltd.), etc. These may be used alone or in combination of two or more.

[0027] The component (B) used in the present invention is a biomass filler. A biomass filler is a filler refined from plants or animals. The use of the component (B) can improve the cohesive failure rate. Specific examples of the component (B) include rice flour, cellulose, lignocellulose, starch, shell powder obtained by crushing shellfish such as scallops and oysters, and eggshell powder obtained by crushing eggshells. These may be used alone or in combination of two or more. From the viewpoint of improving the cohesive failure rate, the component (B) is preferably shell powder or eggshell powder, more preferably unbaked shell powder, and most preferably powder derived from unbaked scallop shells. The term "unbaked" as used here means that no baking step has been performed after crushing.

[0028] Commercially available products of the component (B) include, but are not limited to, Scallop Powder S and Scallop Powder R (manufactured by NC Corporation).

[0029] The average particle size of the component (B) is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and most preferably 3 to 20 μm. By setting the average particle size to 0.1 to 50 μm, the cohesive failure rate can be improved and there is no risk of a decrease in adhesive strength. The average particle size in the present invention is the particle size (D50) value at a cumulative volume ratio of 50% in the particle size distribution determined by a laser diffraction scattering method.

[0030] The blending amount of the component (B) is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass, and most preferably 30 to 80 parts by mass, per 100 parts by mass of the component (A). By blending an amount of 10 to 200 parts by mass, the cohesive failure rate can be improved and there is no risk of a decrease in adhesive strength.

[0031] Component (C) used in the present invention is a filler that has been surface-treated with a fatty acid having 12 to 18 carbon atoms. Component (C) in the present invention does not include component (B). The number of carbon atoms of 12 to 18 referred to here includes the carbon atoms of the carboxylic acid. By including component (C), the cohesive failure rate can be maintained even after heat resistance and oil resistance tests.

[0032] In component (C), the filler to be surface-treated with a fatty acid having 12 to 18 carbon atoms is not particularly limited, but examples include powders of talc, silica, clay, calcium carbonate, magnesium carbonate, calcium silicate, glass, alumina, zinc oxide, magnesium oxide, aluminum nitride, boron nitride, carbon, diamond, gold, silver, copper, nickel, etc. From the viewpoint of maintaining the cohesive failure rate after heat resistance tests and oil resistance tests, calcium carbonate powder is preferred. When calcium carbonate powder is used, examples of the calcium carbonate include light calcium carbonate, heavy calcium carbonate, and colloidal calcium carbonate. However, from the viewpoint of reducing the risk of a decrease in adhesive strength, the calcium carbonate preferably contains heavy calcium carbonate, and more preferably consists solely of heavy calcium carbonate. When the filler to be surface-treated with a fatty acid having 12 to 18 carbon atoms in component (C) is heavy calcium carbonate powder, it is preferable to use one produced by pulverizing and classifying limestone.

[0033] Specific examples of fatty acids having 12 to 18 carbon atoms include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid, and unsaturated fatty acids such as palmitoleic acid, oleic acid, elaidic acid, ricinoleic acid, linoleic acid, γ-linolenic acid, α-linolenic acid, punicic acid, stearic acid, and octadecenoic acid. These may be used alone or in combination of two or more. From the viewpoint of heat resistance and oil resistance, fillers surface-treated with saturated fatty acids are preferred, and fillers surface-treated with both saturated and unsaturated fatty acids are more preferred. Among these, from the viewpoint of maintaining the cohesive failure rate after heat resistance and oil resistance tests, component (C) preferably contains a filler surface-treated with one or more fatty acids selected from the group consisting of palmitic acid, stearic acid, and octadecenoic acid, more preferably a filler surface-treated with palmitic acid and stearic acid, and most preferably a filler surface-treated with palmitic acid, stearic acid, and octadecenoic acid.

[0034] The average particle size of component (C) is preferably 0.1 to 50 μm, more preferably 0.3 to 30 μm, and most preferably 0.5 to 20 μm. By having an average particle size of 0.1 to 50 μm, the cohesive failure rate after heat resistance tests and oil resistance tests can be maintained, and there is no risk of a decrease in adhesive strength.

