Compositions, articles, and batteries

Abstract

The present invention provides a composition with improved balance between adhesive durability and surface curing properties, as well as articles and batteries using the composition. [Solution] The tensile shear adhesive strength of the test specimen obtained by the following <Preparation Condition 1>, measured at 23°C and a tensile speed of 10 mm / min, is defined as F0. After the test specimen obtained by the following <Preparation Condition 1> is exposed to an environment of 95°C × 95%RH for 500 hours, the tensile shear adhesive strength of the test specimen is measured at 23°C and a tensile speed of 10 mm / min, and F0 is defined as F0. 500 When F 500 A composition having an F0 of 0.70 or higher. <Preparation conditions 1> (1) Apply the composition to one side of an aluminum alloy plate (A5052P) to form a film with a thickness of 0.1 mm, (2) Place another aluminum alloy plate (A5052P) on the surface of the film, and allow the resulting laminate to stand at 23°C for 24 hours to cure the film and obtain a test specimen.

Description

[Technical Field]

[0001] This invention relates to compositions, articles, and batteries. [Background technology]

[0002] Various structural adhesives are used in the manufacture of automobiles. Examples of structural adhesives intended for use in automobile manufacturing include those described in the following Patent Documents 1 and 2.

[0003] Patent Document 1 describes a composition containing the following (A) to (D) intended for use as an adhesive in the manufacture of automobiles. (A) Urethane (meth)acrylate with a number average molecular weight of 5000 or more, in 40 to 75 parts by mass per 100 parts by mass of the total of (A) and (B). (B)(meth)acrylic compound containing (B-1)(meth)acrylate without urethane bonds and (B-2)(meth)acrylic acid in 15 to 25 parts by mass per 100 parts by mass of the total of (A) and (B). (C) Polymerization initiator (D) Reducing agent

[0004] Patent Document 2 describes a two-component adhesive comprising a first component containing a free radical initiator and a second component containing a reducing agent, with the aim of providing a two-component adhesive with high heat resistance and moisture resistance that can be used as a structural adhesive. This two-component adhesive contains a first monomer which is methyl methacrylate and a second monomer selected from the group consisting of methacrylic acid, aromatic polyols or their derivatives, polyfunctional (meth)acrylic acid adducts, and combinations thereof. The overlap shear strength of the cured product of this two-component adhesive is 20 MPa or more at 25°C and 7 MPa or more at 120°C, the adhesive strength measured by a T-type peel test at 25°C is 2 kN / m or more, and the glass transition temperature is 130°C or higher. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2020 / 100832 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-155892 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] Since the battery is exposed to a high-temperature and high-humidity environment such as an engine room for a long time, for example, the battery terminal protection material used for the protection material of the battery terminal part is required to have improved durability in a high-temperature and high-humidity environment. According to the study by the present inventors, in order to improve the durability of the battery terminal protection material, when the resin composition is made to have a high Tg and the water resistance is improved by using a low-polarity raw material, it has been clarified that the surface curability deteriorates. That is, there is room for improvement in the conventional battery terminal protection material from the viewpoint of improving the performance balance between adhesive durability and surface curability.

[0007] The present invention has been made in view of the above circumstances, and provides a composition in which the performance balance between adhesive durability and surface curability is improved, and an article and a battery using the composition. [Means for Solving the Problems]

[0008] The present inventors have intensively studied to achieve the above problems. As a result, it has been found that the performance balance between the adhesive durability and the surface curability of the composition can be improved by the ratio of the tensile shear adhesive strength measured under specific conditions being in a specific range, and the present invention has been completed.

[0009] According to the present invention, the following compositions, articles and batteries are provided.

[0010] [1] The tensile shear adhesion strength of a test piece obtained by the following <Production Condition 1> and measured under the conditions of 23°C and a tensile speed of 10 mm / min is defined as F0. After exposing the test piece obtained by the following <Production Condition 1> to an environment of 95°C × 95% RH for 500 hours, the tensile shear adhesion strength of the test piece measured under the conditions of 23°C and a tensile speed of 10 mm / min is F. 500 When F 500 / F0 is 0.70 or more. <Production Condition 1> (1) Apply the composition to one side of an aluminum alloy plate (A5052P) to form a film with a thickness of 0.1 mm. (2) Stack another aluminum alloy plate (A5052P) on the surface of the film, and allow the obtained laminate to stand at 23°C for 24 hours to cure the film and obtain a test piece. [2] The F 500 is 7.0 MPa or more, and the composition according to [1] above. [3] The F0 is 10.0 MPa or more, and the composition according to [1] or [2] above. [4] The glass transition temperature of the cured product composed of the composition, determined by dynamic viscoelasticity measurement, is 80°C or more, and the composition according to any one of [1] to [3] above. [5] The water absorption rate measured by the following Method 1 is 5.0% or less, and the composition according to any one of [l] to [4] above. (Method 1) By treating the composition at 23°C for 24 hours, a cured product sample of 5 mm × 40 mm × 0.5 mm is prepared. Then, the obtained cured product sample is immersed in water at 70°C for 24 hours. When the mass of the cured product sample before immersion in water is W1 (g) and the mass of the cured product sample after immersion in water is W2 (g), the water absorption rate (%) is calculated from the mass change before and after immersion in water based on the formula of (W2 - W1) / W1 × 100. [6] The composition according to any one of [1] to [5] above, wherein the exothermic peak temperature measured by the method 2 below is 50°C or higher. (Method 2) A K-type thermocouple connected to a thermologger is fixed to the bottom of a paper cup, the composition is dispensed into the paper cup, and the exothermic temperature during the hardening of the composition is measured by the thermologger. The highest temperature recorded is defined as the peak exothermic temperature. [7] A composition according to any one of [1] to [6] above, comprising an amide group-containing monomer (A), a monofunctional (meth)acrylate (B), and an elastomer (C). [8] The composition according to any one of [1] to [7], wherein the monofunctional (meth)acrylate (B) comprises a hydroxyl group-containing (meth)acrylate (B1). [9] The composition according to [7] or [8], wherein the monofunctional (meth)acrylate (B) comprises a monofunctional (meth)acrylate (B2) having a cyclic structure.

