Adhesive set, adhesive body, and method for manufacturing the adhesive body

Abstract

To provide an adhesive set capable of forming an adhesive layer having sufficient adhesive strength and a high elongation rate.SOLUTION: The adhesive set according to the present disclosure comprises: a main agent containing a decomplexing agent and an inorganic filler; and an initiator containing an organic borane complex. At least one of the main agent and the initiator further contains radically polymerizable group-containing compounds. At least one of the main agent and the initiator further contains a peroxide.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to an adhesive set, an adherent, and a method for producing an adherent.

Background Art

[0002] For the purpose of weight reduction of automobiles, the multi-materialization of exterior parts has been progressing, and the joining method has been changing from welding to adhesion. As an adhesive for plastics such as polyethylene and polypropylene, an adhesive composition containing an organic borane complex has been 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 radicals by reacting with oxygen. The generated borate radicals act as dormant species in atom transfer radical polymerization (ATRP) that sustains a growth reaction including surface grafting while suppressing the chain transfer or termination reaction of a compound having a radical polymerizable group.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By using an alkyl borane complex, it is possible to adhere a material having no polar group such as polypropylene, but it is difficult to achieve both the adhesive strength and flexibility (high elongation rate, etc.) of the adhesive layer.

[0005] Therefore, the main object of the present disclosure is to provide an adhesive set capable of forming an adhesive layer having sufficient adhesive strength and a high elongation rate.

Means for Solving the Problems

[0006] One aspect of this disclosure relates to an adhesive set, comprising a main component containing a decomplexing agent and an inorganic filler, and an initiator containing an organoborane complex, wherein at least one of the main component and the initiator further contains a compound having a radical polymerizable group, and at least one of the main component and the initiator further contains a peroxide.

[0007] Another aspect of this disclosure relates to an adhesive comprising a first adherend, a second adherend, and an adhesive layer that adheres the first adherend and the second adherend to each other. The adhesive layer contains a cured product of an adhesive composition comprising the main component and initiator in the adhesive set described above.

[0008] Another aspect of this disclosure relates to a method for manufacturing an adhesive, comprising the step of bonding a first adherend and a second adherend via an adhesive composition comprising a main component and an initiator. [Effects of the Invention]

[0009] This disclosure provides an adhesive set capable of forming an adhesive layer having sufficient adhesive strength and high elongation. Furthermore, this disclosure provides an adhesive body using such an adhesive set and a method for manufacturing the same. [Modes for carrying out the invention]

[0010] The embodiments of this disclosure are described below. However, this disclosure is not limited to the embodiments described below.

[0011] The same applies to numerical values ​​and their ranges in this disclosure, and this disclosure is not limited. Numerical ranges indicated using "~" in this specification indicate a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in steps in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in steps. Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples.

[0012] 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 individually or in combination of two or more. The content of each component in the composition means the total amount of any multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition.

[0013] [Adhesive Set] One embodiment of the adhesive set comprises a main component containing a decomplexing agent and an inorganic filler, and an initiator containing an organoborane complex. By mixing the main component and the initiator in this embodiment, an adhesive composition containing the main component and the initiator can be obtained. With such an adhesive set, by mixing the main component and the initiator, it is possible to prepare an adhesive composition that has sufficient adhesive strength and a shortened curing time.

[0014] The main component contains a decomplexing agent and an inorganic filler. The initiator contains an organoborane complex. At least one of the main component and the initiator further contains a compound having a radical polymerizable group. At least one of the main component and the initiator further contains a peroxide. At least one of the main component and the initiator may further contain any of the following: a polymerization control agent, a plasticizer, a crosslinking agent, etc. Each component is described below.

[0015] (Organoborane complex) The initiator contains an organoborane complex. An organoborane complex refers to an organoborane-Lewis base complex, which is formed by coordinating an organoborane with a Lewis base. The organoborane-Lewis base complex is a compound that reacts with the decomplexing agent described later to give an organoborane. Organoboranes can act as initiators for living radical polymerization because they undergo radical cleavage under an oxygen atmosphere, generating dormant species such as boric acid radicals. The organoborane may be, for example, an alkylborane (BR3, R: 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 one amino group constituting the amine and a group containing an atom capable of coordinating to boron (e.g., an oxygen atom) in addition to the nitrogen atom of the amino group (e.g., an alkoxy group). These compounds can be called polydentate amines because they act as polydentate ligands for organoboranes.

