Two-component adhesive composition, three-component adhesive composition, electropenetrating cured product, method for removing electropenetrating cured product

Abstract

This invention provides a novel adhesive composition that allows for the weakening of adhesive strength and subsequent peeling of cured acrylic adhesives by applying a voltage to the adhesive. [Solution] The above problems are solved by using a two-component adhesive composition comprising at least a first agent containing a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, and a second agent containing a reducing agent that forms a redox catalyst system with the organic peroxide, wherein the first or second agent contains an ionic liquid.

Description

[Technical Field]

[0001] This invention relates to a two-component adhesive composition. This invention relates to a three-component adhesive composition. This invention relates to an electro-removable cured product and a method for removing the same. [Background technology]

[0002] As a two-component adhesive composition, for example, a two-component acrylic adhesive is known, comprising a first agent containing an acrylic monomer and a peroxide, and a second agent containing a peroxide decomposition accelerator. When the first and second agents are brought into contact, they react and harden at room temperature. Such acrylic adhesives have advantages such as developing adhesive strength in a short time, a wide tolerance range for the mixing ratio of each component, and excellent adhesion to various materials such as metals and plastics. For this reason, two-component acrylic adhesives are widely used in various fields such as electrical, mechanical, automotive, construction, and civil engineering. As an example of such a two-component acrylic adhesive, Patent Document 1 describes a two-component adhesive comprising agent A containing a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, and agent B containing a compound having a thiol group, a reducing agent that forms a redox catalyst system with the organic peroxide, and an organic compound having an SP value of 12.0 or higher, a melting point of 25°C or lower, and a vapor pressure of less than 1 kPa at 25°C. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-94643 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Normally, the cured product of a two-component acrylic adhesive adheres firmly to the substrate, making it difficult to remove. The present inventors aimed to provide a novel adhesive composition that allows for the weakening of the adhesive strength and subsequent removal of the cured acrylic adhesive by applying a voltage to it. [Means for solving the problem]

[0005] The present invention provides a two-component adhesive composition comprising at least a first agent containing a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, and a second agent containing an organic peroxide and a reducing agent that forms a redox catalyst system, wherein the first or second agent contains an ionic liquid.

[0006] Furthermore, the present invention provides a three-component adhesive composition comprising at least a first agent comprising a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, a second agent comprising an organic peroxide and a reducing agent that forms a redox catalyst system, and a third agent comprising an ionic liquid.

[0007] Furthermore, the present invention provides an electro-removable cured product obtained by curing the above-mentioned two-component adhesive composition or three-component adhesive composition.

[0008] Furthermore, the present invention provides a method for peeling off an electropeelable cured product in a composite in which a first conductor and a second conductor are bonded via an electropeelable cured product obtained by curing the above-mentioned two-component adhesive composition or three-component adhesive composition, the method comprising applying a voltage to the electropeelable cured product. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an adhesive composition that exhibits good adhesion and excellent electropenetration properties after curing. [Brief explanation of the drawing]

[0010] [Figure 1A]In a schematic view when looking at a composite in which a first conductor and a second conductor are adhered via a cured product of an adhesive composition from a horizontal direction, it is a circuit example in which electrode terminals are connected to the first conductor and the second conductor. [Figure 1B] It is a schematic view showing a state in which a voltage is applied to the composite of Fig. 1A and the cured product is electrically peeled off from the first conductor. [Figure 2A] In the composite of Fig. 1A, it is a circuit example when the first conductor is attached to a non-conductor as a conductive auxiliary material. [Figure 2B] It is a schematic view showing a state in which a voltage is applied to the composite of Fig. 2A and the cured product is electrically peeled off from the first conductor. [Figure 3A] In the composite of Fig. 1A, it is a circuit example when the second conductor is attached to a non-conductor as a conductive auxiliary material. [Figure 3B] It is a schematic view showing a state in which a voltage is applied to the composite of Fig. 3A and the cured product is electrically peeled off from the first conductor. [Figure 4A] In the composite of Fig. 1A, it is a circuit example when each of the first and second conductors is attached to a non-conductor as a conductive auxiliary material. [Figure 4B] It is a schematic view showing a state in which a voltage is applied to the composite of Fig. 4A and the cured product is electrically peeled off from the first conductor. [Figure 5A] It is a schematic view when looking at the composite (test piece) produced in the adhesion strength test from a horizontal direction. [Figure 5B] It is a schematic view of a circuit in which electrode terminals are connected to the test piece produced in the electrical peelability test.

Embodiments for Carrying Out the Invention

[0011] <Two-component Adhesive Composition> The two-component adhesive composition of the present invention comprises at least a first agent containing a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, and a second agent containing an organic peroxide and a reducing agent that forms a redox catalyst system. Furthermore, either the first agent or the second agent contains an ionic liquid. Polymerization is initiated and curing occurs when the first agent and the second agent are mixed. Hereinafter, the mixture obtained by mixing the first agent and the second agent before curing will also be referred to as the "adhesive."

[0012] (A compound having one or more (meth)acryloyl groups in its molecule) Compounds having one or more (meth)acryloyl groups in their molecule (hereinafter also referred to as acrylic compounds) are compounds that can be radically polymerized by organic peroxides. In this specification, "(meth)acryloyl group" means acryloyl group (CH2=CH-CO- group) and / or methacryloyl group (CH2=C(CH3)-CO- group). Also, in this specification, the notation "(meth)acrylate" means acrylate and / or methacrylate. For example, the notation "methyl (meth)acrylate" means methyl acrylate and / or methyl methacrylate.

[0013] In acrylic compounds, the number of (meth)acryloyl groups in the molecule is not particularly limited, but from the viewpoint of rapid curing and adhesive properties of the adhesive, it is, for example, 1 to 10, preferably 1 to 8, and more preferably 1 to 6.

[0014] Acrylic compounds themselves are well known, and examples include ester compounds of monohydric alcohols and (meth)acrylic acid, (meth)acrylates having a hydroxyl group, (meth)acrylates having a phosphate ester group, (meth)acrylates having an alkoxy group, amide compounds having a (meth)acryloyl group, (meth)acrylates having an alkyl group which may have a substituent, and (meth)acrylates having a cyclic structure. These acrylic compounds are described, for example, in Japanese Patent Publication No. 2022-43152 and Japanese Patent Publication No. 2023-94643.

[0015] From the viewpoint of adhesive strength and electropenetration properties, the acrylic compound preferably contains at least three types of (meth)acrylates as described below (A) to (C): (A) Monofunctional (meth)acrylates having C1-C6 alkyl groups which may have substituents (except aromatic groups); (B) At least one selected from the group consisting of monofunctional (meth)acrylates having alicyclic groups, bifunctional aliphatic (meth)acrylates, and trifunctional or more (meth)acrylates; and (C)2 Functional aromatic (meth)acrylate.