[10] The composition according to any one of [7] to [9], wherein the elastomer (C) comprises one or more selected from the group consisting of (meth)acrylonitrile butadiene rubber, methyl (meth)acrylate butadiene styrene rubber, and methyl (meth)acrylate butadiene (meth)acrylonitrile styrene rubber.

[11] A curable resin composition, as described in any of [1] to

[10] above.

[12] A composition according to any one of the above [1] to

[11] , used in a battery.

[13] The composition described in

[12] above, which is used as a protective material for battery terminals.

[14] An article comprising a cured product comprising any of the compositions described in [1] to

[13] above.

[15] A battery comprising a cured product comprising any of the compositions described in [1] to

[13] above. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a composition with an improved balance of adhesive durability and surface curing properties, as well as articles and batteries using the composition. [Modes for carrying out the invention]

[0012] Embodiments of the present invention will be described in detail below.

[0013] In this specification, the notation "X~Y" in descriptions of numerical ranges means X or greater and Y or less, unless otherwise specified. For example, "1~5 mass%" means "1 mass% or greater and 5 mass% or less." In this specification, when a composition is in a two-part form consisting of a first agent and a second agent, the content of each component is preferably expressed as the content relative to the total of the first and second agents. In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In this specification, unless otherwise specified, the term "organic group" refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

[0014] [Curable resin composition] The "curable resin composition" of this embodiment will be described in detail below. The curable resin composition of this embodiment has a tensile shear adhesive strength of F0, which is measured at 23°C and a tensile speed of 10 mm / min, on a test specimen obtained under the following <Preparation Condition 1>, and after the test specimen obtained under the following <Preparation Condition 1> is exposed to an environment of 95°C × 95%RH for 500 hours, the tensile shear adhesive strength of the test specimen is measured at 23°C and a tensile speed of 10 mm / min. 500 In that case, F 500 / F0 is 0.70 or higher. <Production Condition 1> (1) Apply the composition to one side of an aluminum alloy plate (A5052P) to form a film with a thickness of 0.1 mm. (2) A test specimen is obtained by placing another aluminum alloy plate (A5052P) on the surface of the film and allowing the resulting laminate to stand at 23°C for 24 hours to harden the film.

[0015] Because batteries are exposed to high-temperature and high-humidity environments such as engine compartments for extended periods, battery terminal protection materials, such as those used to protect battery terminals, require improved durability in these environments. According to the inventors' research, it has become clear that improving the water resistance of a battery terminal protection material by increasing the Tg of the resin composition and using low-polarity raw materials to improve durability results in a deterioration of surface hardening properties. The inventors diligently conducted research to provide a composition with an improved balance of adhesive durability and surface curing properties. As a result, F 500 We found a correlation between / F0 and the balance between adhesive durability and surface curing performance. Based on the above findings, the inventors conducted further intensive studies and found that F 500 We found that by keeping / F0 within the above range, a curable resin composition with improved balance between adhesive durability and surface curing performance, as well as articles and batteries using this curable resin composition, can be obtained. In other words, according to the curable resin composition of this embodiment, F 500When / F0 is within the above range, it is possible to realize articles and batteries with improved performance balance between adhesion durability and surface curability.

[0016] The curable resin composition of this embodiment is controlled such that F 500 / F0 is 0.70 or more. Thereby, the performance balance between adhesion durability and surface curability in the curable resin composition of this embodiment can be improved. The reason for this is not clear, but the following reasons are considered. First, F 500 / F0 is considered to be an index related to the difficulty of change in properties due to moisture absorption and the cured state of the cured product composed of the curable resin composition. And when F 500 / F0 is not less than the above lower limit value, the change in properties due to moisture absorption of the cured product composed of the curable resin composition is suppressed, and further the cured state of the cured product becomes good. Therefore, it is considered that the performance balance between adhesion durability and surface curability can be improved. Here, in order to adjust F 500 / F0 within the above range, for example, it can be adjusted by adjusting the type and content ratio of each component contained in the curable resin composition of this embodiment, the order and mixing method of mixing each component, and the like.

[0017] The F 500 / F0 of the curable resin composition of this embodiment is 0.70 or more. From the viewpoint of further improving the performance balance between adhesion durability and surface curability, it is preferably 0.75 or more, more preferably 0.80 or more, and still more preferably 0.83 or more. The upper limit of the said F 500 / F0 is not particularly limited, but for example, it is 1.5 or less, may be 1.2 or less, may be 1.0 or less, or may be 0.98 or less.

[0018] In the curable resin composition of this embodiment, the tensile shear adhesive strength (F0) of the test specimen obtained by <Production Condition 1>, measured at 23°C and a tensile speed of 10 mm / min, is preferably 10.0 MPa or higher, more preferably 13.0 MPa or higher, even more preferably 15.0 MPa or higher, even more preferably 17.0 MPa or higher, even more preferably 18.0 MPa or higher, and preferably 50.0 MPa or lower, more preferably 30.0 MPa or lower, even more preferably 25.0 MPa or lower, even more preferably 23.0 MPa or lower, even more preferably 21.0 MPa or lower, even more preferably 20.0 MPa or lower, and even more preferably 19.0 MPa or lower.

