Adhesive kit, adhesive body and method for manufacturing the same

Abstract

The present invention discloses an adhesive kit. The adhesive kit comprises: a main agent containing a decomplexing agent; and an initiator containing an organic borane complex. At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group. At least one of the main agent and the initiator further contains a compound having a thiocarbonylsulfide structure.

Description

Technical Field

[0001] The present invention relates to an adhesive kit, an adhesive body and a manufacturing method thereof. Background Art

[0002] As an adhesive for bonding plastics such as polyethylene and polypropylene, an adhesive composition containing an organic borane complex is disclosed (for example, Patent Document 1). The organic borane complex is decomplexed by mixing with a decomplexing agent to give an organic borane. The organic borane acts as an initiator that generates free radicals by reacting with oxygen. The boric acid radicals generated here act as dormant species in atom transfer radical polymerization (ATRP) that inhibits chain transfer of compounds having free radical polymerizable groups or stops reactions and maintains growth reactions including surface grafting.

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application No. 2005-514489 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] However, in adhesive compositions containing organic borane complexes, studies have been conducted to improve the adhesive strength by adding a polymerization control agent such as a halogenated metal salt. It is presumed that by adding such a polymerization control agent, the polymerization control agent further functions as a dormant species of ATRP, and insufficient dormant species are supplemented to accelerate the growth reaction of the compound having a free radical polymerizable group, resulting in an effect of improving the adhesive strength.

[0008] However, the polymerization control agent used in the adhesive composition containing the organic borane complex is limited to the halogenated metal salts such as CuBr2. Therefore, there are problems such as reduced reliability due to the metal ions or halide ions derived from the halogenated metal salts and inability to cope with non-halogenation (halogen-free).

[0009] Therefore, a main object of the present disclosure is to provide an adhesive kit capable of preparing an adhesive composition having excellent adhesive strength even without using a halogenated metal salt.

[0010] Means for solving technical problems

[0011] As a result of conducting studies to solve the above-mentioned problems, the inventors of the present disclosure have found that sufficient adhesive strength can be exhibited by using a compound having a thiocarbonylthio structure instead of a metal halide salt, thereby completing the present disclosure.

[0012] One aspect of the present disclosure relates to an adhesive kit. The adhesive kit comprises: a main agent, containing a decomplexing agent; and an initiator, containing an organic borane complex. At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group. At least one of the main agent and the initiator further contains a compound having a thiocarbonylsulfide structure. According to this adhesive kit, an adhesive composition with excellent bonding strength can be prepared by mixing the main agent and the initiator. The reason for exhibiting this effect is presumed to be as follows: the compound having a thiocarbonylsulfide structure acts efficiently as a dormant species of ATRP. Therefore, the adhesive kit involved in one aspect of the present disclosure can avoid a decrease in reliability through metal ions or halide ions, and can achieve non-halogenation (halogen-free).

[0013] The main agent may contain a compound having a thiocarbonylthio structure.

[0014] Another aspect of the present disclosure relates to an adhesive body. The adhesive body comprises: a first adherend; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other. The adhesive layer contains a cured product of an adhesive composition, and the cured product of the adhesive composition contains a main agent and an initiator in the above-mentioned adhesive kit.

[0015] Another aspect of the present disclosure relates to a method for producing an adhesive body, comprising: bonding a first adherend and a second adherend together via an adhesive composition containing a main agent and an initiator.

[0016] Effects of the Invention

[0017] According to the present disclosure, an adhesive kit is provided that can prepare an adhesive composition having excellent adhesive strength even without using a metal halide salt. Also, according to the present disclosure, an adhesive body using such an adhesive kit and a method for producing the same are provided. DETAILED DESCRIPTION

[0018] Hereinafter, embodiments of the present disclosure will be described, but the present disclosure is not limited to the following embodiments.

[0019] The same is true for the numerical values ​​and ranges disclosed herein, and the disclosure is not limited thereto. In this specification, the numerical range represented by "~" represents the range in which the numerical values ​​recorded before and after "~" are included as the minimum and maximum values, respectively. In the numerical ranges recorded in stages in this specification, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. Furthermore, in the numerical ranges recorded in this specification, the upper limit or lower limit of its numerical range can be replaced by the value shown in the embodiments.