[0016] The substituents of the (meth)acrylate in (A) above are not particularly limited as long as they do not contain aromatic groups, but examples include hydroxyl groups and phosphate ester groups. The first agent preferably includes, as the (meth)acrylate in (A) above, a monofunctional (meth)acrylate having an unsubstituted C1-C6 alkyl group, a monofunctional (meth)acrylate having a hydroxyl group, and a monofunctional (meth)acrylate containing a phosphate ester group. In this specification, "alkyl group" means a group of the chemical formula C n H 2n+1 This refers to a linear or branched saturated hydrocarbon group. Unless otherwise specified, the number of carbon atoms in the alkyl group is, for example, 1 to 30, preferably 1 to 15, and more preferably 1 to 6. In this specification, "C1-C6 alkyl group" refers to an alkyl group having 1 to 6 carbon atoms. In this specification, "monofunctional" means having one (meth)acryloyl group in the molecule. "Bifunctional" means having two (meth)acryloyl groups in the molecule. "Trifunctional or more" means having three or more (meth)acryloyl groups in the molecule.

[0017] Examples of monofunctional (meth)acrylates having unsubstituted C1-C6 alkyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and neopentyl (meth)acrylate. Among these, methyl methacrylate (also known as MMA) is particularly preferred.

[0018] As monofunctional (meth)acrylates having hydroxyl groups, monofunctional (meth)acrylates having hydroxyalkyl groups are preferred. A hydroxyalkyl group is an alkyl group substituted with one or more hydroxyl groups. As hydroxyalkyl groups, hydroxyalkyl groups having one hydroxyl group and a linear or branched alkyl group having 1 to 6 carbon atoms are even more preferred. Examples of monofunctional (meth)acrylates having hydroxyalkyl groups include 2-hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxypentanyl (meth)acrylate, and hydroxyhexyl (meth)acrylate. In the present invention, 2-hydroxypropyl methacrylate (also called 2HPMA) is particularly preferred.

[0019] A phosphate ester group is a group in which all or some of the three hydrogen atoms of phosphoric acid (O=P(OH)3) are replaced by an organic group. Those with 1, 2, or 3 substitutions are called phosphate monoesters, phosphate diesters, and phosphate triesters, respectively, and phosphate ester is a general term for these. As monofunctional (meth)acrylates containing a phosphate ester group, (meth)acryloyloxyalkyl acid phosphates are preferred, and (meth)acryloyloxyalkyl acid phosphates with 1 to 6 carbon atoms in the alkyl group are even more preferred. Examples of (meth)acrylates containing a phosphate ester group include 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxypropyl acid phosphate, and (meth)acryloyloxyhexyl acid phosphate. Among these, 2-methacryloyloxyethyl acid phosphate (also called P-1M) is particularly preferred.

[0020] The (meth)acrylate in (B) above is preferably one of a monofunctional (meth)acrylate having an alicyclic group, a bifunctional aliphatic (meth)acrylate, or a trifunctional or more functional (meth)acrylate. In this specification, "alicyclic group" means a functional group containing saturated or unsaturated carbon rings other than aromatic ones. The carbon rings may contain atoms other than carbon and may be optionally substituted. The carbon rings may contain substituents. Examples of substituents include C1-C6 alkyl groups, hydroxyl groups, C1-C6 alkoxy groups, etc. The alicyclic group may contain two or more carbon rings. As monofunctional (meth)acrylates having an alicyclic group, monofunctional (meth)acrylates having one or more C3-C10 carbon rings are preferred. Examples include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, trimethylcyclohexyl acrylate, and dicyclopentanyl (meth)acrylate. In the present invention, isobornyl acrylate (also known as A-IB) is particularly preferred.

[0021] A difunctional aliphatic (meth)acrylate is a difunctional (meth)acrylate containing a divalent aliphatic group. The divalent aliphatic group is, for example, a linear or branched divalent hydrocarbon group having 2 to 20 carbon atoms, which may have substituents. Examples of substituents include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. The divalent hydrocarbon group may have at least one carbon atom substituted with a heteroatom such as O, S, N, or P. Among these heteroatoms, oxygen is a preferred heteroatom. Examples of difunctional aliphatic (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate. Examples include meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, and ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate. Among these, 1,9-nonanediol diacrylate (also known as 1,9ND-A) is particularly preferred.

[0022] As the trifunctional or higher (meth)acrylate, a trifunctional or higher (meth)acrylate containing a trivalent or higher aliphatic group is preferred. The trivalent or higher aliphatic group is, for example, a linear or branched trivalent or higher hydrocarbon group having 5 to 20 carbon atoms, which may have substituents (except aromatic groups). Examples of substituents include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. The trivalent or higher hydrocarbon group may have at least one carbon atom substituted with a heteroatom such as O, S, N, or P. Among these heteroatoms, O is a preferred heteroatom. Examples of (meth)acrylates with three or more functions include trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxylated pentaerythritol tri(meth)acrylate. Examples include propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Among these, trimethylolpropane trimethacrylate (also known as TMPTM) and ditrimethylolpropane tetraacrylate (also known as DTMPTA) are particularly preferred.

[0023] The (meth)acrylate in (C) above is a difunctional (meth)acrylate (also called a difunctional aromatic (meth)acrylate) containing at least one aromatic ring. The aromatic ring is, for example, a benzene ring which may have substituents. Examples of substituents include C1-C6 alkyl groups, hydroxyl groups, C1-C8 alkoxy groups, etc. The difunctional aromatic (meth)acrylate may also be a compound in which one or more hydrogen atoms of an alkane are substituted with one or more aromatic rings. The alkane is a linear or branched alkane with C1-C6 which may have substituents other than aromatic rings. Examples of other substituents include hydroxyl groups, C1-C4 alkoxy groups, halogens, etc. An example of a difunctional aromatic (meth)acrylate is alkoxylated bisphenol di(meth)acrylate. Preferred alkoxylated bisphenol di(meth)acrylates are epoxidized bisphenol di(meth)acrylate, propoxylated bisphenol di(meth)acrylate, and ethoxylated propoxylated bisphenol di(meth)acrylate. Examples of difunctional aromatic (meth)acrylates include ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, ethoxylated propoxylated bisphenol F di(meth)acrylate, ethoxylated bisphenol AF di(meth)acrylate, propoxylated bisphenol AF di(meth)acrylate, and ethoxylated propoxylated bisphenol AF di(meth)acrylate. In the present invention, ethoxylated bisphenol A dimethacrylate (also known as BPE-100) is particularly preferred.

[0024] The content of the acrylic compound in the first component of the two-component adhesive composition is not particularly limited, but if an ionic liquid is included in the first component, it may be, for example, 50% to 85% by weight relative to 100% by weight of the first component. If an ionic liquid is included in the second component, it may be, for example, 90% to 99% by weight relative to 100% by weight of the first component.

[0025] The respective content amounts of (meth)acrylate in (A) to (C) above are as follows: for example, relative to the total content of the acrylic compound of 91 parts by weight, the content of (meth)acrylate in (A) is 25.5 parts by weight or more and 65 parts by weight or less, the content of (meth)acrylate in (B) is 15 parts by weight or more and 45 parts by weight or less, and the content of (meth)acrylate in (C) is 10 parts by weight or more and 25 parts by weight or less. The preferred combination of (meth)acrylates described in (A) above is C1-C6 alkyl monofunctional (meth)acrylate, monofunctional (meth)acrylate having a hydroxyl group, and monofunctional (meth)acrylate containing a phosphate ester group. For example, with respect to 91 parts by weight of the total content of the acrylic compound, the C1-C6 alkyl monofunctional (meth)acrylate is 15 to 40 parts by weight, the monofunctional (meth)acrylate having a hydroxyl group is 10 to 22 parts by weight, and the monofunctional (meth)acrylate containing a phosphate ester group is 0.5 to 3 parts by weight.