[0016] The organoborane complex may be an alkylborane-amine complex or an alkylborane-polydentate 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 individually 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.

[0017] 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 achieving adhesive strength. The content of the organoborane complex 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.

[0018] 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 main agent and initiator, from the viewpoint of achieving adhesive strength. The content of the organoborane complex 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 main agent and initiator, from the viewpoint of the toughness of the adhesive layer.

[0019] From the viewpoint of achieving adhesive strength, the content of the organoborane complex may be 0.01 mol% or more, 0.05 mol% or more, 0.08 mol% or more, or 0.1 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, 5 mol% or less, 2 mol% or less, or 1 mol% or less, based on the total amount of compounds having radical polymerizable groups.

[0020] (Decomposing agent) The main component contains a decomplexing agent. A decomplexing agent is a compound that can dissociate the Lewis base in an organoborane complex (organoborane-Lewis base complex) to generate an organoborane. Therefore, by mixing the organoborane complex contained in the initiator with the decomplexing agent contained in the main component and reacting them, it is possible to generate an organoborane that can serve as an initiator for living radical polymerization.

[0021] Examples of the decomplexing agent include acids, acid anhydrides, aldehydes, β-ketone compounds, etc. These may be used alone or in combination of two or more. Examples of the acid include Lewis acids such as SnCl4 and TiCl4, and Bronsted acids such as aliphatic carboxylic acids and aromatic carboxylic acids. Examples of the acid anhydride include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, etc. Examples of the aldehyde include benzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, and p-nitrobenzaldehyde. Examples of the β-ketone compound include methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, 2-methacryloyloxyethyl acetoacetate, etc. Among these, the decomplexing agent may be an acid anhydride from the viewpoint of the reactivity of decomplexing with the organoborane complex and the storage stability of the initiator, and may be succinic anhydride from the viewpoint of suppressing the blending mass of the decomplexing agent.

[0022] From the viewpoint of shortening the curing time until the adhesive layer cures and exhibits adhesive strength, 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 main agent. From the viewpoint of ensuring the working time from when the adhesive composition is applied to the adherend until bonding, 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 main agent.

[0023] From the viewpoint of shortening the curing time until the adhesive layer cures and exhibits adhesive strength, 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 main agent and the initiator. From the viewpoint of ensuring the working time from when the adhesive composition is applied to the adherend until bonding, 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 main agent and the initiator.

[0024] The molar amount ratio of the decomplexing agent to the organoborane complex (molar amount of the decomplexing agent / molar amount of the organoborane complex) may be, for example, 0.3 or more, 0.5 or more, 0.8 or more, or 1 or more. When the molar amount ratio is 1 or more, there is a tendency to obtain a more sufficient adhesive strength. The molar amount ratio of the decomplexing agent to the organoborane complex (molar amount of the decomplexing agent / molar amount of the 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. As the molar amount ratio becomes smaller, there is a tendency to more sufficiently secure the working time from applying the adhesive composition to the adherend to bonding.

[0025] (Inorganic filler) The main agent contains an inorganic filler. By containing an inorganic filler in the main agent, it is possible to form an adhesive layer having high adhesive strength and high elongation rate.

[0026] Examples of the inorganic filler include inorganic fine particles such as silica, alumina, silica-alumina, titania, zirconia, magnesia, kaolin, talc, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, wollastonite, zonnolite, whiskers, etc.

[0027] When the inorganic filler in the adhesive composition aggregates, stress concentrates on the aggregated particles and the adhesive layer is likely to be broken. Therefore, it is desirable to use an inorganic filler that is difficult to aggregate. By using a surface-treated inorganic filler as the inorganic filler, aggregation can be further suppressed.

[0028] Examples of the type of surface treatment of the inorganic filler include electroplating, electroless plating, fusion plating, vacuum plating, chemical treatment, anodic oxidation treatment, painting, thermal spraying, surface hardening, and metal penetration.