[0020] In this specification, (meth)acrylate means acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl, (meth)acrylic copolymer, etc. In addition, the materials exemplified below may be used alone or in combination of two or more unless otherwise specified. When there are multiple substances corresponding to each component in the composition, the content of each component in the composition represents the total amount of the multiple substances present in the composition unless otherwise specified.

[0021] [Adhesive Set]

[0022] An adhesive kit according to one embodiment includes: a main agent containing a decomplexing agent; and an initiator containing an organic borane complex. The adhesive kit according to this embodiment can obtain an adhesive composition containing the main agent and the initiator by mixing the main agent and the initiator. According to this adhesive kit, by mixing the main agent and the initiator, an adhesive composition having excellent bonding strength can be prepared even without using a halogenated metal salt.

[0023] The main agent contains a decomplexing agent. The initiator contains an organic borane complex. At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group. At least one of the main agent and the initiator further contains a compound having a thiocarbonylsulfide structure. At least one of the main agent and the initiator may further contain any one of a filler, a plasticizer, a crosslinking agent, etc. The following describes each component.

[0024] (Organoborane complex)

[0025] The initiator contains an organic borane complex. An organic borane complex refers to an organic borane-Lewis base complex formed by coordinating a Lewis base to an organic borane. An organic borane-Lewis base complex is a compound that reacts with a decomplexing agent described later to impart an organic borane. Organic borane can act as an initiator for active radical polymerization because it undergoes free radical splitting in an oxygen environment and generates dormant species, namely, boric acid radicals. For example, an organic borane can be an alkyl borane (BR3, R: alkyl). A Lewis base can be, for example, an amine. For example, an amine can be a compound having multiple amino groups, or a compound having at least an amino group constituting an amine and a group (for example, an alkoxy group, etc.) containing an atom (for example, an oxygen atom, etc.) that can coordinate with boron, in addition to the nitrogen atom of the amino group. Because these compounds play a role relative to the multidentate ligand of the organic borane, they can be called polydentate amines.

[0026] The organic borane complex can be an alkyl borane-amine complex or an alkyl borane-polyamine complex. As the organic borane complex, for example, triethyl borane-1,3-diaminopropane complex, triethyl borane-diethylenetriamine complex, tri-n-butyl borane-3-methoxy-1-propylamine complex, tri-n-butyl borane-1,3-diaminopropane complex, triisobutyl borane-1,3-diaminopropane complex, triethyl borane-1,6-diaminohexane complex, triisobutyl borane-1,3-diaminopropane complex, triisobutyl borane-1,6-diaminohexane complex. These can be used alone or in combination of two or more. Among them, the organic borane complex can be triethyl borane-1,3-diaminopropane complex or tri-n-butyl borane-3-methoxy-1-propylamine complex. As the organoborane complex, a commercially available product may be used, or a synthetic product may be used.

[0027] From the viewpoint of exhibiting adhesive strength, the content of the organoborane complex may be 0.1 mass % or more, 1 mass % or more, 3 mass % or more, or 5 mass % or more based on the total amount of the initiator. From the viewpoint of storage stability, the content of the organoborane complex may be 30 mass % or less, 20 mass % or less, 15 mass % or less, or 10 mass % or less based on the total amount of the initiator.

[0028] From the viewpoint of exhibiting adhesive strength, the content of the organic borane complex may be 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, or 0.2 mass % or more, based on the total amount of the main agent and the initiator. From the viewpoint of the toughness of the adhesive layer, the content of the organic borane complex may be 10 mass % or less, 5 mass % or less, 3 mass % or less, or 1 mass % or less, based on the total amount of the main agent and the initiator.

[0029] From the viewpoint of exhibiting adhesive strength, the content of the organic borane 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 the compound having a free radical polymerizable group. From the viewpoint of the toughness of the adhesive layer, the content of the organic borane 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 the compound having a free radical polymerizable group.

[0030] (Decomplexing Agent)

[0031] The main agent contains a decomplexing agent. The decomplexing agent refers to a compound that can generate an organoborane by dissociating the Lewis base in the organoborane complex (organoborane-Lewis base complex). Therefore, the organoborane complex contained in the initiator and the decomplexing agent contained in the main agent are mixed and reacted to generate an organoborane that can serve as an initiator for living free radical polymerization.