[0026] (organic peroxide) The organic peroxide is not particularly limited as long as it is a compound that acts as a radical polymerization initiator for acrylic compounds. The organic peroxide forms a reducing agent that forms a redox catalyst system with the organic peroxide, and a redox polymerization initiator. Examples of organic peroxides include hydroperoxides, diacyl peroxides, alkyl peroxyesters, peroxydicarbonates, monoperoxycarbonates, peroxyketals, dialkyl peroxides, and ketone peroxides.

[0027] Examples of hydroperoxides include cumene hydroperoxide, paramentane hydroperoxide, tert-butyl hydroperoxide, and diisopropylbenzene dihydroperoxide. Examples of diacyl peroxides include dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, and di(3-methylbenzoyl) peroxide. Examples of alkyl peroxyesters include t-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, t-octyl peroxyneodecanoate, t-butyl peroxypivalate, and t-butyl peroxy-2-ethylhexinoate. Examples of peroxydicarbonates include di(2-ethylhexyl) peroxydicarbonate and diisopropyl peroxydicarbonate. Examples of monoperoxycarbonates include t-butylperoxyisopropyl carbonate and t-pentylperoxy2-ethylhexyl carbonate. Examples of peroxyketals include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di(t-butylperoxy)-butane, n-butyl4,4-di-(t-butylperoxy)valerate and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane. Examples of dialkylperoxides include di-t-butylperoxide, t-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, 1,4-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t-butylperoxy)balate, 2,2-bis(4,4-t-butylperoxycyclohexyl)propane, 2,2-bis(t-butylperoxy)butane, and 1,1-bis(t-butylperoxy)cyclododecane.Examples of ketone peroxides include methyl ethyl ketone peroxide and acetylacetone peroxide.

[0028] These organic peroxides may be used individually or in combination of two or more. Among these organic peroxides, hydroperoxides are preferred because they are stable at room temperature (25°C), easy to handle, and readily initiate reactions at room temperature when used with a reducing agent. Of these, cumene hydroperoxide (also known as CHP) is particularly preferred.

[0029] The content of organic peroxide in the first component of the two-component adhesive composition is not particularly limited, but if the first component contains an ionic liquid, it may be, for example, 0.5% to 5% by weight relative to 100% by weight of the first component. If the second component contains an ionic liquid, it may be, for example, 1.5% to 4.5% by weight relative to 100% by weight of the first component. Preferably, the first component of the two-component adhesive composition contains 1, 2, 3, 4, 5, or 6 parts by weight of organic peroxide per 91 parts by weight of the acrylic compound.

[0030] (Ionic liquid) Ionic liquids are combinations of cations and anions that are liquid at room temperature, and are also called room-temperature molten salts. Ionic liquids possess properties such as non-flammability, non-volatility, and chemical stability. The ionic liquid of the present invention is 10 -4 S / cm or more 10 -1 It has an ionic conductivity of S / cm or less. Having an ionic conductivity within this range allows the adhesive composition to be sufficiently imparted with the property of being peeled off by the application of voltage. The ionic conductivity is 10 -3 S / cm or more 10 -1 It is more preferable that the ionic conductivity is less than or equal to S / cm. The ionic conductivity can be measured by the AC impedance method using, for example, a Solartron 1260 frequency response analyzer. Examples of ionic liquids include those represented by the following formula (1).

[0031] [Chemical formula] (In the formula, R 1 is a divalent or trivalent hydrocarbon group having 2 to 8 carbon atoms which may contain a heteroatom. N in the formula + forms a ring together with it. The hydrocarbon group may contain a substituent, and the substituent is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. R 2 and R 3 are the same or different and are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (however, when the nitrogen atom forms a double bond with an adjacent carbon atom, R 3 does not exist), and X - is an anion selected from Br - , AlCl4 - , Al2Cl7 - , NO3 - , BF4 - , PF6 - , CH3COO - , CF3COO - , CF3SO3 - , (CF3SO2)2N - , (FSO2)2N - , (CF3SO2)3C - , AsF6 - , SbF6 - , F(HF) n - , CF3(CF2)3SO3 - , (CF3CF2SO2)2N - and CF3CF2COO - is an anion selected from)

[0032] In the above formula, R 1 and N +The ring composed of these includes saturated alicyclic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and unsaturated cyclic hydrocarbons such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, and benzene, in which at least one carbon atom constituting a hydrocarbon ring is replaced with a nitrogen atom. Examples of heteroatoms include N, O, S, P, etc., with N being preferred. 1 Examples of alkyl groups having 1 to 4 carbon atoms as substituents include methyl, ethyl, propyl, and butyl groups. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups. Alkyl groups or alkoxy groups having 3 to 4 carbon atoms include structural isomers. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Alkyl groups having 3 to 8 carbon atoms include structural isomers.

[0033] The ionic liquid is a cation selected from pyridinium-based cations and imidazolium-based cations, and (FSO2)2N - and (CF3SO2)2N - It is preferable from the viewpoint of improving electrolytic properties that the salt is with an anion selected from the above. In the present invention, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (also known as EMI-FSI), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (also known as EMI-TFSI), and 1-hexylpyridinium bis(trifluoromethanesulfonyl)imide (also known as IL-P14) are more preferred.

[0034] Ionic liquids are available from companies such as Daiichi Kogyo Seiyaku, Kanto Kagaku, and Koei Kagaku Kogyo. For example, EMI-FSI and EMI-TFSI can be obtained from Daiichi Kogyo Seiyaku, IL-P14 from Koei Kagaku Kogyo, and 1-hexylpyridinium bis(trifluoromethanesulfonyl)imide and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide from Kanto Kagaku. The combinations of cations and anions contained in EMI-FSI and EMI-TFSI are as follows:

[0035] [ka]

[0036] [ka]

[0037] When the first component of a two-component adhesive composition contains an ionic liquid, the content of the ionic liquid is not particularly limited, but it may be 9% to 45% by weight relative to 100% by weight of the first component. Preferably, the first component of the two-component adhesive composition contains more than 10 parts by weight of the ionic liquid per 91 parts by weight of the acrylic compound. The upper limit of the ionic liquid per 91 parts by weight of the acrylic compound may be, for example, 75 parts by weight, 70 parts by weight, 60 parts by weight, or 50 parts by weight. The lower limit of the ionic liquid per 91 parts by weight of the acrylic compound may be, for example, more than 10 parts by weight, such as 15 parts by weight, 20 parts by weight, 30 parts by weight, or 40 parts by weight. These upper and lower limits can be combined arbitrarily. Preferably, it is more than 10 parts by weight and 75 parts by weight or less, and more preferably 15 parts by weight or more and 50 parts by weight or less. If the content of the ionic liquid is 10 parts by weight or less per 91 parts by weight of the acrylic compound, the electropenetration properties of the cured product may decrease. When the second component of a two-component adhesive composition contains an ionic liquid, the content of the ionic liquid is not particularly limited, but it may be 50% to 88.5% by weight relative to 100% by weight of the second component. Preferably, the second component of the two-component adhesive composition contains more than 10 parts by weight of the ionic liquid per 1 part by weight of the reducing agent (hereinafter also referred to as the reducing agent) that forms a redox catalyst system with the organic peroxide. The upper limit of the ionic liquid per 1 part by weight of the reducing agent may be, for example, 75 parts by weight, 70 parts by weight, 60 parts by weight, or 50 parts by weight. The lower limit of the ionic liquid per 1 part by weight of the reducing agent may be, for example, more than 10 parts by weight, such as 15 parts by weight, 20 parts by weight, 30 parts by weight, or 40 parts by weight. These upper and lower limits can be combined arbitrarily. Preferably, it is more than 10 parts by weight and 75 parts by weight or less, and more preferably 15 parts by weight or more and 50 parts by weight or less. If the ionic liquid content is 10 parts by weight or less per 1 part by weight of reducing agent, the electropenetrating properties of the cured product may decrease.