[0035] The BET specific surface area of ​​the component (C) is 10,000 cm ２ / g or more, and 12,000 cm ２ / g or more, and more preferably 15,000 cm ２ / g or more. ２ / g or more, the cohesive failure rate after the heat resistance test and the oil resistance test can be maintained. The upper limit of the BET specific surface area is not particularly limited, but is preferably 50,000 cm ２ / g, more preferably less than 40,000 cm ２ / g or less.

[0036] The surface treatment can be carried out, for example, by kneading or pulverizing the filler and the fatty acid, or by kneading the filler with a solution in which the fatty acid is dissolved in a solvent or the like, and then drying the solvent in a hot air drying oven or the like.

[0037] The blending amount of the component (C) is preferably 1 to 200 parts by mass, more preferably 20 to 150 parts by mass, and most preferably 30 to 100 parts by mass, per 100 parts by mass of the component (A). By blending an amount of 1 to 200 parts by mass, the cohesive failure rate after a heat resistance test and an oil resistance test can be maintained, and there is no risk of a decrease in adhesive strength.

[0038] In the present invention, it is preferable to further include a filler that has not been surface-treated as component (C2). In the present invention, component (B) is not included in component (C2). Component (C2) is not particularly limited, but examples thereof include talc, silica, clay, calcium carbonate, magnesium carbonate, calcium silicate, glass, alumina, zinc oxide, magnesium oxide, aluminum nitride, boron nitride, carbon, diamond, gold, silver, copper, and nickel. From the viewpoint of maintaining the cohesive failure rate after heat resistance tests and oil resistance tests, calcium carbonate is preferred as component (C2). From the viewpoint of reducing the risk of a decrease in adhesive strength, component (C2) preferably contains heavy calcium carbonate, and more preferably consists solely of heavy calcium carbonate. When component (C2) is heavy calcium carbonate, it is preferable to use calcium carbonate produced by pulverizing and classifying limestone.

[0039] The average particle size of component (C2) is preferably 0.1 to 50 μm, more preferably 0.3 to 30 μm, and most preferably 0.5 to 20 μm. By having an average particle size of 0.1 to 50 μm, the cohesive failure rate after heat resistance tests and oil resistance tests can be maintained, and there is no risk of a decrease in adhesive strength.

[0040] The BET specific surface area of ​​the component (C2) is 10,000 cm ２ / g or more, and 12,000 cm ２ / g or more, and more preferably 15,000 cm ２ / g or more. ２ / g or more, the cohesive failure rate after the heat resistance test and the oil resistance test can be maintained. The upper limit of the BET specific surface area is not particularly limited, but is preferably 50,000 cm ２ / g, more preferably less than 40,000 cm ２ / g or less.

[0041] The blend amount of (C2) is preferably 1 to 300 parts by mass, more preferably 30 to 200 parts by mass, and most preferably 50 to 150 parts by mass per 100 parts by mass of component (A). By blending an amount of 1 to 300 parts by mass, the cohesive failure rate after heat resistance tests and oil resistance tests can be maintained, and there is no risk of a decrease in adhesive strength.

[0042] When the moisture-curable resin composition of the present invention contains the component (C2), the mass ratio of the component (C) to the component (C2) is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and most preferably 40:60 to 60:40. When the mass ratio is 20:80 to 80:20, the cohesive failure rate after a heat resistance test and an oil resistance test can be maintained, and there is no risk of a decrease in adhesive strength.

[0043] The component (D) that can be used in the present invention is a metal catalyst as a curing catalyst. The component (D) is not particularly limited as long as it is a catalyst that crosslinks the component (A). Examples of the component (D) include tin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleyl maleate, dibutyltin octoate, dioctyltin oxide, and dioctyltin dilaurate; titanate compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate; lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, zinc octoate, zinc naphthenate, zinc hexacyanocobaltate complex, 1-methylimidazole-bis(2-hexanoate)zinc complex, alkylamine zinc complex, iron compounds, bismuth carboxylate, aluminum acetylacetonate complex, and metal acetylacetonate complexes such as vanadium acetylacetonate complex. These may be used alone or in combination of two or more kinds.Among them, from the viewpoint of complying with legal regulations and from the viewpoint of excellent curability, the component (D) preferably contains a zinc catalyst or a bismuth catalyst, and most preferably contains a zinc catalyst.When a zinc catalyst is used, a zinc catalyst in which an amine is coordinated to the zinc is more preferred, and a zinc catalyst in which an alkylamine is coordinated to the zinc is most preferred.

