Adhesive set, adhesive body, and manufacturing method thereof

Abstract

Disclosed is an adhesive set. The adhesive set comprises: a main agent containing a decomplexing agent; and an initiator containing an organic borane complex. At least one among the main agent and the initiator further contains a compound having a radically polymerizable group. At least one among the main agent and the initiator further contains a compound having a thiocarbonylthio structure.

Description

[Technical Field]

[0001] The present disclosure relates to an adhesive set, an adhesive body, and a method for manufacturing the same. [Background technology]

[0002] Adhesive compositions containing organoborane complexes have been disclosed as adhesives for bonding plastics such as polyethylene and polypropylene (see, for example, Patent Document 1). The organoborane complexes are decomplexed by mixing with a decomplexing agent to give organoboranes. The organoboranes act as initiators that generate radicals by reacting with oxygen. The borinic acid radicals generated here act as dormant species in atom transfer radical polymerization (ATRP), sustaining propagation reactions, including surface grafting, while suppressing chain transfer or termination reactions of compounds with radically polymerizable groups. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2005-514489 Summary of the Invention [Problem to be solved by the invention]

[0004] In adhesive compositions containing organoborane complexes, the addition of a polymerization inhibitor such as a metal halide salt has been investigated to improve adhesive strength. It is presumed that the addition of such a polymerization inhibitor acts as a dormant species for further ATRP, replenishing the lack of dormant species and accelerating the propagation reaction of the compound having a radical polymerizable group, resulting in an improved adhesive strength.

[0005] However, the polymerization inhibitors used in adhesive compositions containing organoborane complexes are limited to metal halide salts such as CuBr2, which leads to problems such as reduced reliability due to metal ions or halide ions derived from metal halide salts and inability to accommodate non-halogen (halogen-free) applications.

[0006] Therefore, a main object of the present disclosure is to provide an adhesive set that makes it possible to prepare an adhesive composition that has excellent adhesive strength without using a metal halide salt. [Means for solving the problem]

[0007] The inventors of the present disclosure conducted studies to solve the above-mentioned problems and found that sufficient adhesive strength can be achieved by using a compound having a thiocarbonylthio structure instead of a metal halide salt, which led to the completion of the present invention.

[0008] One aspect of the present disclosure relates to an adhesive set. The adhesive set includes a base agent containing a decomplexing agent and an initiator containing an organoborane complex. At least one of the base agent and the initiator further contains a compound having a radical polymerizable group. At least one of the base agent and the initiator further contains a compound having a thiocarbonylthio structure. With such an adhesive set, it is possible to prepare an adhesive composition with excellent adhesive strength by mixing the base agent and the initiator. It is presumed that the reason for this effect is that the compound having the thiocarbonylthio structure efficiently functions as a dormant species in ATRP. Therefore, the adhesive set according to one aspect of the present disclosure can avoid a decrease in reliability due to metal ions or halide ions and can achieve non-halogenation (halogen-free).

[0009] The base agent may contain a compound having a thiocarbonylthio structure.

[0010] Another aspect of the present disclosure relates to an adhesive structure comprising a first adherend, a second adherend, and an adhesive layer that bonds the first adherend and the second adherend to each other. The adhesive layer contains a cured product of an adhesive composition comprising the base agent and initiator of the adhesive set described above.

[0011] Another aspect of the present disclosure relates to a method for producing an adhesive bonded structure, which includes a step of bonding a first adherend and a second adherend together via an adhesive composition containing a base agent and an initiator. [Effects of the Invention]

[0012] According to the present disclosure, an adhesive set is provided that makes it possible to prepare an adhesive composition that has excellent adhesive strength without using a metal halide salt. The present disclosure also provides an adhered body using such an adhesive set and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present disclosure will be described, but the present disclosure is not limited to the following embodiments.

[0014] The same applies to the numerical values ​​and ranges in the present disclosure, and do not limit the present disclosure. In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0015] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylic copolymer. Furthermore, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.

[0016] [Adhesive set] An adhesive set according to one embodiment includes a base agent containing a decomplexing agent and an initiator containing an organoborane complex. By mixing the base agent and the initiator, an adhesive composition containing the base agent and the initiator can be obtained. By mixing the base agent and the initiator, this adhesive set makes it possible to prepare an adhesive composition with excellent adhesive strength without using a metal halide salt.