[0038] (A reducing agent that forms a redox catalyst system with organic peroxides) The reducing agent that forms a redox catalyst system with the organic peroxide is not particularly limited as long as it is a reducing agent that reacts with the organic peroxide and generates radicals. Examples include metal compounds, thiourea derivatives, and amine compounds. The reducing agent may be used alone or in combination of two or more.

[0039] Examples of metal compounds include one or more selected from vanadium compounds, iron compounds, copper compounds, tin compounds, cobalt compounds, etc. Examples of vanadium compounds include vanadylacetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium acetylacetonate, vanadium benzoylacetonate, bis(acetylacetonate)oxovanadium, bis(benzoylacetonate)oxovanadium, bis(stearoyloxy)oxovanadium, vanadyl oxalate, and vanadyl naphthenate. Examples of iron compounds include iron acetate, iron formate, iron oxalate, iron stearate, iron bis(2-ethylhexanoate)ferrous, and iron naphthenate. Examples of copper compounds include copper acetate, copper formate, copper oxalate, copper stearate, copper bis(2-ethylhexanoate)copper, and copper naphthenate. Examples of tin compounds include tin (2-ethylhexanoate). Examples of cobalt compounds include cobalt naphthenate and cobalt acetylacetonate.

[0040] Examples of thiourea derivatives include one or more selected from 2-imidazolidinethion, 2-mercaptobenzimidazole, thiourea, methylthiourea, dibutylthiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-dipropylthiourea, N,N'-di-n-butylthiourea, N,N'-dilaurylthiourea, N,N'-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea, tetramethylthiourea, and ethylenethiourea.

[0041] Examples of amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylp-toluidine, N,N-dimethylaniline, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-i-propylaniline, N,N-dimethyl-4-t-butylaniline, and N,N-dimethyl-3,5-di-t-butylaniline. Aniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-i-propylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-di(2-hydroxyethyl)-3,5-di-i-propylaniline, N,N-bis(2-hydroxyethyl)- 3,5-di-t-butylaniline, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate n-butoxyethyl, 4-dimethylaminobenzoate (2-methacryloyloxy)ethyl, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino)ethyl methacrylate, N,N-bis(methacryloyloxyethyl)-N-methylamine, N,N-bis(methacryloyloxyethyl)-N-ethylamine One or more of the following can be selected: N,N-bis(2-hydroxyethyl)-N-methacryloyloxyethylamine, N,N-bis(methacryloyloxyethyl)-N-(2-hydroxyethyl)amine, tris(methacryloyloxyethyl)amine, N,N-dimethylaminoethyl methacrylate, methyl-4-dimethylaminobenzoate, ethyl-4-dimethylaminobenzoate, isoamyl-4-dimethylaminobenzoate, diethylenetriamine, benzimidazole, reaction condensates of amines and aldehydes, etc.

[0042] Of these, one or more selected from vanadium compounds and thiourea derivatives are preferred from the viewpoint of reactivity with organic peroxides, etc. In the present invention, vanadium compounds are more preferred, and vanadylacetylacetonate (also known as AAV) is particularly preferred.

[0043] When an ionic liquid is included in the first component, the content of the reducing agent in the second component of a two-component adhesive composition is not particularly limited, but it may be 5% to 60% by weight, preferably 5% to 30% by weight, and more preferably 5% to 15% by weight, based on 100% by weight of the second component. When the reducing agent is a liquid, the second component may consist only of the reducing agent. When an ionic liquid is included in the second component, the content of the reducing agent in the second component of a two-component adhesive composition is not particularly limited, but it may be 0.5% to 40% by weight, preferably 1.0% to 35% by weight, based on 100% by weight of the second component. When the reducing agent is a liquid, the second component may consist only of the reducing agent and an ionic liquid. When the first and second components are mixed, if radicals are generated by the reaction between the organic peroxide and the reducing agent, the content of the reducing agent is not particularly limited. The upper limit of the reducing agent content per 1 part by weight of organic peroxide is, for example, 0.5 parts by weight, 0.45 parts by weight, 0.4 parts by weight, 0.35 parts by weight, or 0.3 parts by weight, and the lower limit is, for example, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, or 0.25 parts by weight. These upper and lower limits can be combined in any way.

[0044] (Other additives) The two-component adhesive composition of the present invention may contain other additives, as long as they do not impair the electropenetrating properties of the cured product. Examples of other additives include elastomers, plasticizers, storage stabilizers, polymerizable vinyl monomers (reactive diluents), adhesion promoters, tackifying resins, fillers, bulking agents, property modifiers, reinforcing agents, colorants, flame retardants, anti-sagging agents, thixotropic agents, anti-precipitation agents, antioxidants, anti-aging agents, UV absorbers, fragrances, and various reaction accelerators and curing modifiers to adjust the curing rate.

[0045] (Elastomer) The elastomer is not particularly limited as long as it is a component that has rubber elasticity. For example, various synthetic rubbers such as acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-methyl methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-styrene-butadiene copolymer, acrylonitrile-butadiene rubber, urethane rubber, styrene-butadiene rubber, chloroprene rubber, polyisoprene rubber, nitrile rubber, acrylic rubber, epichlorohydrin rubber, and butadiene rubber; natural rubber; liquid rubber such as liquid polybutadiene, acrylic-terminated liquid polybutadiene, and liquid acrylonitrile-butadiene copolymer. Examples include: styrene-based thermoplastic elastomers such as styrene-polybutadiene-styrene synthetic rubber; olefin-based thermoplastic elastomers such as polyethylene-EPDM synthetic rubber; urethane-based thermoplastic elastomers such as caprolactone type, adipate type, and PTMG type; polyester-based thermoplastic elastomers such as polybutylene terephthalate-polytetramethylene glycol multiblock polymer; polyamide-based thermoplastic elastomers such as nylon-polyol block copolymer and nylon-polyester block copolymer; 1,2-polybutadiene-based thermoplastic elastomers; and PVC-based thermoplastic elastomers.