[0032] As decomplexing agents, for example, acids, anhydrides, aldehydes, β-keto compounds, etc. can be cited. These can be used alone or in combination of two or more. As acids, for example, Lewis acids such as SnCl4 and TiCl4, Bronsted acids such as aliphatic carboxylic acids and aromatic carboxylic acids can be cited. As anhydrides, for example, acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, etc. can be cited. As aldehydes, for example, benzaldehyde, o-, m- and p-nitrobenzaldehyde, etc. can be cited. As β-keto compounds, for example, methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, 2-methylacyloxyethyl acetoacetate, etc. can be cited. Among them, from the viewpoint of the decomplexing reactivity with the organic borane complex and the storage stability of the initiator, the decomplexing agent can be an acid anhydride, and from the viewpoint of suppressing the coordination quality of the decomplexing agent, it can be succinic anhydride.

[0033] From the viewpoint of shortening the curing time until the adhesive layer is cured and exhibits adhesive strength, the content of the decomplexing agent can be 0.01 mass %, 0.1 mass %, or 0.3 mass % or more based on the total amount of the main agent. From the viewpoint of ensuring the working time from applying the adhesive composition to the adherend to laminating, the content of the decomplexing agent can be 10 mass %, 5 mass %, 3 mass % or 2 mass % or less based on the total amount of the main agent.

[0034] From the viewpoint of shortening the curing time until the adhesive layer is cured and exhibits adhesive strength, the content of the decomplexing agent can be 0.01 mass %, 0.1 mass %, 0.2 mass % or 0.3 mass % based on the total amount of the main agent and the initiator. From the viewpoint of ensuring the working time from applying the adhesive composition to the adherend to laminating, the content of the decomplexing agent can be 10 mass %, 7 mass %, 5 mass % or 3 mass % based on the total amount of the main agent and the initiator.

[0035] The molar mass ratio of decomplexer to organoborane complex (molar mass of decomplexer / molar mass of organoborane complex) can be, for example, more than 0.9, more than 1, more than 1.5 or more than 2. If the molar mass ratio is more than 1, more sufficient bonding strength can be obtained. The molar mass ratio of decomplexer to organoborane complex (molar mass of decomplexer / molar mass of organoborane complex) can be, for example, less than 50, less than 30, less than 10, less than 7, less than 5 or less than 3. The smaller the molar mass ratio, the more inclined to the tendency of being able to more fully ensure the working time from applying the adhesive composition to the adherend to the lamination.

[0036] (Compound having a radical polymerizable group)

[0037] At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group. The compound having a free radical polymerizable group is a compound having a polymerizable group due to a free radical reaction. As the free radical polymerizable group, for example, (meth) acryloyl, vinyl, allyl, styryl, alkenyl, alkenylene, maleimide, etc. can be cited.

[0038] The compound having a free radical polymerizable group may contain, for example, a compound having a (meth)acryloyl group. Examples of the compound having a (meth)acryloyl group include: a monofunctional (meth)acrylate having one (meth)acryloyl group, a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups, and a (meth)acrylamide derivative.

[0039] Examples of the monofunctional (meth)acrylate 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-dodecyl (meth)acrylate), isomyristyl (meth)acrylate , alkyl (meth)acrylates having an alkyl group, such as 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, methoxyoctaethylene glycol (meth)acrylate, methoxynonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol Alkoxypolyalkylene glycol (meth)acrylates such as (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate; (meth)acrylates having an alicyclic group such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate; (meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, (meth)acrylates having an amino group such as methacryloyloxyethoxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and the like; (meth)acrylates having an isocyanate group such as tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, hexapropylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, and hexapropylene glycol mono(meth)acrylate; (meth)acrylates having a siloxane skeleton. These may be used alone or in combination of two or more.

