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 excellent flexibility.SOLUTION: The adhesive set according to the present disclosure comprises: a main agent containing a decomplexing agent and radically polymerizable group-containing compounds; and an initiator containing an organic borane complex. At least one of the main agent and the initiator further contains a polymerization control agent. The radically polymerizable group-containing compounds include a monofunctional polymerizable compound whose homopolymer has a glass transition temperature of 80°C or higher, a monofunctional polymerizable compound having an aromatic ring, and a polyfunctional polymerizable compound having a weight average molecular weight of 10,000 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to an adhesive set, an adherent, and a method for manufacturing 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 boronic acid radicals act as dormant species for 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 radically 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 bond a material having no polar group such as polypropylene, but it is difficult to achieve both the adhesive strength and flexibility of the adhesive layer.

[0005] Therefore, the main object of the present disclosure is to provide an adhesive set that can form an adhesive layer having sufficient adhesive strength and excellent flexibility.

Means for Solving the Problems

[0006] One aspect of this disclosure relates to an adhesive set. The adhesive set comprises a main component containing a decomplexing agent and a compound having a radical polymerizable group, and an initiator containing an organoborane complex, wherein at least one of the main component and the initiator further contains a polymerization control agent, and the compound having a radical polymerizable group includes a monofunctional polymerizable compound having a homopolymer glass transition temperature of 80°C or higher, a monofunctional polymerizable compound having an aromatic ring, and a polyfunctional polymerizable compound having a weight-average molecular weight of 10,000 or higher.

[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 excellent flexibility. Furthermore, this disclosure also 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, a compound having one radical polymerizable group is referred to as a monofunctional polymerizable compound, and a compound having two or more radical polymerizable groups is referred to as a polyfunctional polymerizable compound. (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 multiple substances present in the composition if multiple substances corresponding to each component exist in the composition, unless otherwise specified.

[0013] [Adhesive Set] One embodiment of the adhesive set comprises a main component containing a decomplexing agent and a compound having a radical polymerizable group, and an initiator containing an organoborane complex. By mixing the main component and the initiator of 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 can shorten the curing time.

[0014] The main component contains a decomplexing agent and a compound having a radical polymerizable group. The compound having a radical polymerizable group includes monofunctional polymerizable compounds having a homopolymer glass transition temperature of 80°C or higher, monofunctional polymerizable compounds having an aromatic ring, and polyfunctional polymerizable compounds having a weight-average molecular weight of 10,000 or higher. The initiator contains an organoborane complex. At least one of the main component and the initiator further contains a polymerization control agent. At least one of the main component and the initiator may further contain any of the following: fillers, peroxides, plasticizers, crosslinking agents, 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 decomplexing agents include acids, acid anhydrides, aldehydes, and β-ketone compounds. These may be used individually or in combination of two or more. Examples of acids include Lewis acids such as SnCl4 and TiCl4, and Brønsted 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-nitrobenzaldehyde, m-nitrobenzaldehyde, 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 viewpoint of reactivity in decomplexing with the organoborane complex and storage stability of the initiator, or succinic anhydride from the viewpoint of suppressing the amount of decomplexing agent used.

[0022] From the perspective of shortening the curing time until the adhesive layer cures and exhibits adhesive strength, the content of the deblocking 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 perspective of ensuring the working time from when the adhesive composition is applied to the adherend until laminating, the content of the deblocking 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 perspective of shortening the curing time until the adhesive layer cures and exhibits adhesive strength, the content of the deblocking 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 perspective of ensuring the working time from when the adhesive composition is applied to the adherend until laminating, the content of the deblocking 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 ratio of the deblocking agent to the organoborane complex (molar amount of deblocking agent / molar amount of 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 ratio is 1 or more, there is a tendency to obtain more sufficient adhesive strength. The molar ratio of the deblocking agent to the organoborane complex (molar amount of deblocking 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 likely it is to sufficiently ensure the working time from when the adhesive composition is applied to the adherend until laminating.

[0025] (Compound having a radically polymerizable group) The main agent contains a compound having a radically polymerizable group. A compound having a radically polymerizable group is a compound having a polymerizable group that reacts with radicals. Examples of the radically polymerizable group include, for example, (meth)acryloyl group, vinyl group, allyl group, styryl group, alkenyl group, alkenylene group, and maleimide group.

[0026] Compounds having radical polymerizable groups include monofunctional polymerizable compounds (hereinafter referred to as "polymerizable compound A") having a homopolymer glass transition temperature of 80°C or higher, monofunctional polymerizable compounds having an aromatic ring (hereinafter referred to as "polymerizable compound B"), and polyfunctional polymerizable compounds (hereinafter referred to as "polymerizable compound C") having a weight-average molecular weight of 10,000 or higher. This makes it possible to form an adhesive layer with sufficient adhesive strength and excellent flexibility.

[0027] The Tg of the homopolymer of polymerizable compound A may be 85°C or higher, 90°C or higher, or 95°C or higher from the viewpoint of further increasing the strength of the adhesive layer, and may be 200°C, 190°C or lower, or 180°C or lower from the viewpoint of further increasing flexibility.