[0046] Furthermore, the rubber microparticles may be rubber microparticles having at least a rubber layer, or core-shell type rubber microparticles having a core layer made of rubber and a shell layer further covered with a resin layer. Core-shell rubber microparticles can be synthesized as polymer microparticles in which a shell layer is formed by graft polymerization of graft copolymerizable monomer components in the presence of a core layer. As the rubber for the core layer, silicone rubber, butadiene rubber, styrene-butadiene rubber, acrylic rubber, etc. can be used, but are not limited to these. The shell layer generally uses (meth)acrylate monomers, aromatic vinyl monomers, acrylonitrile, etc., but other monomers may also be used. One or more types of rubber for the core layer and monomers for the shell layer may be used depending on the desired properties.

[0047] The elastomer has functions such as an impact absorber for the cured adhesive layer and / or a function to adjust the viscosity and thixotropy of the adhesive composition. Furthermore, the elastomer can further increase the adhesive strength of the cured product of the present invention. These elastomers may be used individually or in combination of two or more. In the present invention, various synthetic rubbers are preferred, and among them, nitrile rubber (also called NBR) is more preferred from the viewpoint of increasing adhesive strength.

[0048] The elastomer is preferably included in the first component. The elastomer content in the first component of the two-component adhesive composition is not particularly limited. The upper limit of the elastomer per 91 parts by weight of the acrylic compound is, for example, 13 parts by weight, 11 parts by weight, or 9 parts by weight, and the lower limit is, for example, 3 parts by weight, 5 parts by weight, or 7 parts by weight. These upper and lower limits can be combined in any way.

[0049] (Plasticizer) Examples of plasticizers include carboxylic acid esters such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), dimethyl phthalate, diethyl phthalate, diheptyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate, diisoundecyl phthalate, butyl benzyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, diisobutyl adipate (DIBA), dioctyl adipate, diisodecyl adipate, and DBE (a mixture of dimethyl succinate, dimethyl glutarate, and dimethyl adipate). Examples of plasticizers include epoxy plasticizers such as alkyl epoxy stearate, epoxidized soybean oil, epoxidized linseed oil, and benzyl epoxy stearate; polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols, such as propylene glycol adipate and butylene glycol adipate; polyether plasticizers such as polypropylene glycol or its derivatives; polystyrene plasticizers such as poly-α-methylstyrene and polystyrene; and olefin plasticizers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and chlorinated paraffin. These plasticizers may be used individually or in combination of two or more. In the present invention, carboxylic acid ester compounds are preferred, and diisononyl phthalate and diisobutyl adipate are particularly preferred.

[0050] The plasticizer is preferably included in the second agent. When the first agent contains an ionic liquid, the plasticizer content in the second agent is not particularly limited, but it may be 40% to 95% by weight, preferably 70% to 95% by weight, and more preferably 85% to 95% by weight, based on 100% by weight of the second agent. Alternatively, the upper limit of the plasticizer content per 1 part by weight of the reducing agent is, for example, 13 parts by weight, 12 parts by weight, or 10 parts by weight, and the lower limit is, for example, 0.5 parts by weight, 1 part by weight, or 3 parts by weight. These upper and lower limits can be arbitrarily combined. When the second agent contains an ionic liquid, the plasticizer content in the second agent is not particularly limited, but it may be 3% to 50% by weight, preferably 4% to 48% by weight, based on 100% by weight of the second agent. The plasticizer content per 1 part by weight of the reducing agent is the same as when the first agent contains an ionic liquid.

[0051] (Storage stabilizer) Various antioxidants, including polymerization inhibitors, can be used as storage stabilizers. Examples of antioxidants include p-methoxyphenol, hydroquinone, benzoquinone, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), triphenyl phosphite, phenothiazine, and N-isopropyl-N'-phenyl-p-phenylenediamine, ethylenediaminetetraacetic acid, or their salts. These storage stabilizers may be used individually or in combination of two or more.

[0052] The storage stabilizer is preferably included in the first component. The amount of storage stabilizer in the first component is not particularly limited. The upper limit of the storage stabilizer per 91 parts by weight of the acrylic compound is, for example, 1 part by weight, 0.5 parts by weight, 0.3 parts by weight, or 0.1 parts by weight, and the lower limit is, for example, 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, or 0.07 parts by weight. These upper and lower limits can be combined arbitrarily.

[0053] The mixing ratio of the first agent and the second agent in this invention is not particularly limited. The upper limit of the second agent per 1 part by weight of the first agent is, for example, 1 part by weight, 0.5 parts by weight, 0.3 parts by weight, or 0.1 parts by weight, and the lower limit is, for example, 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, or 0.07 parts by weight. These upper and lower limits can be combined arbitrarily. If more than 1 part by weight of the second agent is mixed with 1 part by weight of the first agent, the required adhesive strength may not be obtained. If less than 0.01 parts by weight of the second agent is mixed with 1 part by weight of the first agent, the adhesive may not harden.

[0054] A preferred two-component adhesive composition includes, for example, a monofunctional (meth)acrylate having an unsubstituted C1-C6 alkyl group, a monofunctional (meth)acrylate having a hydroxyalkyl group having one hydroxyl group and a linear or branched alkyl group having 1-6 carbon atoms, a (meth)acryloyloxyalkyl acid phosphate with an alkyl group having 1-6 carbon atoms, at least one selected from the group consisting of a monofunctional (meth)acrylate having one or more carbon rings having 3-10 carbon atoms, a bifunctional (meth)acrylate containing a linear or branched divalent hydrocarbon group having 2-20 carbon atoms, and a trifunctional or more (meth)acrylate containing a linear or branched trivalent or higher hydrocarbon group having 5-20 carbon atoms, a bifunctional (meth)acrylate containing a benzene ring having an alkoxy group having 1-8 carbon atoms, hydroperoxides, a cation selected from pyridinium-based cations and imidazolium-based cations, and (FSO2)2N - and (CF3SO2)2N - It consists of a first agent comprising a salt with an anion selected from, and a second agent comprising a vanadium compound.

[0055] (Uses of two-component adhesive compositions) The two-component adhesive composition of the present invention can be used to bond solid objects of various materials and shapes. The bonding method itself is the same as that of conventional two-component acrylic adhesives. The shape of the objects to be bonded is not particularly limited, but examples include films, plates, rods, meshes, fibers, etc. The material of the objects may be either conductive or non-conductive. When electrolytically peeling off the cured product, the two-component adhesive composition of the present invention is used to bond conductive objects. By attaching a conductive auxiliary material to a non-conductive object, the non-conductive object can also be electrolytically peeled indirectly via the conductive auxiliary material. Any adhesive or tack (collectively referred to as "adhesive") can be used to attach the conductive auxiliary material. Examples of conductive objects include metals such as iron, aluminum, copper, silver, and gold, alloys of these metals, and conductive resins. Examples of non-conductive objects include resins, glass, ceramics, paper, cloth, fibers, wood, and bamboo. Examples of conductive auxiliary materials include plates, films, meshes, etc., made of conductive materials.

[0056] Once the two-component adhesive composition of the present invention has cured, the cured material can be easily peeled off by applying a voltage. Therefore, the two-component adhesive composition of the present invention can be suitably used for bonding opaque materials that cannot be subjected to UV irradiation, or materials that are sensitive to heat. Furthermore, the two-component adhesive composition of the present invention can be suitably used for fixing materials that require high processing accuracy, or for fixing materials that are difficult to physically fix, such as thin metal plates or substrates. For example, the two-component adhesive composition of the present invention can be used for temporary fixing of components in the electronic component manufacturing process (for example, temporary fixing of wafers during dicing of LSI chips). The temporary fixing can be easily released by applying a voltage to the cured material.