[0040] Examples of the polyfunctional (meth)acrylate 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, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol 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 aliphatic (meth)acrylates such as di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, 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, propoxylated bisphenol F Aromatic (meth)acrylates such as di(meth)acrylate, ethoxylated propoxylated bisphenol F di(meth)acrylate, ethoxylated fluorene di(meth)acrylate, propoxylated fluorene di(meth)acrylate, ethoxylated propoxylated fluorene di(meth)acrylate, etc.; Aromatic epoxy (meth)acrylates such as bisphenol epoxy (meth)acrylate, phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0041] 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.

[0042] The compound having a radical polymerizable group may include, for example, a copolymerizable compound copolymerizable with a (meth)acryloyl group in addition to a compound having a (meth)acryloyl group. 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.

[0043] The compound having a radical polymerizable group may be contained in at least one of the main agent and the initiator. For example, the main agent may contain a compound having a radical polymerizable group.

[0044] From the viewpoint of improving the toughness of the adhesive layer and improving the adhesive strength, the content of the compound having a free radical polymerizable group can 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 main agent and the initiator. From the viewpoint of suppressing the sagging of the applied adhesive composition and suppressing the reduction in the toughness of the adhesive layer, the content of the compound having a free radical polymerizable group can 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 main agent and the initiator.

[0045] (Compounds having a thiocarbonylthio structure)

[0046] 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 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 appropriately used.

[0047]

[0048] 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)).

[0049]

[0050] Examples of the compound having a structure represented by formula (1a) (or formula (2a)) include the following compounds (1a-1), (2a-1), and (2a-2).

[0051]

[0052] The compound having a thiocarbonylthio structure may be contained in at least one of the main agent and the initiator. For example, the main agent may contain a compound having a thiocarbonylthio structure.

[0053] From the viewpoint of ensuring the working time from applying the adhesive composition to the adherend to laminating and improving the adhesive strength, the content of the compound having a thiocarbonylthio structure can be 0.01 mass % or more, 0.02 mass % or more, 0.03 mass % or more, or 0.05 mass % or more based on the total amount of the main agent and the initiator. From the viewpoint of the storage stability of the main agent, the content of the compound having a thiocarbonylthio structure can be 5 mass % or less, 3 mass % or less, 1 mass % or less, or 0.5 mass % or less based on the total amount of the main agent and the initiator.

[0054] From the viewpoint of ensuring the working time from applying the adhesive composition to the adherend to bonding and improving the adhesive strength, the content of the compound having a thiocarbonylthio structure can 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 the compound having a free radical polymerizable group. From the viewpoint of the storage stability of the main agent, the content of the compound having a thiocarbonylthio structure can 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 the compound having a free radical polymerizable group.

[0055] (filler)

[0056] The filler may be, for example, an inorganic filler or an organic filler. As an inorganic filler, for example, inorganic particles such as silicon oxide, aluminum oxide, silicon oxide-aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, kaolin, talc, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, wollastonite, xonotlite, whiskers, etc. may be cited. As an organic filler, for example, organic particles such as silicone, acrylic silicone, acrylic rubber, MBS (methacrylate·butadiene·styrene), polyamide, polyimide, etc. may be cited. These fillers (particles) may have a uniform structure or a core-shell structure.

[0057] The content of the filler may be 0.1 mass % or more, 0.2 mass % or more, or 0.3 mass % or more, and may be 40 mass % or less, 30 mass % or less, or 30 mass % or less, based on the total amount of the main agent and the initiator.

[0058] (Plasticizer)

[0059] Examples of the plasticizer include phthalate-based compounds, alkylsulfonate-based compounds, and adipate-based compounds.

[0060] The content of the plasticizer may be 0.1 mass % or more, 1 mass % or more, or 3 mass % or less, 20 mass % or less, or 10 mass % or less, based on the total amount of the main agent and the initiator.

[0061] (Crosslinking agent)

[0062] Examples of the cross-linking agent include aziridine-based cross-linking agents and carbodiimide-based cross-linking agents.

[0063] The content of the crosslinking agent may be 0.01 mass % or more, 0.1 mass % or more, or 0.5 mass % or less, or 5 mass % or less, or 3 mass % or less, or 2 mass % or less, based on the total amount of the main agent and the initiator.

[0064] At least one of the main agent and the initiator may further contain, in addition to the above-mentioned components, an ultraviolet absorber, a dehydrating agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, a tackifier, a dispersant, a solvent, and the like.