[0017] The main agent contains a decomplexing agent. The initiator contains an organoborane complex. At least one of the main agent and the initiator further contains a compound having a radical polymerizable group. At least one of the main agent and the initiator further contains a compound having a thiocarbonylthio structure. At least one of the main agent and the initiator may further contain any of a filler, a plasticizer, a crosslinking agent, etc. Each component will be described below.

[0018] (organoborane complex) The initiator contains an organoborane complex. The organoborane complex refers to an organoborane-Lewis base complex formed by coordinating a Lewis base to an organoborane to form a complex. The organoborane-Lewis base complex is a compound that reacts with a decomplexing agent (described below) to give an organoborane. The organoborane undergoes radical cleavage in an oxygen atmosphere to generate a dormant species, such as a borinic acid radical, and can therefore act as an initiator for living radical polymerization. The organoborane may be, for example, an alkylborane (BR3, where R is an alkyl group). The Lewis base may be, for example, an amine. The amine may be, for example, a compound having multiple amino groups, or a compound having at least an amino group constituting the amine and a group (e.g., an alkoxy group) containing an atom capable of coordinating to boron (e.g., an oxygen atom) in addition to the nitrogen atom of the amino group. These compounds act as multidentate ligands for organoborane and can therefore be referred to as multidentate amines.

[0019] The organoborane complex may be an alkylborane-amine complex or an alkylborane-multidentate amine complex. Examples of organoborane complexes include triethylborane-1,3-diaminopropane complex, triethylborane-diethylenetriamine complex, tri-n-butylborane-3-methoxy-1-propylamine complex, tri-n-butylborane-1,3-diaminopropane complex, triisobutylborane-1,3-diaminopropane complex, triethylborane-1,6-diaminohexane complex, triisobutylborane-1,3-diaminopropane complex, and triisobutylborane-1,6-diaminohexane complex. These may be used alone or in combination of two or more. Among these, the organoborane complex may be triethylborane-1,3-diaminopropane complex or tri-n-butylborane-3-methoxy-1-propylamine complex. The organoborane complex may be a commercially available product or a synthesized product.

[0020] The content of the organoborane complex may be 0.1% by mass or more, 1% by mass or more, 3% by mass or more, or 5% by mass or more based on the total amount of the initiator from the viewpoint of adhesive strength development, and may be 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less based on the total amount of the initiator from the viewpoint of storage stability.

[0021] The content of the organoborane complex may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more based on the total amount of the base agent and the initiator from the viewpoint of adhesive strength development, and may be 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less based on the total amount of the base agent and the initiator from the viewpoint of toughness of the adhesive layer.

[0022] From the viewpoint of adhesive strength development, the content of the organoborane complex may be 0.01 mol% or more, 0.1 mol% or more, 0.3 mol% or more, or 0.5 mol% or more based on the total amount of compounds having radical polymerizable groups. From the viewpoint of toughness of the adhesive layer, the content of the organoborane complex may be 10 mol% or less, 6 mol% or less, 4 mol% or less, or 2 mol% or less based on the total amount of compounds having radical polymerizable groups.

[0023] (decomplexing agent) The main component contains a decomplexing agent. The decomplexing agent is a compound that can dissociate the Lewis base in the organoborane complex (organoborane-Lewis base complex) to generate an organoborane. Therefore, by mixing and reacting the organoborane complex contained in the initiator and the decomplexing agent contained in the main component, it is possible to generate an organoborane that can serve as an initiator for living radical polymerization.

[0024] Examples of decomplexing agents include acids, acid anhydrides, aldehydes, β-ketone compounds, etc. These may be used alone or in combination of two or more. Examples of acids include Lewis acids such as SnCl4 and TiCl4, and Bronsted acids such as aliphatic carboxylic acids and aromatic carboxylic acids. Examples of acid anhydrides include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride. Examples of aldehydes include benzaldehyde, o-, m-, and p-nitrobenzaldehyde. Examples of β-ketone compounds include methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, and 2-methacryloyloxyethyl acetoacetate. Among these, the decomplexing agent may be an acid anhydride from the viewpoints of decomplexing reactivity with the organoborane complex and storage stability of the initiator, or succinic anhydride from the viewpoint of reducing the blend mass of the decomplexing agent.