[0057] The two-component adhesive composition of the present invention is also useful from the viewpoint of recycling and reuse. For example, products such as automobiles, home appliances, mobile phones, and PCs may contain parts that are rare or valuable, or parts that should be safely recovered and reused. If such parts are fixed in the product with the two-component adhesive composition of the present invention, the fixed parts can be easily recovered by applying a voltage to the fixed parts after the product has been discarded and recovered. Another application is the bonding of sensors to conductive objects. In this application as well, the sensor can be easily recovered by detaching it by applying a low voltage, and the sensor can be reused repeatedly, making it economical.

[0058] <Three-component adhesive composition> The three-component adhesive composition of the present invention comprises at least three components: a first component containing one or more compounds having one or more (meth)acryloyl groups in their molecules and an organic peroxide; a second component containing an organic peroxide and a reducing agent that forms a redox catalyst system; and a third component containing an ionic liquid. The content (percentage) of each component of the three-component adhesive composition, and the content of components other than the acrylic compound and organic peroxide relative to 100% by weight of the first component, are the same as those described for the two-component adhesive composition. The uses of the three-component adhesive composition are also the same as those of the two-component adhesive composition. Polymerization is initiated and curing occurs when the first, second, and third components are mixed. Hereinafter, the mixture obtained by mixing the first, second, and third components before curing will also be referred to as the "adhesive."

[0059] The content of the acrylic compound in the first component of the three-component adhesive composition is not particularly limited, but it may be, for example, 90% to 99% by weight or less, relative to 100% by weight of the first component. The content of organic peroxide in the first component of the three-component adhesive is not particularly limited, but may be 1% to 7% by weight relative to 100% by weight of the first component.

[0060] In the present invention, the first agent may further contain other additives such as elastomers. Preferably, the first agent contains an elastomer. The second agent may further contain plasticizers or the like.

[0061] <Electrorelease cured product> The electropenetrating cured product of the present invention (hereinafter also simply referred to as "cured product") is a substance obtained by curing the two-component adhesive composition or the three-component adhesive composition of the present invention. Curing of the adhesive composition is performed by mixing the first and second components of the two-component adhesive composition or by mixing the first, second, and third components of the three-component adhesive composition and initiating polymerization. That is, the cured product of the present invention is produced when a mixture (adhesive) of the first and second (and third) components hardens. The temperature during mixing and polymerization can be room temperature (5°C to 40°C) or higher.

[0062] Preferably, the cured material is formed between the surface of the first conductor and the surface of the second conductor. This allows the first conductor and the second conductor to be bonded together via the cured material. The materials of the first and second conductors are the same as those of the conductive objects described above. The materials of the first and second conductors may be the same or different.

[0063] The method for bonding the first conductor and the second conductor is not particularly limited. For example, a mixture of the first agent, the second agent, and (the third agent) can be applied to at least a portion of the surface of the first conductor, and the surface of the second conductor can be brought into contact with the applied surface to bond them. The mixture of the first agent and the second agent (and the third agent) may be prepared in advance, or it may be prepared by mixing the first agent and the second agent (and the third agent) on the surface of the conductor. Alternatively, the first agent or a mixture of the first agent and the third agent can be applied to at least a portion of the surface of the first conductor, and the second agent can be applied to at least a portion of the surface of the second conductor, and the respective applied surfaces can be brought into contact to bond them. Alternatively, the first agent can be applied to at least a portion of the surface of the first conductor, and a mixture of the second agent and the third agent can be applied to at least a portion of the surface of the second conductor, and the respective applied surfaces can be brought into contact to bond them. The thickness of the cured layer is not particularly limited and may be, for example, 0.01 mm or more and 10 mm or less.

[0064] The adhesive strength of the electropenetrating cured product of the present invention before the application of voltage may be, for example, 1.0 MPa or more, and preferably 1.5 MPa or more.

[0065] <Method for removing electrolyzable cured materials> The present invention relates to a method for removing an electropeelable cured product, which involves applying a voltage to an electropeelable cured product in a composite in which a first conductor and a second conductor are bonded together via the electropeelable cured product. The application of voltage significantly reduces the adhesive strength of the electropeelable cured product, allowing it to be easily removed from the conductors. The removal itself can be performed, for example, by peeling the conductors off with one's hands or a suitable tool. Referring to Figure 1A, the application of voltage to the electropeelable cured product 2 can be performed, for example, by connecting the terminals of a wire with terminals connected to a DC power supply 4 to the first conductor 1 and the second conductor 3, respectively, and then starting the power supply. Referring to Figure 1B, the application of voltage energizes the electropeelable cured product 2 through the first conductor 1 and the second conductor 3, allowing the electropeelable cured product 2 to be removed from the conductors. In the example in Figure 1B, the electropeelable cured product is removed from the first conductor, but the present invention is not limited to this example. In electrolytically cured materials to which voltage is applied, the adhesive strength decreases and peeling mainly occurs from the negative side. However, whether the cured material peels from the first or second conductor depends on how the force applied for peeling is handled, etc.

[0066] The electropeelable cured product of the present invention can achieve electropeelability at low voltages, but this does not preclude its use at high voltages. The range of applied voltage can be determined by selecting an upper limit from, for example, 500V, 450V, 400V, 350V, 300V, 250V, 200V, 150V, 100V, 90V, 80V, 70V, 60V, and 50V, and a lower limit from 0.5V, 1V, 2V, 3V, 4V, 5V, 6V, 7V, 8V, 9V, and 10V. The range of applied voltage is preferably 1V to 100V, more preferably 3V to 100V, and even more preferably 10V to 50V. The voltage application time is not particularly limited as long as it can cause electrolysis in the composite, but is usually 1 second to 1200 seconds, preferably 1 second to 600 seconds, more preferably 1 second to 300 seconds, even more preferably 1 second to 180 seconds, and particularly preferably 1 second to 90 seconds. The adhesive strength of the electropeelable cured product of the present invention, after application of the above-mentioned voltage range and application time, should be such that it can be peeled off, for example, less than 1.0 MPa, and preferably less than 0.6 MPa. Furthermore, the reduction rate of the adhesive strength of the electropeelable cured product of the present invention after application is, for example, 70% or more, preferably 80% or more, and more preferably 90% or more. The definition of the reduction rate of adhesive strength after application will be explained in the examples.

[0067] When bonding a non-conductive object and a conductive object using the adhesive composition of the present invention, the bonding can be done indirectly via a conductive auxiliary material, as described above. For example, referring to Figure 2A, first, the first conductor 1 is attached to the non-conductive object 5 as a conductive auxiliary material. The attachment is done using an adhesive 6. Then, the attached conductive auxiliary material (first conductor 1) and the second conductor 3 are bonded together using the adhesive composition of the present invention to form a cured product. As a result, the non-conductive object 5 and the second conductor 3 are bonded together via the conductive auxiliary material and the electropenetrating cured product 2, forming a composite. When peeling off the electropenetrating cured product 2 from this composite, the terminals of a wire with terminals connected to a DC power supply 4 are connected to the conductive auxiliary material (first conductor 1) and the second conductor 3, respectively, to form a circuit. Referring to Figure 2B, by applying a voltage, current is passed through the conductive auxiliary material (first conductor 1) and the second conductor 3 to the electropeelable cured product 2, allowing the electropeelable cured product 2 to be peeled off from the conductor.