[0028] Polymerizable compound A may be a monofunctional polymerizable compound that does not have an aromatic ring. Examples of polymerizable compound A include acrylic acid (Tg: 106°C), methacrylic acid (Tg: 228°C), methyl methacrylate (Tg: 100°C), tert-butyl methacrylate (Tg: 107°C), isobornyl acrylate (Tg: 97°C), isobornyl methacrylate (Tg: 180°C), dicyclopentanyl acrylate (Tg: 120°C), dicyclopentanyl methacrylate (Tg: 175°C), dimethylacrylamide (Tg: 119°C), dimethylaminopropylacrylamide (Tg: 134°C), isopropylacrylamide (Tg: 134°C), diethylacrylamide (Tg: 81°C), N-hydroxyethylacrylamide (Tg: 98°C), and acryloylmorpholine (Tg: 145°C).

[0029] The content of polymerizable compound A may be 20% by mass or more, 25% by mass or more, or 30% by mass or more, or 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the total amount of compounds having radical polymerizable groups.

[0030] By using a monofunctional polymerizable compound having an aromatic ring as polymerizable compound B, adhesion to materials without polar groups, such as polypropylene, can be improved. The Tg of the homopolymer of polymerizable compound B is preferably less than 80°C, and may be -90 to 60°C, -50 to 40°C, or -10 to 20°C. Examples of polymerizable compound B include phenoxyethyl acrylate, phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxydiethylene glycol acrylate, EO-modified phenol acrylate, EO-modified nonylphenol acrylate, EO-modified orthophenylphenol acrylate, phenylglycidyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, and neopentyl glycol-acrylic acid-benzoic acid ester.

[0031] From the viewpoint of further improving adhesion, the content of polymerizable compound B may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, or 50% by mass or less, 40% by mass or less, or 30% by mass or less, based on the total amount of compounds having radical polymerizable groups.

[0032] By using a polyfunctional polymerizable compound C having a weight-average molecular weight (Mw) of 10,000 or more, the flexibility and adhesive strength of the adhesive layer can be improved. From the viewpoint of further enhancing the flexibility of the adhesive layer, the Mw of polymerizable compound C may be 15,000 to 60,000, 20,000 to 50,000, or 30,000 to 40,000.

[0033] Mw is measured by gel permeation chromatography (GPC) and is expressed as a value converted to standard polystyrene. In this specification, GPC measurements for determining Mw can be performed, for example, under the following conditions. Columns: "Gelpack GLA130-S", "Gelpack GLA150-S", and "Gelpack GLA160-S" (manufactured by Showa Denko Materials Co., Ltd., packed columns for HPLC) Eluent: Tetrahydrofuran Flow rate: 0.5mL / min Column temperature: 45℃ Detector: RI

[0034] The Tg of the cured product of polymerizable compound C is preferably less than 20°C from the viewpoint of further increasing the flexibility of the adhesive layer, and may be -100 to 10°C, -60 to -20°C, or -50 to -40°C.

[0035] Examples of polymerizable compound C include urethane acrylate, acrylic resin acrylate, polyester acrylate, and epoxy acrylate.

[0036] Polymerizable compound C is preferably a bifunctional polymerizable compound having two radical polymerizable groups, and more preferably a bifunctional urethane acrylate, because it offers an excellent balance between the adhesive strength and flexibility of the adhesive layer.

[0037] From the viewpoint of further improving adhesive strength and flexibility, the content of polymerizable compound C may be 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total amount of compounds having radical polymerizable groups, and may also be 60% by mass or less, 50% by mass or less, or 40% by mass or less.

[0038] The compound having a radical polymerizable group may further contain compounds other than the polymerizable compound described above (hereinafter referred to as "polymerizable compound D"). Polymerizable compound D may be a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate.

[0039] Examples of monofunctional (meth)acrylates include methyl acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl 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- Alkyl (meth)acrylates having alkyl groups such as uryl (meth)acrylate, isomiristyl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate; alkenyl (meth)acrylates having alkenyl groups such as 3-butenyl (meth)acrylate; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxyoctaethylene glycol (meth)acrylate, methoxy Alkoxypolyalkylene glycol (meth)acrylates such as cinonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, and butoxydiethylene glycol (meth)acrylate; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate; hydroxyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; amino (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; isocyanate (meth)acrylates 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.

[0040] 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 Polypropylene 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- Aliphatic (meth)acrylates such as candiol di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, and 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, and propoxylated bisphenol F Examples include aromatic (meth)acrylates such as di(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 individually or in combination of two or more types.

[0041] The total amount 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 and adhesive strength of the adhesive layer. The content of compounds having radical polymerizable groups may be 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% 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.

[0042] (Polymerization control agent) At least one of the main component and the initiator further contains 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] (Peroxide) At least one of the main component and the initiator may further contain 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] (Filler) The filler may be either an inorganic filler or an organic filler. Examples of inorganic fillers include 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, xonotlite, whiskers, and other inorganic fine particles. Examples of organic fillers include silicone, acrylic silicone, acrylic rubber, MBS (methacrylate-butadiene-styrene), polyamide, polyimide, and other organic fine particles. These fillers (fine particles) may have a uniform structure or a core-shell structure. The filler may contain organic fillers or acrylic core-shell particles, as this can significantly shorten the curing time.