[0029] The surface of the inorganic filler may be chemically treated with a surface treatment agent. Examples of surface treatment agents include fatty acids, resin acids, surfactants, phosphate ester coupling agents, titanium coupling agents, and silane coupling agents. Surface treatment of particles with a surface treatment agent reduces the surface energy, making it easier to suppress the formation of aggregated particles.

[0030] The inorganic filler preferably contains at least one selected from the group consisting of silica and calcium carbonate. Since silica and calcium carbonate have a higher specific gravity than the resin components, it is thought that the density per unit area in the adhesive layer will increase, making it easier to exhibit high strength. Surface-treated calcium carbonate and silica suppress the formation of aggregated particles that can become the starting point of fracture, making it easier to further improve the strength of the adhesive layer.

[0031] The inorganic filler content may be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, based on the total mass of the main component, and may be 40% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less.

[0032] Both the main component and the initiator may contain an inorganic filler. The inorganic filler content may be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 40% by mass or less, 30% by mass or less, or 25% by mass or less, based on the total amount of the main component and the initiator.

[0033] (Compounds having radical polymerizable groups) At least one of the main component 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 radicals. Examples of radical polymerizable groups include (meth)acryloyl groups, vinyl groups, allyl groups, styryl groups, alkenyl groups, alkenylene groups, and maleimide groups.

[0034] Compounds having radical polymerizable groups may include, for example, compounds having a (meth)acryloyl group. Examples of compounds 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.

[0035] 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 alkyl groups such as isomiristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl acrylate; alkenyl (meth)acrylates having alkenyl groups such as 3-butenyl (meth)acrylate; (meth)acrylates having aromatic groups such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxy octaethylene glycol Alkoxy polyalkylene glycol (meth)acrylates such as methyl hydrate (meth)acrylate, methoxynonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, etc.; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentane (Meth)acrylates having alicyclic groups such as 2-(meth)acrylate; (meth)acrylates having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylates having amino groups such as N,N-dimethylaminoethyl (meth)acrylate; (meth)acrylates having isocyanate groups such as 2-(2-methacryloyloxyethyl oxy)ethyl isocyanate and 2-(meth)acryloyloxyethyl isocyanate;Examples include polyalkylene glycol mono(meth)acrylates such as 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 individually or in combination of two or more types.

[0036] 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, and polypropylene glycol di(meth)acrylate. 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-decanediol di(meth)acrylate Aliphatic (meth)acrylates such as acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate; ethoxylated bisphenol A type di(meth)acrylate, propoxylated bisphenol A type di(meth)acrylate, ethoxylated propoxylated bisphenol A type di(meth)acrylate, ethoxylated bisphenol F type di(meth)acrylate, propoxylated bisphenol F type di(meth)acrylate, Examples include aromatic (meth)acrylates such as 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; aromatic epoxy (meth)acrylates such as bisphenol type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, and cresol novolac type epoxy (meth)acrylate; and urethane (meth)acrylate. These may be used individually or in combination of two or more.

[0037] 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, and (meth)acryloylmorpholine. These may be used individually or in combination of two or more.

[0038] Compounds having radical polymerizable groups may include, for example, compounds having (meth)acryloyl groups, as well as copolymerizable compounds that can copolymerize with them. Examples of copolymerizable compounds include compounds having radical polymerizable groups other than (meth)acryloyl groups, such as styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride.

[0039] The compound having a radical polymerizable group only needs to be contained in at least one of the main component and the initiator; for example, the main component may contain the compound having a radical polymerizable group.

[0040] The content of compounds having radical polymerizable groups may be 40% by mass or more, 50% by mass or more, 60% by mass or more, or 65% by mass or more, based on the total amount of the main agent and initiator, from the viewpoint of improving the toughness of the adhesive layer and improving the adhesive strength. The content of compounds having radical polymerizable groups may be 99% by mass or less, 98% by mass or less, 95% by mass or less, or 90% by mass or less, based on the total amount of the main agent and initiator, from the viewpoint of suppressing sagging of the applied adhesive composition and suppressing a decrease in the toughness of the adhesive layer.