[0019] The tensile shear adhesive strength (F0) of the curable resin composition of this embodiment can be adjusted, for example, by adjusting the type and content ratio of each component contained in the curable resin composition of this embodiment, the mixing order of each component, and the mixing method.

[0020] In the curable resin composition of this embodiment, the tensile shear adhesive strength (F) of the test specimen obtained by the above-mentioned <Preparation Condition 1> is measured after exposure to an environment of 95°C × 95%RH for 500 hours, and then measured at 23°C and a tensile speed of 10 mm / min. 500 From the viewpoint of further improving the balance of performance in heat resistance, adhesive durability and surface hardening, the pressure is preferably 7.0 MPa or higher, more preferably 8.0 MPa or higher, more preferably 10.0 MPa or higher, even more preferably 12.0 MPa or higher, even more preferably 14.0 MPa or higher, even more preferably 15.0 MPa or higher, even more preferably 15.5 MPa or higher, and also preferably 45.0 MPa or lower, more preferably 25.0 MPa or lower, even more preferably 23.0 MPa or lower, even more preferably 20.0 MPa or lower, even more preferably 18.0 MPa or lower, and even more preferably 17.5 MPa or lower. The tensile shear adhesive strength (F) of the curable resin composition of this embodiment 500This can be adjusted, for example, by adjusting the types and proportions of each component contained in the curable resin composition of this embodiment, the mixing order and method of each component, etc.

[0021] The following describes each component of the curable resin composition of this embodiment.

[0022] The curable resin composition of this embodiment includes an amide group-containing monomer (A), a monofunctional (meth)acrylate (B), and an elastomer (C), from the viewpoint of further improving the balance between adhesive durability and surface curability.

[0023] <Monomer components> From the viewpoint of further improving the balance between adhesive durability and surface curability, the curable resin composition of this embodiment preferably contains an amide group-containing monomer (A) and a monofunctional (meth)acrylate (B) as monomer components. In this specification, monomer components refer to compounds having one or more carbon-carbon double bonds, such as (meth)acryloyl groups, vinyl groups, and allyl groups. The monomer component of this embodiment does not contain elastomer (C).

[0024] (Amide group-containing monomer (A)) The curable resin composition of this embodiment preferably contains an amide group-containing monomer (A) from the viewpoint of further improving the balance between adhesive durability and surface curability. Amide group-containing monomer (A) refers to a compound having an amide group and a carbon-carbon double bond such as a (meth)acryloyl group, vinyl group, or allyl group.

[0025] Examples of amide group-containing monomers (A) include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, hydroxymethyl(meth)acrylamide, hydroxyethyl(meth)acrylamide, isopropyl(meth)acrylamide, N,N'-methylenebis(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, and 4-(meth)acryloylmol It comprises one or more selected from the group consisting of forin and N-vinylpyrrolidone, preferably one or more selected from the group consisting of N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and 4-(meth)acryloylmorpholine, more preferably one or more selected from the group consisting of N,N-diethyl(meth)acrylamide and 4-(meth)acryloylmorpholine, and even more preferably N,N-diethyl(meth)acrylamide.

[0026] The content of the amide group-containing monomer (A) in the curable resin composition of this embodiment is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, when the total content of the monomer component and elastomer (C) is 100 parts by mass.

[0027] (Monofunctional (meth)acrylate (B)) The curable resin composition of this embodiment preferably contains a monofunctional (meth)acrylate (B) from the viewpoint of further improving the balance between adhesive durability and surface curability. A monofunctional (meth)acrylate (B) is a compound having one (meth)acryloyl group. However, monofunctional (meth)acrylates (B) exclude amide group-containing monomers (A) and phosphate ester compounds having a (meth)acryloyl group as described below. The monofunctional (meth)acrylate (B) of this embodiment does not contain elastomer (C).

[0028] • Hydroxyl group-containing (meth)acrylate (B1) The monofunctional (meth)acrylate (B) of this embodiment preferably includes a hydroxyl group-containing (meth)acrylate (B1) from the viewpoint of further improving the balance between adhesive durability and surface curing performance. A hydroxyl group-containing (meth)acrylate (B1) refers to a monofunctional (meth)acrylate having one or more hydroxyl groups in its molecule. The hydroxyl group-containing (meth)acrylate (B1) of this embodiment does not contain a phosphate ester compound having a (meth)acryloyl group, represented by formula (1) described later. Hydroxylate-containing (meth)acrylates (B1) are, for example, from the group consisting of 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, and 1,4-butanediol mono(meth)acrylate, etc. It comprises one or more selected from the group consisting of 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, more preferably it comprises one or more selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, and even more preferably it comprises 2-hydroxyethyl (meth)acrylate.

[0029] The content of hydroxyl group-containing (meth)acrylate (B1) in the curable resin composition of this embodiment is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0030] The total content of amide group-containing monomer (A) and hydroxyl group-containing (meth)acrylate (B1) in the curable resin composition of this embodiment is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 13 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 18 parts by mass or more, and preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.

[0031] • Monofunctional (meth)acrylate with a cyclic structure (B2) The monofunctional (meth)acrylate (B) of this embodiment preferably includes a monofunctional (meth)acrylate (B2) having an annular structure, from the viewpoint of further improving the balance of performance in terms of heat resistance, adhesive durability, and surface curability. The monofunctional (meth)acrylate (B2) having a cyclic structure preferably contains a monomer represented by the following general formula (I). CH2=CHR 1 -COO-R 2 (I) In general formula (I), R 1 R is a hydrogen atom or a methyl group, 2 R is a group containing a cyclic hydrocarbon skeleton, preferably a group containing a polycyclic cyclic hydrocarbon skeleton. 2 The cyclic hydrocarbon skeleton contained therein is preferably an alicyclic skeleton that does not contain an aromatic ring.