[0065] The adhesive kit of this embodiment can prepare an adhesive composition by mixing a main agent and an initiator. The temperature when the main agent and the initiator are mixed can be, for example, 10 to 35° C. The pot life of the adhesive kit can be, for example, 0.1 to 3 minutes.

[0066] When the main agent and the initiator are mixed, it is preferred that the molar mass ratio of the decomplexer in the main agent to the organic borane complex in the initiator (molar mass of the decomplexer / molar mass of the organic borane complex) be greater than 0.9, greater than 1, greater than 1.5 or greater than 2, or less than 50, less than 30, less than 10, less than 7, less than 5 or less than 3.

[0067] When mixing the main agent and the initiator, it is preferred that the main agent be mixed so that the mass ratio of the main agent to the initiator (mass of the main agent / mass of the initiator) is, for example, 1 or more, 3 or more, or 5 or less, 200 or less, 100 or less, or 50 or less.

[0068] There are no particular restrictions on the method of mixing the main agent and the initiator as long as the two are mixed. For example, there can be cited: a method of mixing manually, a method of mixing by manual coating using a conventional caulking gun, a method of mixing by using a pump (for example, a gear pump, a plunger pump, etc.) that has quantitative liquid delivery of the raw materials and a throttle valve, a method of mixing using a mechanical rotary mixer, a static mixer, etc.

[0069] The prepared adhesive composition can be applied to a predetermined position to form an adhesive layer. The compound having a free radical polymerizable group is cured by high molecular weight, and the adhesive layer thus formed functions as an adhesive layer for bonding substrates to each other. The method of applying at a predetermined position can be applied by a method using a dispenser or the like, and other conventionally known methods.

[0070] 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.

[0071] [Adhesive body and method for producing the same]

[0072] An adhesive body according to one embodiment comprises: a first adherend; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other. The adhesive layer contains a cured product of an adhesive composition, and the cured product of the adhesive composition contains a main agent and an initiator in the above-mentioned adhesive kit.

[0073] As the first adherend and the second adherend, for example, there can be mentioned plastic substrates such as polypropylene (PP), polyvinyl chloride, acrylonitrile / butadiene / styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), polymethyl methacrylate (PMMA), polyester, epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyethylene (PE), ethylene / propylene copolymer (EPM), ethylene / propylene / diene polymer (EPDM), and metal substrates such as aluminum, steel, copper, and stainless steel.

[0074] Examples of the bonded body include plastic laminated substrates, metal laminated substrates, electronic components, semiconductor devices, and display components.

[0075] The manufacturing method of an adhesive body of one embodiment comprises the step of bonding a first adherend and a second adherend via an adhesive composition containing a main agent and an initiator. The temperature when mixing the main agent and the initiator in the adhesive set and the conditions for curing the adhesive composition can be the same as above.

[0076] Example

[0077] Hereinafter, the present disclosure will be described in further detail with reference to Examples, but the present disclosure is not limited to these Examples.

[0078] <Examples 1 to 10>

[0079] [Adhesive kit production]

[0080] (Preparation of raw materials)

[0081] Organoborane complex

[0082] TEB-DAP: triethylborane-1,3-diaminopropane complex (molecular weight: 172.1, KISHIDA CHEMICAL Co., Ltd.)

[0083] TnBB-MOPA: tri-n-butylborane-3-methoxy-1-propylamine complex (molecular weight: 271.3, KISHIDACHEMICAL Co., Ltd.)

[0084] ·Decomplexing agent

[0085] Succinic anhydride (molecular weight: 100.1, FUJIFILM Wako Pure Chemical Corporation)

[0086] ·Compounds having free radical polymerizable groups (polymerizable compounds)

[0087] FA-513AS: Dicyclopentyl acrylate (molecular weight: 206.3, SHOWA DENKO MATERIALS CO., LTD.)

[0088] FA-310A: phenoxyethyl acrylate (molecular weight: 192.2, SHOWA DENKO MATERIALS CO., LTD.)