[0054] The filler only needs to be contained in at least one of the main component and the initiator. For example, the main component may contain an organic filler, or an acrylic core-shell particle filler, as this can significantly shorten the curing time.

[0055] The organic filler may contain an antioxidant. The inventors of this disclosure have found that the lower the amount of antioxidant in the organic filler, the more significantly the curing time can be shortened. The antioxidant content in the organic filler may be, for example, 15,000 ppm by mass or less, 10,000 ppm by mass or less, 5,000 ppm by mass or less, or 3,000 ppm by mass or less.

[0056] The filler content may be 1% by mass or more, 3% by mass or more, or 5% 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 main agent and the initiator.

[0057] (Plasticizer) Examples of plasticizers include phthalate ester compounds, alkyl sulfonic acid ester compounds, and adipic acid ester compounds.

[0058] 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.

[0059] (Crosslinking agent) Examples of crosslinking agents include aziridine-based crosslinking agents and carbodiimide-based crosslinking agents.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] [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.

[0069] 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.

[0070] Examples of adhesives include plastic laminated substrates, metal laminated substrates, electronic components, semiconductor components, and display components.

[0071] 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]

[0072] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to these examples.

[0073] [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 (Tg of homopolymer: 97°C, Molecular weight: 208.3, Kyoeisha Chemical Co., Ltd.) FA-513AS: Dicyclopentanyl acrylate (homopolymer Tg: 120°C, molecular weight: 206.3, Showa Denko Materials Co., Ltd.) FA-513M: Dicyclopentanyl methacrylate (homopolymer Tg: 175℃, molecular weight: 206.3, Showa Denko Materials Co., Ltd.) Dimethylacrylamide (homopolymer Tg: 119°C, molecular weight: 99.13, Fujifilm Wako Pure Chemical Corporation) FA-310AH: Phenoxyethyl acrylate (homopolymer Tg: 5℃, molecular weight: 192.2, Showa Denko Materials Co., Ltd.) CHA: Cyclohexyl acrylate (homopolymer Tg: 15℃, molecular weight: 154.2, Osaka Organic Chemical Industry Co., Ltd.) EBECRYL 8413: Aliphatic urethane acrylate (isobornyl acrylate content: 35%, weight-average molecular weight: 37000, Daicel-Ornescu 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 RY200S: Surface-treated silica (hydrophobic fumed silica surface-treated with silicone oil, manufactured by Nippon Aerosil Co., Ltd.) • Organic fillers B564: MBS-type core-shell particles (Kaneka Corporation, containing Irganox PS 800: 7800 ppm by mass and Irganox 245: 6000 ppm by mass as antioxidants) 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)

[0074] (Preparation of the main ingredient) The decomplexing agent, a compound having a radical polymerizable group, a polymerization control agent, a peroxide, and a filler were weighed into a poly bottle in the types and proportions (unit: parts by mass) shown in Table 1 or Table 2. The mixture was then mixed for 15 minutes at 2000 rpm using a rotary mixer (Thinky Co., Ltd., Awatori Rentaro), and then degassed for 5 minutes at 2000 rpm to prepare the main components for Examples 1-5 and Comparative Examples 1-7.

[0075] (Preparation of the initiator) The types and proportions (in parts by mass) of organoborane complexes, plasticizers, crosslinking agents, and fillers shown in Table 1 or Table 2 were weighed into a poly bottle and mixed for 15 minutes at 2000 rpm using a rotary mixer (Thinky Co., Ltd., Awatori Rentaro) at 2000 rpm. The mixture was then degassed for 5 minutes at 2000 rpm to prepare the initiators for Examples 1-5 and Comparative Examples 1-7. The initiators for Examples 1-5 and Comparative Examples 1-7 are identical in composition.

[0076] [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.

[0077] [Evaluation of flexibility] 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 cured release sheet and adhesive composition. Following 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. Higher values ​​for breaking strength and elongation indicate better flexibility.

[0078] [Table 1]

[0079] [Table 2]

Claims

1. The invention comprises a main component containing a decomplexing agent and a compound having a radical polymerizable group, and an initiator containing an organoborane complex, At least one of the main component and the initiator further contains a polymerization control agent, The compound having the radical polymerizable group includes a monofunctional polymerizable compound having a homopolymer glass transition temperature of 80°C or higher, a monofunctional polymerizable compound having an aromatic ring, and a polyfunctional polymerizable compound having a weight-average molecular weight of 15,000 to 60,000. An adhesive set in which the content of the polyfunctional polymerizable compound is 20% by mass or more and 60% by mass or less, based on the total amount of the compound having the radical polymerizable group.

2. The adhesive set according to claim 1, wherein the content of the polyfunctional polymerizable compound is 25% by mass or more and 60% by mass or less, based on the total amount of the compound having the radical polymerizable group.

3. The adhesive set according to claim 1 or 2, wherein the polyfunctional polymerizable compound comprises urethane acrylate.

4. 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 3.

5. A method for manufacturing an adhesive according to claim 4, 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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