[0044] The blending amount of the component (D) is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and most preferably 0.01 to 5 parts by mass, per 100 parts by mass of the component (A). By blending an amount of 0.01 to 20 parts by mass, a moisture-curable resin composition excellent in curability and storage stability can be obtained.

[0045] Commercially available products of the component (D) include K-KAT670 and K-KATXK-648 (manufactured by KING INDUSTRIES), Borchikat 0244, Borchikat 15, and Borchikat 22 (manufactured by OMG Borchers GmbH), but are not limited to these.

[0046] The moisture-curable resin composition of the present invention may further contain a promoter that can be used in combination with component (D). Examples of promoters include amine salts such as dibutylamine-2-ethylhexoate, organic phosphoric acid compounds such as monomethyl phosphate and di-n-butyl phosphate, other acidic catalysts, and basic catalysts. These may be used alone, or two or more types may be used in combination.

[0047] In the present invention, it is preferable to further include a plasticizer as component (E). Component (E) can be broadly classified into phthalate ester plasticizers and non-phthalate ester plasticizers, with non-phthalate ester plasticizers being preferred because they are less carcinogenic and can maintain the effects of the present invention. Examples of non-phthalate ester plasticizers include, but are not limited to, (meth)acrylic polymer plasticizers obtained by polymerizing (meth)acrylic monomers; polyether polyol plasticizers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyester plasticizers obtained from dibasic acids such as sebacic acid and adipic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; process oil plasticizers; alkylsulfonic acid phenyl esters, acetyl tributyl citrate; and castor oil-modified fatty acid esters. These may be used alone or in combination of two or more. From the viewpoint of not decreasing the cohesive failure rate after the heat resistance test and the oil resistance test, the component (E) is preferably a castor oil-modified fatty acid ester or an alkylsulfonic acid phenyl ester, and most preferably a castor oil-modified fatty acid ester.

[0048] The blending amount of the component (E) is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and most preferably 30 to 70 parts by mass, per 100 parts by mass of the component (A). By blending an amount of 10 to 100 parts by mass, there is no risk of the adhesive or sealant performance being reduced in heat resistance tests and oil resistance tests, and a cohesive failure state can be maintained.

[0049] The moisture-curable resin composition of the present invention may contain an appropriate amount of additives such as a storage stabilizer, an adhesion aid, a colorant, or an antioxidant, as long as the additives do not impair the properties of the composition. Addition of these additives can improve storage stability and performance as an adhesive or sealant.

[0050] Examples of the storage stabilizer include silane compounds that do not have reactive functional groups other than alkoxysilyl groups. Examples of silane compounds that do not have reactive functional groups other than alkoxysilyl groups include alkylsilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, and decyltriethoxysilane. These may be used alone or in combination of two or more. From the viewpoint of improving the storage stability of the moisture-curable resin composition of the present invention, the storage stabilizer preferably contains methylmethoxysilane and / or diphenyldimethoxysilane, and more preferably contains methylmethoxysilane and diphenyldimethoxysilane.

[0051] The amount of the storage stabilizer is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 1.0 to 8 parts by mass, per 100 parts by mass of component (A). A blend amount of 0.1 to 20 parts by mass improves storage stability and prevents deterioration of curability. When the storage stabilizer contains both methylmethoxysilane and diphenyldimethoxysilane, the mass ratio of methylmethoxysilane:diphenyldimethoxysilane is preferably 99:1 to 50:50, more preferably 95:5 to 50:50, and most preferably 90:10 to 50:50. A mass ratio of 99:1 to 50:50 can further improve storage stability and heat resistance.