[0032] The cyclic monofunctional (meth)acrylate (B2) preferably comprises one or more selected from the group consisting of dicyclopentenyloxyethyl (meth)acrylate, norbornene (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and cyclohexyl (meth)acrylate; more preferably comprises one or more selected from the group consisting of phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; even more preferably comprises one or more selected from the group consisting of phenoxyethyl (meth)acrylate and isobornyl (meth)acrylate; and even more preferably comprises isobornyl (meth)acrylate.

[0033] The content of the cyclic monofunctional (meth)acrylate (B2) in the curable resin composition of this embodiment is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0034] The content of monofunctional (meth)acrylate (B) in the curable resin composition of this embodiment is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0035] (Polyfunctional (meth)acrylate (D)) The curable resin composition of this embodiment may contain a polyfunctional (meth)acrylate (D) as a monomer component, from the viewpoint of further improving the balance between adhesive durability and surface curability. A polyfunctional (meth)acrylate (D) is a compound having two or more (meth)acryloyl groups. However, amide group-containing monomers (A) and phosphate ester compounds having (meth)acryloyl groups, as described below, are excluded from the definition of polyfunctional (meth)acrylate (D). The polyfunctional (meth)acrylate (D) of this embodiment does not contain elastomer (C). The polyfunctional (meth)acrylate (D) preferably contains 2 to 6 (meth)acryloyl groups, more preferably 2 to 4 (meth)acryloyl groups, even more preferably 2 to 3 (meth)acryloyl groups, and even more preferably 2 (meth)acryloyl groups.

[0036] The polyfunctional (meth)acrylate (D) preferably includes one or more selected from the group consisting of polyfunctional (meth)acrylates having an alicyclic structure, polyfunctional (meth)acrylates having an aromatic ring structure, and polyfunctional (meth)acrylates having an aliphatic chain structure. Examples of polyfunctional (meth)acrylates having an alicyclic structure include one or more selected from the group consisting of dicyclopentanyl di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tricyclodecanedimethyl di(meth)acrylate, dimethylol-tricyclodecanedi(meth)acrylate, and dimethylol-cyclohexanedi(meth)acrylate. Examples of polyfunctional (meth)acrylates having an aromatic ring structure include one or more selected from the group consisting of 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloxytetraethoxyphenyl)propane, ethylene oxide-added bisphenol A di(meth)acrylate (EO-modified BPA di(meth)acrylate), ethylene oxide-added bisphenol F di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, and propylene oxide-added bisphenol F di(meth)acrylate. Examples of polyfunctional (meth)acrylates having an aliphatic chain structure include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexadiol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and isocyanurate-modified ethylene oxide di(meth)acrylate. This includes one or more selected from the group consisting of ethylene oxide-modified isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris[(meth)acrylooxyethyl]isocyanurate, ditrimethylolpropanetetra(meth)acrylate, dimethylolpropanetetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0037] The polyfunctional (meth)acrylate (D) more preferably comprises one or more selected from the group consisting of dicyclopentanyl di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and even more preferably comprises dicyclopentanyl di(meth)acrylate.

[0038] The content of polyfunctional (meth)acrylate (D) in the curable resin composition of this embodiment is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0039] The monomer content in the curable resin composition of this embodiment is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, even more preferably 60 parts by mass or more, and preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0040] <Elastomer (C)> The curable resin composition of this embodiment preferably contains an elastomer (C) from the viewpoint of further improving the balance between adhesive durability and surface curability. The elastomer (C) preferably has soft segment units. The soft segment units preferably include one or more selected from the group consisting of diene structures, ethylene structures, propylene structures, isoprene structures, urethane structures, ethylene glycol structures, propylene glycol structures, silicone structures, and chloroprene structures, and more preferably include diene structures such as butadiene structures. The elastomer (C) may have hard segments in addition to the soft segment units. The "soft segment" represents the flexible portion that exhibits rubber elasticity. The "hard segment" represents the molecularly constrained portion that acts as a crosslinking point for crosslinked rubber to prevent plastic deformation.

[0041] The content of soft segment units in elastomer (C) is preferably 15% by mass or more and 90% by mass or less, and more preferably 25% by mass or more and 85% by mass or less, of the total elastomer (C) of this embodiment.

[0042] The elastomer (C) preferably comprises one or more selected from the group consisting of (meth)acrylonitrile butadiene rubber, methyl (meth)acrylate butadiene styrene rubber, and methyl (meth)acrylate butadiene / (meth)acrylonitrile styrene rubber, more preferably comprising one or more selected from the group consisting of (meth)acrylonitrile butadiene rubber and methyl (meth)acrylate butadiene / (meth)acrylonitrile styrene rubber, and even more preferably comprising both (meth)acrylonitrile butadiene rubber and methyl (meth)acrylate butadiene / (meth)acrylonitrile styrene rubber.

[0043] The curable resin composition of this embodiment may contain only one elastomer or two or more elastomers. For example, one or two selected from the group consisting of the above-mentioned methyl (meth)acrylate-butadiene-styrene rubber and methyl (meth)acrylate-butadiene-(meth)acrylonitrile-styrene rubber may be used in combination with (meth)acrylonitrile-butadiene rubber. When used in combination, the combination ratio is preferably, by mass ratio, the former:latter = 0.5:9.5 to 9.5:0.5, more preferably, the former:latter = 0.8:9.2 to 9.2:0.8, and even more preferably, the former:latter = 1.0:9.0 to 9.0:1.0.