[0041] (Peroxide) At least one of the main component and the initiator further contains a peroxide. The peroxide can be any peroxide having an -OO- bond, and commercially available products can be used, for example. These may be used individually or in combination of two or more types.

[0042] Examples of commercially available peroxides include Perloyl L (half-life temperature of 1 minute: 116°C, NOF Corporation), Perbutyl O (half-life temperature of 1 minute: 134°C, NOF Corporation), Perbutyl E (half-life temperature of 1 minute: 161°C, NOF Corporation), and Permil H (half-life temperature of 1 minute: 254°C, NOF Corporation). Among these, the peroxide may be one with a half-life temperature of 270°C or lower, from the viewpoint of shortening the curing time and storage stability. The half-life temperature of the peroxide may be, for example, 250°C or lower, 220°C or lower, 200°C or lower, 180°C or lower, 160°C or lower, 150°C or lower, 140°C or lower, 135°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower. The half-life temperature of the peroxide may be, for example, 80°C or higher, 90°C or higher, or 100°C or higher.

[0043] From the viewpoint of shortening the curing time, the peroxide content may be 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, based on the total amount of the main agent and initiator. From the viewpoint of storage stability, the peroxide content may be 5% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less, based on the total amount of the main agent and initiator.

[0044] From the viewpoint of shortening the curing time, the peroxide content may be 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more, based on the total amount of the organoborane complex. From the viewpoint of storage stability, the peroxide content may be 90 mol% or less, 80 mol% or less, 70 mol% or less, or 60 mol% or less, based on the total amount of the organoborane complex.

[0045] The peroxide only needs to be contained in at least one of the main component and the initiator; for example, the main component may contain the peroxide.

[0046] (Polymerization control agent) At least one of the main component and the initiator may further contain a polymerization control agent. Examples of polymerization control agents include metal halide salts and compounds having a thiocarbonylthio structure. The polymerization control agent may be at least one selected from the group consisting of metal halide salts and compounds having a thiocarbonylthio structure.

[0047] Examples of metal halide salts include copper(II) bromide, copper(II) chloride, iron(III) bromide, vanadium(III) bromide, chromium(III) bromide, ruthenium(III) bromide, copper(I) bromide, iron(II) bromide, manganese(II) bromide, cobalt(II) bromide, nickel(II) bromide, and palladium(II) bromide. These may be used individually or in combination of two or more. For example, the metal halide salt may be copper(II) bromide.

[0048] Compounds having a thiocarbonylthio structure can be used without particular limitations as long as they have a thiocarbonylthio structure. For example, chain transfer agents (RAFT agents) used in the field of RAFT polymerization (Reversible Addition / Fragmentation Chain Transfer) can be suitably used.

[0049] The polymerization control agent only needs to be contained in at least one of the main component and the initiator; for example, the main component may contain the polymerization control agent.

[0050] The content of the polymerization control agent 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 main agent and initiator, from the viewpoint of ensuring sufficient working time from the application of the adhesive composition to the adherend to bonding and improving adhesive strength. The content of the polymerization control agent 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 main agent and initiator, from the viewpoint of the storage stability of the main agent.

[0051] The content of the polymerization control agent may be 0.01 mol% or more, 0.03 mol% or more, 0.05 mol% or more, or 0.08 mol% or more, based on the total amount of compounds having radical polymerizable groups, from the viewpoint of ensuring sufficient working time from the application of the adhesive composition to the adherends until bonding and improving adhesive strength. The content of the polymerization control agent 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 the storage stability of the main component.

[0052] (Plasticizer) Examples of plasticizers include phthalate ester compounds, alkyl sulfonic acid ester compounds, and adipic acid ester compounds.

[0053] The plasticizer content may be 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 main component and the initiator, and may be 30% by mass or less, 20% by mass or less, or 10% by mass or less.

[0054] (Crosslinking agent) Examples of crosslinking agents include aziridine-based crosslinking agents and carbodiimide-based crosslinking agents.

[0055] The crosslinking agent content 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 main agent and the initiator.

[0056] At least one of the main component and the initiator may further contain, in addition to the above components, UV absorbers, dehydrating agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion promoters, dispersants, solvents, and the like.