[0052] Examples of the adhesion aid include silane coupling agents. Silane coupling agents are compounds having an alkoxysilyl group and a reactive functional group. Specific examples of silane coupling agents include glycidyl group-containing silane coupling agents such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; (meth)acrylic group-containing silane coupling agents such as γ-methacryloxypropyltrimethoxysilane; amino group-containing silane coupling agents such as N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane; γ-chloropropyltrimethoxysilane; and oligomers thereof. These may be used alone or in combination of two or more. From the viewpoint of improving the adhesive strength and cohesive failure rate to the moisture-curable resin composition of the present invention, the adhesion aid preferably contains an amino group-containing silane coupling agent such as N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or N-phenyl-γ-aminopropyltrimethoxysilane, and more preferably contains N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

[0053] The amount of the adhesive aid blended is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and most preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). By blending an amount of 0.01 to 10 parts by mass, it is possible to improve adhesive strength and cohesive failure rate without reducing storage stability.

[0054] The colorant is not particularly limited as long as it can color the moisture-curable resin composition of the present invention. Specific examples of the colorant include inorganic pigments such as carbon black, barium sulfate, alumina white, clay, and titanium oxide, organic pigments such as indanthrone blue, quinacridone red, dioxazine violet, and phthalocyanine blue, ZnS:Ag, ZnS:Cu, ZnS:Mn, and SrAl. ２ O ４ : Eu, Sr ４ Al １４ O ２５ : Eu, Y ２ O ２ S: Eu, Y ２ O ３ Examples of the colorant include fluorescent inorganic pigments such as Eu, fluorescent organic pigments, and dyes. These may be used alone or in combination of two or more. From the viewpoint of excellent heat resistance and oil resistance, inorganic pigments such as carbon black, barium sulfate, alumina white, clay, and titanium oxide are preferred as the colorant, with carbon black being more preferred.

[0055] The blending amount of the colorant is preferably 0.05 to 3 mass% and more preferably 0.1 to 2 mass% relative to 100 mass% of the entire moisture-curable resin composition. If the blending amount is 0.05 to 3 mass%, the visibility as an adhesive or sealant can be improved, and there is no risk of reducing the adhesive strength or cohesive failure rate.

[0056] Examples of the antioxidant include quinone compounds such as β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, and 2-butyl-4-methyl-6-tert-butylphenol; butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 3,9-bis[2-[3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], methyl 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoate, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-tolyl)tri-p-cresol, calcium diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trimethyl- phenols such as 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, reaction products of N-phenylbenzenamine and 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, picric acid, and citric acid; tris(2,4-di-tert-butylphenyl)phosphite, tris[2 -[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphen-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetrakis(2,4-di-tert-butylphenyl)[1,1-bisphenyl]-4,4'-diylbisphosphonite, 6-[3-(3-tert-butyl-4- Phosphorus compounds such as [hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphene; sulfur compounds such as dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiopropionate), 2-mercaptobenzimidazole; thioether compounds; phenothiazine, 4,4'-bis(α,Examples of the antioxidant include amine compounds such as (α-dimethylbenzyl)diphenylamine; lactone compounds; and vitamin E compounds. These may be used alone or in combination of two or more. From the viewpoint of improving storage stability and heat resistance, the antioxidant preferably contains an amine antioxidant and / or a thioether antioxidant, and more preferably contains an amine antioxidant and a thioether antioxidant.

[0057] The amount of antioxidant blended is preferably 0.01 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A). A blend amount of 0.01 to 5 parts by mass can improve storage stability and heat resistance. When the antioxidant contains both an amine-based antioxidant and a thioether-based antioxidant, the mass ratio of amine-based antioxidant:thioether-based antioxidant is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and most preferably 30:70 to 70:30. A mass ratio of 10:90 to 90:10 can improve storage stability and heat resistance.

[0058] The moisture-curable resin composition of the present invention has excellent curability even without the use of an organotin catalyst. Therefore, the moisture-curable resin composition of the present invention contains substantially no organotin catalyst or organotin compound, or no organotin compound at all. "Substantially no" means that the content of the organotin catalyst or organotin compound relative to the total mass of the moisture-curable resin composition is preferably 0.001% by mass or less, more preferably 0.0001% by mass or less.

[0059] The moisture-curable resin composition of the present invention is substantially free of or completely free of low-molecular-weight siloxanes. The low-molecular-weight siloxanes particularly refer to cyclic low-molecular-weight siloxanes, and refer to siloxanes having 20 or fewer siloxane units (D20).