[0044] The elastomer (C) content in the curable resin composition of this embodiment is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0045] The total content of monomer components and elastomer (C) in the curable resin composition of this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 93% by mass or more, when the total curable resin composition of this embodiment is considered to be 100% by mass, and may also be 100% by mass or less, 98% by mass or less, or 97% by mass or less.

[0046] <Polymerization initiator> The curable resin composition of this embodiment preferably contains a polymerization initiator. The polymerization initiator polymerizes the carbon-carbon double bonds of the monomer components, thereby improving adhesion.

[0047] The polymerization initiator preferably includes a thermal radical polymerization initiator. From the viewpoint of further improving reactivity, the thermal radical polymerization initiator preferably includes an organic peroxide, more preferably one or more selected from the group consisting of cumene hydroperoxide, paramentane hydroperoxide, tert-butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, and tert-butyl peroxybenzoate, and even more preferably cumene hydroperoxide.

[0048] The content of polymerization initiator in the curable resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, and preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, even more preferably 12.0 parts by mass or less, even more preferably 10.0 parts by mass or less, even more preferably 8.0 parts by mass or less, even more preferably 6.0 parts by mass or less, even more preferably 4.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0049] <Reducing agent> The curable resin composition of this embodiment preferably contains a reducing agent. The curable resin composition of this embodiment can have its curability further improved by using a polymerization initiator and a reducing agent in combination. The reducing agent can be any reducing agent that reacts with the polymerization initiator to generate radicals. The reducing agent preferably comprises one or more selected from the group consisting of tertiary amines, thiourea derivatives, and transition metal salts, and more preferably comprises a transition metal salt.

[0050] Examples of tertiary amines include one or more selected from the group consisting of triethylamine, tripropylamine, tributylamine, and N,N-dimethylparatoluidine. Examples of thiourea derivatives include one or more selected from the group consisting of 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, ethylenethiourea, acetyl-2-thiourea, benzoylthiourea, N,N-diphenylthiourea, N,N-diethylthiourea, N,N-dibutylthiourea, and tetramethylthiourea. Examples of transition metal salts include one or more selected from the group consisting of cobalt naphthenate, copper naphthenate, and vanadylacetylacetonate. The transition metal salt more preferably includes vanadylacetylacetonate.

[0051] The reducing agent content in the curable resin composition of this embodiment is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, even more preferably 0.15 parts by mass or more, even more preferably 0.20 parts by mass or more, and preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, even more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, even more preferably 1.0 part by mass or less, and even more preferably 0.50 parts by mass or less, when the total content of monomer components and elastomer (C) is 100 parts by mass.

[0052] <Other ingredients> The curable resin composition of this embodiment may or may not contain other components other than those mentioned above. Other components include, for example, phosphate ester compounds having a (meth)acryloyl group, paraffin, and stabilizers. The curable resin composition of this embodiment may contain various stabilizers from the viewpoint of further improving storage stability. Examples of stabilizers include (i) phenolic antioxidants (e.g., 2,2'-methylenebis(4-methyl-6-t-butylphenol), etc.), (ii) quinone compounds (e.g., p-benzoquinone, hydroquinone monomethyl ether, etc.), (iii) compounds known as polymerization inhibitors (e.g., amine polymerization inhibitors such as phenothiazine, citric acid, etc.), and (iv) stable radical-type compounds having stable radicals. Among the other components, phosphate ester compounds having a (meth)acryloyl group are preferred in terms of improving surface hardening properties. One or more phosphate ester compounds having a (meth)acryloyl group may be used in combination. The phosphate ester compound having a (meth)acryloyl group is preferably the compound represented by formula (1).

[0053] [ka] R is CH2=CR 1 CO(OR 2 ) m -(R 1 , R 2 R is a hydrocarbon group, m is 1-10, and n is 1 or 2. 1 -H or -CH3 is preferred. 2 An alkylene group is preferred. 2 -C2H4-, -C3H6-, -CH2CH(CH3)-, -C4H8-, -C5H 10 -, -C6H 12 -or-C2H4-O-CO-C5H 10 - is preferable.

[0054] If the curable resin composition of this embodiment contains other components, the total content of the other components in the curable resin composition of this embodiment is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 1.0 parts by mass or more, and more preferably 30.0 parts by mass or less, more preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, and more preferably 5.0 parts by mass or less.

[0055] <Characteristics of curable resin compositions> In the curable resin composition of this embodiment, the glass transition temperature of the cured product obtained by curing the composition at 23°C for 24 hours, as determined by dynamic viscoelasticity measurement, is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, even more preferably 100°C or higher, even more preferably 106°C or higher, and even more preferably 108°C or higher, from the viewpoint of further improving the balance of performance of heat resistance, adhesive durability, and surface curability. The upper limit of the glass transition temperature is not particularly limited, but for example, it may be 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, or 115°C or lower. The glass transition temperature of the cured product of the curable resin composition of this embodiment can be adjusted, for example, by adjusting the type and content ratio of each component contained in the curable resin composition of this embodiment, the mixing order of each component, and the mixing method.

[0056] In the curable resin composition of this embodiment, the water absorption rate measured by the following method 1 is preferably 5.0% or less, more preferably 3.0% or less, even more preferably 2.5% or less, even more preferably 2.0% or less, and even more preferably 1.8% or less, from the viewpoint of further improving the balance between adhesive durability and surface curability performance. The lower limit of the water absorption rate is not particularly limited, but for example, it may be 0.1% or more, 0.5% or more, 0.8% or more, 1.0% or more, or 1.2% or more. (Method 1) A cured resin composition measuring 5 mm × 40 mm × 0.5 mm is prepared by treating it at 23°C for 24 hours. The cured sample is then immersed in water at 70°C for 24 hours. The mass of the cured sample before immersion in water is denoted as W1 (g), and the mass of the cured sample after immersion in water is denoted as W2 (g). The water absorption rate (%) is then calculated from the change in mass before and after immersion in water based on the formula (W2 - W1) / W1 × 100.