[0057] The adhesive set of this embodiment allows for the preparation of an adhesive composition by mixing a main component and an initiator. The temperature when mixing the main component and the initiator may be, for example, 10 to 35°C. The pot life of the adhesive set may be, for example, 0.1 to 3 minutes.

[0058] When mixing the main component and the initiator, it is preferable to mix them so that the molar ratio of the decomplexing agent in the main component to the organoborane complex in the initiator (moles of decomplexing agent / molars of organoborane complex) is 0.3 or higher, 0.5 or higher, 0.8 or higher, or 1 or higher, or 50 or lower, 30 or lower, 10 or lower, 7 or lower, 5 or lower, or 3 or lower.

[0059] When mixing the main component and the initiator, it is preferable to mix them so that the mass ratio of the main component to the initiator (mass of main component / mass of 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.

[0060] The method of mixing the main component and the initiator is not particularly limited as long as the two are mixed. Examples of methods for mixing the main component and the initiator include manual mixing, mixing by hand using a standard caulking gun, and mixing using a mechanical rotary mixer, static mixer, etc., in combination with a quantitative pump (e.g., gear pump, plunger pump, etc.) and throttle valve for supplying the raw materials.

[0061] The prepared adhesive composition can form an adhesive layer by being applied to a predetermined location. The formed adhesive layer gradually hardens as the compounds having radical polymerizable groups increase in molecular weight, thus acting as an adhesive layer that bonds substrates together. Conventional known methods, such as using a dispenser, can be applied to the predetermined location.

[0062] 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.

[0063] [Adhesive and method for manufacturing the same] An adhesive body according to one embodiment comprises a first adherend, a second adherend, and an adhesive layer that adheres the first adherend and the second adherend to each other. The adhesive layer contains a cured product of an adhesive composition including the main agent and initiator in the adhesive set described above.

[0064] Examples of the first and second adherends 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), as well as metal substrates such as aluminum, steel, copper, and stainless steel.

[0065] Examples of adhesives include plastic laminated substrates, metal laminated substrates, electronic components, semiconductor components, and display components.

[0066] A method for manufacturing an adhesive according to one embodiment comprises the step of bonding a first adherend and a second adherend together via an adhesive composition containing a main component and an initiator. The temperature when mixing the main component and the initiator in the adhesive set, the conditions for curing the adhesive composition, etc., may be the same as described above. [Examples]

[0067] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to these examples.

[0068] <Examples 1-3 and Comparative Example 1> [Making an adhesive kit] (Preparation of raw materials) • Organoborane complex TEB-DAP: Triethylborane-1,3-diaminopropane complex (Molecular weight: 172.1, Kishida Chemical Co., Ltd.) • Decomposing agent Succinic anhydride (molecular weight: 100.1, Fujifilm Wako Pure Chemical Corporation) • Compounds having radical polymerizable groups (polymerizable compounds) IBXA: Isobornyl acrylate (Molecular weight: 208.3, Kyoeisha Chemical Co., Ltd.) FA-310AH: Phenoxyethyl acrylate (Molecular weight: 192.2, Showa Denko Materials Co., Ltd.) EBECRYL 8413: Aliphatic urethane acrylate (Molecular weight: 37000, Daicel-Ornesk Corporation) Dimethylacrylamide (Molecular weight: 99.13, Fujifilm Wako Pure Chemical Corporation) • Polymerization control agent Copper(II) bromide (molecular weight: 223.4, Fujifilm Wako Pure Chemical Industries, Ltd.) • Peroxides Perloyl L (Molecular weight: 398.6, Half-life temperature at 1 minute: 116°C, NOF Corporation) • Inorganic filler Shirotsuya CC-R: Surface-treated calcium carbonate (Shiraishi Calcium Co., Ltd.) RY200S: Surface-treated silica (hydrophobic fumed silica surface-treated with silicone oil, manufactured by Nippon Aerosil Co., Ltd.) NS#2300: Calcium Carbonate (Nitto Powdering Industry Co., Ltd.) • Organic fillers M210: Acrylic core-shell particles (Kaneka Corporation, antioxidant not detected) • Plasticizer PN-5090: Polyester adipic acid (ADEKA Corporation) • Crosslinking agent Triaziridine: Tris[3-(1-aziridinyl)propionic acid]trimethylolpropane (Fujifilm Wako Pure Chemical Corporation)