[0025] The content of the decomplexing agent may be 0.01% by mass or more, 0.1% by mass or more, or 0.3% by mass or more based on the total amount of the base agent, from the viewpoint of shortening the curing time until the adhesive layer cures and develops adhesive strength. The content of the decomplexing agent may be 10% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less based on the total amount of the base agent, from the viewpoint of ensuring the working time from applying the adhesive composition to the adherends to laminating them.

[0026] The content of the decomplexing agent may be 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more based on the total amount of the base agent and initiator, from the viewpoint of shortening the curing time until the adhesive layer cures and develops adhesive strength. The content of the decomplexing agent may be 10% by mass or less, 7% by mass or less, 5% by mass or less, or 3% by mass or less based on the total amount of the base agent and initiator, from the viewpoint of ensuring the working time from applying the adhesive composition to the adherends until bonding them together.

[0027] The molar ratio of the decomplexing agent to the organoborane complex (molar amount of decomplexing agent / molar amount of organoborane complex) may be, for example, 0.9 or more, 1 or more, 1.5 or more, or 2 or more. When the molar ratio is 1 or more, more sufficient adhesive strength tends to be obtained. The molar ratio of the decomplexing agent to the organoborane complex (molar amount of decomplexing agent / molar amount of organoborane complex) may be, for example, 50 or less, 30 or less, 10 or less, 7 or less, 5 or less, or 3 or less. The smaller the molar ratio, the more sufficient the working time from applying the adhesive composition to the adherend until bonding tends to be ensured.

[0028] (Compound having a radical polymerizable group) At least one of the base agent and the initiator further contains a compound having a radical polymerizable group. The compound having a radical polymerizable group is a compound having a polymerizable group that reacts with a radical. Examples of the radical polymerizable group include a (meth)acryloyl group, a vinyl group, an allyl group, a styryl group, an alkenyl group, an alkenylene group, and a maleimide group.

[0029] The compound having a radical polymerizable group may include, for example, a compound having a (meth)acryloyl group. Examples of the compound having a (meth)acryloyl group include monofunctional (meth)acrylates having one (meth)acryloyl group, polyfunctional (meth)acrylates having two or more (meth)acryloyl groups, and (meth)acrylamide derivatives.

[0030] Examples of monofunctional (meth)acrylates include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate (n-lauryl (meth)acrylate), Alkyl (meth)acrylates having an alkyl group such as isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl acrylate; alkenyl (meth)acrylates having an alkenyl group such as 3-butenyl (meth)acrylate; (meth)acrylates having an aromatic group such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, and methoxyoctaethylene glycol Alkoxypolyalkylene glycol (meth)acrylates such as methyl acrylate, methoxynonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, and butoxydiethylene glycol (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (Meth)acrylates having an alicyclic group such as (meth)acrylate; (meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; (meth)acrylates having an amino group such as N,N-dimethylaminoethyl (meth)acrylate; (meth)acrylates having an isocyanate group such as 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate;Examples of the polyalkylene glycol mono(meth)acrylate include tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, and octapropylene glycol mono(meth)acrylate; and (meth)acrylates having a siloxane skeleton. These may be used alone or in combination of two or more.

[0031] Examples of polyfunctional (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, Polyethylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(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-decamethylpropanediol Aliphatic (meth)acrylates such as ethylenediol di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, and ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate; 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, and propoxylated bisphenol F di(meth)acrylate. Examples of the epoxy (meth)acrylate include aromatic (meth)acrylates such as (meth)acrylate, ethoxylated propoxylated bisphenol F type di(meth)acrylate, ethoxylated fluorene type di(meth)acrylate, propoxylated fluorene type di(meth)acrylate, and ethoxylated propoxylated fluorene type di(meth)acrylate; and aromatic epoxy (meth)acrylates such as bisphenol type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, and cresol novolac type epoxy (meth)acrylate. These may be used alone or in combination of two or more.