[0057] In the curable resin composition of this embodiment, the exothermic peak temperature measured by the method 2 described below is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, even more preferably 80°C or higher, even more preferably 90°C or higher, even more preferably 100°C or higher, and even more preferably 110°C or higher, from the viewpoint of further improving the balance between adhesive durability and surface curability performance. The upper limit of the exothermic peak temperature is not particularly limited, but for example, it may be 200°C or lower, 150°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower. (Method 2) A K-type thermocouple connected to a thermologger is fixed to the bottom of a paper cup, the curable resin composition is dispensed into the paper cup, and the exothermic temperature during the curing of the curable resin composition is measured by the thermologger. The highest temperature recorded is defined as the peak exothermic temperature.

[0058] <Single dosage form / Two dosage forms> The curable resin composition of this embodiment may be a one-component type or a two-component type (a form in which two components filled in separate containers are mixed immediately before use). In the case of a two-component type, preferably, the polymerization initiator is included in the first component and the reducing agent is included in the second component. When the curable resin composition of this embodiment is a two-part type, it is preferable to adjust the amounts of each component in the first and second components so that the curable resin composition after mixing the first and second components contains each component within the range of preferred content of each component as described above. Furthermore, the various properties of the curable resin composition described herein relate to the curable resin composition after mixing the first and second components.

[0059] <Method for producing a curable resin composition> In manufacturing the curable resin composition of this embodiment, it is preferable not to simply mix the above-mentioned components, but to appropriately adjust the mixing order and method of each component. In the production of the curable resin composition of this embodiment, it is particularly preferable that the monomer component and the elastomer (C) are thoroughly mixed. For this reason, it is preferable to (i) first thoroughly and uniformly mix at least a portion of the monomer component and at least a portion of the elastomer (C) at 50 to 80°C to form a mixture, and (ii) then add the other components to the mixture and stir. It is believed that this ensures that the monomer component and the elastomer (C) are thoroughly and uniformly mixed. The curable resin composition produced in this manner tends to satisfy the above-mentioned characteristics of the curable resin composition (glass transition temperature, tensile shear adhesive strength, etc.) more easily than curable resin compositions obtained by other production methods.

[0060] <Application> The curable resin composition of this embodiment has an improved balance of adhesive durability and surface curing properties, making it suitable for use as a material for batteries that are exposed to high temperature and high humidity environments such as engine compartments for long periods of time. It is more suitable for use as a protective material for battery terminals, and even more suitable for use as a protective material for vehicle battery terminals. Here, the protective material for the battery terminals refers to a coating applied to the battery terminals to prevent corrosion. The battery terminals are made of a metal material such as aluminum.

[0061] <Goods> The article of this embodiment includes a cured product made from the curable resin composition of this embodiment. By applying the curable resin composition of this embodiment to an article and curing it, an article containing a cured product of the curable resin composition can be obtained. The curable resin composition of this embodiment preferably cures without heating (at room temperature) and can bond articles (especially when it contains a polymerization initiator and a reducing agent). Of course, heating during the bonding of articles is not excluded.

[0062] <Battery> The battery of this embodiment includes a cured product made from the curable resin composition of this embodiment. The battery of this embodiment comprises, for example, a battery body and a battery terminal, and the protective material for protecting the battery terminal includes a cured product made from the curable resin composition of this embodiment. In this case, it is preferable that the battery terminal in the battery of this embodiment is covered with a cured product made from the curable resin composition of this embodiment. The battery of this embodiment contains a cured product made from the curable resin composition of this embodiment, thus improving its durability in high-temperature and high-humidity environments.

[0063] This specification primarily describes "curable resin compositions." However, the curable resin compositions described herein can also be used in fields other than protective materials, such as adhesives, coatings, and injection materials. In other words, the curable resin compositions described herein can also be used as compositions, coatings, and adhesive compositions without limiting their applications. The compositions of this embodiment can be used, for example, as so-called adhesives, sealants, photosensitive resin layers, insulating resin layers, thermally conductive resin layers, coatings, etc.

[0064] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope of achieving the objectives of the present invention are included. [Examples]

[0065] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples.

[0066] <Examples 1-6 and Comparative Examples 1-2> The first and second components were prepared by thoroughly mixing each component in the proportions shown in Table 1 (unit: parts by mass) using a stirring device equipped with stirring blades. Next, the first and second components were mixed in equal amounts to prepare a curable resin composition. The following evaluations were performed using the obtained curable resin compositions. The results are shown in Table 1. Note that all units for the proportions of each component in Table 1 are parts by mass. In the preparation of the first and second components, the monomer component and elastomer (C) were thoroughly and uniformly mixed at 50-80°C to form a mixture, then other components were added to the mixture and stirred, and then the mixture was defoamed to prepare the first and second components, respectively.

[0067] Some of the information listed in Table 1 is provided below. BL-20: Methyl methacrylate, butadiene, acrylonitrile, styrene rubber (methyl methacrylate content 15% by mass, butadiene content 46% by mass, acrylonitrile content 3% by mass, styrene content 36% by mass, soft segment unit content 46% by mass) • 1300X33VTBNX LC: Acrylonitrile-butadiene rubber with methacryloyl groups at both ends (acrylonitrile content 18% by mass, soft segment unit content 82% by mass) • N250SL: Acrylonitrile butadiene rubber (acrylonitrile content 19.5% by mass, soft segment unit content 81% by mass) • DCPD-type dimethacrylate: dicyclopentanyl dimethacrylate • SIPOMER PAM 4000: 2-hydroxyethyl methacrylate phosphate ester (In formula (1) above, R is CH2=CR 1 CO(OR 2 ) m-(R 1 -CH3, R 2 (where n is -C2H4- and m is 1). It is a mixture of phosphate esters where n is 1 and phosphate esters where n is 2.