[0069] (Preparation of the main ingredient) The decomplexing agent, compound having a radical polymerizable group, polymerization control agent, peroxide, and filler were weighed into a poly bottle in the types and proportions (unit: parts by mass) shown in Table 1. They were then mixed for 15 minutes at 2000 rpm using a self-rotating mixer (Thinky Co., Ltd., Awatori Rentaro) and degassed for 5 minutes at 2000 rpm to prepare the main components for Examples 1-3 and Comparative Example 1.

[0070] (Preparation of the initiator) The organoborane complex, plasticizer, crosslinking agent, and filler were weighed into a poly bottle in the types and proportions (unit: parts by mass) shown in Table 1. They were then mixed for 15 minutes at 2000 rpm using a rotary mixer (Thinky Co., Ltd., Awatori Rentaro) and degassed for 5 minutes at 2000 rpm to prepare the initiators for Examples 1-3 and Comparative Example 1. The initiators for Examples 1-3 and Comparative Example 1 are identical in composition.

[0071] [Evaluation of adhesive strength] Two polypropylene substrates (adhesion substrates) (size: 100 mm x 25 mm, thickness: 2 mm) were placed with a 0.5 mm spacer between them so that the adhesive layer thickness was 0.5 mm. The main component and initiator were mixed by filling a manual dispenser with each component and initiator. The mixture was applied between the polypropylene substrates using the manual dispenser, and the two polypropylene substrates were bonded together to obtain a laminate. The resulting laminate was left to cure at 23°C and 55% RH for 72 hours to prepare an evaluation sample. A tensile test was performed on the prepared evaluation sample with a chuck distance of 100 mm and a test speed of 50 mm / min to measure the shear strength (MPa) against the polypropylene substrate. A shear strength of 1 MPa or more indicates sufficient adhesive strength.

[0072] [Evaluation of coating properties] A 2mm spacer was placed on a release sheet (size: 150mm x 150mm, thickness: 0.1mm, material: polytetrafluoroethylene) so that the adhesive layer thickness was 2mm. After applying the adhesive composition, which was a mixture of each main component and each initiator, to the release sheet, another release sheet was laminated on top, and the sheet was left at 23°C and 55%RH for 72 hours to obtain a laminated sheet of the cured release sheet and adhesive composition. In accordance with JIS K 6251, the laminated sheet was punched out into a dumbbell shape (size 3), and the release sheet was peeled off to prepare test specimens. Using an Autograph (Shimadzu Corporation, model number: AGS-1kNX, load cell: 50kN), the breaking strength and elongation of the test specimens were measured with a chuck distance of 70mm and a tensile speed of 200mm / min. The higher the values ​​for breaking strength and elongation, the higher the strength of the cured material.

[0073] [Table 1]

Claims

1. The product comprises a main component containing a decomplexing agent and an inorganic filler, and an initiator containing an organoborane complex, At least one of the main component and the initiator further contains a compound having a radical polymerizable group, At least one of the main component and the initiator further contains a peroxide, An adhesive set wherein the content of the inorganic filler is 10% by mass or more and 25% by mass or less, based on the total mass of the main component.

2. The adhesive set according to Claim 1, wherein the content of the compound having a radical polymerizable group is 65% by mass or more and 90% by mass or less, based on the total amount of the main agent and the initiator.

3. The adhesive set according to claim 1 or 2, wherein the inorganic filler comprises at least one selected from the group consisting of silica and calcium carbonate.

4. The adhesive set according to any one of claims 1 to 3, wherein the initiator further contains an inorganic filler.

5. The device comprises a first adherend, a second adherend, and an adhesive layer that adheres the first adherend and the second adherend to each other. An adhesive body wherein the adhesive layer contains a cured product of an adhesive composition comprising the main component and the initiator in the adhesive set according to any one of claims 1 to 4.

6. A method for manufacturing an adhesive according to claim 5, A method for manufacturing an adhesive, comprising the step of bonding the first adherend and the second adherend via an adhesive composition containing the main component and the initiator.

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