[0089] Compounds with a thiocarbonylsulfide structure (polymerization control agent)

[0090] CTA1: 2'-cyanobutane-2'-yl 3,5-dimethylpyrazole-1-dithiocarboxylate (Compound (1a-1), molecular weight: 253.4, FUJIFILM Wako Pure Chemical Corporation)

[0091] CTA2: 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]methylvalerate (compound (2a-1), molecular weight: 417.7, FUJIFILM Wako Pure Chemical Corporation)

[0092] CTA3: 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanovaleric acid (Compound (2a-2), molecular weight: 307.4, FUJIFILM Wako Pure Chemical Corporation)

[0093] ·filler

[0094] RY200S: Fumed silica (hydrophobic fumed silica surface treated with silicone oil, Nippon Aerosil Co., Ltd.)

[0095] R805: Silica particles (hydrophobic silica particles surface-treated with octylsilane, Nippon Aerosil Co., Ltd.)

[0096] M210: Acrylic resin core-shell particles (Kaneka Corporation)

[0097] EZ-004: MBS core-shell particles (Kaneka Corporation)

[0098] B564: MBS core-shell particles (Kaneka Corporation)

[0099] Plasticizer

[0100] PN-5090: Adipic acid polyester (ADEKA Corporation)

[0101] Cross-linking agent

[0102] Triaziridine series: tris[3-(1-aziridinyl)propionic acid]trimethylolpropane (FUJIFILM Wako PureChemical Corporation)

[0103] (Preparation of main agent)

[0104] The decomplexer, the compound having a free radical polymerizable group, the compound having a thiocarbonylsulfide structure and the filler were weighed into a plastic bottle in the types and proportions (unit: parts by mass) shown in Table 1, and mixed at 2000 rpm for 15 minutes using an autorotation-revolution mixer (THINKYCORPORATION, Awatori Rentaro), and further defoamed at 2000 rpm for 5 minutes to prepare the main agents of Examples 1 to 10.

[0105] (Preparation of Initiator)

[0106] The organic borane complex, plasticizer, crosslinking agent and filler were weighed into a plastic bottle in the types and proportions (unit: parts by mass) shown in Table 1, and mixed at 2000 rpm for 15 minutes using an autorotating and orbiting stirrer (THINKY CORPORATION, Awatori Rentaro), and further defoamed at 2000 rpm for 5 minutes to prepare the initiators of Examples 1 to 10.

[0107] [Measurement of adhesive strength]

[0108] A 0.5 mm spacer was arranged between two polypropylene substrates (adhesive bodies) (size: 100 mm × 25 mm, thickness: 2 mm) in such a way that the thickness of the adhesive layer became 0.5 mm. The main agent and the initiator were mixed by filling the main agent in each embodiment and the initiator in each embodiment into a manual dispenser. A manual dispenser was used to apply between the polypropylene substrates, and the polypropylene substrates were bonded to each other to obtain a laminate. The obtained laminate was placed at 25°C for 24 hours (or 96 hours) to cure, and an evaluation sample was prepared. For the prepared evaluation sample, a tensile test was carried out with a chuck spacing of 100 mm and a test speed of 5 mm / min to measure the shear strength (MPa) against the polypropylene substrate. If the shear strength is 1 MPa or more, it can be said that it has sufficient bonding strength. The results are shown in Table 1.

[0109] [Table 1]

[0110]

[0111] As shown in Table 1, the adhesive compositions prepared from the adhesive sets of Examples 1 to 10 had sufficient adhesive strength. From these results, it was confirmed that the adhesive set of the present disclosure can prepare an adhesive composition having excellent adhesive strength even without using a halogenated metal salt.

Claims

1. An adhesive kit comprising: A main agent, containing a decomplexing agent; and Initiator, containing an organoborane complex, At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group, 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 (1a) or the following formula (2a), 2. The adhesive kit according to claim 1, wherein: The main agent contains a compound having a thiocarbonylsulfide structure.

3. An adhesive body, comprising: The first bonded body; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other, The adhesive layer contains a cured product of an adhesive composition, and the cured product of the adhesive composition includes the main agent and the initiator in the adhesive kit according to claim 1 or 2.

4. A method for producing an adhesive body, which is the method for producing an adhesive body according to claim 3, comprising: A step of bonding the first adherend and the second adherend together via an adhesive composition containing the main agent and the initiator.

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