[0068] <Rating> Each of the following measurements and evaluations was performed three times, and the average of the three resulting values ​​was used as the final result.

[0069] [Tensile shear bonding test (aluminum alloy plate - aluminum alloy plate)] The tensile shear adhesive strength was evaluated in accordance with JIS K 6850:1999, Test Method for Adhesives - Rigid Adhesion. Specifically, a curable resin composition (mixed for two-part types) was applied to one side of a test specimen (aluminum alloy plate measuring 25 mm × 100 mm × 2.0 mm thick (JIS H 4000:2022, A5052P, manufactured by UACJ), which had been degreased with acetone) to form a film. Another test specimen (aluminum alloy plate measuring 25 mm × 100 mm × 2.0 mm thick (JIS H 4000:2022, A5052P, manufactured by UACJ), which had been degreased with acetone) was immediately placed on top of the film surface and bonded together. The specimens were then cured at room temperature (23°C) for 24 hours. In this way, test specimens for measuring tensile shear adhesive strength were obtained. Here, polyethylene filler with a particle size of 100 μm (manufactured by Prime Polymer Co., Ltd., product name: Hyzex 2100JPD) was added to the curable resin composition, and the film thickness of the curable resin composition was adjusted to 100 μm (= 0.1 mm) by the action of the polyethylene filler (spacer for adjusting film thickness). The amount of polyethylene filler used was 0.5 parts by mass per 100 parts by mass of monomer component. Next, using the above-mentioned test specimens for measuring tensile shear adhesive strength, a tensile shear adhesive test was performed using an Instron Model 5967 universal testing machine under the conditions of a temperature of 23°C, a relative humidity of 50%, and a tensile speed of 10 mm / min, and the tensile shear adhesive strength F0 was measured. Furthermore, the test specimens used to measure the tensile shear adhesive strength were placed in a constant temperature and humidity chamber (GPL-3, manufactured by ESPEC) and exposed to an environment of 95°C × 95%RH for 500 hours. Next, using test specimens for measuring tensile shear bond strength after 500 hours of exposure, a tensile shear bond test was performed using an Instron Model 5967 universal testing machine under the conditions of a temperature of 23°C, a relative humidity of 50%, and a tensile speed of 10 mm / min, and the tensile shear bond strength F was determined. 500 We measured it. The obtained tensile shear bond strengths F0 and F 500 From F 500 / F0 was calculated.

[0070] [Dynamic Viscoelasticity (DMA) Measurement] First, cured specimens (test pieces) of a curable resin composition were prepared for dynamic viscoelasticity measurement. Specifically, the test pieces were prepared as follows (1) to (3). (1) First, a 0.5 mm thick silicone sheet with 5 mm x 40 mm holes was placed on a PET film. A curable resin composition was applied to the area with the holes to form a coating film. (2) Another PET film was laminated onto the above coated film. Then, both sides were sandwiched between 1 cm thick glass plates and weights were placed on top to compress it. In this state, it was cured for 24 hours in a room at a temperature of 23°C and a relative humidity of 50 RH%. After that, the compression was released and the PET film was peeled off. A sheet-like cured product was obtained in this way. The film thickness was adjusted to approximately 500 μm depending on the thickness of the silicone sheet. (3) The above-mentioned sheet-like hardened material was cut to obtain strip-shaped test pieces with dimensions of 5 mm × 40 mm × 0.5 mm.

[0071] The dynamic viscoelastic properties of the obtained specimens were measured using a dynamic viscoelasticity measuring device (DMS7100, manufactured by SII Corporation) under the following conditions: frequency: 1.0 Hz, mode: tensile mode, measurement temperature range: 0°C to 250°C, heating rate: 5°C / min. Based on the obtained data, the peak-top temperature of the loss tangent (tanδ) (tanδ peak value, i.e., glass transition temperature) was determined from the temperature-loss tangent (tanδ) curve.

[0072] [Water absorption rate] First, cured specimens (test pieces) of a curable resin composition were prepared for measuring water absorption. Specifically, the test pieces were prepared as follows (1) to (3). (1) First, a 0.5 mm thick silicone sheet with 5 mm x 40 mm holes was placed on a PET film. A curable resin composition was applied to the area with the holes to form a coating film. (2) Another PET film was laminated onto the above coated film. Then, both sides were sandwiched between 1 cm thick glass plates and weights were placed on top to compress it. In this state, it was cured for 24 hours in a room at a temperature of 23°C and a relative humidity of 50 RH%. After that, the compression was released and the PET film was peeled off. A sheet-like cured product was obtained in this way. The film thickness was adjusted to approximately 500 μm depending on the thickness of the silicone sheet. (3) The above-mentioned sheet-like hardened material was cut to obtain strip-shaped test pieces with dimensions of 5 mm × 40 mm × 0.5 mm. Next, the obtained test specimens were immersed in 70°C water for 24 hours. The mass of the test specimen before immersion was denoted as W1 (g), and the mass of the test specimen after immersion was denoted as W2 (g). The water absorption rate (%) was then calculated from the change in mass before and after immersion using the formula (W2-W1) / W1×100.