[0032] Examples of (meth)acrylamide derivatives include N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, (meth)acryloylmorpholine, etc. These may be used alone or in combination of two or more.

[0033] The compound having a radical polymerizable group may contain, in addition to a compound having a (meth)acryloyl group, a copolymerizable compound copolymerizable with the compound. Examples of the copolymerizable compound include compounds having a radical polymerizable group other than a (meth)acryloyl group, such as styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride.

[0034] The compound having a radical polymerizable group may be contained in at least one of the main agent and the initiator, and for example, the main agent may contain the compound having a radical polymerizable group.

[0035] The content of the compound having a radical polymerizable group may be 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more based on the total amount of the base agent and the initiator, from the viewpoint of improving the toughness and adhesive strength of the adhesive layer. The content of the compound having a radical polymerizable group may be 99% by mass or less, 98% by mass or less, 95% by mass or less, or 93% by mass or less based on the total amount of the base agent and the initiator, from the viewpoint of suppressing sagging of the applied adhesive composition and suppressing a decrease in the toughness of the adhesive layer.

[0036] (Compounds with a thiocarbonylthio structure) At least one of the main agent and the initiator further contains a compound having a thiocarbonylthio structure. The compound having a thiocarbonylthio structure is a compound having a structure represented by the following formula (1) (or the following formula (2)). The compound having a thiocarbonylthio structure can be used without any particular limitation as long as it is a compound having such a structure. For example, a chain transfer agent (RAFT agent) used in the field of RAFT polymerization (Reversible Addition / Fragmentation Chain Transfer) can be suitably used.

[0037] [ka]

[0038] The compound having a thiocarbonylthio structure may be, for example, a compound having a structure represented by the following formula (1a) (or the following formula (2a)).

[0039] [ka]

[0040] Examples of compounds having a structure represented by formula (1a) (or formula (2a)) include the following compounds (1a-1), (2a-1), and (2a-2).

[0041] [ka]

[0042] The compound having a thiocarbonylthio structure may be contained in at least one of the main agent and the initiator, and for example, the main agent may contain a compound having a thiocarbonylthio structure.

[0043] The content of the compound having a thiocarbonylthio structure may be 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, or 0.05% by mass or more based on the total amount of the base agent and initiator, from the viewpoint of ensuring the working time from applying the adhesive composition to the adherends until bonding and improving adhesive strength. The content of the compound having a thiocarbonylthio structure may be 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.5% by mass or less based on the total amount of the base agent and initiator, from the viewpoint of storage stability of the base agent.

[0044] The content of the compound having a thiocarbonylthio structure may be 0.01 mol% or more, 0.03 mol% or more, 0.05 mol% or more, or 0.1 mol% or more, based on the total amount of compounds having radical polymerizable groups, from the viewpoint of ensuring the working time from applying the adhesive composition to the adherends until bonding and improving adhesive strength. The content of the compound having a thiocarbonylthio structure may be 5 mol% or less, 3 mol% or less, 1 mol% or less, or 0.7 mol% or less, based on the total amount of compounds having radical polymerizable groups, from the viewpoint of storage stability of the main component.

[0045] (filler) The filler may be, for example, either an inorganic filler or an organic filler. Examples of inorganic fillers include inorganic fine particles such as silica, alumina, silica-alumina, titania, zirconia, magnesia, kaolin, talc, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fiber, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, wollastonite, xonotlite, and whiskers. Examples of organic fillers include organic fine particles such as silicone, acrylic silicone, MBS (methacrylate-butadiene-styrene), polyamide, and polyimide. These fillers (fine particles) may have a uniform structure or a core-shell structure.

[0046] The filler content may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and may be 40% by mass or less, 30% by mass or less, or 30% by mass or less, based on the total amount of the base agent and the initiator.

[0047] (plasticizer) Examples of the plasticizer include phthalate ester compounds, alkylsulfonate ester compounds, and adipate ester compounds.

[0048] The content of the plasticizer may be 0.1% by mass or more, 1% by mass or more, or 3% by mass or more, and may be 30% by mass or less, 20% by mass or less, or 10% by mass or less, based on the total amount of the base agent and the initiator.

[0049] (Crosslinking agent) Examples of the crosslinking agent include an aziridine-based crosslinking agent and a carbodiimide-based crosslinking agent.