[0068] In a composite formed by bonding a non-conductive object and a conductive object, the electropenetrating cured product can also be peeled off by using a second conductor as a conductive auxiliary material. Referring to Figure 3A, first, the second conductor 3 is attached to the non-conductive object 5 as a conductive auxiliary material. The attachment is done using adhesive 6. Then, the attached conductive auxiliary material (second conductor 3) and the first conductor 1 are bonded together using the adhesive composition of the present invention to form a cured product. As a result, the non-conductive object 5 and the first conductor 1 are bonded together via the conductive auxiliary material and the electropenetrating cured product 2, forming a composite. To peel off the electropenetrating cured product 2 in this composite, the terminals of a wire with terminals connected to a DC power supply 4 are connected to the conductive auxiliary material (second conductor 3) and the first conductor 1, respectively, to form a circuit. Referring to Figure 3B, by applying a voltage, current is passed through the conductive auxiliary material (second conductor 3) and the first conductor 1 to the electropeelable cured product 2, allowing the electropeelable cured product 2 to be peeled off from the conductor.

[0069] In a composite formed by bonding non-conductive objects using both the first and second conductors as conductive auxiliary materials, the electropenetrating cured product can also be peeled off. Referring to Figure 4A, first, the first conductor 1 and the second conductor 3 are attached to the non-conductive objects 5 and 5', respectively, as conductive auxiliary materials. The attachment is done using adhesive 6. Then, the first conductor 1 and the second conductor 3, which have been attached as conductive auxiliary materials, are bonded together using the adhesive composition of the present invention to form a cured product. As a result, the non-conductive objects 5 and 5' are bonded together via the first conductor 1, the electropenetrating cured product 2, and the second conductor 3, forming a composite. To peel off the electropenetrating cured product 2 in this composite, terminals of a wire with terminals connected to a DC power supply 4 are connected to each of the first conductor 1 and the second conductor 3, which are conductive auxiliary materials, to form a circuit. Referring to Figure 4B, by applying a voltage, current is passed through the first conductor 1 and the second conductor 3 to the electropeelable cured product 2, allowing the electropeelable cured product 2 to be peeled off from the conductors.

[0070] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. [Examples]

[0071] <Preparation of a two-component adhesive composition> [Example 1] • Preparation of the first agent 30 parts by weight of MMA (Tokyo Chemical Industries Co., Ltd.), 30 parts by weight of A-IB (Shin Nakamura Chemical Industry Co., Ltd.), 15 parts by weight of 2HPMA (Tokyo Chemical Industries Co., Ltd.), 15 parts by weight of BPE-100 (Shin Nakamura Chemical Industry Co., Ltd.), 1 part by weight of P-1M (Kyoeisha Chemical Co., Ltd.), 7 parts by weight of NBR (ENEOS Material Co., Ltd.), and 3 parts by weight of CHP (Tokyo Chemical Industries Co., Ltd.) were added to a beaker and stirred with a stirring bar at room temperature to obtain a mixture. 25 parts by weight of EMI-FSI (Daiichi Kogyo Seiyaku Co., Ltd.) was added to this mixture and stirred to obtain 126 parts by weight of the first component.

[0072] • Preparation of the second drug In a separate beaker, 9 parts by weight of DINP (J-Plus Co., Ltd.) and 1 part by weight of AAV (Nippon Chemical Industries Co., Ltd.) were added and stirred with a stirring bar at room temperature to obtain 10 parts by weight of the second component. The second component was prepared in the same manner in Examples 2 to 10 and Comparative Examples 1 to 3 described below.

[0073] [Example 2] Except for adding 30 parts by weight of DTMPTA (Tokyo Chemical Industries Co., Ltd.) instead of A-IB, 126 parts by weight of the first agent was obtained in the same manner as in Example 1. [Example 3] Except for adding 20 parts by weight of DTMPTA (Tokyo Chemical Industries Co., Ltd.) and 10 parts by weight of TMPTM (Tokyo Chemical Industries Co., Ltd.) in place of A-IB, 126 parts by weight of the first agent was obtained in the same manner as in Example 1. [Example 4] Except for adding 15 parts by weight of DTMPTA (Tokyo Chemical Industries, Ltd.) and 15 parts by weight of TMPTM (Tokyo Chemical Industries, Ltd.) in place of A-IB, 126 parts by weight of the first agent was obtained in the same manner as in Example 1. [Example 5] Except for adding 30 parts by weight of 1.9ND-A (Kyoeisha Chemical Co., Ltd.) instead of A-IB, and changing the amount of EMI-FSI added from 25 parts by weight to 15 parts by weight, 116 parts by weight of the first agent was obtained in the same manner as in Example 1.

[0074] [Example 6] Except for changing the amount of EMI-FSI added from 25 parts by weight to 20 parts by weight, 121 parts by weight of the first agent was obtained in the same manner as in Example 2. [Example 7] Except for changing the amount of EMI-FSI added from 25 parts by weight to 50 parts by weight, 151 parts by weight of the first agent was obtained in the same manner as in Example 2. [Example 8] Except for changing the amount of EMI-FSI added from 25 parts by weight to 75 parts by weight, 176 parts by weight of the first agent was obtained in the same manner as in Example 2. [Example 9] Except for adding 25 parts by weight of EMI-TFSI (Daiichi Kogyo Seiyaku Co., Ltd.) instead of EMI-FSI, 126 parts by weight of the first agent was obtained in the same manner as in Example 2. [Example 10] Except for adding 25 parts by weight of IL-P14 (Koei Chemical Industry Co., Ltd.) instead of EMI-FSI, 126 parts by weight of the first agent was obtained in the same manner as in Example 2.

[0075] [Comparative Example 1] 101 parts by weight of the first agent was obtained in the same manner as in Example 2, except that EMI-FSI was not added. [Comparative Example 2] Except for changing the amount of EMI-FSI added from 25 parts by weight to 5 parts by weight, 106 parts by weight of the first agent was obtained in the same manner as in Example 2. [Comparative Example 3] Except for changing the amount of EMI-FSI added from 25 parts by weight to 10 parts by weight, 111 parts by weight of the first agent was obtained in the same manner as in Example 2.

[0076] <Adhesive strength test> To each of the first agent obtained in Examples 1-10 and Comparative Examples 1-3 by weight in a beaker, 10 parts by weight of the second agent was added and stirred with a stirring bar to obtain the adhesives of Examples 1-10 and Comparative Examples 1-3. Each adhesive was applied to the longitudinal edge of a 100 mm x 25 mm aluminum plate A1050 (H24) that had been degreased with acetone, so that the bonding area was 25 mm x 12.5 mm and the adhesive layer was 0.2 mm thick. The longitudinal edge of another aluminum plate of the same size was bonded to the adhesive-coated surface. The bonded aluminum plates were cured for one day at 23°C and 50% RH to obtain a composite (also called a test specimen) (see Figure 5A). The adhesive strength of the test specimen was measured in accordance with JIS K6850 (1999) using a tensile testing machine (Shimadzu Corporation, Autograph, AGS-10kNX) at 23°C and 50% RH at a tensile speed of 1 mm / min. The measurement results are shown in Tables 1-1 to 1-3.