[0073] [Peak heat generation temperature] A K-type thermocouple connected to a thermologger was fixed to the bottom of a paper cup, and 10g of a curable resin composition was dispensed into the paper cup. The exothermic temperature during the curing of the resin composition was measured using the thermologger, and the highest temperature recorded was defined as the peak exothermic temperature.

[0074] [Surface hardening] First, cured specimens (test pieces) of the curable resin composition were prepared for surface hardening evaluation. Specifically, the test pieces were prepared as follows (1) to (2). (1) First, a 0.5 mm thick silicone sheet with 5 mm x 40 mm holes was placed on a PET film. A curable resin composition was applied to the area with the holes to form a coating film. (2) In this state, the material was cured for 5 hours in a room at a temperature of 23°C and a relative humidity of 50 RH. A sheet-like cured material (test specimen) was obtained in this manner. Next, the surface condition of the obtained test specimens was observed, and the surface hardening properties were evaluated according to the following criteria: AA indicated no tackiness at all, A indicated almost no tackiness (slightly noticeable), B indicated sufficient tackiness, and C indicated sticky.

[0075] [Adhesion durability] The aforementioned test specimens for measuring tensile shear adhesive strength were placed in a constant temperature and humidity chamber (GPL-3, manufactured by ESPEC) and exposed to an environment of 95°C × 95%RH for 500 hours. Next, using test specimens for measuring tensile shear adhesive strength after 500 hours of exposure, tensile shear adhesive tests were performed using an Instron Model 5967 universal tester under conditions of a temperature of 23°C, relative humidity of 50%, and a tensile speed of 10 mm / min, and the failure state was confirmed. A was defined as when the curable resin composition underwent cohesive failure across the entire surface; B was defined as when more than 50% of the adhesive area underwent cohesive failure of the curable resin composition, with the remainder delaminating at the interface between the aluminum alloy plate and the curable resin composition; C was defined as when less than 50% of the adhesive area underwent cohesive failure of the curable resin composition, with the remainder delaminating at the interface between the aluminum alloy plate and the curable resin composition; and D was defined as when the entire surface delaminated at the interface between the aluminum alloy plate and the curable resin composition.

[0076] Table 1 summarizes the composition of the curable resin composition and the measurement and evaluation results. In Table 1, the unit of measurement for the amount of each component of the curable resin composition is parts by mass.

[0077] [Table 1]

[0078] The curable resin compositions of Examples 1 to 6 showed an improved balance of adhesive durability and surface curability compared to the curable resin compositions of Comparative Examples 1 to 2.

Claims

1. The tensile shear adhesive strength of the test specimen obtained by the following <Preparation Condition 1>, measured at 23°C and a tensile speed of 10 mm / min, is F. ０ year, The test specimen obtained according to the following <Preparation Condition 1> is exposed to an environment of 95°C × 95% RH for 500 hours, and then the tensile shear adhesive strength of the test specimen is measured at 23°C and a tensile speed of 10 mm / min, and the value of the test specimen is F. ５００ In that case, F ５００ / F ０ A composition having a value of 0.70 or higher. <Manufacturing Condition 1> (1) Apply the composition to one side of an aluminum alloy plate (A5052P) to form a film with a thickness of 0.1 mm. (2) A test piece is obtained by placing another aluminum alloy plate (A5052P) on the surface of the film and allowing the resulting laminate to stand at 23°C for 24 hours to harden the film.

2. Said F ５００ The composition according to claim 1, wherein the pressure is 7.0 MPa or higher.

3. Said F ０ The composition according to claim 1 or 2, wherein the pressure is 10.0 MPa or more.

4. The composition according to claim 1 or 2, wherein the glass transition temperature of the cured product made from the composition, as determined by dynamic viscoelasticity measurement, is 80°C or higher.

5. The composition according to claim 1 or 2, wherein the water absorption rate measured by the method 1 below is 5.0% or less. (Method 1) By treating the composition at 23°C for 24 hours, a cured product sample of 5 mm × 40 mm × 0.5 mm is prepared. Then, the obtained cured product sample is immersed in water at 70°C for 24 hours, and the mass of the cured product sample before immersion in water is W １ (g), and when the mass of the cured product sample after immersion in water is W ２ (g), the water absorption rate (%) is calculated from the mass change before and after water immersion based on the formula of (W ２ −W １ ) / W １ × 100.

6. The composition according to claim 1 or 2, wherein the exothermic peak temperature measured by the method 2 below is 50°C or higher. (Method 2) A K-type thermocouple connected to a thermologger is fixed to the bottom of a paper cup, the composition is dispensed into the paper cup, and the exothermic temperature when the composition hardens is measured by the thermologger. The highest temperature recorded is defined as the peak exothermic temperature.

7. The composition according to claim 1 or 2, comprising an amide group-containing monomer (A), a monofunctional (meth)acrylate (B), and an elastomer (C).

8. The composition according to claim 7, wherein the monofunctional (meth)acrylate (B) comprises a hydroxyl group-containing (meth)acrylate (B1).

9. The composition according to claim 7, wherein the monofunctional (meth)acrylate (B) comprises a monofunctional (meth)acrylate (B2) having a cyclic structure.

10. The composition according to claim 7, wherein the elastomer (C) comprises one or more selected from the group consisting of (meth)acrylonitrile butadiene rubber, methyl (meth)acrylate butadiene styrene rubber, and methyl (meth)acrylate butadiene (meth)acrylonitrile styrene rubber.

11. The composition according to claim 1 or 2, which is a curable resin composition.

12. A composition according to claim 1 or 2, used in a battery.

13. The composition according to claim 12, which is used as a protective material for battery terminals.

14. An article comprising a cured product made from the composition according to claim 1 or 2.

15. A battery comprising a cured product made from the composition according to claim 1 or 2.

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