[0050] The content of the crosslinking agent may be 0.01% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, and may be 5% by mass or less, 3% by mass or less, or 2% by mass or less, based on the total amount of the base agent and the initiator.

[0051] At least one of the base agent and the initiator may further contain, in addition to the above components, an ultraviolet absorber, a dehydrating agent, a pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion promoter, a dispersant, a solvent, etc.

[0052] The adhesive set of this embodiment can be prepared by mixing the main component and the initiator to form an adhesive composition. The temperature when mixing the main component and the initiator may be, for example, 10 to 35°C. The usable time of the adhesive set may be, for example, 0.1 to 3 minutes.

[0053] When mixing the main agent and the initiator, it is preferable to mix them so that the molar ratio of the decomplexing agent in the main agent to the organoborane complex in the initiator (molar amount of decomplexing agent / molar amount of organoborane complex) is 0.9 or more, 1 or more, 1.5 or more, or 2 or more, or 50 or less, 30 or less, 10 or less, 7 or less, 5 or less, or 3 or less.

[0054] When mixing the base agent and the initiator, it is preferable to mix them so that the mass ratio of the base agent to the initiator (mass of the base agent / mass of the initiator) is, for example, 1 or more, 3 or more, or 5 or more, or 200 or less, 100 or less, or 50 or less.

[0055] The method for mixing the base agent and the initiator is not particularly limited as long as the two are mixed, and examples thereof include a method of mixing them manually, a method of mixing them by hand application using a conventional caulking gun, and a method of mixing them using a mechanical rotary mixer, static mixer, or the like in combination with a metering pump (e.g., a gear pump, a plunger pump, or the like) and a throttle valve for feeding the raw materials.

[0056] The prepared adhesive composition can be applied to a predetermined location to form an adhesive layer. The formed adhesive layer functions as an adhesive layer that bonds substrates together because the compound having a radical polymerizable group gradually becomes high molecular weight and hardens. The application method to a predetermined location can be a conventionally known method, such as a method using a dispenser.

[0057] The conditions for curing the adhesive composition may be, for example, a curing temperature of 10 to 35°C and a curing time of 24 to 96 hours.

[0058] [Adhesive body and its manufacturing method] In one embodiment, the adhesive structure includes a first adherend, a second adherend, and an adhesive layer that bonds the first adherend and the second adherend together. The adhesive layer contains a cured product of the adhesive composition that includes the base agent and initiator in the adhesive set.

[0059] Examples of the first adherend and the second adherend include plastic substrates such as polypropylene (PP), polyvinyl chloride, acrylonitrile / butadiene / styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), poly(methyl methacrylate) (PMMA), polyester, epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyethylene (PE), ethylene / propylene copolymer (EPM), and ethylene / propylene / diene polymer (EPDM), and metal substrates such as aluminum, steel, copper, and stainless steel.

[0060] Examples of adhesive bodies include plastic laminate substrates, metal laminate substrates, electronic components, semiconductor components, and display components.

[0061] In one embodiment, a method for producing an adhesive bonded structure includes bonding a first adherend to a second adherend via an adhesive composition containing a base agent and an initiator. The temperature at which the base agent and the initiator are mixed in the adhesive set, the conditions for curing the adhesive composition, and the like may be the same as those described above. [Example]

[0062] The present disclosure will be described in more detail below with reference to examples, although the present disclosure is not limited to these examples.