[0060] The moisture-curable resin composition of the present invention can be a one-component type or a two-component type as needed. Furthermore, the moisture-curable resin composition of the present invention is most suitable for use as a sealant, but can also be used as an adhesive, pressure-sensitive adhesive, coating agent, potting agent, etc. as needed. The present invention relates to, for example, an adhesive or sealant comprising the moisture-curable resin composition.

[0061] When the moisture-curable resin composition of the present invention is used as a sealant, the hardness measured in accordance with JIS K6249 is preferably A10 or more. From the viewpoint of good performance as a sealant, the hardness is preferably A10 or more, more preferably A20 or more. The upper limit of the hardness is not particularly limited, but may be, for example, A60 or less. More specifically, the hardness is measured by the method described in the examples below.

[0062] When the moisture-curable resin composition of the present invention is used as a sealant, the tensile strength measured by the method described in the Examples below is preferably 1.0 MPa or more. From the viewpoint of good performance as a sealant, the tensile strength is preferably 1.0 MPa or more, more preferably 1.3 MPa or more. The upper limit of the tensile strength is not particularly limited, but may be, for example, 3.0 MPa or less.

[0063] When the moisture-curable resin composition of the present invention is used as a sealant, the elongation measured in accordance with JIS K6251 is preferably 200% or more. From the viewpoint of good performance as a sealant, the elongation is preferably 200% or more, more preferably 300% or more. The upper limit of the elongation is not particularly limited, but may be, for example, 600% or less. More specifically, the elongation is measured by the method described in the examples below.

[0064] The moisture-curable resin composition of the present invention can be used in various electrical and electronic fields, buildings, automobiles, civil engineering, and the like. However, since it does not contain cyclic low-molecular-weight siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, it is particularly suitable for use in electrical and electronic components and automotive electrical components.

[0065] <Application Method> The moisture-curable resin composition of the present invention can be applied to an adherend by a known application method for a sealant or adhesive. For example, methods such as dispensing using an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, and spin coating can be used. Note that the moisture-curable resin composition of the present invention is liquid at 25°C from the viewpoint of coatability.

[0066] <Curing Method> The present invention also relates to a cured product obtained by curing the moisture-curable resin composition. The curing temperature is not particularly limited, but is preferably 10 to 50°C, and more preferably 15 to 30°C. The relative humidity during curing is preferably 40% RH or higher. The curing time is preferably 1 hour or longer and shorter than 2 weeks.

[0067] <Sealing Method> The sealing method using the moisture-curable resin composition of the present invention is not particularly limited, but representative examples include FIPG (formed-in-place gasket), CIPG (cured-in-place gasket), MIPG (molded-in-place gasket), liquid injection molding, etc.

[0068] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. (Hereinafter, the moisture-curable resin composition will also be referred to simply as the "composition.")

[0069] Examples 1 to 6, Comparative Examples 1 and 2 The following components were prepared to prepare the compositions. Component (A): Oxyalkylene polymer having trimethoxysilyl groups at both ends, Trade name: Kaneka Silyl SAX575 (manufactured by Kaneka Corporation), Viscosity (23°C): 50 Pa·s Component (B-1): Unburned scallop shell powder, Trade name: Scallop Powder S (manufactured by NC Corporation), Average particle size: 5.8 μm Component (B-2): Unburned scallop shell powder, Trade name: Scallop Powder R (manufactured by NC Corporation), Average particle size: 13 μm Component (C): Filler 1, Heavy calcium carbonate surface-treated with palmitic acid, stearic acid, and octadecenoic acid, Average particle size: 1.0 μm, BET specific surface area: 22,000 cm ２ / g (C2-1) Component: Filler 2 Surface-untreated heavy calcium carbonate Average particle size 1.25 μm BET specific surface area 18,000 cm ２ / g (C2-2) Component: Filler 3 Surface-untreated heavy calcium carbonate Average particle size 1.0 μm BET specific surface area 22,000 cm ２ / g Component (D): Zinc catalyst coordinated with alkylamine Trade name: K-KAT670 (manufactured by King Industries) Component (E-1): Castor oil modified fatty acid ester Trade name: Rickcizer GR-301 (manufactured by Ito Oil Manufacturing Co., Ltd.) Component (E-2): Alkyl sulfonic acid phenyl ester Trade name: MESAMOLL (manufactured by LANXESS) (Other components) Silane compound (storage stabilizer or adhesion aid) Methyltrimethoxysilane Trade name: KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.) N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane Trade name: KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.) Diphenyldimethoxysilane Trade name: KBM-202SS (manufactured by Shin-Etsu Chemical Co., Ltd.) Colorant Carbon black Antioxidant 4,4'-Bis(α,α-dimethylbenzyl)diphenylamine, trade name: Nocrac CD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], trade name: Adekastab AO-60 (manufactured by ADEKA Corporation)