[0077] <Electropeel test> Test specimens were prepared using each adhesive in the same manner as in the adhesive strength test described above. Electrodes were attached to both ends of the longitudinal direction of each test specimen (see Figure 5B). At 23°C and 50%RH, 30V was applied to each test specimen for 60 seconds. The adhesive strength of the test specimens after application was measured in the same manner as in the adhesive strength test described above. The measurement results are shown in Tables 1-1 to 1-3. These tables also show the percentage decrease in adhesive strength. The percentage decrease in adhesive strength was calculated by dividing the difference between the adhesive strength before and after application by the adhesive strength before application. In the "Electropeelability" column of each table, "○" is written if the percentage decrease in adhesive strength is 90% or more and the adhesive strength after application is less than 1 MPa, and "×" is written if the percentage decrease is less than 90% or the adhesive strength after application is 1 MPa or more.

[0078] [Table 1-1]

[0079] [Table 1-2] [Table 1-3]

[0080] Referring to the results of Example 1, the adhesive strength before application was 4.4 MPa, indicating good adhesion. Furthermore, the adhesive strength after application was only 0.05 MPa, and the reduction rate of adhesive strength was 99%, indicating excellent electropenetration properties of the cured product. Referring to the results of Examples 2 to 4, even when the acrylic compound was changed, good adhesion and excellent electropenetration properties were observed, similar to Example 1. Referring to the results of Example 5, even when the type of acrylic compound and the amount of ionic liquid added were changed, good adhesion and excellent electropenetration properties were observed, similar to Example 1.

[0081] Referring to the results of Comparative Example 1, the adhesive strength after application did not decrease at all from the adhesive strength before application, and the electropenetrating properties of the cured product did not appear. Furthermore, referring to the results of Examples 6-8 and Comparative Examples 2 and 3, it was found that a lower ionic liquid content tended to result in higher adhesive strength before application. However, in Comparative Examples 2 and 3, the decrease in adhesive strength was low, at 26% and 55%, respectively. In addition, the adhesive strength after application in Comparative Examples 2 and 3 was 4.5 MPa and 2.5 MPa, respectively. This was not an adhesive strength that could be peeled off by hand. Therefore, it was suggested that by adding more than 10 parts by weight but no more than 75 parts by weight of ionic liquid per 91 parts by weight of acrylic compound, the decrease in adhesive strength could be 90% or more. Furthermore, it was suggested that by adding more than 10 parts by weight but no more than 50 parts by weight of ionic liquid per 91 parts by weight of acrylic compound, the adhesive strength before application could be higher than 3 MPa. [Explanation of Symbols]

[0082] 1: First conductor, 2: Cured product of adhesive composition, 3: Second conductor, 4: DC power supply, 5, 5': Non-conductor, 6: Adhesive

Claims

1. A first agent comprising a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, and The second agent includes the aforementioned organic peroxide and a reducing agent that forms a redox catalyst system. A two-component adhesive composition comprising at least the first or second agent, wherein the first agent or the second agent contains an ionic liquid.

2. The compound having one or more (meth)acryloyl groups in the molecule may have at least one selected from the group consisting of monofunctional (meth)acrylates having alicyclic groups, difunctional aliphatic (meth)acrylates, and trifunctional or more (meth)acrylates, and a substituent (except aromatic groups) C １ ~C ６ The composition according to claim 1, comprising a monofunctional (meth)acrylate having an alkyl group and a difunctional aromatic (meth)acrylate.

3. The composition according to claim 1, wherein the ionic liquid is contained in an amount of 9% to 45% by weight relative to 100% by weight of the first agent, or the ionic liquid is contained in an amount of 50% to 88.5% by weight relative to 100% by weight of the second agent.

4. The composition according to claim 1, wherein the ionic liquid is represented by the following formula (1). 【Chemistry 1】 (In the formula, R 1 This is a divalent or trivalent hydrocarbon group having 2 to 8 carbon atoms, which may contain heteroatoms, and the N in the formula + Together with the ring, the hydrocarbon group may contain substituents, and the substituents are alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1 to 4 carbon atoms. R 2 and R 3 R is the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms (however, if the nitrogen atom forms a double bond with an adjacent carbon atom, R 3 (It does not exist), X - is Br - , AlCl 4 - , Al 2 Cl 7 - , NO 3 - , BF 4 - , PF 6 - , CH 3 COO - , CF 3 COO - , CF 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , (CF 3 SO 2 ) 3 C - , AsF 6 - , SbF 6 - , F(HF) n - , CF 3 (CF 2 ) 3 SO 3 - , (CF 3 CF 2 SO 2 ) 2 N - and CF 3 CF 2 COO - is an anion selected from)

5. C may have the aforementioned substituents (excluding aromatic groups). １ ~C ６ A monofunctional (meth)acrylate having an alkyl group is an unsubstituted C １ ~C ６ The composition according to claim 2, comprising a monofunctional (meth)acrylate having an alkyl group, a monofunctional (meth)acrylate having a hydroxyl group, and a monofunctional (meth)acrylate containing a phosphate ester group.

6. The composition according to claim 1, wherein the total amount of compounds having one or more (meth)acryloyl groups in the molecule is 50% by weight or more and 85% by weight or less based on 100% by weight of the first agent.

7. The composition according to claim 1, wherein the organic peroxide is a hydroperoxide.

8. A first agent comprising a compound having one or more (meth)acryloyl groups in its molecule and an organic peroxide, A second agent comprising the aforementioned organic peroxide and a reducing agent that forms a redox catalyst system, and Third agent containing ionic liquid A three-component adhesive composition comprising at least the following.

9. The total of the compounds having one or more (meth)acryloyl groups in the molecule consists of at least one selected from the group consisting of monofunctional (meth)acrylates having alicyclic groups, difunctional aliphatic (meth)acrylates, and trifunctional or more functional (meth)acrylates, and C which may have substituents (except aromatic groups). １ ~C ６ The composition according to claim 8, comprising a monofunctional (meth)acrylate having an alkyl group and a difunctional aromatic (meth)acrylate.

10. The composition according to claim 8, wherein the total amount of compounds having one or more (meth)acryloyl groups in the molecule is 90% to 99% by weight relative to 100% by weight of the first agent.

11. The composition according to claim 8, wherein the organic peroxide is a hydroperoxide.

12. An electropeelable cured product, which is a cured product obtained by curing the composition according to any one of claims 1 to 11.

13. A method for peeling off an electropeelable cured material in a composite in which a first conductor and a second conductor are bonded together via the electropeelable cured material described in claim 12, comprising applying a voltage to the electropeelable cured material.

14. The method according to claim 13, wherein the voltage is 3V or more and 100V or less.

15. The method according to claim 13, wherein the voltage application time is 1 second or more and 1200 seconds or less.

Images