[0063] <Examples 1 to 10> [Preparing adhesive sets] (Preparation of ingredients) Organoborane complexes TEB-DAP: Triethylborane-1,3-diaminopropane complex (molecular weight: 172.1, Kishida Chemical Co., Ltd.) TnBB-MOPA: Tri-n-butylborane-3-methoxy-1-propylamine complex (molecular weight: 271.3, Kishida Chemical Co., Ltd.) Decomplexing agent Succinic anhydride (molecular weight: 100.1, Fujifilm Wako Pure Chemical Industries, Ltd.) Compounds with radical polymerizable groups (polymerizable compounds) FA-513AS: Dicyclopentanyl acrylate (molecular weight: 206.3, Showa Denko Materials Co., Ltd.) FA-310A: Phenoxyethyl acrylate (molecular weight: 192.2, Showa Denko Materials Co., Ltd.) Compounds with a thiocarbonylthio structure (polymerization inhibitors) CTA1: 2'-cyanobutan-2'-yl 3,5-dimethylpyrazole-1-carbodithioate (compound (1a-1), molecular weight: 253.4, Fujifilm Wako Pure Chemical Industries, Ltd.) CTA2: methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate (compound (2a-1), molecular weight: 417.7, Fujifilm Wako Pure Chemical Industries, Ltd.) CTA3: 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid (compound (2a-2), molecular weight: 307.4, Fujifilm Wako Pure Chemical Industries, Ltd.) Filler RY200S: Fumed silica (hydrophobic fumed silica surface-treated with silicone oil, Nippon Aerosil Co., Ltd.) R805: Silica microparticles (hydrophobic silica particles surface-treated with octylsilane, Nippon Aerosil Co., Ltd.) M210: Acrylic resin core-shell particles (Kaneka Corporation) EZ-004: MBS-based core-shell particles (Kaneka Corporation) B564: MBS-based core-shell particles (Kaneka Corporation) Plasticizers PN-5090: Adipic acid polyester (ADEKA Corporation) Crosslinking agent Triaziridine: Tris[3-(1-aziridinyl)propionic acid]trimethylolpropane (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0064] (Preparation of the main agent) The types and proportions (unit: parts by mass) of a decomplexing agent, a compound having a radical polymerizable group, a compound having a thiocarbonylthio structure, and a filler shown in Table 1 were weighed into a plastic bottle and mixed for 15 minutes at 2000 rpm using a planetary mixer (Thinky Corporation, Awatori Rentaro), and then degassed for another 5 minutes at 2000 rpm to prepare the main components of Examples 1 to 10.

[0065] (Preparation of initiator) The organoborane complex, plasticizer, crosslinker, and filler were weighed into a plastic bottle in the types and proportions (unit: parts by mass) shown in Table 1, and mixed for 15 minutes at 2000 rpm using a planetary mixer (Thinky Corporation, Awatori Rentaro), and then degassed for 5 minutes at 2000 rpm to prepare the initiators of Examples 1 to 10.

[0066] [Adhesion strength measurement] A 0.5 mm spacer was placed between two polypropylene substrates (adherends) (size: 100 mm x 25 mm, thickness: 2 mm) to ensure a 0.5 mm adhesive layer thickness. The base agent and initiator for each example were mixed by filling a manual dispenser. The mixture was applied between the polypropylene substrates using the manual dispenser, and the polypropylene substrates were bonded together to obtain a laminate. The resulting laminate was left to cure at 25°C for 24 hours (or 96 hours) to prepare an evaluation sample. The prepared evaluation sample was subjected to a tensile test with a chuck distance of 100 mm and a test speed of 5 mm / min to measure the shear strength (MPa) against the polypropylene substrate. A shear strength of 1 MPa or greater was considered to have sufficient adhesive strength. The results are shown in Table 1.

[0067] [Table 1]

[0068] As shown in Table 1, the adhesive compositions prepared from the adhesive sets of Examples 1 to 10 had sufficient adhesive strength. These results confirmed that the adhesive set of the present disclosure makes it possible to prepare adhesive compositions with excellent adhesive strength without using a metal halide salt.

Claims

1. a base agent containing a decomplexing agent; an initiator comprising an organoborane complex; Equipped with At least one of the base agent and the initiator further contains a compound having a radical polymerizable group, At least one of the base agent and the initiator further contains a compound having a thiocarbonylthio structure. Adhesive set.

2. The base agent contains a compound having a thiocarbonylthio structure. The adhesive set according to claim 1 .

3. a first adherend; and a second adherend; and an adhesive layer that bonds the first adherend and the second adherend to each other; Equipped with The adhesive layer contains a cured product of an adhesive composition comprising the main agent and the initiator in the adhesive set according to claim 1 or 2. Adhesive body.

4. A method for producing the adhesive body according to claim 3, a step of bonding the first adherend and the second adherend together via an adhesive composition containing the base agent and the initiator, Method for manufacturing an adhesive body.

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