[0070] The components (A), (B), (C), (C2), and (E) were weighed into a stirring vessel and stirred for 30 minutes. The other components were weighed and added, and the mixture was stirred for 30 minutes. Finally, the component (D) was weighed and added, and the mixture was stirred for 10 minutes to obtain a moisture-curable resin composition. The detailed amounts prepared are shown in Table 1, and all values ​​are expressed in parts by mass.

[0071] [Tensile Shear Adhesion Strength] A moisture-curable resin composition was applied to an aluminum (A1050P) test piece measuring 25 mm wide x 100 mm long x 1 mm thick. Then, another aluminum (A1050P) test piece was attached to the test piece, with an overlapping surface of 25 mm x 10 mm x 1 mm clearance. The test piece was then aged for 7 days at 23°C and 50% RH to obtain a test specimen. The shear adhesive strength (unit: MPa) was measured at 25°C using a universal tensile tester (tensile speed: 50 mm / min) in accordance with JIS K 6850:1999. The shear adhesive strength was the value at maximum strength. The measurement results are shown in Table 1 under the heading "Initial" under "Tensile Shear Adhesion Strength." The pass criterion was 1.0 MPa or more.

[0072] [Cohesive Failure Rate] The state of failure of the test piece after the shear adhesive strength test was visually confirmed, and the occupied area rate of the cohesive failure state was calculated. The measurement results are shown in Table 1 as the "Initial" item in "Cohesive Failure Rate". The pass criterion is 100% or more.

[0073] [Durability Test] The tensile shear adhesive strength and cohesive failure rate after the durability test were examined. The durability test in this example consisted of a heat resistance test and an oil resistance test. Note that the test was not conducted on compositions whose initial cohesive failure rate before the durability test did not meet the pass criteria.

[0074] Heat resistance test: Test pieces were prepared in the same manner as in the tensile shear adhesive strength test and left to stand in a hot air drying oven at 120°C for 240 hours. The test pieces were removed and allowed to cool naturally to 25°C, after which the tensile shear adhesive strength and cohesive failure rate were measured. The measurement results are shown in Table 1 as the "heat resistance" item in "tensile shear adhesive strength" or "cohesive failure rate."

[0075] Oil Resistance Test: Test specimens were prepared in the same manner as in the tensile shear adhesive strength test. Test specimens were immersed in a metal container filled with gear oil (Toyota Genuine MG Gear Oil Special GL-3 75W-90) so that the adhesive surface was immersed in the gear oil, and the container was sealed. The sealed metal container was placed in a hot air drying oven at 120°C for 240 hours. The metal container was removed from the hot air drying oven and allowed to cool naturally to 25°C, after which the test specimens were removed from the metal container. Excess gear oil was wiped off the test specimens with a cloth, and the tensile shear adhesive strength and cohesive failure rate were measured. The measurement results are shown in Table 1 as the "oil resistance" item in "tensile shear adhesive strength" or "cohesive failure rate."

[0076]

[0077] According to Table 1, Examples 1 to 6 showed good adhesive strength and cohesive failure state in all stages, including the initial stage, after the heat resistance test, and after the oil resistance test. Comparative Example 1, which did not contain component (C), showed no decrease in adhesive strength after the heat resistance test or the oil resistance test, but the cohesive failure rate was significantly reduced. Comparative Example 2, which did not contain component (B), showed a low initial cohesive failure rate. From the above, it can be seen that the moisture-curable resin composition containing all of components (A) to (D) has an excellent cohesive failure rate, and furthermore, maintains the cohesive failure rate even after the durability test, allowing it to maintain a stable adhesive state.

[0078] In order to confirm the performance (flexibility and resin strength) of Examples 1 to 6 as a sealing agent, the following tests were carried out.

[0079] [Hardness] A sheet having a thickness of 1 mm was prepared using the moisture-curable resin composition and cured for 7 days in an atmosphere of 23°C and 50% RH to obtain a sheet-like cured product. Six sheets of the cured sheet were stacked, and the pressure surface of an A-type durometer hardness tester was pressed with a force of 10 N while keeping the pressure surface parallel to the cured product, so that the pressure surface and the cured product were in close contact. The maximum value at the time of contact was read, and this maximum value was recorded as the "hardness." The test details were in accordance with JIS K6249. The pass criterion was A10 or higher.

[0080] [Tensile strength (resin strength)] A sheet of 2 mm thick was prepared using the moisture-curable resin composition and allowed to stand for 7 days in an atmosphere of 23°C and 50% RH to obtain a sheet-like cured product. A test piece in the shape of a No. 3 dumbbell was cut out from the sheet-like cured product. The test piece was pulled at 500 mm / min using a tensile tester with a base line distance of 25 mm, and the maximum strength until the dumbbell-shaped test piece broke was recorded as the tensile strength (MPa). The pass criterion was 1.0 MPa or more.

[0081] [Elongation (Flexibility)] A sheet of 2 mm thick was prepared using the moisture-curable resin composition and allowed to stand for 7 days in an atmosphere of 23°C and 50% RH to obtain a sheet-like cured product. A test piece in the shape of a No. 3 dumbbell was cut out from the sheet-like cured product. The test piece had a base line distance of 25 mm, and was pulled at 500 mm / min using a tensile tester, and the base line distance until the dumbbell-shaped test piece broke was measured. The elongation (%) was calculated from (base line distance at break - initial base line distance) / initial base line distance x 100 (%). The details of the test were in accordance with JIS K6251. The pass criterion was 200% or more.

[0082]

[0083] According to Table 2, all of Examples 1 to 6 had excellent performance as a sealing agent.

[0084] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-214804) filed on December 20, 2023, the contents of which are incorporated herein by reference.

[0085] The moisture-curable resin composition of the present invention has good curability even without containing an organotin catalyst, and the failure state after adhesion is stable cohesive failure. Furthermore, the cohesive failure state is maintained even after durability tests such as heat resistance tests and oil resistance tests, and the composition has stable adhesive performance, making it extremely useful as an adhesive or sealant.

Claims

1. A moisture-curable resin composition comprising the following components (A), (B), (C) and (D): Component (A): an oxyalkylene polymer having a hydrolyzable silyl group; Component (B): a biomass filler; Component (C): a filler that has been surface-treated with a fatty acid having a carbon number of C12 to C18; and Component (D): a metal catalyst.

2. The moisture-curable resin composition according to claim 1, wherein the component (D) is a zinc catalyst.

3. The moisture-curable resin composition according to claim 1 or 2, wherein the component (C) is a filler that has been surface-treated with one or more fatty acids selected from the group consisting of palmitic acid, stearic acid and octadecenoic acid.

4. The moisture-curable resin composition according to claim 1 or 2, wherein the component (C) is ground calcium carbonate that has been surface-treated with a fatty acid having a carbon number of C12 to C18.

5. The BET specific surface area of ​​the component (C) is 10,000 cm ２ The moisture-curable resin composition according to claim 1 or 2, wherein the moisture content is 1 / g or more.

6. The moisture-curable resin composition according to claim 1 or 2, further comprising a plasticizer as component (E).

7. The moisture-curable resin composition according to claim 6, wherein the component (E) comprises a castor oil-modified fatty acid ester.

8. The moisture-curable resin composition according to claim 1 or 2, further comprising a non-surface-treated filler as component (C2).

9. An adhesive comprising the moisture-curable resin composition according to claim 1 or 2.

10. A sealant comprising the moisture-curable resin composition according to claim 1 or 2.

11. A cured product obtained by curing the moisture-curable resin composition according to claim 1 or 2.

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